Progress in Energy and Combustion Science 66 (2018) 141
175

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Advances and challenges in alkaline anion exchange membrane fuel cells

TagedPZ.F. Pana, L. Ana,*, T.S. Zhaob,*, Z.K. Tangc
a
TagedP Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China
b
Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
c
Department of Physics, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

TAGEDPA R T I C L E I N F O TAGEDPA B S T R A C T

Article History: The last several decades have witnessed the rapid development of alkaline anion exchange membrane fuel
Received 25 September 2017 cells (AAEMFCs) that possess a series of advantages as compared to acid proton exchange membrane fuel
Accepted 8 January 2018 cells, such as the enhanced electrochemical kinetics of oxygen reduction reaction and the use of inexpen-
Available online xxx
sive non-platinum electrocatalysts, both of which are rendered by the alkaline medium. As an emerging
power generation technology, the significant progress has been made in developing the alkaline anion
TagedPKeywords:
exchange membrane fuel cells in recent years. This review article starts with a general description of the
Fuel cells
setup of AAEMFCs running on hydrogen and physical and chemical processes occurring in multi-layered
Alkaline anion exchange membranes
Electrocatalysts
porous structure. Then, the electrocatalytic materials and mechanisms for both hydrogen oxidation and
Single-cell designs oxygen reduction are introduced, including metal-based, metal oxide-based, and non-metal based electro-
Power density catalysts. In addition, the chemistries of alkaline anion exchange membranes (AAEMs), e.g. polymer back-
bone and function groups, are reviewed. The effects of pre-treatment, carbonate, and radiation on the
performance of AAEMs are concluded as well. The effects of anode and cathode ionomers, structural
designs, and water flooding on the performance of the single-cell are explained, and the durability and
power output of a single-cell are summarized. Afterwards, two innovative system designs that are hybrid
fuel cells and regenerative fuel cells are presented and mathematical modeling on mass transport phe-
nomenon in AAEMFCs are highlighted. Finally, the challenges and perspectives for the future development
of the AAEMFCs are discussed.
© 2018 Elsevier Ltd. All rights reserved.

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
2. General description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3. Electrocatalytic materials and mechanisms for hydrogen oxidation reaction in alkaline media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.1. Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.2. Metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4. Electrocatalytic materials and mechanisms for oxygen reduction reaction in alkaline media. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4.1. Precious metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.2. Non-precious metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
4.3. Metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
4.4. Non-metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5. Alkaline anion exchange membranes (AAEMs): chemistries and performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.1. Polymer backbone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.1.1. Poly(vinyl alcohol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.1.2. Poly(arylene ether)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
5.1.3. Poly(2,6-dimethyl-1,4-phenyleneoxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
5.1.4. Poly(tetrafluoroethylene). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
5.1.5. Polysulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
5.2. Functional groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
5.2.1. Quaternary ammonium (QA). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

* Corresponding authors.
E-mail address: [email protected] (L. An), [email protected] (T.S. Zhao).

http://dx.doi.org/10.1016/j.pecs.2018.01.001
0360-1285/© 2018 Elsevier Ltd. All rights reserved.
142 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

5.2.2. Imidazolium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

5.3.
Other chemistries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
5.4.
AAEM performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
5.4.1. Effect of pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
5.4.2. Effect of carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
5.4.3. Effect of radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6. Single-cell: designs and performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
6.1. Effect of anode ionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
6.2. Effect of cathode ionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
6.3. Effect of structural designs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
6.4. Effect of water flooding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
6.5. Single-cell durability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
6.6. Single-cell performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
7. Innovative system designs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
7.1. Hybrid fuel cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
7.2. Regenerative fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
8. Mathematical modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
9. Remaining challenges and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
10. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171

1. Introduction TagedPBorohydrides with high energy density are also recognized as a suit-
able fuel for AAEMFCs due to the fact that they are easy to handle,
TagedPWe have to adopt new energy supply technologies that utilize store, and transport as well. In addition, the products in the anode
renewable energy sources [1
8], due to the current energy and envi- effluent can be converted back to borohydrides, which is beneficial
ronmental issues we are facing today. Among them, fuel cells have for a sustainable future [18]. In consideration of degree of commer-
been considered as one of the most promising clean and efficient cialization, this article will focus on the AAEMFCs running on hydro-
power generation technologies for a sustainable future [9
15]. gen that is the maturest in commercialization. The objective of this
Hence, tremendous efforts have been made on the development of review is to provide a general description of this type of fuel cell,
fuel cells [16
22]. Alkaline fuel cells (AFCs) that use potassium introduce electrocatalytic materials for hydrogen oxidation and oxy-
hydroxide (KOH) solution as the liquid electrolyte have shown much gen reduction reactions, summarize the alkaline anion exchange
success since the 1960s, particularly working as the energy supply membranes (AAEM) and single-cell performance, as well as highlight
devices powering the Gemini and Apollo spacecraft, due to the fact the remaining challenges and future directions.
that the electrochemical kinetics of the oxygen reduction reaction
(ORR) is much enhanced resulting from the alkaline environment, 2. General description
allowing the absence of expensive noble metals in preparing the
electrocatalysts and thus reducing the cost of the fuel cell system TagedPIn principle, the structure of AAEMFCs is just borrowed from pro-
[23
25]. Despite its compelling merits, however, this fuel cell tech- ton exchange membrane fuel cells (PEMFCs), with the main differ-
nology has not made sufficient progress in market presence yet. One ence that the solid membrane is an AAEM instead of a proton
significant factor preventing widespread commercialization is the exchange membrane (PEM). In AAEMFCs, the charge carrier is OH¡
use of the alkaline liquid electrolyte, which may cause two problems transporting through the AAEM from the cathode to the anode,
[26]. One is the carbonate, the product of the side reaction between while H+ works as charge carrier transporting through the PEM from
hydroxide ions in the liquid electrolyte and carbon dioxide in the air, the anode to the cathode in PEMFCs. Hence, AAEMFCs have been
reducing the concentration of hydroxide ions and potentially block- considered as an alternative to PEMFCs and garnered renewed atten-
ing the pores of the porous electrode via the precipitation of the tion recently due to the above-mentioned advantages. Currently,
metal carbonate [27
29]. The other is electrode flooding and drying many researchers have put their focus on the synthesis of polymeric
problems, which are more likely to arise if the liquid electrolyte is alkaline anion exchange membranes with high ionic conductivity
not well controlled [30,31]. and excellent chemical stability, as well as novel electrocatalysts
TagedPTo address the issues caused by involving the liquid electrolyte, that are favorable and low cost [53
63].
ion exchange membrane fuel cells that employ solid electrolyte have TagedPLike other fuel cells, a single AAEMFC consists of three main com-
received ever-increasing attention [32
36]. The use of solid electro- ponents, i.e. an anode, a cathode, and an AAEM, so-called membrane
lyte membranes in fuel cells can remove the carbonate problem and electrode assembly (MEA), as shown in Fig. 1. Specifically, the inte-
avoid the liquid electrolyte management. Hence, extensive efforts grated multi-layered porous structure is constituted sequentially by
have been devoted to developing alkaline AAEMFCs and remarkable an anode gas diffusion layer (GDL), an anode catalyst layer (CL), an
achievements have been made [37
39]. In addition, many other AAEM, a cathode CL, and a cathode GDL. The GDLs in the anode and
advantages of the AAEMFCs are summarized as follows: (1) faster cathode that are both composed of two layers, a backing layer (BL)
electrochemical kinetics of the ORR in alkaline media [40,41], based on carbon paper or carbon cloth and a micro-porous layer
(2) absence of noble metal electrocatalysts [42,43], (3) minimized (MPL) that is comprised of carbon powders mixed with hydrophobic
corrosion problems in the alkaline environment [44,45], and polymer (typically PTFE). The CLs are usually made of electrocata-
(4) cogeneration of electricity and valuable chemicals [46
48]. Cur- lysts mixed with ionomer, resulting in the formation of triple-phase
rently, compressed hydrogen and liquid alcohol are the most com- boundaries (TPBs) for the electrochemical reactions, i.e., hydrogen
mon fuels used in AAEMFCs. The liquid alcohols, e.g. methanol, oxidation reaction (HOR) and ORR. Particularly, the GDL provides
ethanol, formate, and small polyalcohols, are convenient to handle, the support for the corresponding CL, distributes the reactants uni-
store, and transport [49
51]. Another advantage is that they are formly, and transports electrons to the current collector. Recently, Li
easy to be acquired from the abundant biomass, suggesting that the et al. [64] proposed a metal foam-based electrode integrating the
process is carbon-neutral and the sources are sufficient [52]. flow field, BL, MPL, and CL into a whole, which facilitates the mass
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 143

3. Electrocatalytic materials and mechanisms for hydrogen

oxidation reaction in alkaline media

TagedPPlatinum (Pt) is generally used as the electrocatalysts for hydro-

gen oxidation in AAEMFCs, which negates a prime advantage of
alkaline fuel cells, which is potentially free from Pt-based electroca-
talysts. The anodic reaction in acid media is expressed:
H2 ! 2Hþ þ 2e
ð4Þ

while, the product of the anodic reaction in alkaline media is water:

H2 þ 2OH
! 2H2 O þ 2e
ð5Þ
TagedPParticularly, the HOR activity on the platinum group metals
(PGM) decreases with increasing the pH value. Sheng et al. [65]
reported that the electrochemical kinetics of the HOR were at least
two orders of magnitude slower in alkaline media than that in acid
media. Similarly, Durst et al. [66] demonstrated that the exchange
current densities on Pt/C, Pd/C, and Ir/C in acidic media (pH = 0)
were all declined by about two orders of magnitude when the pH
increased to 13. The oxophilicity did not contribute to enhancing the
HOR activity in high pH. They suggested that the pH-dependent HOR
activity was associated with the hydrogen binding energy (HBE). It
Fig. 1. Schematic of a typical alkaline anion exchange membrane fuel cell (AAEMFC).
was explained by Sheng et al. [67] that HBE is likely the sole descrip-
tor for the HOR/HER activity on Pt in pH-buffered electrolytes. The
TagedPand charge transport and extends the TPBs. The anode and the cath- results from the rotating disk electrode test and cyclic voltammetry
ode are separated by an AAEM, preventing the hydrogen crossover test showed that the HOR/HER activity decreased and HBE linearly
to the cathode, which causes the fuel loss and mixed potential. increased with the increasing pH, respectively. It was proposed that
Meanwhile, the pathway for conducting hydroxide ions is built up. the adsorbed OH species did not participate in the reaction, but
The external circuit provides the channel for the electrons to form influenced the HBE, leading to the reduce of HOR/HER activity. How-
the loop. ever, Ledezma-Yanez et al. [68] argued that the pH-dependent HBE
TagedPOn the anode, humidified hydrogen is fed to the anode flow chan- change did not account for the HER overpotential on Pt(111). They
nel and transported through the anode GDL, finally to the anode CL, observed that both the HER and H-underpotential deposition
where hydrogen reacts with hydroxide ions to produce water and (H-UPD) were slower in alkaline media even if the thermodynamic
electrons. The anodic reaction is: driving force was the same, implying that hydrogen adsorption was
a kinetically hindered step. Therefore, it was elucidated that at the
H2 þ 2OH
! 2H2 O þ 2e
E0a ¼
0:83V ð1Þ
potential of H-UPD and HER, the interfacial water network inter-
TagedPOn the cathode, humidified oxygen supplied by the cathode flow acted with the strong interfacial electric field in alkaline media,
channel is transported through the cathode GDL to the cathode CL, resulting in the water network more rigid and more difficult to reor-
where oxygen is reduced in the presence of water to produce ganize during the charge transfer through the electrical double layer.
hydroxide ions: Consequently, the rate of hydrogen adsorption was severely influ-
enced by the energetic barrier derived from the strength of the inter-
1
O2 þ H2 O þ 2e
! 2OH
E0c ¼ 0:40V ð2Þ facial electric field. To overcome this constrain, many efforts have
2
been made to develop non-platinum catalysts for HOR with high
TagedPThen, the generated hydroxide ions are conducted through the activity at a lower cost [69
84]. This section will describe some
AAEM for the HOR. types of electrocatalyst, including metals and metal oxides.
TagedPTherefore, the overall reaction combining the HOR given by
Eq. (1) and the ORR given by Eq. (2) is expressed as follows: 3.1. Metals
1
H2 þ O 2 ! H2 O E0 ¼ 1:23V ð3Þ TagedPMany efforts have been made to increase the metal electrocata-
2
lyst activity aiming at reducing the amount of Pt, even replacing Pt
TagedPIt should be noted that the theoretical cell voltage cannot be real- [53,69,70,74,77,79-81]. Since palladium (Pd) is similar to Pt in elec-
ized due to a series of irreversible losses, such as overpotentials tronic properties, the HOR on the Pd surface may follow the same
caused by activation, ohmic, and mass-transport processes. In addi- mechanism. In addition, Pd/C and Pt/C exhibited comparable HOR
tion, it is worthwhile to note that the hydrogen and oxygen gases activity examined by the thin-film rotating disk electrode in acid
need humidification before fed into the fuel cell in order to achieve environment [78]. Hence, many efforts have been conducted to
better performance. The major reasons can be summarized as fol- improve the electrocatalytic activity of Pd [53,69,79-81]. Bakos et al.
lows: (1) one of the main deficiencies of AAEMs is that the conduc- [53] studied the synergetic activity of Pd/Ni for the HOR in alkaline
tivity of AAEMs is sensitive to relative humidity. Hence, the media. Fig. 2 illustrated the surface and size distribution of the
humidified gases that are supplied to the channel can humidify the Pd/Ni. It was shown that 17% of a Ni film covered by a Pd layer of
membrane, enhancing the ionic conductivity and thus reducing the around 1.5 nm thickness exhibited the highest HOR activity than
internal resistance; (2) in consideration of the electrochemical reac- other Pd coverages. For the Pd coverage lower than 17%, the current
tion on the cathode, humidified oxygen provides the essential water density increased linearly with the coverage, and then reached a pla-
molecular that will react with oxygen to form hydroxide ions. In the teau upon further increase, which is attributed to the diffusion limit
following section, the electrocatalytic materials for HOR, including for the HOR process. Similarly, Alesker et al. [69] used Pd nanopar-
metal electrocatalysts and metal oxide electrocatalysts, are reviewed ticles to grow onto Ni nanoparticles as the HOR electrocatalyst,
and discussed. resulting in a peak power density of 400 mW cm¡2 in an AAEMFC
144 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Fig. 2. AFM images of the Pd/Ni surfaces and size distribution of the grains observed for (A) 17% Pd coverage and (B) 35% Pd coverage [53]. Reproduced with permission from
Elsevier.

agedPfT abricated with Pd (1.5 mg cm¡2) as anode electrocatalyst and Ag TagedP eakened hydrogen binding energy on CoNiMo. Zhuang et al. [76]
w
(3 mg cm¡2) as cathode electrocatalyst with dry hydrogen fed at a prepared a composite electrocatalyst, nitrogen-doped carbon nano-
flow rate of 200 standard-state cubic centimeter per minute (sccm) tubes supporting nickel nanoparticles (Ni/N-CNT), to replace Pt for
and the air fed at a flow rate of 1000 sccm. It was indicated that the an efficient HOR. Although the N-CNT did not directly contribute the
HOR activity was enhanced, which was evidenced by the negative HOR activity, it could significantly improve the catalytic activity of
shift of the HOR onset potential. In addition, it was believed that the Ni nanoparticles, meaning that the mass activity and exchange cur-
high activity was ascribed to the presence of the OHads on the Ni sur- rent density of the Ni/N-CNT were increased 33 and 21 times than
face, providing a faster reaction route for the HOR. In addition, the that of bare Ni nanoparticles, respectively. It was indicated that the
nickel-based electrocatalysts for the HOR have also been investi- high HOR activity was ascribed to the synergetic effect of N atom
gated [74
76]. Hu et al. [74] studied the feasibility of tungsten and Ni. Ohyama et al. [70] synthesized small ruthenium nanopar-
doped nickel (Ni
W) as the anode electrocatalyst for AAEMFCs. The ticles by liquid phase reduction of RuCl3 by NaBH4 under pH control
results showed that the equilibrium potential of the HOR on Ni
W and characterized the structure of the Ru/C via X-Ray diffraction
was established in 200 s, indicating that the electronic surface of Ni (XRD), transmission electron microscope (TEM), and X-ray absorp-
was tuned and the oxidation tolerance of Ni surface was significantly tion fine structure (XAFS) spectroscopy. The results indicated that
enhanced. It was shown that the highest power density reached the diameter of Ru particles was 3 nm under pH control (pH = 7),
40 mW cm¡2 with humidified hydrogen and oxygen both at a flow which was much smaller than that without pH control (pH = 2). The
rate of 50 sccm at 60°C, when Ni
W (17.5 mg cm¡2) and CoPPY/C peak power densities of a H2/O2 fuel cell fed with humidified H2 and
(2 mg cm¡2) were employed as anode and cathode electrocatalysts, O2 both at a flow rate of 500 sccm employing Tokuyama A201 as
respectively. To further improve the HOR activity, Sheng et al. [75] AAEM, Pt/C (0.5 mg cm¡2) as cathode electrocatalyst, and 3 nm Ru/C,
synthesized noble-metal-free electrocatalyst via electro-depositing 3 nm Pt/C, and 11 nm Ru/C as anode electrocatalysts are 250, 185,
a ternary metallic CoNiMo on a polycrystalline gold (Au) disk elec- and 134 mW cm¡2, respectively. In addition, the cell performance
trode. It was shown that the HOR activity of CoNiMo was 20 times with using Ru/C was increased with the cycle of fuel cell operation,
higher than pure Ni in alkaline media, which is attributed to the primarily because the Ru species was reduced during fuel cell
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 145

TagedPoperation, resulting in the highly active sites for hydrogen adsorp- 4. Electrocatalytic materials and mechanisms for oxygen
tion and oxidation. Recently, Alia et al. [77] synthesized copper (Cu) reduction reaction in alkaline media
nanowires (NWs) supported Pt (Pt/CuNWs) with a 100-nm diameter
and a 25
40 mm length for HOR in alkaline media. It was indicated TagedPExtensive studies have been conducted on the oxygen reduction
that compared to Pt/C, the area and mass exchange current densities reaction in alkaline media. The electrocatalytic reduction of oxygen
of Pt/CuNWs were promoted by 3.5 and 1.9 times, respectively. proceeds either two-electron pathway or four-electron pathway
Therefore, the improved performance was attributed to compressive [85]. Fig. 3(a) generally illustrated the ORR process in alkaline media.
strain on Pt and more adsorption of hydroxyl species provided by The subscripts of sa, a, b, and *denoted strongly adsorbed, weakly
inclusion of Cu. In summary, the novel HOR metal electrocatalysts adsorbed, bulk, and the vicinity of the electrode, respectively. All
that exhibit comparable performance with Pt are mainly based on reactions could be concluded as follows:
Pd, Ni, and Ru. Although the great progress has been made recently,
O2;a þ e
! O
2;a ð6Þ
attentions also should be paid to developing other substrate materi-
als that are more cost-effective. O
2;a þ H2 O þ e
$ HO
2;a þ OH
ð7Þ

Osa þ e
! O
sa ð8Þ

3.2. Metal oxides
O
2;sa þ H2 O þ e
! HO
2;sa þ OH

ð9Þ
T lthough the metal electrocatalysts are promising, metal oxide
agedPA
electrocatalysts that are inexpensive as well have been extensively HO
2;sa þ e
$ O
sa þ OH
ð10Þ
studied [71-73,82,83]. Lu et al. [71] synthesized Cr-decorated Ni
(CDN) nanoparticles and tested the effect of modulation on the sur- O
sa þ e
þ H2 O ! 2OH
ð11Þ
face reactivity toward oxygen via XRD and X-ray photoelectron
2O
2;a þ H2 O ! O2;a þ HO
2;a þ OH
ð12Þ
spectroscopy (XPS). It was indicated that CDN can be easily activated
by gaseous hydrogen at room temperature, resulting in the employ-
2HO
2:a ! 2OH
þ O2;a ð13Þ
ment of CDN as anode electrocatalyst. They showed that a peak
power density of 50 mW cm¡2 was achieved when CrOx/Ni HO
2;sa ! OH
þ Osa ð14Þ
(5 mg cm¡2) and Ag/C (1 mg cm¡2) were used as anode and cathode
electrocatalysts, respectively, as well as a quaternary ammonium O
2;sa ! Osa þ O
sa ð15Þ
polysulphone membrane with H2 (relative humidity (RH) = 100%) in
TagedPIt should note that only one electron was involved in the above
the anode and O2 (RH = 100%) in the cathode at 60°C. Lu et al. [72]
mentioned reactions. In the direct four-electron pathway, the first
also indicated that the CrOx was believed to weaken the binding of
oxygen to the Ni nanoparticles, resulting in the mild deactivation of
Ni via oxidation. Miller et al. [73] demonstrated that Pd nanopar-
ticles deposited by CeO2 showed excellent HOR activity. The single
fuel cell fabricated with Pd/C

CeO2 (0.3 mg cm¡2) as anode electro-
catalyst and Ag (3 mg cm¡2) as cathode electrocatalyst yielded a
maximum power density of 500 mW cm¡2, when dry hydrogen was
fed into the anode at a flow rate of 200 sccm and air was fed into the
cathode at a flow rate of 1000 sccm. While pure Pd was employed as
anode electrocatalyst, the peak power density was decreased to
100 mW cm¡2. CeO2, one of the most oxygen deficient compounds,
is known for the rapid saturation with hydroxide ions [82] and spill-
over of hydroxide ions to support metal nanoparticles [83]. It was
demonstrated that the Pd

H bonds were weakened and the supply
of the OHad was enhanced, accelerating the overall HOR. Recently,
Miller et al. [84] studied the effect of Pd loadings on the performance
of Pd/C

CeO2. The results from the single fuel-cell test showed that
the Pd/C

CeO2 with 10 wt% Pd loading yielded the highest power
density of 500 mW cm¡2 with Pd/C

CeO2 (0.3 mg cm¡2) as anode
¡2
electrocatalyst and Ag (3 mg cm ) as cathode electrocatalyst when
dry hydrogen was fed into the anode at a flow rate of 200 sccm and
air was fed into the cathode at a flow rate of 1000 sccm. While 6 wt%
Pd and 20 wt% Pd loadings in the single fuel cell exhibited 390 and
460 mW cm¡2 under the same conditions, respectively. Meanwhile,
the stability of Pd/C

CeO2 was superior than Pd/C under harsh
potential cycling.
TagedPIn summary, great progress has been made in the development of
HOR electrocatalysts with high catalytic activity and low cost to
replace Pt in AAEMFCs. Although numerous investigations have
been reported in recent literature, the stability of non-platinum elec-
trocatalysts is still the major limiting factor for the commercial
applications, which is derived from the morphological changes dur-
ing the process of electrocatalyst operation. Therefore, the future
research direction could be focused on enhancing the durability of Fig. 3. (a) General scheme of oxygen reduction reaction. [85]. Reproduced with per-
the newly synthesized electrocatalysts without sacrificing the HOR mission from Elsevier. (b) Modified form of Pourbaix diagram [86]. Reproduced with
activity. permission from The Electrochemical Society.
146 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedPstep was the formation of weakly adsorbed species via the diffusion TagedP roperty and performance of the electrocatalysts reported in recent
p
of bulk oxygen. Then the weakly adsorbed species became the literatures, including precious metal electrocatalysts, non-precious
strongly adsorbed species through chemisorption, which were the metal electrocatalysts, and non-metal electrocatalysts.
key intermediate in the process. As the strongly adsorbed species
were chemisorbed, the reactions associated with them were mainly 4.1. Precious metals
irreversible processes (k3, k4, k12, k13,). In the two-electron pathway,
the weakly adsorbed species were the critical intermediate. The dif- TagedPUndoubtedly, Pt/C is still the most commonly used electrocata-
ference of the strongly adsorbed species and the weakly adsorbed lyst, which is also the performance criterion of newly developed
species lied on the ability to desorb directly and go into solution. materials. However, the high cost and rarity have hindered the utili-
Since the weakly adsorbed species were more likely to be physi- zation of Pt in fuel cells, resulting in numerous research efforts led to
sorbed, adsorption-desorption equilibrium with corresponding spe- the development of non-Pt noble metal electrocatalysts with high
cies in solution was established as shown in k2 and k¡2, k20 and k¡20, activity for AAEMFCs [55,87-93]. Fortunately, Ag- and Pd-based elec-
as well as k25 and k¡25. It was believed that a superoxide ion HO
2;a trocatalysts, more abundant noble metals than Pt, have exhibited
could be formed after the oxygen molecule received an electron. promising ORR activity via various modification methods, including
Subsequently, as the weakly bound superoxide ion was unstable in dispersing nanoparticles evenly on functionalized support, estab-
aqueous solution, thus it could rapidly go through either a chemical lishing core
shell structure, and inserting other elements. Vinodh
pathway decomposing into HO
2;a and oxygen or a electrochemical et al. [55] synthesized carbon supported silver (Ag/C) with different
pathway receiving an electron and a proton to form HO
2;a . Analo- metal loadings via wet impregnation method. The schematic repre-
gously, the HO
2;a possessed two reaction routes: one was to be sentation of cathode was illustrated in Fig. 4(a). The characteristics
chemisorbed producing HO
2;sa , and the other was to diffuse into the of the electrocatalysts were investigated by XRD, thermogravimetric
bulk solution. It can be seen from Fig. 3(b) that the formation of per- analysis (TGA), UV
visible diffuse reflectance spectra (DRS-UV), and
oxide intermediate species, HO2¡ and H2O2, is more energetically Raman spectroscopy. The results indicated that the Ag particles in a
favorable during the ORR due to the lower overpotential. Thus, the range of 5
11 nm were well distributed and stable at 800°C as well
ORR kinetics are dramatically more sluggish in acid media than that as the maximum cell voltage and power density of 0.69 V and
in alkaline one, which can be explained by the stabilization effect of 109 mW cm¡2 were obtained with 10 wt% metal electrocatalysts,
the peroxide intermediate of HO2¡ caused by the negative charge respectively. The higher ORR activity was attributed to the larger
[86]. When the fuel cell is discharging, the cathode potential is surface area, enhanced electrical conductivities, and high densities
higher than the potential of zero charge, resulting in the positive of surface defects. Maheswari et al. [90] investigated the electro-
charge on the electrode Hence, it is HO2¡ rather than the neutral chemical kinetics of Pd/C, Pt/C, and Au/C as cathode electrocatalysts
molecule of H2O2 that can be adsorbed on the cathode derived from via steady-state performance test and linear sweep voltammetry
the electrostatic attraction and further to be reduced on the active (LSV). It was reported that the Pd/C showed higher performance
sites. As the ORR obstruction has been unveiled, a gate of synthesiz- (55 mW cm¡2) than Pt/C (40 mW cm¡2) and Au/C (1 mW cm¡2) with
ing variety of electrodes has been opened. We herein summarize the both humidified hydrogen and oxygen fed at a rate of 500 sccm,

Fig. 4. (a) Schematic of cathode side in the MEA using Ag/C as a catalyst [55]. Reproduced with permission from Springer. (b) Optimal structure of rGO(N)
Co(II)
O

Co(II)
rGO
(N) [97]. (c) ORR current densities of thin film of (I) LaNiO3, LaCoO3, LaFeO3, LaMnO3, and LaCrO3 and (II) LaNi0.5Co0.5O3, LaNi0.5Fe0.5O3, LaNi0.5Mn0.5O3, and LaNi0.5Cr0.5O3. (III) (IV)
Magnified portion to pinpoint the onset ORR potentials on panels I and II, respectively. Reproduced with permission from American Chemical Society [99]. (d) Schematic of the
selectivity inside and outside of MMT during NG synthesis [109]. Reproduced with permission from Wiley.
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 147

TagedPresulting from the Pd surface exhibiting the optimum balance fTagedP uture utilization. Hence, further to reduce the cost, tremendous
between the kinetics of O = O bond breaking and electrocatalytic efforts have been made to develop non-precious metal electrocata-
reduction of the oxygenated intermediates or O

H formation. How- lysts [94
97]. However, the abundant 3d transition metals do not
ever, the carbon support will face two main challenges that interfere show ORR activity due to the affinities with oxygen. Fortunately, a
the performance of electrocatalysts. One is that carbon support may breakthrough has been reported that metal macrocycle compounds
suffer from drastic corrosion and oxidation during fuel cell opera- exhibit promising ORR activity, in which the N-metal bond plays an
tion. The other is that the completion of four-electron ORR may be essential role in the progress [94]. On one hand, the formidable
hindered due to the fact that the two-electron outer-sphere electron anchoring effect between the metal and surrounding N elevates the
transfer is promoted. Hence, Zhang et al. [92] proposed that the gra- stability of the compounds. On the other hand, the redox potential
phene oxide (GO) had the potential to serve as support material due can be relocated by the metal
N bond that serves as the bridge for
to the abundant oxygen containing functional groups that offer large the p-conjugated ligands on the outer periphery. Recently, Kruu-
surface area. Alloyed Pd
Au nanochains networks were uniformly senberg et al. [94] synthesized Co and Fe phthalocyanine electroca-
anchored on reduced graphene oxide (Pd
Au NNs/RGO) via a one- talysts employing multi-walled carbon nanotubes (MWCNTs) as
pot wet-chemical co-reduction method with the assistance of caf- support materials via a simple thermal method. The results from
feine. The results from cyclic voltammetry (CV) demonstrated that the rotating disk electrode (RDE) tests showed that the onset
the Pd
Au NNs/RGO exhibited much more positive onset potential potentials of CoPc/MWCNT and FePc/MWCNT electrocatalysts was
and half-wave potential than those achieved by using Pd black and ¡0.1 V and ¡0.15 V, respectively, indicating that the CoPc/MWCNT
Pd/C, indicating that the ORR activity was significantly improved. possessed high ORR electrocatalytic activity than FePc/MWCNT.
Meanwhile, it was shown from the ORR polarization curves that no The single fuel cell test demonstrated that the peak power densities
obvious degradation occurred after the Pd
Au NNs/RGO modified were 100, 60, and 120 mW cm¡2 with CoPc, FePc, and Pt
electrode underwent 1000 times tests. It is worthy to note that there (0.6 mg cm¡2) as cathode electrocatalysts and Pt (0.4 mg cm¡2) as
are various support materials for nanoparticles, including Ti, Ni anode electrocatalyst with humidified H2 fed into the anode at a
foam, carbon nanotubes (CNTs), carbon nitride, and carbon nanofib- rate of 200 sccm and humidified O2 fed into the cathode at a rate of
ers. Similarly, bimetallic core
shell nanostructures possess the 400 sccm at 45°C. Li et al. [95] synthesized non-precious metal
enhanced ORR activity, primarily due to the rough and porous surfa- electrocatalysts (denoted as CoFeN/C

H, CoFeN/C

HL, and CoFeN/
ces. Recently, Fu et al. [93] synthesized Au@Pd core-shell nanothorns C

HLH) consisting of carbon, nitrogen and transition metal via dif-
(CSNTs) via a facile co-chemical reduction method with poly(allyl- ferent post-treatment methods. They investigated the post-treat-
amine hydrochloride) (PAH) and ethylene glycol (EG) as agents at ment methods on the performance of electrocatalysts for ORR in
room temperature. The results from CV showed that the Au@Pd alkaline media via RDE technique. It was reported that the heat
CSNTs had a positive shift of 34 mV and 30 mV of onset and half- treatment played a crucial role in generating highly active catalytic
wave potentials, respectively, compared with Pd black, demonstrat- sites. It was also shown that a peak power density of 177 mW cm¡2
ing that the ORR activity was more competitive. It was concluded and open circuit voltage (OCV) of 0.97 V were obtained when
that the improved ORR activity could be attributed to: (1) the high CoFeN/C

HLH (4 mg cm¡2) has been employed as cathode electro-
electrochemically active surface area (ECSA) resulted in sufficient catalyst and Pt (0.4 mg cm¡2) as anode electrocatalyst with humidi-
active sites, (2) the electron and oxygen transport was facilitated by fied H2 fed into the anode at a rate of 200 sccm and humidified
the unique porous construction, (3) the coverage of the active sites O2 fed into the cathode at a rate of 400 sccm at 50°C. While for Pt
by the hydroxyl and superhydroxyl groups was suppressed due to electrocatalyst, the peak power density was 196 mW cm¡2 and the
the core
shell structure. Inserting other elements into noble metal OCV was 1.04 V, showing that the CoFeN/C

HLH electrocatalyst
electrocatalysts is another way to improve the ORR performance of had the possibility to replace expensive Pt. Song et al. [96] prepared
the alloy electrocatalysts. Generally, the 3d transition metals have carbon black based Fe
Nx/C electrocatalysts for the ORR. It
been widely used as the alloying elements to promote the activity was demonstrated that the activity order of different active sites
and stability of the electrocatalysts. Maheswari et al. [91] synthe- is Fe
N4/2

C > Fe4

N

C > N

C >> Fe4

C  C and the one
sized PdCo electrocatalysts in varying atomic ratios of Pd to Co, with Fe 10 wt% and N 1.57 wt% exhibited the best performance
namely 1:1, 2:1, and 3:1, and investigated the structure, dispersion, (107 mW cm¡2). In addition, the Fe
N/C electrocatalysts could
electrochemical characterization and surface area of PdCo/C via XRD, be synthesized by direct pyrolysis of precursors, which was cost-
TEM, and CV, respectively. It was confirmed that the alloy formation efficient and batch manufacturing, giving the possibility of Fe
N/C
and lattice contraction existed between Pd and Co. The TEM images electrocatalysts for large-scale commercial applications. He et al.
indicated that the nanoparticles were crystallized and uniformly [97] synthesized a new nanocomposite electrocatalyst containing
dispersed on carbon. It was also shown that when Co content in high loading cobalt oxide (24.7 wt%, Co) via incorporating CoO onto
the alloy increased, the mean particle size decreased due to the nitrogen-doped reduced GO as shown in Fig. 4(b). They reported
increased average Pd
Pd bond distance. The results from the single that a synergistic effect between rGO and CoO, resulting from the
fuel cell test indicated that Pd/Co (3:1) possessed higher perfor- unique rGO(N)
Co(II)
O

Co(II)
rGO(N) structure, might facilitate
mance (85 mW cm¡2) with both humidified H2 and O2 fed at rates of the ORR in alkaline media and enhance the four-electron selectivity
500 sccm at atmospheric pressure than PdCo (2:1)/C (75 mW cm¡2), as well. Furthermore, abundant defects and nitrogen doping
PdCo (1:1)/C (26 mW cm¡2) as well as Pd/C (56 mW cm¡2), which resulted in the accommodation of graphene-based supports for a
was attributed to the higher ORR activity and selectivity of PdCo high Co loading. The fuel cell test results showed that the perfor-
(3:1)/C than PdCo (2:1)/C, PdCo (1:1)/C as well as Pd/C. In summary, mance of the CoO/rGO(N) did not exhibit significant difference with
the precious metal electrocatalysts show comparable ORR electroca- Pt up to 400 mA cm¡2. While the power density of the CoO/rGO(N)
talytic activity with Pt. One of the future directions is to enhance the experienced a large drop compared to Pt (248 mW cm¡2 vs
durability of the existing electrocatalysts, while the other is to exca- 387 mW cm¡2), which was ascribed to the relatively low electron
vate the potential precious electrocatalysts with high ORR activity. conductivity. In conclusion, compared to precious electrocatalysts,
the use of non-precious metal electrocatalysts has further reduced
4.2. Non-precious metals the cost. However, the electrocatalysts suffer severe corrosion and
degradation during the fuel cell operation, especially at high cur-
TagedPThough the precious metal electrocatalysts catalyze the ORR rent densities. Hence, the stability of the electrocatalysts in harsh
efficiently, the high cost and insufficient durability shadow their environment needs to be enhanced.
148 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

4.3. Metal oxides TagedP RR. It is believed that a near unity eg orbital occupancy in transition
O
metal cation, closer transition metal D-band and oxygen p-band
TagedPIn recent years, great attention has been paid into a different center relative to the Fermi level, high covalency of the
class of metal oxides electrocatalysts so-called perovskite electroca- metal
oxygen bond, and oxygen deficiency are favorable for the
talysts for ORR, which are considered as alternatives to precious ORR activity of the perovskites. Future research direction can
metal electrocatalysts due to the ORR activity and low cost be elucidating the active sites and the relevant ORR mechanism
[98
106]. Generally, the perovskite electrocatalysts can be denoted that are essential to provide valid guidance to tune the structures
as of perovskite allowing enhanced O2 adsorption and subsequent dis-
A1¡x¡yA’ xA’’yB1¡x¡yB’xB’’yO3, in which A always represents rare-earth association. In addition, the other research focus can be integrating
elements (La, Pr, and Gd) or alkaline earth metal elements (Sr and perovskite electrocatalysts with ORR-active nanocarbons to
Ba) and B always refers to transition-metal elements (Mn, Co, Ni, significantly improve mass activity by increasing the active surface
and Fe). Suntivich et al. [98] indicated that the ORR activity of perov- areas and enhance charge/mass transport due to its low electrical
skite electrocatatlysts was primarily related to s *-orbital (eg) occu- conductivity [104].
pation and the extent of B-site transition-metal-oxygen covalency,
which could serve as the design principle for synthesizing perovskite 4.4. Non-metals
electrocatalysts with promising ORR activity. The principle could be
claimed that the perovskite electrocatalysts that possessed an eg-fill- TagedPA non-metal electrocatalyst, also called metal-free electrocata-
ing (s *-orbital occupation) close to 1 exhibited the highest ORR lyst, does not include any metal element. To further reduce the cost
activity. Moreover, enhancing the covalency between the metal 3d and increase the ORR activity, considerable progress has been made
and oxygen 2p orbitals also contributed to improving the ORR activ- in the synthesis of metal-free electrocatalysts. Recently, it has been
ity. In a recent publication by Sunarso et al. [99], the ORR activity of reported that the carbon doped with nitrogen shows good ORR
La-based perovskite electrocatalysts was investigated via a thin-film activity [107
113]. Higgins et al. [107] synthesized three types of
rotating ring-disk electrode test. Fig. 4(c) showed the results that nitrogen doped carbon nanotubes (N-CNTs), denoted as ethylenedi-
LaCrO3 performed largest ORR current density and most positive amine (ED-CNTs), 1,3 diaminopropane (DAP-CNTs), and 1,4 diamino-
onset potential among the LaMO3 (M = Ni, Co, Fe, Mn, and Cr). Nota- butane (DAB-CNTs), via a simplistic single injection chemical vapor
bly, when half of the Ni in LaNiO3 was substituted with Co, Fe, Mn, deposition (CVD) setup. Then thin and free standing films, fabricated
and Cr, a more positive shift of onset potential was observed for all with the N-CNTs, were tested as the ORR electrocatalyst in a single
the newly obtained electrocatalysts, which could be explained by fuel cell with hydrogen and oxygen both fed at a rate of 300 sccm. It
the valence state change of transition-metal cation. The Kouteck- was indicated that the ED-CNT film displayed the significantly
y
Levich analysis implied that the ORR proceeded for-electron path- higher performance in alkaline media than commercial carbon sup-
way on all the perovskite electrocatalysts, which was consistent ported platinum (25.5 mW cm¡2 vs 19.1 mW cm¡2), which was
with that little hydroperoxide ion was detected during the negative ascribed to the high extent of nitrogen doping, resulting in the dis-
scan from 0.5 V to ¡0.75 V. Jin et al. [100] prepared an urchin-like tinct structural properties of N-CNTs and enhanced electronic prop-
La0.8Sr0.2MnO3 (LSM) perovskite oxide as electrocatalyst for both erties. Similarly, Rao et al. [108] prepared nitrogen doped aligned
ORR and OER via a co-precipitation method with urea as a precipita- carbon nanotubes via an alumina template technique. It was
tor. The results from the SEM and BET analysis showed that the mor- depicted from microscopic images that the nanotubes exhibited an
phology was spherical particles with thorns radially distributed on outer diameter of 100 nm and length of 60 mm. The OCV of the
the surface and the specific surface area was 48 m2 g¡1. It was indi- AAEMFC employing the N-CNT (5 mg cm¡2) as the cathode electro-
cated that the four-electron pathway was dominant during ORR and catalyst was »0.87 V, which was comparable to that achieved by
a maximum cathodic current density was 5.2 mA cm¡2 at ¡1.0 V vs. using the commercial Pt/C (0.5 mg cm¡2) as the cathode electrocata-
Ag/AgCl with 2500 rpm. Stoerzinger et al. [101] found that the lyst. In addition, a peak power density of 37.3 mW cm¡2 was
(001)-oriented LaMnO3-based (LMO) perovskite films have intrinsic achieved with the humidified H2 (95% RH, flow rate = 500 sccm) as
ORR activities comparable to those of high-surface-area LMO pow- fuel at the anode and humidified O2 (95% RH, flow rate = 1000 sccm)
der catalysts, which was attributed to (001) surface being the activ- as oxidant at the cathode. Though the performance was a little infe-
ity dominant facet. When the thickness of LMO film grown on rior in comparison to that of the AAEMFC fabricated with Pt/C elec-
Nb-doped SrTiO3 (NSTO) reduced, the ORR activity decreased. This trocatalyst (61.7 mW cm¡2), it exhibited potential to replace the
phenomenon was explained by the barrier rooted in interfacial band precious metal electrocatalysts. Ding et al. [109] proposed a novel
bending that hindered electron transfer at the electrode-electrolyte method to synthesize pyridinic- and pyrrolic-doped graphene for
junction and the increased eg orbital occupancy due to the charge the ORR with the aid of layered montmorillonite (MMT). A high yield
transfer from the NSTO to LMO. Recently, Risch et al. [102] utilized of planar N that was catalytically active toward the ORR was
pulsed laser deposition to synthesize well-defined surfaces consist- observed, as shown in Fig. 4(d). The fuel cell fabricated with
ing of Ba0.5Sr0.5Co0.8Fe0.2O3¡d (BSCF) on thin film La0.8Sr0.2MnO3¡d the NG@MMT (4 mg cm¡2) as cathode electrocatalyst and Pt
(LSMO) grown on (001)-oriented NSTO as a bifunctional electrocata- (0.3 mg cm¡2) as anode electrocatalyst showed a peak power density
lyst. The combined overpotentials from both OER and ORR kinetics of 320 mW cm¡2 with hydrogen and oxygen supplied to the anode
on BSCF|LSMO|NSTO could be as low as 0.7 V, which rivaled the and the cathode at flow rates of 150 and 200 sccm, respectively.
intrinsic activities of state-of-the-art catalysts in the literature. Addi- Notably, the performance, which was comparable to that of single
tionally, the surface stability of the LSMO|NSTO was promoted by the fuel cell employing commercial Pt as anode electrocatalyst
decoration of BSCF. A hybrid electrocatalyst composed of NiCoMnO4 (451 mW cm¡2), could be further enhanced by reinforcing the oxy-
nanoparticles that were anchored on N-doped graphene nanosheets gen transport. Lu et al. [113] synthesized nitrogen-doped reduced
with high efficiency and low cost was proposed [103]. It was demon- graphene oxide (N-RGO) via facial treatment of grapheme employ-
strated that the NiCoMnO4/N-rGO exhibited excellent ORR activity ing urea as agents at different temperatures. It could be seen from
(Eonset = 1.5 V vs. RHE and high current density of 14 mA cm¡2) and CV results that the N-RGO based electrode showed a specific
catalyzed ORR mostly through four-electron process. cathodic peak at ¡0.4 V in the presence of oxygen, indicating that
TagedPIn summary, the unique perovskite structure provides a great the N-RGO electrocatalyst possessed the excellent ORR activity. In
flexibility to design and synthesize a large amount of electrocatalysts addition, it was demonstrated that the peak potential of the N-RGO
with controlled electronic and geometric structures for efficient was more positive than the bare RGO, which means that the doped
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 149

TagedPnitrogen plays an important role in enhancing the ORR activity. Nev- TagedP nd his group synthesized three types of polymer electrolyte mem-
a
ertheless, the reduction current reached the maximum value when branes using PVA as matrix crosslinked with potassium hydroxide,
the mass ratio of urea and GRO was increased to 1:10. poly(acrylamide-co-diallyldimethylammonium chloride), and poly
TagedPIn summary, the most attractive advantage of AAEMFCs is the (diallyldimethylammonium chloride), denoted as PVA-KOH [58],
absence of noble metal electrocatalysts on the cathode, thereby PVA
PAADDA
GA [119] and PVA/PDDA-OH¡ [120,121], respec-
reducing the cost. Though it has not been practically realized, tre- tively. Analogously, all the prepared membranes exhibited excellent
mendous efforts have been made to develop substitute electrocata- chemical and thermal stability, as well as good ionic conductivity. It
lysts, including non-precious metal electrocatalysts, and non-metal was indicated that the hydroxide-ion conductivities of these mem-
electrocatalysts for the ORR in alkaline media. The fuel cell, fabri- branes were substantially boosted from 2.75 £ 10¡4 S cm¡1 to
cated with Pt-based anode and NG@MMT based cathode, results in 0.02 S cm¡1 at room temperature. Zhang et al. [115] investigated the
the highest power density (320 mW cm¡2). The future research effect of molecular weight on the performance of the membranes,
direction is suggested to study the mechanisms of catalysis and the which were developed employing PVA as polymer matrix and poly
structure of electrocatalysts and then to synthesize non-PGM cata- (diallyldimethylammonium chloride) (PDDA) as anion charge car-
lysts with the high ORR activity. riers. They claimed that PVA/PDDA-HMw membrane possessed the
maximum OH¡ conductivity of 0.027 S cm¡1, the best mechanical
5. Alkaline anion exchange membranes (AAEMs): chemistries property, highest tensile strength of 15.3 MPa and tensile elongation
and performance of 16.8%, and excellent thermal stability, high onset degradation
temperature above 170°C, which was ascribed to the most compact
TagedPAnion exchange membrane is typically composed of a polymer and dense network structure. Peak power densities of 35.1, 28.5,
backbone onto which fixed cationic sites are tethered. It is the cat- 23.4, and 18.2 mW cm¡2 were obtained in a H2/O2 fuel cell fabricated
ionic groups that contribute to the mobility of hydroxide ions from with Pt (0.5 mg cm¡2) both at anode and cathode with humidified
cathode to anode through membrane. Recently, great attention has hydrogen fed at a rate of 100 sccm and humidified oxygen fed at a
been paid to the development of solid polymer electrolytes served rate of 70 sccm at room temperature employing PVA/PDDA-HMw,
as a thin membrane of a few tens of micrometers in thickness, which PVA/PDDA-MMw, PVA/PDDA-LMw, and PVA/PDDA-ULMw, respec-
alleviates the carbonate problem caused by the use of alkaline aque- tively. Merle et al. [114] fabricated AAEMs based on PVA crosslinked
ous electrolyte [26]. However, the carbonate problem still cannot be with poly(ethylene glycol) diglycidyl ether (PEGDGE) for alkaline
completely eliminated, as the AAEMFCs are still sensitive to the CO2 fuel cells via simply blending the cheap materials. It was shown that
atmosphere. Additionally, the AAEMs are also facing two more chal- the membranes exhibited high long-term ionic conductivity and
lenging issues. One is to further promote the ionic conductivity, high chemical stability, as shown in Fig. 5(a) and (b). In addtion, a
resulting in a better performance. Since the diffusion coefficient of maximum power density of 72 mW cm¡2 was achieved in an alka-
OH¡ is much lower than H+, a higher ion exchange capacity (IEC) is line fuel cell fabricated with Pt (4 mg cm¡2) both at anode and cath-
needed so that a similar conductivity could be achieved. Neverthe- ode employing PVA membrane with 15 wt% acrylic acid, which was
less, higher IEC leads to the sacrifice of mechanical properties due to the only candidate for the application due to the denser structure
the excessive polymer swelling. The other is to continue to improve with hydrogen (RH = 100%) supplied at a flow rate of 40 sccm and
the stability of the AAEMs in the harsh environment and at elevated oxygen supplied at a flow rate of 80 sccm. Lu et al. [122] synthesized
temperatures. The polymer backbones and functional groups related PVA-poly(vinylbenzyl chloride) (PVBC) membrane with a macromo-
to the conductivity, mechanical and chemical stability can be easily lecular crosslinker, in which PVBC acted as conducting polymers and
attacked by the OH¡ and radicals [30]. Hence, tremendous research PVAc containing dimethylamino groups worked as crosslinker and
has been conducted on improving the conductivity as well as the supporting matrix simultaneously. The results from Fourier
enhancing the thermal and chemical stability of AAEMs [114
118]. transform infrared (FT-IR) and XPS showed that the PVBC and PVAc
were crosslinked successfully. In addition, it was indicated that
5.1. Polymer backbone hydroxide-ion conductivity was larger than 0.01 S cm¡1 at room
temperature and swelling ratio (SR) was suppressed when the tem-
TagedP5.1.1. Poly(vinyl alcohol) perature was elevated. A peak power density of 124.7 mW cm¡2 was
TagedPPoly(vinyl alcohol) (PVA) is a polyhydroxy polymer, which is obtained in an AAEMFC fabricated with Pt (0.4 mg cm¡2) both at
very common in practical applications because of its easy prepara- anode and cathode employing the crosslinked membrane with
tion and biodegradability. Moreover, PVA shows a good chemical hydrogen (RH = 100%) supplied at a flow rate of 40 sccm and oxygen
stability and hydrophilicity due to the hydroxyl groups. Qiao et al. supplied at a flow rate of 70 sccm at 40°C.

Fig. 5. Effect of (a) the temperature and (b) the time on ionic conductivity [114]. Reproduced with permission from Elsevier.
150 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedP5.1.2. Poly(arylene ether)s TagedPgroups [127], denoted as GPPO, BImPPO, and DImPPO, respectively.
TagedPPoly(arylene ether)s possesses excellent stability and water resis- It was indicated that the GPPO membrane possessed high anion con-
tance that are preferable properties of AAEMs. Thus, some AAEMs ductivities resulting from the high basicity of guanidinium groups,
based on poly(arylene ether)s have been reported [116,117,123]. and short-term thermal and long-term alkali stabilities due to the p
Tanaka et al. [123] synthesized aromatic multiblock copolymer electron conjugated system. Meanwhile, a peak power density of
membrane, poly(arylene ether)s containing quaternized ammonio- 16 mW cm¡2 was achieved at 50°C when the GPPO membrane was
substituted fluorene groups, via block copolycondensation of fluo- fabricated into a H2/O2 fuel cell utilizing Pt (0.4 mg cm¡2) both at
rene-containing hydrophilic oligomers and linear hydrophobic anode and cathode with both humidified hydrogen and oxygen fed
oligomers, chloromethylation, quaternization, and ion-exchange at rates of 600 sccm. In comparison with the analogous PPO mem-
reactions. It was reported that this membrane exhibited consider- branes containing the classical pendant quaternary ammonium and
ably high hydroxide-ion conductivities, reaching 144 mS cm¡1 at imidazolium cations, the BImPPO membrane showed advantages in
80°C, and retained the high conductivity for 5000 h. They claimed ionic conductivity, dimensional, thermal, and mechanical stabilities.
that introducing highly ionized hydrophilic blocks into multi-block Furthermore, the peak power density was 13 mW cm¡2 at 35°C in
structure was an efficient way to promote the ionic conductivity. the case of the utilization of optimal BIm-PPO-0.54 AAEM. In addi-
Jasti et al. [116] proposed a facial synthesis of aminated multiblock tion, the DImPPO membrane also exhibited comparative conductiv-
poly(arylene ether)s with hydrophilic blocks via nucleophilic substi- ity, in the ranges of 10
40 mS cm¡1 and 18
75 mS cm¡1 at 30°C
tution poly condensation followed by quaternization and alkaliza- and 60°C, respectively. Nevertheless, the power density employing
tion reactions. It was shown that hydrophilic/hydrophobic phase DImPPO membrane was much higher than that of other PPO mem-
separation due to the interconnected ion transport pathway, result- brane, reaching 56 mW cm¡2, whereas it decreased dramatically to
ing in a high ionic conductivity of 150 mS cm¡1 at 80°C. In the pres- 31 mW cm¡2 after three-time repetition of the test, suggesting the
ence of two vicinal quaternary ammonium groups, the membrane poorer stability. Li et al. [128] synthesized quaternized PPOs materi-
exhibited promising alkaline stability, because nucleophilic attack als containing clicked 1,2,3-triazoles for AAEMs via CuI-catalyzed
was hindered, as well as the degradation was avoided. Li et al. [117] “click chemistry”. It was shown that the obtained membranes
prepared functionalized quaternary ammonium poly(arylene ether) possessed higher WU, hydroxide-ion diffusion coefficient and
s (QBMPAEs) containing tetramethyl triphenyl methane moieties via anion conductivities due to the formation of efficient and continuous
polycondensation, benzylic bromination, quaternization, and alkali- hydrogen-bond networks. A hydroxide-ion conductivity of
zation. It was demonstrated that the IECs could be adjusted from 27.8
62 mS cm¡1 was achieved at 20°C in water, which was several
0.90 to 1.73 mmol g¡1 by controlling the conditions of the bromina- times higher than that of a typical PPO-based AAEM (TMA-20). An
tion reaction. In addition, the water uptake (WU) and SRs of the improved peak power density of 188.7 mW cm¡2 was obtained in a
QBMPAEs membranes were moderate and could be adjusted by con- H2/O2 fuel cell fabricated with Pt (0.5 mg cm¡2) both at anode and
trolling their degree of bromination (DBM) values. One of the syn- cathode with hydrogen (RH = 100%) supplied at a flow rate of
thesized membranes, QBMPAE-d membrane, possessed excellent 200 sccm and oxygen supplied at a flow rate of 200 sccm at 50°C
long-term alkaline stability for 30 days. It was indicated that the employing the membrane with alkyne-functionalized quaternary
QBMPAE-d membrane resulted in the highest conductivity of ammonium (QA). A recent publication by Dang et al. [129] demon-
46.6 mS cm¡1 at 80°C and a peak power density of 20.1 mW cm¡2 strated that the position of QA cations in the polymer structure, ring
was achieved in a H2/air single fuel cell with hydrogen (RH = 100%) size, the presence of an additional heteroatom, and ring substitution
supplied at a flow rate of 300 sccm and air supplied at a flow rate of pattern played a crucial role in the performance of the PPO based
800 sccm along with 0.1 mg cm¡2 Pt on the anode and 0.2 mg cm¡2 AAEMs. The results are beneficial for selecting optimal QA groups to
Pt on the cathode at 70°C. enhance the lifetime and performance of the AAEMs. Wang et al.
[130] proposed a strategy of supramolecular modalities for strength-
TagedP5.1.3. Poly(2,6-dimethyl-1,4-phenyleneoxide) ening the mechanical stability of the PPO based AAEMs substantially.
TagedPPoly(2,6-dimethyl-1,4-phenyleneoxide) (PPO) has outstanding A secondary amide was introduced into the AAEMs to serve as a
physical properties, including high dimensional stability, excellent hydrogen-bonding crosslinking motif, which was evidenced by the
mechanical properties, high thermal stability, low moisture uptake, 101% elongation at break, whereas the AAEMs without hydrogen-
low flammability, and exceptional electrical properties, including a bonding crosslinking showed the elongation at break in the range of
low dielectric constant and a low dielectric dissipation factor. More- 10
20%.
over, another superiority of PPO is the safety. The toxicity of many
other materials has restricted their development for AAEMFC appli- TagedP5.1.4. Poly(tetrafluoroethylene)
cations. In view of these characteristics, PPO has been regarded as an TagedPPoly(tetrafluoroethylene) (PTFE) has been widely used in chemi-
excellent candidate for high-frequency substrates. Ong et al. [124] cal industry and other related industries due to its unique properties,
synthesized PPO based membranes via bromination/amination serial which can be conclude as follows: (1) high chemical stability; (2)
reactions, which reduced the number of involved toxic chemicals excellent thermal stability; (3) minimal water absorption; and
and reaction time. Though the synthesis route was relatively simple, (4) no toxicity. Due to the high thermal and chemical stability, as
the obtained membrane, prepared from 5 wt% PPO, bromine/PPO well as low WU, PTFE has been introduced to synthesize AAEMs
molar ratio at 10, nitrogen-free atmosphere, with hydroxylation [61,131-134]. Wang et al. [61] synthesized a thin (30 mm) composite
treatment and N-methyl-2-pyrrolidone (NMP) as the membrane membrane by impregnating quaternary 1,4-diazabicyclo[2.2.2]-
casting solvent, possessed competitive ionic conductivity of octane polysulfone (QDPSU) solution in PTFE. The results from the
1.64 £ 10¡2 S cm¡1 at 60°C. The peak power density increased from scanning electron microscope (SEM) exhibited that the obtained
3 mW cm¡2 to 19.5 mW cm¡2 with the temperature going up from membrane possessed a dense and homogenous structure. It was
25°C to 70°C with hydrogen (RH = 100%) supplied at a flow rate of shown that the composite membrane exhibited better mechanical
5 sccm and oxygen supplied at a flow rate of 10 sccm along with Pt strength (a 32 MPa maximum load), lower WU (61 § 3%) and less
(0.65 mg cm¡2) both at anode and cathode. Further increasing the swelling degree (17 § 2%) than pristine QDPSU membrane. Further-
temperature, a dramatic degradation occurred primarily due to the more, a considerable peak power density of 146 and 103 mW cm¡2
thermal degradation of AAEM. Lin et al. prepared PPO based AAEMs were achieved with Pt (0.5 mg cm¡2) both at anode and cathode
containing pendant guanidinium groups [125], benzimidazolium along with hydrogen (80 sccm, RH = 100%) and oxygen or air
(BIm) groups [126], and 1,2-dimethylimidazolium (DIm) functional (100 sccm, RH = 100%) as oxidant, respectively. Zhao et al. reported
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 151

TagedPthat the quaternized polyvinyl benzyl chloride (QPVBC) could pro- TagedP n IEC value of 1.23 mmol g¡1, hydroxide-ion conductivity of
a
vide sufficient ionic exchange group, but it became brittle after cast- 55.2 mS cm¡1 at 80°C, and tensile strength of 32.0 MPa, which pos-
ing membrane [132]. Hence, they prepared quaternary ammonia sessed almost the best comprehensive properties.
polysulfone (QAPS)/PTFE composite membrane by employing TagedPPolysulfone membrane exhibits prime mechanical, biological,
porous PTFE membrane as the substrate and QAPS polymer as the and chemical stability, and has a wide operating range at tempera-
anionic conductor [133]. It was indicated that the obtained mem- ture ( > 80 °C), which attracts worldwide attentions. Zhang et al.
brane possessed better mechanical strength, lower SR and WU than [138] prepared a porous polysulfone AAEM filled with (3-acrylami-
the previous QAPS alkaline AAEM. The fuel cell fabricated with the dopropyl)trimethylammonium chloride and N,N’ -methylenebisa-
20 mm thickness membrane and Pt (0.4 mg cm¡2) both at anode and crylamide with a grid-plug microstructure via phase-inversion,
cathode with hydrogen (RH = 100%) supplied at a flow rate of interfacial diffusion, and in-situ polymerization. It was indicated
100 sccm and oxygen supplied at a flow rate of 200 sccm resulted in that the PSU-PATC(1.2) membrane with optimal content of PATC
a peak power density of 315 mW cm¡2 at 50°C. Nevertheless, the performed best (55 mW cm¡2) in a single fuel cell fabricated with
QAPS was inclined to leach out gradually during the operation of the Pt (2 mg cm¡2) both at anode and cathode with H2 (800 sccm,
fuel cell, resulting from the poor interaction between the QAPS guest RH = 100%) supplied to anode and O2 (600 sccm, RH = 100%) supplied
and the PTFE host. As consequence, Li et al. [134] proposed a new to cathode due to the maximum ionic conductivity. He et al. [139]
approach for making ultrathin composite membranes of alkaline suggested that one of the obstacles for the application of AAEMs was
polymer electrolytes (APEs), which could avoid the leach out prob- the poor ionic conductivity, which was partially attributed to the
lem. They impregnated the APE ionomer TQAPS into a porous poorly-defined morphologies of AAEMs, resulting in the tortuous ion
PTFE film, followed by a self-crosslinking process, forming a semi- transport pathways. As a consequence, they proposed a novel strat-
interpenetrating network. It was indicated that the obtained mem- egy, grafting hydrophilic poly(ethylene glycol) side-chains along a
brane (xQAPS@PTFE, 25 mm thick) showed low area resistance model benzyltrimethylammonium polysulfone-based AAEM to form
(0.09 V cm2), a low swelling degree (3.1% at 60°C) and high mechan- nanoscale (5
10 nm diameter) anion transport channels, to enhance
ical strength (31 MPa). A peak power density of 550 mW cm¡2 was the ionic conductivities of AAEM. It was indicated that the IEC-
achieved in a H2/O2 AAEMFC fabricated with Pt (0.4 mg cm¡2) both normalized hydroxide conductivity increased by 100% from 20.2 to
at anode and cathode employing the membrane with both humidi- 40.3 mS g cm¡1 mmol¡1 and the power density increased by 50%
fied hydrogen and oxygen fed at rates of 120 sccm at 60°C. from 118 mW cm¡2 to 180 mW cm¡2 in a fuel cell fabricated with Pt
(0.5 mg cm¡2) at anode and Pt (2 mg cm¡2) at cathode with humidi-
TagedP5.1.5. Polysulfones fied H2 supplied to anode at a flow rate at 150 sccm and humidified
TagedPPoly(arylene ether sulfone) exhibits promising mechanical and O2 supplied to cathode at a flow rate at 200 sccm, simultaneously.
thermal stability, as well as hydrolysis resistance. Recently, some Vinodh et al. [140] synthesized a quaternized polysulfone/ZrO2 com-
attempts have been made to the synthesis of membranes based on posite membrane via solution casting method and determined its
poly(arylene ether sulfone) [135
137]. Zhou et al. [135] prepared characteristic properties via XRD, TGA, and electrochemical imped-
the poly(arylene ether sulfone) based membranes, containing fluo- ance spectroscopy (EIS). The results from the tests indicated that the
renyl groups (QAPSF), functionalized with benzyltrimethylammo- ZrO2 nano fillers were distributed homogeneously, showing no obvi-
nium groups via the polycondensation, chloromethylation, and ous agglomeration. In addition, the composite membrane exhibited
amination reactions. It was reported that the QAPSF membranes long-term thermal and chemical stability. Typically, a peak power
were stable at pH 11 and showed slow degradation at pH > 14. A density of 250 mW cm¡2 was obtained in a single H2/O2 fuel cell fab-
peak power density of 4.1 mW cm¡2 was obtained in an AAEMFC ricated with Pt (0.375 mg cm¡2) at anode and Pt (0.125 mg cm¡2) at
fabricated with Pt (1 mg cm¡2) both at anode and cathode operating cathode at 60°C as the QPSU/10% ZrO2 has been employed.
on H2 (6 sccm, RH = 100%) supplied to anode and O2 (3 sccm,
RH = 100%) and CO2 (6 sccm, RH = 100%) supplied to cathode. Sur- 5.2. Functional groups
prisingly, the addition of CO2 resulted in a promotion of power den-
sity, from 2.2 to 3.2 mW cm¡2, because CO2 was involved in the TagedP5.2.1. Quaternary ammonium (QA)
chemical progress and transported through the AAEM. Yang et al. TagedPQA groups are more thermally and chemically stable than tertiary
[136] synthesized a series of poly(arylene ether sulfone) containing ammonium (TA) and primary ammonium (PA), resulting in the most
bulky imidazole groups (PSf-Im-x) based on a novel monomer 2,20 - common utilization of quaternary ammonium as hydroxide ions
bis-(2-ethyl-4-methyl-imidazole-1-ylmethyl)-biphenyl-4,40 -diol transfer carriers. Varcoe et al. [141] developed a novel alkaline poly-
(EMIPO), followed quaternization by n-bromobutane. The attached mer, employing N,N,N’,N’ -tetramethylhexane-1,6-diamine as the
bulky groups around the imidazolium ring reduced the access of cross-linking agent and poly-(vinylbenzyl chloride) as the polymer
OH¡ to imidazolium, which leaded to the enhancement of alkaline backbone. After the treatment of KOH exchange, the obtained poly-
stability, showing an OH¡ conductivity of 0.014 S cm¡1 at 30°C and mer was coated on the electrodes working as the AAEM, which not
retaining the 80% of the conductivity for 144 h. It was revealed that only increased the power density of a single fuel cell using Pt
some inorganic materials could be added into polymer matrix, (0.5 mg cm¡2) both at anode and cathode with H2 (2000 sccm,
improving the mechanical, thermal and chemical properties. Li et al. RH = 100%) fed to anode and O2 (2000 sccm, RH = 100%) fed to cath-
[137] synthesized a series of cross-linked multiblock copoly(arylene ode from 1.6 to 55 mW cm¡2 at 50°C, but also avoided undesirable
ether sulfone) ionomer (CLQCPAES)/nano-ZrO2 composite AAEMs carbonate precipitation. Pan et al. [142] replaced a part of the QA in
via block copolymerization, bromomethylation, ultrasonication QAPS with a TA, and the two substances crosslinked two nearest
blending, self-crosslinking, quaternization, and alkalization. It was neighboring chains generating xTQAPS membrane upon solidifica-
shown that the CLQCPAES/nano-ZrO2 composite membranes were tion. It was found that the self-crosslinked membrane did not show
complex cross-linking networks of hydrophobic domains/hydro- any obvious degradation of mechanical stability and IEC in pure
philic domains/nano-ZrO2 with a clear zonal distribution of uniform water at 90°C for 500 h, which suggested the membrane exhibited
nano-sized particles in the hydrophilic domains. The WU, mechani- extraordinary both physical and chemical stability, breaking the con-
cal properties, hydroxide conductivity, and alkaline stability were tradiction between the IEC and dimensional stability. This phenome-
enhanced significantly by the modification with block-ionomer non could be attributed to the stereo-hindrance effect of the two
structure, cross-link treatment and the introduction of nano-ZrO2 benzyl groups in proximity suppressing the Hofmann elimination
particles. Particularly, the CLQCPAES/7.5% ZrO2 membrane showed reaction. Zhou et al. [143] prepared AAEMs with varying amounts of
152 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedPQA groups (0.51, 0.70, and 0.90 mmol g¡1) grafted onto a SEBS block rTagedP eported a polysulfone-imidazolium AAEM (PSf-ImOH) via function-
copolymer and investigated the impacts of AAEMs with various IECs alization of chloromethylated polysulfone with methylimidazole,
on the performance of H2/O2 fuel cells. The peak power density of added different degrees of chloromethylation of PSf to control the
the AAEMFCs utilizing Pt (0.5 mg cm¡2) both at anode and cathode membrane properties. They found that the membranes possessed
with H2 (200 sccm, RH = 100%) supplied to anode and O2 (200 sccm, comparable IEC, conductivity, and thermal stability with the conven-
RH = 100%) supplied to cathode employing these AAEMs with IEC of tional AAEMs. In spite of the low power density (16 mW cm¡2), a
0.51, 0.70, and 0.90 mmol g¡1 were 169, 222, and 285 mW cm¡2, new route for non-QA AAEM design and fabrication was offered.
respectively. It was indicated that a higher content of QA groups in Ran et al. [148] developed imidazolium-type AAEMs (Im-AAEM)
the membranes leaded to higher ionic conductivity, resulting in the based on bromomethylated poly(2,6-dimethyl-1,4-phenyleneoxide)
lower overpotential and higher power density. They revealed that (BPPO) polymer chains via solution casting of NMP solutions. Addi-
the transportation resistance of the OH¡ ions was a controlling factor tionally, a favorable conductivity up to 100 mS cm¡1 was obtained at
when fewer functional groups were contained in the membrane or 80°C, resulting from the nano-scale phase-separated construction by
the cell voltage was higher. Li et al. [144] reported highly stable, the solution casting method. It was indicated that different IECs
anion conductive and comb-shaped copolymers containing long ranging from 1.1 to 2.4 mmol g¡1 could be obtained by tuning the
alkyl side chains pendant to the nitrogen-centered cation via a Men- molar ratio of 1-methylimidazole to CH2Br groups in the starting
shutkin reaction to form comb-shaped structures. It showed that the polymer. A peak power density of 30 mW cm¡2 was achieved in a
membrane with long alkyl chain of up to 16 carbon atoms, which single fuel cell using Pt (0.5 mg cm¡2) both at anode and cathode
had the longest hexadecyl chain, exhibited higher hydroxide-ion with Im-AAEM with both humidified hydrogen and air fed at flow
conductivity, more distinct ionic domains, and lower WU than that rates of 600 sccm at 50°C.
with a hexyl side chain. The peak power density of fuel cell fabri-
cated with Pt (0.5 mg cm¡2) both at anode and cathode using both 5.3. Other chemistries
humidified H2 O2 fed at flow rates at 200 sccm with C16D40 mem-
brane was 77 mW cm¡2, which was slightly higher than that using TagedPIn addition to the above-mentioned AAEMs, extensive other
C6D60 (67 mW cm¡2). Increasing the flow rates of hydrogen and types of AAEMs based on various materials have been synthesized
oxygen, the peak power density of C6D60 could reach 145 mW cm¡2 and reported [149
163]. Xing et al. [149] found that the conductiv-
when the flow rates of anode and cathode were both at 2000 sccm. ity of KOH-doped polybenzimidazole (PBI) was remarkable, reaching
However, the C16 membrane was inferior in the film-forming ability to 9 £ 10¡2 S cm¡1 at 25°C, which was much higher than that of pre-
due to the poor compatibility between long alkyl side chain and ciously obtained on acid-doped PBI. In addition, the H2/O2 fuel cell
polymer backbone. Ren et al. [145] reported highly conductive using this polymer electrolyte exhibited the same performance as
AAEM with styrenic diblock copolymer, a quaternary ammonium- those based on Nafion 117 membrane. Li et al. [150] reported that
functionalized hydrophilic block and a cross-linkable hydrophobic grafting long side-chain cations onto PBI was an effective way to
block, which possessed high ionic conductivity at 98 mS cm¡1 and improve the OH¡ conductivity, mechanical and thermal stability, as
controlled membrane swelling with WU at 117 wt% at 22°C. It was well as reduce swelling ratio. Wan et al. [151] synthesized different
ascribed to the reduced tortuosity of the ionic conduction pathways. solid polymer electrolyte membranes using chitosan as matrices
Moreover, excessive WU was suppressed because the mechanical incorporated with potassium hydroxide as ionic carrier. After hydra-
integrity of the membrane was maintained due to the hydrophobic tion for 1 h, the conductivity of the membrane was about
network. A peak power density of 168 mW cm¡2 was obtained in a 10 mS cm¡1. When being integrated into the fuel cells, the maxi-
H2/air fuel cell fabricated with Pt (1 mg cm¡2) both at anode and mum current density reached 35 mA cm¡2 and the open circuit volt-
cathode using newly developed AAEM (C30D70-1.7) with H2 age of 1 V was achieved. Additionally, they also proposed two
(250 sccm, RH = 95%) supplied to anode and air (250 sccm, RH = 95%) approaches to improve the fuel cell performance [152]. One was to
supplied to cathode at 50°C. add an alkaline and ionic-conductive interfacial gel, and the other
was to decrease the thickness of the membrane. Luo et al. [153] syn-
TagedP5.2.2. Imidazolium thesized a novel high molecular weight copolymer quaternized poly
TagedPThough the QA groups are more thermally and chemically stable (methyl methacrylate-co-butyl acrylate-co-vinyl benzylchloride)
than TA and PA groups, the AAEMs with QA groups are still facing (denoted as QPMBV) composed of methyl methacrylate (MMA),
the facile degradation and excessive swelling problems. Hence, a butyl acrylate (BA), and VBC. It was reported that polymer electro-
resurgence of exploring substituted functional groups has occurred. lytes could be designed bottom-up through mini-emulsion polymer-
Imidazolium salts (IMSs) are well-known as a type of ionic liquid, ization by selecting desirable monomer [154]. Furthermore, the
which can act as electrolytes due to their high chemical stability and conductivity reached 8.2 mS cm¡1 at 80°C. The results from the fuel
low vapor pressure. It seems that imidazolium chemistry is more cell performance evaluation demonstrated that the peak power den-
amenable to AAEM fabrication through post-functionalization, sity of 25 mW cm¡2 was achieved in a single fuel cell fabricated with
resulting in the formation of ion clusters for efficient transport of Pt (0.5 mg cm¡2) both at anode and cathode with H2 (80 sccm,
OH¡. Recently, Lu et al. [146] synthesized imidazolium-functional- RH = 80%) supplied to anode and air (80 sccm, RH = 80%) supplied to
ized AAEMs via functionalization of chloromethylated poly(ether cathode at 60°C, suggesting that the preparation concept of these
sulfone) (PES) with 1-alkylimidazole. It was revealed that the WU, membranes was feasible [155]. Moreover, the conductivity and the
SR and solubility of AAEMs increased but the OH¡ conductivity mechanical strength were balanced by utilizing the designed hydro-
decreased with the increment of the alkyl line length on the imida- phobic and hydrophilic segments [154]. Hence, they concluded the
zolium group. They claimed that the ionic conductivity was deter- membrane properties as follows [156]: (1) higher molecular weight
mined by the ionic concentration, which was affected by IEC and SR. resulted in the improvement of the mechanical strength as well as
Accordingly, the quotient of IEC divided by SR (IEC/SR) could be reduction of the WU; (2) higher concentration of the conductive
regarded as an indirect indicator of the ionic concentration. More- sites resulted in the enhancement of conductivity but simulta-
over, a peak power density of »30 mW cm¡2 was obtained in a neously impairment of the mechanical properties; (3) higher glass
H2/O2 AAEMFC fabricated with Pt (0.4 mg cm¡2) both at anode and transition temperature resulted in the promotion of the membrane
cathode employing the fabricated AAEM and anion exchange ionom- durability; and (4) the water hydrophilicity of the mechanical sup-
ers (AEIs) with H2 (50 sccm, RH = 100%) supplied to anode and air port played an important role in the WU. Wu et al. [157] prepared a
(100 sccm, RH = 100%) supplied to cathode at 45°C. Zhang et al. [147] high ion-conduction alkaline membrane by sulfonation with lower
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 153

TagedPcost using non-woven polypropylene/polyethylene (PP/PE). It was TagedP erformance was enhanced with higher IEC AAEMs. Park et al. [166]
p
shown that the ionic conductivity was improved from 8.8 to investigated the effect of the length of alkyl chain of the diamines
17.5 mS cm¡1, while the decline of thermal resistance (4%) and on ionic conductivity and thermal characteristics via employing
mechanical strength (21%) was reduced. Sollogoub et al. [158] devel- TMA as a monoamine and N,N,N’,N’ -tetramethylmethanediamine
oped an AAEM using a poly(epichlorhydrin) as matrix and incorpo- (TMMDA), N,N,N’,N’ -tetramethylethylenediamine (TMEDA), N,N,N’,
rated two cyclic diamines, namely 1,4-diazabicyclo[2,2,2]-octane N’ -tetramethyl-1,3-propandiamine (TMPDA), N,N,N’,N’ -tetra-
(DABCO) and 1-azabicyclo[2,2,2]-octane (Quinuclidine), into the methyl-1,4-butanediamine (TMBDA) and N,N,N’,N’ -tetramethyl-
matrix to ensure anionic conduction properties. They illustrated that 1,6-hexanediamine (TMHDA) as various diamines. The results
the transport number is usually 0.99 and the peak power density showed that the mixture of TMA and TMHDA had a better hydroxyl
was nearly 100 mW cm¡2 when the membrane was assembled in a ion conductivity and thermal stability than others, suggesting that a
H2/O2 fuel cell utilizing Pt (0.17 mg cm¡2) as both anode and cathode longer alkyl chain resulted in higher performance. Wang et al. [167]
electrocatalysts. Hibino et al. [159] developed a series of hydroxide- demonstrated that the parameters, including reaction time, reaction
ion conducting antimony (V)-doped Tin pyrophosphate electrolyte, temperature, concentration of polymer, concentration of chlorome-
Sn1¡xAxP2O7 (A = V, Nb, Ta, and Sb) compounds, for intermediate- thylation agent, and the amount of catalyst, possessed significant
temperature alkaline fuel cells. It was indicated that Sn0.92Sb0.08P2O7 impacts on chloromethylation. When these parameters were well
exhibited the highest electrical conductivity in the temperature controlled, the gelation could be avoided. Among the parameters,
range of 50
200°C. Additionally, the peak power densities of the concentration of the chloromethylation agent played a dominant
76 mW cm¡2, 94 mW cm¡2, 114 mW cm¡2, 130 mW cm¡2, role in enhancing the attachment of chloromethyl functional group
132 mW cm¡2 and 147 mW cm¡2 were obtained with Pt onto the polymer. Luo et al. [168] investigated the effects of polymer
(2 mg cm¡2) both at anode and cathode and humidified hydrogen composition drift, molecular weight, and polymer crosslinking on
and air at rates of 50 sccm at 75°C, 100°C, 125°C, 150°C, 175°C, and the properties of quaternized poly(methylmethacrylate-co-vinyl-
200°C, respectively [160]. Zhao et al. [161] reported a series of pore- benzyl chloride) (QPMV)-based AAEM. It was indicated that the ini-
filled AAEMs via thermal polymerization of chloromethyl monomer tial monomer ratio and the resulted copolymer composition could
in a porous PE substrate followed by amination with trimethyl- influence the hydrophobic/hydrophilic portions in the membrane.
amine. It was indicated that a hydroxide conductivity of They demonstrated that decreasing initiator potassium persulfate
0.057 S cm¡1 was obtained at 30°C, in deionized water and the syn- (KPS) and increasing surfactant sodium dodecyl sulfate (SDS) could
thesized membrane possessed long term alkaline stability. A peak increase the molecular weight, simultaneously improving the
power density of 370 mW cm¡2 was achieved in a H2/O2 fuel cell uti- mechanical properties. It was believed that crosslinking method
lizing Pt (0.5 mg cm¡2) both at anode and cathode with hydrogen could alleviate the WU problem due to the less distinct phase sepa-
(100 sccm, RH = 100%) fed to anode and oxygen (200 sccm, ration feature. Pan et al. [169] proposed two strategies for develop-
RH = 100%) fed to cathode at 50°C. Kim et al. [162] fabricated pen- ing advanced APEs which were highly resistant to swelling and
tamethylguanidinium functionalized perfluorinated hydroxide-ion showed conductivities comparable with Nafion: self-crosslinking
conducting ionomers for AAEM. It was shown that the alkaline sta- and self-aggregating designs. It was indicated that a short-range
bility of the ionomers largely depended on the adjacent group that cross-linker, tertiary amino groups, was grafted onto the QAPS and
connected the cation. Meanwhile, the phenylguanidinium function- the membrane swelled by less than 3% at 80°C. In self-aggregating
alized ionomer exhibited better stability than sulfone guanidinium design, long alkyl side-chains were attached to the QAPS, which pro-
functionalized ionomer due to the charge delocalization of the duced enlarged and aggregated ionic channels.
formed resonance structure. When the membrane was fabricated
into a H2/O2 fuel cell using Pt (3.4 mg cm¡2) on the anode and Pt 5.4. AAEM performance
(6.5 mg cm¡2) on the cathode with supplied humidified hydrogen
and oxygen, a peak power density of 577 mW cm¡2 was obtained. TagedP5.4.1. Effect of pre-treatment
Recently, Chen et al. [163] found that both introducing ionic liquids TagedPBefore being integrated into the fuel cell, the membrane would
and adding nano-TiO2 into the AAEMs contributed to improving the be immersed into water or alkaline electrolyte to improve the con-
OH¡ conductivity. The ionic liquids dispersed in the membrane func- ductivity. Under pure water operation, the characterization of mem-
tioned active sites for secondary OH¡ conduction, and the nano-TiO2 brane has been extensively conducted [170,171]. Li et al. [170]
particles could significantly alleviate the ionic liquid loss and stabi- prepared AAEMs with significant ionic conductivities over the order
lize the ionic liquid monomer in the membrane. of 10¡2 S cm¡1 in DI water at room temperature. The fuel cell using
TagedPThe effects of the cations chemistries, the length of alkyl chain of Pt (0.5 mg cm¡2) both at anode and cathode yielded an OCV of
the diamines, the reaction conditions of chloromethylation, and the 1.028 V and a peak power density of 33 mW cm¡2 with hydrogen
parameters of polymers on the AAEMs have been extensively inves- (50 sccm, RH = 100%) supplied on the anode and oxygen (100 sccm,
tigated [164
169]. Einsla et al. [164] tested the stability of cations RH = 100%) supplied on the cathode in the absence of liquid electro-
for anion exchange membrane fuel cells and illustrated that the sta- lyte, such as KOH and NaOH, at 30°C, suggesting the possibility of
bility of benzyltrimethylammonium hydroxides was much better the membrane for AAEMFCs application. Mamlouk et al. [171] stud-
than that of phenyltrimethylammonium hydroxides under similar ied the effect of anion functional groups on the conductivity and per-
conditions. Furthermore, they showed the degradation of stability of formance of AAEMs. It showed that TMA functionalized membrane
the cation when the concentration of the ammonium hydroxides possessed the highest conductivity among amine/sulphide-based
was increased. Arges et al. [165] studied the influence of different functional groups with conductivities values up to 0.25 and
cation chemistries, 1,4-dimethylpiperazinium (DMP + ), trimethy- 0.043 S cm¡1 in plane and through plane, respectively. The highest
lammonium (TMA + ), and trimethylphosphonium (TMP + ), on ionic power density of 478 mW cm¡2 was achieved when TMA functional-
conductivity and alkaline stability of AAEMs. They concluded from ized electrodes fabricated with Pt (0.4 mg cm¡2) were employed, fol-
the obtained experimental evidence as follows: (1) phosphonium lowed by the second highest power density of 236 mW cm¡2
cations with similar or greater basicity degraded more rapidly than achieved by the TMHDA electrodes. Trimethylamine (TEA) and
ammonium cations; (2) phosphonium cations degraded through a DABCO electrodes showed analogous power densities of 100 and
fundamentally different mechanism (ylide formation) than ammo- 116 mW cm¡2, respectively. Finally, the dimethyl sulfide (DMS)
nium cations (direct nucleophilic substitution); (3) as long as the functionalized electrodes performed the lowest power density of
issue of significant WU did not come into play, the fuel cell 58 mW cm¡2. As a consequence, it was demonstrated that the
154 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedPionomer functional groups affected the oxygen permeability, the TagedP 3 mW cm¡2 at 20°C, respectively. It was suggested that electrolyte
1
activation energy and the exchange current density for oxygen concentration could change the cell impedance, resulting in the
reduction and anode flooding. Thus, the type of functional groups change of cell performance. Finally, the effects of organic molecular
used for the ionomer can severely restrict cell performance. size on the performance have been studied [172]. It was shown that
TagedPWhen the pure water changes to alkaline electrolyte, the perfor- the smaller organic molecular size resulted in the higher power den-
mance has also been studied [58,119,121]. Fu et al. [58] demon- sity due to the more active sites on the electrode surface. Moreover,
strated that the ionic conductivity of the membrane was promoted when the organic alkaline electrolyte was used, the cell performance
to 0.473 mS cm¡1 after alkali (2
4 M) doping due to the KOH pene- decreased significantly caused by CO2 and acid.
trated into the polymer. However, there was no significant contribu-
tion to the conductivity when the concentration of the KOH was TagedP5.4.2. Effect of carbonate
larger than 4 M, which was attributed to the weak ionic mobility. TagedPThe absorption of the CO2 on the membrane, denoted as carbon-
Similarly, Zhang et al. [121] found that the conductivity of the AAEM ate effect, has negative effects on the performance of the AAEMFCs.
reached to a maximum value of 0.025 S cm¡1 after the KOH (2 M) Due to the formation of carbonates within the CL and AAEM,
doping. Qiao et al. [119] claimed that this phenomenon could be the conductivity will decrease significantly, resulting in a large per-
explained by the two following reasons: one was that the QA groups formance drop [173,174]. Hence, the carbonate effect has been
would decompose in such harsh basic environment, and the other extensively studied [175
182]. Fukuta et al. [175] found that the
was that the ionic mobility became weak due to the increase of the maximum power density of the alkaline fuel cell in the case of pure
viscosity or the formation of ion-pairs. Jiang et al. [172] designed air was 290 mW cm¡2, which was as twice as that in the case of
an air-breathing cell for fast screening of electrolytes as shown in ambient air. It was determined that the OH¡ form membrane could
Fig. 6(a) and (b), which was suitable for using various liquid electro- easily absorb CO2, change to HCO3¡ form, then through the self-
lytes, thus reproducible data could be obtained. Subsequently, purging phenomenon, finally return to OH¡ form. Vega et al. studied
the effects of different electrolytes, i.e. 1.0 M tetramethylammonium the effects of CO2, HCO3¡, and CO32¡ on the AAEMFC operation
hydroxide (TMAOH), 1.0 M tetraethylammonium hydroxide [176
179]. They found that a 26% conductivity decrease occurred
(TEAOH), 1.0 M tetrapropylammonium hydroxide (TPrAOH), 1.0 M when the membrane was exposed to hydroxide ions due to the
KOH, and 0.5 M H2SO4, on the performance of fuel cells were investi- nucleophilic attack degradation mechanisms and Hofmann elimina-
gated. First, the inorganic electrolytes were evaluated at various tion, while the effect of exposure to carbonate environments was
temperatures. The results showed that the performance of the fuel not significant because the carbonate was weaker nucleophiles.
cell utilizing Pt (0.5 mg cm¡2) both at anode and cathode with 1.0 M However, the overall conductivity of the membrane exposed to
KOH increased from 13 to 29 mW cm¡2 with the temperature rising hydroxide ions was higher, which was attributed to the carbonate
from 20 to 80°C when hydrogen (250 sccm, RH = 95%) was fed on the adsorption on the electrode, reducing the active area. Inaba et al.
anode and air (250 sccm, RH = 95%) was fed on the cathode. In con- [180] and Matsui et al. [181] showed that the membrane resistance
trast, the fuel cell employing 0.5 M H2SO4 yielded an increasing decreased due to the self-purging mechanism at high current densi-
power density of 17
28 mW cm¡2 with temperature elevating from ties, while the cell voltage was reduced significantly. It was demon-
20°C to 60°C. Further increasing the temperature to 80°C, there was strated that a high anodic overpotential occurred because of the
no obvious performance promotion occurring, which was probably accumulation of carbonate/bicarbonate ions at the anode, while the
attributed to the electrocatalyst passivation in H2SO4 at high tem- overpotential of the cathode was hardly changed, suggesting that it
peratures. Second, it could be seen from the performance tests was important to suppress the accumulation. Suzuki et al. [182]
that the peak power densities of fuel cells employing 0.5 M H2SO4, investigated the effect of CO2 dissolution into anion exchange mem-
1.0 M TMAOH, and 1.0 M KOH as electrolytes were 17, 14, and brane on fuel cell performance. They found that the conductivity of
AAEM and potential difference decreased with an increase in car-
bonate ion species. It was indicated that the increment of ohmic
resistance was noticeable by the supply of CO2 to cathode, but not
obvious by the supply of CO2 to anode. They demonstrated that the
formation and exclusion of carbonate ion species and/or carbonic
acid in the vicinity of TPB played the dominant role for the electrode
overpotential.

TagedP5.4.3. Effect of radiation

TagedPRecently, the radiation-grafted AAEMs have attracted worldwide
attention, which is attributed to several advantages [183,184]: (1)
Radiation grafting is one of the most versatile techniques for prepar-
ing membrane materials; (2) No film formation process is required
due to the use of pre-formed polymer films; (3) The degree of mono-
mer grafting is tunable, which can be achieved by optimizing the
grafting parameters; and (4) Simple preparation procedures and
absence of highly reactive chemical initiators and catalysts result in
reduction of cost. Hence, a large amount of radiation-grafted AAEMs
have been synthesized [185
191]. Varcoe et al. [185] synthesized
an alkaline AAEM based on ethylene-co-tetrafluoroethylene (ETFE),
which was physically strong, quaternary-ammonium-functional-
ized, and radiation-grafted. The results from H2/O2 fuel cell fabri-
cated with Pt (0.5 mg cm¡2) both at anode and cathode showed that
a peak power density of 130 mW cm¡2 has been achieved with both
humidified hydrogen and oxygen fed at flow rates of 2000 sccm at
Fig. 6. Schematic of (a) an air-breathing cell and (b) the electrode configuration [172]. 60°C. They stated that the performance was substantially limited by
Reproduced with permission from Elsevier. the mass transport in the electrodes. In addition, Poynton et al. [186]
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 155

TagedPsynthesized various ETFE AAEMs via e-beam irradiation. Afterwards, TagedPIn summary, various materials based AAEMs have been synthe-
it was found that the conductivities of the thinnest membrane sized, and the performance of the fabricated MEAs have been evalu-
(17 mm, denoted as S20) reached to 60 mS cm¡1, and the fuel cell ated in H2/O2 fuel cells subsequently. Meanwhile, novel structures in
fabricated with S20 membrane and Pt (0.5 mg cm¡2) both at anode the MEA have been proposed, which possess superior properties
and cathode yielded a peak power density of 230 mWcm¡2 along than conventional MEAs. Though significant progress has been made
with both humidified hydrogen and oxygen at flow rates at in developing AAEMs with high performance as well as low cost, it
2000 sccm at 50°C. The improvement in the performance was attrib- should be noted that the AAEMs are still facing variety of challenges,
uted to the better mass transport. Similarly, Nikolic et al. [187] pre- including hydroxide-ion conductivity, as well as mechanical, chemi-
pared three different types of modified PVA based membranes, cal, and thermal stability.
namely plain PVA, g -PVA cross-linked using gamma irradiation, and
PVA doped with Mo (PVA-Mo). The results from the power output 6. Single-cell: designs and performance
tests showed that the peak power density of the fuel cell fabricated
with Pt (0.2 mg cm¡2) both at anode and cathode employing modi- 6.1. Effect of anode ionomers
fied g -PVA and PVA-Mo membranes were 6.4 and 6.8 mW cm¡2,
which were better than that using plain PVA membrane TagedPIn the anode, novel ionomers and fine microstructures have been
(5.0 mW cm¡2) due to larger absorption of alkaline solution. Deavin proposed for the enhancement of the mass transport and current
et al. [188] prepared radiation-grafted alkaline AAEMs containing collection [192
196]. Recently, Sun et al. [192] prepared pendant
pendent groups with either benzyltrimethylammonium (BTM) or quaternary ammonium-based ionomers employing styrene-ethyl-
benzylmethylimidazolium (BMI) and made comparison of two ene/butylene-styrene (SEBS) as the starting material, which were
AAEMs. It was indicated that, though the BMI-AAEM possessed com- dimensionally stable without drastic sacrifice of the ionic conductiv-
parable conductivity to the BTM-benchmark AAEM, the BMI-AAEM ity as compared to the polysulfone (PSf)-based ionomers. It was indi-
showed severe in-situ degradation due to the intrinsically poor cated that a peak power density of 210 mW cm¡2 was obtained in a
chemical stability in strong alkaline media. It was demonstrated that single cell using Pt (1.28 mg cm¡2) both at the anode and cathode
there was no real advantage in using anion-exchange polymer elec- with hydrogen (RH = 100%) and oxygen (RH = 100%) fed at a rate of
trolytes containing pendent imidazolium groups in strong alkaline 200 sccm at 50°C. They demonstrated that the superior performance
systems. Fang et al. [189] developed radiation-grafted ETFE-based of the ionomers was attributed to the lower internal resistance and
membrane via quaternization and crosslinking with DABCO, alkyl- charge transfer resistance owing to the excellent dimensional stabil-
ation with p-Xylylenedichloride (DCX), and quaternization again ity and the balanced conductivity-hydrophobicity. Matsumoto et al.
with TMA, of which the ionic conductivity is 3.9 £ 10¡2 S cm¡1 at [193] described a novel structure composed of CNTs and KOH-doped
20°C in DI water. Importantly, the conductivity increases to PBI, forming a nanometer thickness wrapping layer, on which the Pt
7.4 £ 10¡2 S cm¡1 at 80°C. Meanwhile, the conductivity could be nanoparticles were loaded, as shown in Fig. 7(a) and (b). It was
retained for 120 h after being treated in KOH solution at 60°C. An shown that the CNTs and the KOH-doped PBI layer functioned
OCV of 1.034 V and a peak power density of 48 mW cm¡2 were as electron and hydroxide conductive pathways, respectively. The
obtained under 100% relative humidity with H2 and O2 both fed at sufficient formation of the interfacial structure resulted in the
rates of 100 mL min¡1. The performance was derived from good leak excellent mass transport around the TPBs. A peak power density of
tightness of electrodes and enhanced electrochemical reaction kinet- 256 mW cm¡2 was achieved with the newly developed electrode
ics. Recently, Wang et al. [190] utilized 30 kGy absorbed dose, 5 vol% fabricated with Pt (0.45 mg cm¡2) both at the anode and cathode
VBC monomer, and water as diluent to synthesize a ETFE-based radi- when hydrogen (RH = 95%) and oxygen (RH = 95%) were supplied at
ation-grafted AAEM. When comparing to the prior state-of-the-art flow rates of 100 and 200 sccm, respectively, which is much higher
protocol, this new method was closer to a commercially-relevant than that of the AS-4 cell primarily due to the better mass transport.
roll-to-roll process. The obtained AAEM exhibited a similar IEC of Yang et al. [194] reported that the ionomer content played an impor-
2.1 mmol g¡1, a higher Cl¡ anion-conductivity of 68 mS cm¡1 vs. tant role in the cell activation, ohmic and concentration losses and
48 mS cm¡1 at 80°C, and a better mechanical stability. Meanwhile, resulted in a high-performance electrode with fine microstructure
they employed a non-fluorinated polymer film (low-density poly- synthesized by 20 wt% ionomer content and the proper dispersion
ethylene (LDPE)) as precursor to prepare radiation-drafted AAEM solvent, including solutions and colloid. It was indicated when the
[191]. As a result, the LDPE-AAEM showed a OH¡ anion conductivity n-butyl acetate (NBA) worked as solvent and ionomer content was
of 145 mS cm¡1 at 80°C with 95% RH and a Cl¡ anion conductivity of kept at 20 wt%, the colloidal electrode increased the pore volume
76 mS cm¡1 at 80°C when fully hydrated. It was indicated that the and pore diameter, serialized ionomer networks and decreased
LDPE-AAEM outperformed the ETFE-AAEM in an AAEMFC, which ohmic and concentration losses, resulting in a peak power density of
was attributed to higher anion conductivity and enhanced in situ 407 mW cm¡2 in an AAEMFC fabricated with Pt (0.4 mg cm¡2) both
water transport. It was worthwhile to note that the LDPE-AAEM was at anode and cathode with hydrogen (RH = 100%) fed at a flow rate
more mechanically robust than ETFE-AAEM, resulting in the ability of 100 sccm and oxygen (RH = 100%) fed at a flow rate of 200 sccm at
to routinely evaluate them in fuel cells at 80°C, whereas the ETFE- 50°C. Ewing et al. [195] synthesized dendritic nano-sized nickel
AAEM was limited to operation at 60°C. nanoparticles via a hydrazine reduction method in ethylene glycol

Fig. 7. Schematic of (a) the preparation of the MWNT/PyPBI/Pt samples and (b) TEM image of the MWNT/PyPBI/Pt [193]. Reproduced with permission from Wiley.
156 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedPfrom a nickel chloride precursor. They characterized the resulting TagedP ensity of 208 mW cm¡2, which was more than double of that of the
d
particles by XRD, TEM, and SEM. The results showed that the single Ag
ammonium ionomer interface and slightly higher than that of
nickel particles gradually connected to form nickel chains, and sub- the Pt based electrode. Unl€ u € et al. [199] used an ionomer impregna-
sequently the chains connected to form the dendritic structures. Fur- tion method to elevate the performance by tailoring the ionomer
thermore, the nickel particle was amorphous, which provided more distribution and balancing the ionic, electronic, and reactant trans-
active sites. In addition, they used the dendritic nickels with a net- port within the catalyst layer as shown in Fig. 8(a) and (b). It was
work structure as the anode for an AAEMFC, resulting in a current shown that the maximum power density was promoted from
density of 11.5 mA cm¡2. Kucernak et al. [196] proposed porous sil- 44 mW cm¡2 to 120 mW cm¡2 via the ionomer impregnation
ver membranes as potential substrates for gas transport electrodes method, and further increased to 315 mW cm¡2 via adding hydro-
in alkaline fuel cells. The silver membrane possessed three inte- phobic additive with Pt (0.5 mg cm¡2) both at anode and cathode at
grated functions, including electrocatalytic function, mechanical 70°C due to the higher catalyst utilization and free volumes close to
support and current collection. An OCV of 1.05 V and a maximum diffusion layer. Zhou et al. [200] prepared a series of partially fluori-
power density of 60 mW cm¡2 were obtained in an alkaline AAEMFC nated copoly(arylene ether) alkaline ionomers (QAPAE) via chloro-
constructed with these electrodes with Pt (0.05 mg cm¡2) both at methylation of copoly(arylene ether) followed by amination with
anode and cathode with hydrogen (RH = 75%) and oxygen (RH = 75%) trimethylamine. The WU of QAPAE was significantly reduced
at 50°C. It was indicated that the gas transport layers were as three because of the presence of the hydrophobic octafluoro-biphenyl
times expensive as carbon-based layers, but especially considering groups in the backbone. It was demonstrated that the QAPAE-4 and
their significantly reduced thickness, 700-fold superior electrical QAPSF ionomers employed as cathode in a hybrid AAEM/PEM fuel
conductance, and thermal conductivity, the Ag electrode still had cell fabricated with Pt (0.5 mg cm¡2) both at anode and cathode uti-
the potential to be used in AAEMFCs. lizing humidified hydrogen as fuel and oxygen as oxidant yielded
TagedPIn summary, the ionomers play an important role in enhancing the peak power density of 315 mW cm¡2 and 215 mW cm¡2 at 60°C,
the mass transport and lowering internal resistance that further respectively. The interfacial adhesion of MEAs still remained a chal-
leads to superior power output. In addition, the well-dispersed elec- lenge because the hydrocarbon ionomer possessed low binding abil-
trocatalysts result in the sufficient TPBs, which is beneficial to ity. Kubo et al. [201] reported the effect of hydroxide-ion conducting
improving the cell performance. layered double hydroxides (LDHs) on the ORR. Two types of LDH
were prepared, denoted as Ni
Al CO32¡ LDH and Mg
Al CO32¡ LDH.
6.2. Effect of cathode ionomers It was indicated that the addition of LDHs to the catalyst layer
increased the reduction current for ORR due to the introduced
TagedPIn the cathode, novel ionomers and structures have been OH¡conducting paths and the increased TPB region. In addition, the
reported recently [197
202]. Unl € u€ et al. [197] synthesized AEIs with Ni
Al CO32¡ LDH possessed better performance than the Mg
Al
different quaternary ammonium density and evaluated the perfor- CO32¡ LDH. Tamain et al. [202] came up with a hypothesis that the
mance via impedance spectroscopy and voltammetry. The obtained limited power output was mainly attributed to limitation of the
results indicated that the limited cell performance on the cathode mass transport of reactant water to the cathode reaction sites, which
was the low catalyst utilization, which was primarily attributed to kept the membrane hydrated for sufficient conductivity. Hence, the
the low ionic conductivities and high WUs of the AEIs. Hence, tre- hydrophobic binder, PTFE, was replaced by Toray carbon paper, aim-
mendous efforts have been devoted into synthesizing various ion- ing at improving the characteristics of the water transport. The
omers with high hydroxide ions conductivity and low WU for H2/O2 fuel cell with the cathode fabricated from Toray carbon paper
promoting the mass transport in order to enhance the catalyst utili- and Pt/C catalyst (20 wt% Pt on Vulcan XC-72R carbon support)
zation. Gu et al. [198] reported a phosphonium based ionomer resulted in a peak power density of 125 mW cm¡2, which was
(TPQPOH) and simply used it to prepare the catalyst layer with Ag. 25
36% more than the power output compared to the that of the
The Ag
phosphonium ionomer interface yielded a high peak power fuel cells fabricated with the PTFE-containing cathodes.

Fig. 8. Schematic of the electrode structures made by (a) thin-film and (b) ionomer impregnation methods [199]. Reproduced with permission from Elsevier.
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 157

TagedPIn summary, the ionomers on the cathode play an important role TagedP node and consumed in the cathode. Therefore, the flooding prob-
a
in the property of the cathode. It should be noted that lower WUs, lem that limits the cell performance is more likely to arise in the
higher ionic conductivities, and higher catalyst utilizations result in anode. To achieve a better power output, it is essential to undertake
the improvement of the power output. In addition, since water is water management to mitigate the flooding problem. Zhang et al.
consumed in cathode, humidification of oxygen is necessary in cath- [16] confirmed that the direction of water movement was from the
ode. Otherwise, the ORR is difficult to proceed in the absence of anode to the cathode via a water collection method, which indicated
water at the cathode. the diffusion water was much larger than the electro-osmosis water.
At high current densities, much more water moved from the anode
6.3. Effect of structural designs to cathode, which not only alleviates the flooding problem at the
anode but also reduces membrane resistance. Oshiba et al. [204] pro-
TagedPThe performance of the AAEMFC lies on three primary parame- posed two methods to suppress the anode flooding. One was to
ters as follows: (1) the electrocatalysts for HOR and ORR that deter- increase the anode flow rate: when the RH at the anode outlet
mine the electrochemical kinetics; (2) the structure of MEA that reached 100%, the current density increased with the anode flow
influences the transport of mass, ions, and electrons; and (3) the rate, indicating that the anode flooding problem was alleviated. The
operation conditions that affect the electrochemical and transport other was to reduce the membrane thickness: when the membrane
behaviors and thus the power output. became thinner, the water produced in the anode was easily perme-
TagedPIn addition to the development of novel electrocatalysts for the ated to the cathode. Recently, Omasta et al. [205] pointed out that
HOR and ORR, the effects of structural designs also have been investi- the amount and balance of water was a critical issue to obtain high
gated [16,203,204]. It is widely believed that a superior design of performance that could be achieved by tuning the cell water to opti-
flow field, anode, and cathode leads to a better performance, result- mize the dynamic balance between membrane hydration and elec-
ing from the enhanced mass transport and the sufficient TPBs. It trode flooding/dry-out. It was indicated that the cell water was able
should be noted that the mass transport also plays an important role to be actively manipulated via several variables, including gas feed
in the fuel cell performance. For the mass transport in the anode, it dew points, catalyst layer hydrophobicity, anode and cathode gas
is vitally important to design the flow field and diffusion layer to flow rates, flow channel design, catalyst layer engineering, and the
lead hydrogen to distribute as even as possible, maximizing the cell physicochemical properties of the AAEM and AEIs.
voltage. On the cathode, the critical mass transport issues can be con-
cluded as follows: (1) it is necessary to design the flow field and dif- 6.5. Single-cell durability
fusion layer; (2) it is critical to enhance the transport of oxygen in
the through-plane direction; (3) in the in-plane direction, the distri- TagedPDurability of fuel cells is one of the critical issues in realizing the
bution of oxygen needs to be uniform over the CL. For the mass commercialization [206
208]. Hence, Slade et al. [206] demon-
transport through the membrane, the key issue is to suppress the strated that the AAEMs must be evaluated in H2/O2, H2/air, and
hydrogen crossover so that the mixed potential problem can be alle- methanol/air fuel cells for several thousand hours to ensure ade-
viated and hydrogen will not be wasted. The reduction of crossover quate in-situ membrane stability. Though some synthesized AAEMs
can be achieved when the design of the MEA is optimal, particularly exhibited exceptional fuel cell performance, the poor durability has
the cathode backing layer and microporous layer. Mamlouk et al. still not been solved yet. Luo et al. [207] proposed two strategies to
[203] studied the effects of ionomer content, anode and cathode CL improve the durability of QPMBV membranes. The first was to
thicknesses, and membrane thickness on the performance of an increase glass transition temperature and molecular weight via
AAEMFC. It was indicated that an optimum ionomer content eliminating butyl acrylate from the monomers. The second was to
depended on a balance between the OH¡ ion/water mobility and the reduce the WU and SR via crosslinking to lock the functionalized
oxygen solubility/diffusivity through it. When the ionomer content in QPMV into a poly (divinylbenzene) (PDVB) polymer network. It was
the CL was too high, the mass transport through the ionomer could indicated that the fuel cell employing crosslinked QPMV-PDVB
be impeded. Moreover, the electrocatalyst and carbon particles could AAEM could continuously work for 420 h at 50°C and 146 h at 70°C,
be electron-isolated. When too low, the insufficient ECSA resulted in which was eight and three times longer than that in previous study,
the lower utilization of the electrocatalysts. In addition, the limiting respectively, as shown in Fig. 9(a) and (b). Fujimoto et al. [208]
OH¡ mobility leaded to the larger ohmic loss. It was suggested that investigated the backbone stability of benzyl-trimethyl ammonium
thick anode CL was necessary because the flooding problem could be (BTMA) functionalized polyaromatics in two structurally differing
avoided when the fuel cell was operated at high current densities, polymer architectures: quaternized poly(aryleneether) (PAE) and PP.
meaning that more water was produced in the anode CL. Meanwhile, It was indicated that the cleavage of aryl-ether linkages substantially
the effect of the cathode CL on the performance have been studied. It impacted the mechanical properties and moderately the hydroxide
was indicated that an optimum of the cathode CL thickness conductivity. The results showed that the PAE MEA experienced fail-
depended on the operating conditions, including oxygen partial pres- ure at 55 h due to the degraded mechanical stability while the PP
sure and ionomer used. A thicker CL with smaller particle size might MEA exhibited stable performance during 300-h operation.
suffer from the oxygen starvation problem, when the oxygen supply
was inadequate. While a thinner layer with larger particle size might 6.6. Single-cell performance
not possess the enough ECSA. The AAEM, the key component of the
AAEMFC, worked as the barrier separating the anode and cathode, as TagedPHerein, we summarize the peak power densities reported in the
well as the pathway for OH¡ transport. Thus, the optimal membrane recent literatures. Tables 1
4 show the selected hydrogen/oxygen
thickness lay on the equilibrium of the OH¡ transport and gas per- fuel cell performance with different HOR electrocatalysts, ORR
meability. The single fuel cell tests showed that the membrane with electrocatalysts, AAEMs, and MEA structures, respectively. It can be
hydrated thickness of 57 mm resulted in a peak power density of seen from Tables that power density has been boosted from
337 mW cm¡2 with the air at 60°C. »0.4 mW cm¡2 to 1450 mW cm¡2 in recent years, suggesting that
the AAEMFC is a promising energy technology and tremendous
6.4. Effect of water flooding efforts have been paid into this field [70,74,97,190,191,194,
205,209,210]. Hu et al. [74] fabricated an AAEMFC, which exhibited
TagedPAdditionally, water management is critical to achieve better per- the highest power density of 40 mW cm¡2 with humidified hydro-
formance and durability. In AAEMFCs, water is produced in the gen and oxygen both at a flow rate of 50 sccm at 60°C, when Ni
W
158 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Fig. 9. (a) Durability tests of uncrosslinked QPMV and 10% crosslinked QPMV-PDVB AAEMs at 70 °C, (b) Durability test of 10% crosslinked AAEM at 50 °C [207]. Reproduced with
permission from Elsevier. (c) Cell performance of the AEMFC using the PtRu anode or Pt anode [210]. Reproduced with permission from The Royal Society of Chemistry. (d) Perfor-
mance of H2/O2 AEMFC test data at 60 °C for E-R (squares) and E-6 (circles) using PtRu/C anodes and Pt/C cathodes and with no gas back-pressurization of the fully humidified
gases [190]. (e) Performance of the AEMFC with different hypothesized distribution of water across the AEM and electrodes in an AEMFC [205]. (f) Performance of H2/O2 AEMFC at
80 °C with the LDPE-AEM with Pt/C (circles) or Ag/C (squares) as cathodes as well as PtRu/C anode [191]. Reproduced with permission from Elsevier.

TagedP(17.5 mg cm¡2), CoPPY/C (2 mg cm¡2), and xQAPS were employed as TagedP s anode electrocatalyst, 0.5 mg cm¡2 Pt/C as cathode electrocata-
a
anode electrocatalyst, cathode electrocatalyst and AAEM, respec- lyst, and an AAEM (Tokuyama A201), resulting in an excellent peak
tively. Carmo et al. [209] developed an AAEMFC with 20 wt% Pt/C power density of 250 mW cm¡2. The significant enhancement was
(0.8 mg cm¡2) and 25% FAA-3 ionomer in the catalyst layer for both substantially attributed to the larger surface area per unit weight of
the cathode and anode. It was indicated that a peak power density of Ru/C, which resulted in the higher limiting current density. He et al.
223 mW cm¡2 was obtained using hydrogen (100% humidity) as fuel [97] reported a novel cathode electrocatalyst, CoO/rGO(N). The
at 200 sccm and oxygen (100% humidity) as oxidation at 200 sccm. results from the fuel cell tests showed that the peak power density
In addition, the platinum requirement could be decreased to reached 387 mW cm¡2 with the hydrogen (62% RH) fed to the anode
0.5 mg cm¡2 without sacrificing the performance. Recently, Ohyama at a rate of 250 sccm and the oxygen (100% RH) fed to the cathode at
et al. [70] developed a fuel cell employing 0.5 mg cm¡2 Ru/C (3 nm) a rate of 200 sccm, when the Pt and CoO/rGO(N) are employed as

Table 1
Selected hydrogen/oxygen fuel cell performance with different HOR electrocatalysts reported in open literature.

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mWcm¡2)

H2 (RH = 100%) / O2 (RH = 100%) Cr/Ni (5 mg cm¡2) Ag (1 mg cm¡2) quaternary ammonium 60 50 54

polysulphone membranes
¡2 ¡2
200 sccm dry H2 / 1000 sccm air Pd/Ni (1.5 mg cm ) Ag (3 mg cm ) AAEM 73 400 69
200 sccm dry H2 / 1000 sccm air Pd (1.5 mg cm¡2) Ag (3 mg cm¡2) AAEM 73 180 69
200 sccm dry H2 / 1000 sccm air Ni (1.5 mg cm¡2) Ag (3 mg cm¡2) AAEM 73 70 69
500 sccm H2 (RH = 100%) / 500 sccm O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A201 50 »185 70
500 sccm H2 (RH = 100%) / 500 sccm O2 (RH = 100%) 3 nm Ru/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A201 50 »250 70
500 sccm H2 (RH = 100%) / 500 sccm O2 (RH = 100%) 11 nm Ru/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A201 50 »135 70
200 sccm dry H2 / 1000 sccm air Pd/C (0.3 mg cm¡2) Ag (3 mg cm¡2) AAEM 73 100 73
200 sccm dry H2 / 1000 sccm air Pd/C

CeO2 (0.3 mg cm¡2) Ag (3 mg cm¡2) AAEM 73 500 73
50 sccm H2 (RH = 100%) / 50 sccm O2 (RH = 100%) Ni
W (17.5 mg cm¡2) Coppy/C (2 mg cm¡2) xQAPS membrane 60 40 74
50 sccm H2 (RH = 100%) / 50 sccm air (RH = 100%) Ni
W (17.5 mg cm¡2) Coppy/C (2 mg cm¡2) xQAPS membrane 60 27.5 74
200 sccm dry H2 / 1000 sccm air Pd/C

CeO2 (0.3 mg cm¡2, Pd 6%) Ag (3 mg cm¡2) AAEM 73 390 84
200 sccm dry H2 / 1000 sccm air Pd/C

CeO2 (0.3 mg cm¡2, Pd 10%) Ag (3 mg cm¡2) AAEM 73 500 84
200 sccm dry H2 / 1000 sccm air Pd/C

CeO2 (0.3 mg cm¡2, Pd 20%) Ag (3 mg cm¡2) AAEM 73 460 84
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 159

Table 2
Selected hydrogen/oxygen fuel cell performance with different ORR electrocatalysts reported in open literature.

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

H2 / O2 Pt/C (0.375 mg cm¡2) Ag/C (0.5 mg cm¡2) AEM 60 109 55

2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.5 mg cm¡2) Pt/C (20 wt%) (0.5 mg cm¡2) AAEM-MEAs 50 »54 87
2000 sccm O2 (RH = 100%)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.5 mg cm¡2) Ag/C (60 wt%) (4 mg cm¡2) AAEM-MEAs 50 »47 87
2000 sccm O2 (RH = 100%)
¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.5 mg cm ) Au/C (60 wt%) (4 mg cm ) AAEM-MEAs 50 »20 87
2000 sccm O2 (RH = 100%)
¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.5 mg cm ) Pt/C (20 wt%) (0.5 mg cm ) AAEM-MEAs 50 »28 87
2000 sccm O2 (RH = 82%)
2000 sccm H2 (RH = 82%) / Pt/C (20 wt%) (0.5 mg cm¡2) Pt/C (20 wt%) (0.5 mg cm¡2) AAEM-MEAs 50 »25 87
2000 sccm O2 (RH = 100%)
H2 (RH = 100%) / Air (RH = 100%) Pt/C (40 wt%) (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) the mixture of TMA and TMHDA 60 28.2 88
with a ratio of 3:1
¡2 ¡2
H2 (RH = 100%) / Air (RH = 100%) Pt/C (40 wt%) (0.5 mg cm ) Ag/C (0.5 mg cm ) the mixture of TMA and TMHDA 60 8.1 88
with a ratio of 3:1
H2 (RH = 100%) / Air (RH = 100%) Pt/C (40 wt%) (0.5 mg cm¡2) Ag/C (1.0 mg cm¡2) the mixture of TMA and TMHDA 60 19.9 88
with a ratio of 3:1
H2 (RH = 100%) / Air (RH = 100%) Pt/C (40 wt%) (0.5 mg cm¡2) Ag/C (2.0 mg cm¡2) the mixture of TMA and TMHDA 60 30.1 88
with a ratio of 3:1
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) AHA Membrane (without ionomer R.T. »6 90
500 sccm O2 (RH = 100%) in both anode and cathode)
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) ACS Membrane (without ionomer R.T. 2 90
500 sccm O2 (RH = 100%) in both anode and cathode)
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) AHA Membrane (with ionomer R.T. 55 90
500 sccm O2 (RH = 100%) in both anode and cathode)
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) AHA Membrane (with ionomer R.T. 40 90
500 sccm O2 (RH = 100%) in cathode and without at anode)
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pd/C (0.5 mg cm ) AHA Membrane (with ionomer R.T. 55 90
500 sccm O2 (RH = 100%) in cathode and without at anode)
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) AHA Membrane (with ionomer R.T. 40 90
500 sccm O2 (RH = 100%) in cathode and without at anode)
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Au/C (0.5 mg cm¡2) AHA Membrane (with ionomer R.T. 1 90
500 sccm O2 (RH = 100%) in cathode and without at anode)
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pd/C (0.5 mg cm ) alkaline polymer electrolyte 30 56 91
500 sccm O2 (RH = 100%) membrane
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) PdCo(1:1)/C (0.5 mg cm ) alkaline polymer electrolyte 30 26 91
500 sccm O2 (RH = 100%) membrane
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) PdCo(2:1)/C (0.5 mg cm¡2) alkaline polymer electrolyte 30 75 91
500 sccm O2 (RH = 100%) membrane
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) PdCo(3:1)/C (0.5 mg cm¡2) alkaline polymer electrolyte 30 85 91
500 sccm O2 (RH = 100%) membrane
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pd/C (0.5 mg cm ) alkaline polymer electrolyte 30 19 91
500 sccm air (RH = 100%) membrane
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) PdCo(1:1)/C (0.5 mg cm¡2) alkaline polymer electrolyte 30 15 91
500 sccm air (RH = 100%) membrane
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) PdCo(2:1)/C (0.5 mg cm¡2) alkaline polymer electrolyte 30 26 91
500 sccm air (RH = 100%) membrane
¡2 ¡2
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) PdCo(3:1)/C (0.5 mg cm ) alkaline polymer electrolyte 30 37 91
500 sccm air (RH = 100%) membrane
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Tanaka Pt/C (0.6 mg cm ) Tokuyama A201 membrane 45 »130 94
400 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) E-Tek Pt/C (0.6 mg cm¡2) Tokuyama A201 membrane 45 »120 94
400 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) CoPc/MWCNT (0.6 mg cm¡2) Tokuyama A201 membrane 45 »100 94
400 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) FePc/MWCNT (0.6 mg cm ) Tokuyama A201 membrane 45 »60 94
400 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) MWCNT (0.6 mg cm¡2) Tokuyama A201 membrane 45 »25 94
400 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) anion exchange membrane 50 196 95
400 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm )
HLH (4 mg cm
CoFeN/C
) anion exchange membrane 50 177 95
400 sccm O2 (RH = 100%)
¡2 ¡2
250 sccm H2 (RH = 57%) / Pt/C (1.5 mg cm ) Pt/C (1.5 mg cm ) Tokuyama A201 60 387 97
500 sccm O2 (RH = 100%)
250 sccm H2 (RH = 57%) / Pt/C (1.5 mg cm¡2) CoO/rGO(N) (0.6 mg cm¡2) Tokuyama A201 60 248 97
500 sccm O2 (RH = 100%)
300 sccm H2 / 300 sccm O2 Pt/C (0.5 mg cm¡2) ED-CNT (0.2 mg cm¡2) commercial FAA anion exchange 80 25.5 107
membrane
¡2 ¡2
300 sccm H2 / 300 sccm O2 Pt/C (0.5 mg cm ) Pt/C (0.2 mg cm ) commercial FAA anion exchange 80 19.1 107
membrane
160 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Table 3
Selected hydrogen/oxygen fuel cell performance with different AEMs reported in open literature.

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

H2/O2 Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-23 AAEM 60 823 3
H2/O2 Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-23 AAEM 50 718 3
H2/O2 Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-19 AAEM 40 640 3
H2/O2 Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-19 AAEM 20 648 3
H2/Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-5 AAEM 60 506 3
H2/Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-5 AAEM 50 464 3
H2/Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) X-23 AAEM 40 450 3
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) radiation-grafted AAEMs-S80 50 »100 9
2000 sccm O2 (RH = 100%)
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) radiation-grafted AAEMs-S50 50 »150 9
2000 sccm O2 (RH = 100%)
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) radiation-grafted AAEMs-S20 50 »230 9
2000 sccm O2 (RH = 100%)
¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Au/C (0.5 mg cm ) radiation-grafted AAEMs-S80 50 36.6 9
2000 sccm O2 (RH = 100%)
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Ag/C (0.5 mg cm¡2) radiation-grafted AAEMs-S80 50 19.1 9
2000 sccm O2 (RH = 100%)
80 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PTFE-QDPSU composite membrane 30 »60 61
100 sccm O2 (RH = 100%)
¡2 ¡2
80 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PTFE-QDPSU composite membrane 40 »100 61
100 sccm O2 (RH = 100%)
¡2 ¡2
80 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PTFE-QDPSU composite membrane 50 146 61
100 sccm O2 (RH = 100%)
80 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PTFE-QDPSU composite membrane 50 103 61
100 sccm CO2 free air (RH = 100%)
40 sccm H2 (RH = 100%) / Pt/C (4 mg cm¡2) Pt/C (4 mg cm¡2) PVA15 membrane 25 72 114
80 sccm O2 (RH = 100%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PVA/PDDA AAEM (HMw) 25 35.1 115
70 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PVA/PDDA AAEM (MMw) 25 28.5 115
70 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PVA/PDDA AAEM (LMw) 25 23.4 115
70 sccm O2 (RH = 100%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PVA/PDDA AAEM (ULMw) 25 18.2 115
70 sccm O2 (RH = 100%)
¡2 ¡2
300 sccm H2 (RH = 100%) / Pt/C (0.1 mg cm ) Pt/C (0.2 mg cm ) QBMPAE-d alkaline anion exchange 70 20.1 117
800 sccm air (RH = 100%) membrane
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PVA/PDDA-OH¡membrane 25 32.7 120
70 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A901 R.T. 37.7 121
70 sccm O2 (RH = 100%)
¡2 ¡2 ¡
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PVA/PDDA-OH alkaline membranes R.T. 14.8 121
70 sccm O2 (RH = 100%) (PVA:PDDA = 1:0.75)
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PVA/PDDA-OH¡ alkaline membranes R.T. 35.1 121
70 sccm O2 (RH = 100%) (PVA:PDDA = 1:0.5)
100 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PVA/PDDA-OH¡ alkaline membranes R.T. 11.5 121
70 sccm O2 (RH = 100%) (PVA:PDDA = 1:0.25)
¡2 ¡2
40 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) PVAc(1)-c-PVBC(1)/OH membrane 40 124.7 122
70 sccm O2 (RH = 100%)
¡2 ¡2
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm ) Pt/C (0.65 mg cm ) PPO-based anion exchange membrane 25 »3 124
10 sccm O2 (RH = 100%)
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm¡2) Pt/C (0.65 mg cm¡2) PPO-based anion exchange membrane 30 »3 124
10 sccm O2 (RH = 100%)
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm¡2) Pt/C (0.65 mg cm¡2) PPO-based anion exchange membrane 40 »8.5 124
10 sccm O2 (RH = 100%)
¡2 ¡2
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm ) Pt/C (0.65 mg cm ) PPO-based anion exchange membrane 50 »8 124
10 sccm O2 (RH = 100%)
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm¡2) Pt/C (0.65 mg cm¡2) PPO-based anion exchange membrane 60 »11.5 124
10 sccm O2 (RH = 100%)
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm¡2) Pt/C (0.65 mg cm¡2) PPO-based anion exchange membrane 70 19.5 124
10 sccm O2 (RH = 100%)
¡2 ¡2
5 sccm H2 (RH = 100%) / Pt/C (0.65 mg cm ) Pt/C (0.65 mg cm ) PPO-based anion exchange membrane 80 »15 124
10 sccm O2 (RH = 100%)
¡2 ¡2
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) BIm-PPO-0.54 AAEM 35 13 126
600 sccm O2 (RH = 100%)
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) alkaline polymer electrolyte 35 56 127
600 sccm O2 (RH = 100%) membrane (DIm-PPO-0.54)
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) alkaline polymer electrolyte 35 40 127
600 sccm O2 (RH = 100%) membrane (DIm-PPO-0.43)
¡2 ¡2
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) alkaline polymer electrolyte 50 30 127
600 sccm O2 (RH = 100%) membrane (Im-PPO)

(continued)
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 161

Table 3 (Continued)

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) 1a electrolyte membrane 50 188.7 128
200 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) TMA-20 electrolyte membrane 50 62.3 128
200 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) TPPVBN30 50 268 132
2000 sccm O2 (RH = 100%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) TPPVBN30 60 348 132
2000 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QAPS/PTFE 29 um CCM 50 252 133
200 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QAPS/PTFE 20 um CCM 50 315 133
200 sccm O2 (RH = 100%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QAPS/PTFE 29 um GDE 50 152 133
200 sccm O2 (RH = 100%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QAPS 30 um GDE 50 145 133
200 sccm O2 (RH = 100%)
120 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) xQAPS@PTFE membrane 40 (0 MPa) »180 134
120 sccm O2 (RH = 100%)
120 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mgcm¡2) xQAPS@PTFE membrane 50 (0 MPa) »400 134
120 sccm O2 (RH = 100%)
¡2 ¡2
120 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) xQAPS@PTFE membrane 60 (0 MPa) »450 134
120 sccm O2 (RH = 100%)
120 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) xQAPS@PTFE membrane 60 (0.1 MPa) 550 134
120 sccm O2 (RH = 100%)
800 sccm H2 (RH = 100%) / Pt/C (2 mg cm¡2) Pt/C (2 mg cm¡2) PSU-PATC(1.2) 60 55 138
600 sccm O2 (RH = 100%)
¡2 ¡2
800 sccm H2 (RH = 100%) / Pt/C (2 mg cm ) Pt/C (2 mg cm ) PSU-PATC(1.5) 60 19 138
600 sccm O2 (RH = 100%)
¡2 ¡2
150 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (2 mg cm ) QA-PSf membrane 60 115 139
200 sccm O2 (RH = 100%)
150 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (2 mg cm¡2) QA-PSf-g-PEG350 membrane 60 »138 139
200 sccm O2 (RH = 100%)
150 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (2 mg cm¡2) QA-PSf-g-PEG750 membrane 60 180 139
200 sccm O2 (RH = 100%)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm ) Pt/C (0.125 mg cm ) QPSU membrane R.T. »70 140
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU/2.5% ZrO2 composite membrane R.T. »75 140
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 5% ZrO2 composite membrane R.T. »80 140
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 7.5% ZrO2 composite R.T. »110 140
membrane
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 10% ZrO2 composite R.T. 140 140
membrane
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm ) Pt/C (0.125 mg cm ) QPSU membrane 60 »155 140
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 2.5% ZrO2 composite 60 »165 140
membrane
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 5% ZrO2 composite membrane 60 »175 140
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 7.5% ZrO2 composite 60 »210 140
membrane
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.375 mg cm¡2) Pt/C (0.125 mg cm¡2) QPSU / 10% ZrO2 composite 60 250 140
membrane
¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) AAEM-MEAs with alkaline interface 50 55 141
2000 sccm O2 (RH = 100%) polymer
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) AAEM-MEAs without alkaline 50 1.6 141
2000 sccm O2 (RH = 100%) interface polymer
200 sccm H2 (RH = 100%) / Pt/C (1 mg cm¡2) Pt/C (1 mg cm¡2) A901:0.97 50 343 143
200 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (1 mg cm ) Pt/C (1 mg cm ) SEBS:0.51 50 169 143
200 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (1 mg cm¡2) Pt/C (1 mg cm¡2) SEBS:0.70 50 222 143
200 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (1 mg cm¡2) Pt/C (1 mg cm¡2) SEBS:0.90 50 285 143
200 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) Tokuyama A201 (C16D40) 50 77 144
200 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) Tokuyama A201 (C6D60) 50 67 144
200 sccm O2 (RH = 100%)
500 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A201 (C6D60) 50 »80 144
200 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A201 (C6D60) 50 »105 144
200 sccm O2 (RH = 100%)
¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) Tokuyama A201 (C6D60) 50 »120 144
200 sccm O2 (RH = 100%)
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Tokuyama A201 (C6D60) 50 145 144
2000 sccm O2 (RH = 100%)

(continued)
162 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Table 3 (Continued)

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

250 sccm H2 (RH = 95%) / Pt/C (1 mg cm¡2) Pt/C (1 mg cm¡2) Tokuyama A201 50 148 145
250 sccm air (RH = 95%)
250 sccm H2 (RH = 95%) / Pt/C (1 mg cm¡2) Pt/C (1 mg cm¡2) C30D70-1.7 AEM 50 168 145
250 sccm air (RH = 95%)
50 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) PES-MeIm/OH-#4 (FC-#1) 45 0.81 146
100 sccm O2 (RH = 100%)
¡2 ¡2
50 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) PES-MeIm/OH-#4 (FC-#2) 45 7.1 146
100 sccm O2 (RH = 100%)
50 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) PES-MeIm/OH-#4 (FC-#3) 45 22.5 146
100 sccm O2 (RH = 100%)
50 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) PES-MeIm/OH-#4 (FC-#4) 45 21.0 146
100 sccm O2 (RH = 100%)
¡2 ¡2
50 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) PES-MeIm/OH-#4 (FC-#5) 45 29.5 146
100 sccm O2 (RH = 100%)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (2 mg cm ) Pt/C (1 mg cm ) PSf135-ImOH membrane 60 16 147
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (2 mg cm¡2) Pt/C (1 mg cm¡2) PSf102-ImOH membrane 60 »6 147
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Alkaline anion exchange membrane 5 50 30 148
600 sccm air (RH = 100%)
80 sccm H2 (RH = 60%) / Pt/C (1.0 mg cm¡2) Pt/C (1.0 mg cm¡2) QPMBV-1 membrane 60 35 153
80 sccm O2 (RH = 60%)
¡2 ¡2
80 sccm H2 (RH = 60%) / Pt/C (1.0 mg cm ) Pt/C (1.0 mg cm ) QPMBV-2 membrane 60 »22 153
80 sccm O2 (RH = 60%)
80 sccm H2 (RH = 60%) / Pt/C (1.0 mg cm¡2) Pt/C (1.0 mg cm¡2) QPMBV-3 membrane 60 »5 153
80 sccm O2 (RH = 60%)
80 sccm H2 (RH = 60%) / Pt/C (1.0 mg cm¡2) Pt/C (1.0 mg cm¡2) QPMBV-1 membrane 40 »11 153
80 sccm O2 (RH = 60%)
¡2 ¡2
80 sccm H2 (RH = 60%) / Pt/C (1.0 mg cm ) Pt/C (1.0 mg cm ) QPMBV-1 membrane 80 59 153
80 sccm O2 (RH = 60%)
¡2 ¡2
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QPMBV-APE 50 115 154
100 sccm O2 (RH = 80%)
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-APE 60 160 154
100 sccm O2 (RH = 80%)
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-APE 70 180 154
100 sccm O2 (RH = 80%)
¡2 ¡2
80 sccm H2 (RH = 80%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) QPMBV AEM 50 »15 155
80 sccm O2 (RH = 80%)
80 sccm H2 (RH = 80%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) QPMBV AEM 60 25 155
80 sccm O2 (RH = 80%)
80 sccm H2 (RH = 80%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) QPMBV AEM 70 »21 155
80 sccm O2 (RH = 80%)
¡2 ¡2
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QPMBV-1 membrane 70 80 156
100 sccm O2 (RH = 80%)
¡2 ¡2
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QPMBV-2 membrane 70 »150 156
100 sccm O2 (RH = 80%)
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-3 membrane 70 180 156
100 sccm O2 (RH = 80%)
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-1 membrane 60 »30 156
100 sccm O2 (RH = 80%)
¡2 ¡2
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QPMBV-2 membrane 60 »95 156
100 sccm O2 (RH = 80%)
100 sccm H2 (RH = 80%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-3 membrane 60 »105 156
100 sccm O2 (RH = 80%)
100 sccm H2 (RH = 70%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-2 membrane 70 »115 156
100 sccm O2 (RH = 70%)
¡2 ¡2
100 sccm H2 (RH = 60%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QPMBV-2 membrane 70 »75 156
100 sccm O2 (RH = 60%)
¡2 ¡2
100 sccm H2 (RH = 50%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) QPMBV-2 membrane 70 »50 156
100 sccm O2 (RH = 50%)
100 sccm H2 (RH = 40%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) QPMBV-2 membrane 70 »15 156
100 sccm O2 (RH = 40%)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.17 mg cm¡2) Pt/C (0.17 mg cm¡2) Anion exchange crosslinked 25 100 158
membrane (cell 1)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.17 mg cm ) Pt/C (0.17 mg cm ) Anion exchange crosslinked 25 »100 158
membrane (cell 2)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.17 mg cm¡2) Pt/C (0.17 mg cm¡2) Anion exchange crosslinked 25 »95 158
membrane (cell 3)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.17 mg cm¡2) Pt/C (0.17 mg cm¡2) Anion exchange crosslinked 25 »90 158
membrane (cell 4)
50 sccm H2 (RH = 100%) / Pt/C (unmodified) Pt/C (unmodified) Sn0.92Sb0.08P2O7-PTFE composite 75 15 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (unmodified) Pt/C (unmodified) Sn0.92Sb0.08P2O7-PTFE composite 100 »20 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (unmodified) Pt/C (unmodified) Sn0.92Sb0.08P2O7-PTFE composite 125 »28 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane

(continued)
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 163

Table 3 (Continued)

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

50 sccm H2 (RH = 100%) / Pt/C (unmodified) Pt/C (unmodified) Sn0.92Sb0.08P2O7-PTFE composite 150 »35 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (unmodified) Pt/C (unmodified) Sn0.92Sb0.08P2O7-PTFE composite 175 »50 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (unmodified) Pt/C (unmodified) Sn0.92Sb0.08P2O7-PTFE composite 200 61 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (modified) Pt/C (modified) Sn0.92Sb0.08P2O7-PTFE composite 75 76 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (modified) Pt/C (modified) Sn0.92Sb0.08P2O7-PTFE composite 100 94 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (modified) Pt/C (modified) Sn0.92Sb0.08P2O7-PTFE composite 125 114 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (modified) Pt/C (modified) Sn0.92Sb0.08P2O7-PTFE composite 150 130 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (modified) Pt/C (modified) Sn0.92Sb0.08P2O7-PTFE composite 175 132 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
50 sccm H2 (RH = 100%) / Pt/C (modified) Pt/C (modified) Sn0.92Sb0.08P2O7-PTFE composite 200 147 160
50 sccm air (RH = 100%) (2 mg cm¡2) (2 mg cm¡2) membrane
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) ACDH96 membrane (electrode1) 50 252 161
200 sccm O2 (RH = 100%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) ACDH98 membrane 50 278 161
200 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) CD96 membrane 50 237 161
200 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) ACDH96 membrane (electrode2) 50 370 161
200 sccm O2 (RH = 100%)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (3.4 mg cm ) Pt/C (6.5 mg cm ) ATM-PP (ionomer: M-Nafion- FA- 80 577 162
TMG)
¡2 ¡2
H2 (RH = 100%) / air (RH = 100%) Pt/C (3.4 mg cm ) Pt/C (6.5 mg cm ) ATM-PP (ionomer: M-Nafion- FA- 80 466 162
TMG)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (3.4 mg cm¡2) Pt/C (6.5 mg cm¡2) ATM-PP (ionomer: ATM-PP) 80 335 162
200 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PSF-DMP AEM (IEC = 1.81 mmol g¡1) 70 »8 165
200 sccm O2 (RH = 95%)
200 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PSF-TMA AEM (IEC = 1.79 mmol g¡1) 70 46 165
200 sccm O2 (RH = 95%)
¡2 ¡2 ¡1
200 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PSF-TMA AEM (IEC = 2.05 mmol g ) 70 179 165
200 sccm O2 (RH = 95%)
200 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PSF-DMP AEM (IEC = 1.81 mmol g¡1) 70 »53 165
200 sccm air (RH = 95%)
200 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) PSF-TMA AEM (IEC = 1.79 mmol g¡1) 70 »2 165
200 sccm air (RH = 95%)
¡2 ¡2 ¡1
200 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) PSF-TMA AEM (IEC = 2.05 mmol g ) 70 »40 165
200 sccm air (RH = 95%)
50 sccm H2 (RH = 100%) / Pt/C (2 mg cm¡2) Pt/C (2 mg cm¡2) AEM based on [VBMI]Cl 30 33 170
100 sccm O2 (RH = 100%)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 »10 172
(1 M KOH)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 40 »17 172
(1 M KOH)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 60 »22 172
(1 M KOH)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 80 »28 172
(1 M KOH)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 13.6 172
(1 M TMAOH)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 20 »12.5 172
(1 M TEAOH)
20vsccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 »12 172
(0.5 M TPrAOH)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 2.4 172
(0.05 M TMAOH)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 20 7.0 172
(0.2 M TMAOH)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 20 13.5 172
(0.6 M TMAOH)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 40 16.3 172
(1 M TMAOH)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 60 18.6 172
(1 M TMAOH)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 80 20.2 172
(1 M TMAOH)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 4.1 172
(1 M TMACO3 pH = 8)

(continued)
164 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Table 3 (Continued)

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 2.1 172
(1 M TMA-Ac pH = 7.6)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 20 1.1 172
(1 M TMA-SO4 pH = 4.6)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 40 »4.8 172
(1 M TMACO3 pH = 8)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 60 »6.5 172
(1 M TMACO3 pH = 8)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 80 9.7 172
(1 M TMACO3 pH = 8)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 40 »2.2 172
(1 M TMA-Ac pH = 7.6)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 60 »2.6 172
(1 M TMA-Ac pH = 7.6)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 80 »3.0 172
(1 M TMA-Ac pH = 7.6)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 40 »1.2 172
(1 M TMA-SO4 pH = 4.6)
20 sccm H2 / Air Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) solid alkaline electrolyte membrane 60 »1.4 172
(1 M TMA-SO4 pH = 4.6)
¡2 ¡2
20 sccm H2 / Air Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) solid alkaline electrolyte membrane 80 »1.6 172
(1 M TMA-SO4 pH = 4.6)
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) ETFE-based AAEM 60 110 185
2000 sccm O2 (RH = 100%)
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) ETFE-based AAEM 50 90 185
2000 sccm O2 (RH = 100%)
¡2 ¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) 4 mg cm catalysed AAEM 50 130 185
2000 sccm O2 (RH = 100%)
¡2 ¡2
H2 / O2 Pt/C (0.2 mg cm ) Pt/C (0.2 mg cm ) PVA membrane R.T. »5.0 187
H2 / O2 Pt/C (0.2 mg cm¡2) Pt/C (0.2 mg cm¡2) g -PVA membrane R.T. »6.4 187
H2 / O2 Pt/C (0.2 mg cm¡2) Pt/C (0.2 mg cm¡2) PVA-Mo membrane R.T. »6.8 187
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) PVBTMA-OH¡ (1) AAEM 50 »140 188
600 sccm O2 (RH = 100%)
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) PVBMI-OH¡ (1) AAEM 50 »0.8 188
600 sccm O2 (RH = 100%)
¡2 ¡2 ¡
600 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) PVBMI-OH (2) AAEM 50 »1.1 188
600 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 100%) / PtRu/C (0.4 mgpt cm¡2) Pt/C (0.4 mg cm¡2) E-6 AAEM 60 1160 190
1000 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 100%) / PtRu/C (0.4 mgpt cm¡2) Pt/C (0.4 mg cm¡2) E-R AAEM 60 910 190
1000 sccm O2 (RH = 100%)
¡2 ¡2
1000 sccm H2 (RH = 100%) / PtRu/C (0.4 mgpt cm ) Pt/C (0.4 mg cm ) LDPE-AAEM 80 1450 191
1000 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 100%) / PtRu/C (0.4 mgpt cm¡2) Pt/C (0.4 mg cm¡2) ETFE-AAEM 80 1210 191
1000 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 68%) / PtRu/C (0.4 mgpt cm¡2) Pt/C (0.4 mg cm¡2) LDPE-AAEM 60 960 191
1000 sccm O2 (RH = 68%)
¡2 ¡2
1000 sccm H2 (RH = 68%) / PtRu/C (0.4 mgpt cm ) Pt/C (0.4 mg cm ) ETFE-AAEM 60 910 191
1000 sccm O2 (RH = 68%)
¡2 ¡2
1000 sccm H2 (RH = 100%) / PtRu/C (0.4 mgpt cm ) Ag/C (0.8 mg cm ) LDPE-AAEM 80 »980 191
1000 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 100%) / PtRu/C (0.4 mgpt cm¡2) Pt/C (0.4 mg cm¡2) LDPE-AAEM 80 630 191
1000 sccm air (RH = 100%)
1000 sccm H2 (RH = 75%) / PtRu/C (0.67 mg cm¡2) Pt/C (0.53 mg cm¡2) ETFE-g-VBCTMA AAEM 60 1400 205
1000 sccm O2 (RH = 85%)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) 10% crosslinked QPMV-PDVB AAEM 50 46 207
100 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) 5% crosslinked QPMV-PDVB AAEM 50 »45 207
100 sccm O2 (RH = 100%)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) 0% crosslinked QPMV-PDVB AAEM 50 »55 207
100 sccm O2 (RH = 100%)
¡2 ¡2
H2 / O2 Pt/C (3 mg cm ) Pt/C (3 mg cm ) F-PAE AEM 60 193 208
H2 / O2 Pt/C (3 mg cm¡2) Pt/C (3 mg cm¡2) ATM-PP 1 AEM 60 205 208
H2 / O2 Pt/C (3 mg cm¡2) Pt/C (3 mg cm¡2) ATM-PP 2 AEM 60 80 208
H2 / O2 Pt/C (3 mg cm¡2) Pt/C (3 mg cm¡2) ATM-PP 3 AEM 60 »20 208
400 sccm H2 (RH = 100%) / PtRu/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) aQAPS-S8 membrane 60 1000 210
400 sccm O2 (RH = 100%)
400 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) aQAPS-S8 membrane 60 870 210
400 sccm O2 (RH = 100%)
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 165

Table 4
Selected hydrogen/oxygen fuel cell performance with different MEA structures reported in open literature.

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Anion exchange polymer membrane 50 478 171
(ionomer: TMA)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Anion exchange polymer membrane 50 236 171
(ionomer: TMHDA)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Anion exchange polymer membrane 50 116 171
(ionomer: DABCO)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) Anion exchange polymer membrane 50 100 171
(ionomer: TEA)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Anion exchange polymer membrane 50 58 171
(ionomer: DMS)
200 sccm H2 (RH = 100%) / Pt/C (1.28 mg cm¡2) Pt/C (1.28 mg cm¡2) Tokuyama A901 (ionomer: QSEBS-L) 50 »70 192
200 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (1.28 mg cm ) Pt/C (1.28 mg cm ) Tokuyama A901 (ionomer: QSEBS-M) 50 210 192
200 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (1.28 mg cm ) Pt/C (1.28 mg cm ) Tokuyama A901 (ionomer: QSEBS-H) 50 »200 192
200 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (1.28 mg cm¡2) Pt/C (1.28 mg cm¡2) Tokuyama A901 (ionomer: QBSF) 50 30 192
200 sccm O2 (RH = 100%)
1000 sccm H2 (RH = 95%) / Pt/C (0.45 mg cm¡2) Pt/C (0.45 mg cm¡2) Tokuyama A2012 AEM (ionomer: 50 256 193
2000 sccm air (RH = 95%) PyPBI)
¡2 ¡2
1000 sccm H2 (RH = 95%) / Pt/C (0.45 mg cm ) Pt/C (0.45 mg cm ) Tokuyama A2012 AEM (ionomer: 50 174 193
2000 sccm O2 (RH = 95%) AS-4)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Tokuyama A201 (ionomer content: 10) 50 »85 194
200 sccm O2 (RH = 100%) (solvent: IPA)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Tokuyama A201 (ionomer content: 15) 50 »330 194
200 sccm O2 (RH = 100%) (solvent: IPA)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) Tokuyama A201 (ionomer content: 20) 50 358 194
200 sccm O2 (RH = 100%) (solvent: IPA)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) Tokuyama A201 (ionomer content: 25) 50 »135 194
200 sccm O2 (RH = 100%) (solvent: IPA)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Tokuyama A201 (ionomer content: 20) 50 321 194
200 sccm O2 (RH = 100%) (solvent: EtOH)
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) Tokuyama A201 (ionomer content: 20) 50 220 194
200 sccm O2 (RH = 100%) (solvent: PA)
¡2 ¡2
100 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) Tokuyama A201 (ionomer content: 20) 50 407 194
200 sccm O2 (RH = 100%) (solvent: NBA)
H2 (RH = 75%) / O2 (RH = 75%) Pt/C (50 ug cm¡2) Pt/C (50 ug cm¡2) porous silver membrane (Laminated) 50 »5 196
H2 (RH = 75%) / O2 (RH = 75%) Pt/C (50 ug cm¡2) Pt/C (50 ug cm¡2) porous silver membrane (Not 50 »7.5 196
Laminated)
H2 (RH = 75%) / O2 (RH = 75%) Pt/C (50 ug cm¡2) Pt/C (50 ug cm¡2) porous silver membrane (Not 50 30 196
Laminated, Tokuyama ionomer)
¡2 ¡2
H2 (RH = 75%) / O2 (RH = 75%) Pt/C (50 ug cm ) Pt/C (50 ug cm ) porous silver membrane (Nafion 50 30 196
ionomer in catalyst layer + AS4
interface layer)
H2 (RH = 75%) / O2 (RH = 75%) Pt/C (50 ug cm¡2) Pt/C (50 ug cm¡2) porous silver membrane (AS4 ionomer 50 60 196
in catalyst layer + AS4 interface
layer)
H2 (RH = 0%) / O2 (RH = 0%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) MEA-2 70 »180 197
H2 (RH = 50%) / O2 (RH = 50%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) MEA-2 70 »100 197
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) MEA-2 70 »56 197
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Ag/P (0.5 mg cm¡2) FAA commercial membrane 80 208 198
200 sccm O2 (RH = 100%)
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) FAA commercial membrane 80 196 198
200 sccm O2 (RH = 100%)
¡2 ¡2
200 sccm H2 (RH = 100%) / Ni/C (5 mg cm ) Ag/TPQPOH (0.5 mg cm ) TPQPOH152 membrane 70 76 198
200 sccm O2 (RH = 100%)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) Nafion membrane and AEM (thin-film 70 44 199
method)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Nafion membrane and AEM (ionomer 70 125 199
impregnation)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Nafion membrane and AEM (ionomer 70 315 199
impregnation with 9% PTFE)
¡2 ¡2
H2 (RH = 0%) / O2 (RH = 0%) Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) Nafion membrane and AEM (thin-film 70 144 199
method)
H2 (RH = 0%) / O2 (RH = 0%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Nafion membrane and AEM (ionomer 70 191 199
impregnation)
H2 (RH = 0%) / O2 (RH = 0%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) Nafion membrane and AEM (ionomer 70 369 199
impregnation with 9% PTFE)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) AEM and Nafion membrane (thin-film 70 95 199
method)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) AEM and Nafion membrane (ionomer 70 375 199
impregnation)
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) QAPSF 25 »160 200

(continued)
166 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Table 4 (Continued)

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) QAPAE-4 25 »230 200
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) QAPSF 60 215 200
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) QAPAE-4 60 315 200
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.5 mg cm¡2) Pt/C (20 wt%) (0.5 mg cm¡2) MEA-A (Solvay AAEM) 50 55 202
2000 sccm O2 (RH = 100%) XC-72 (2 mg cm¡2) XC-72 (2 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.53 mg cm¡2) Pt/C (20 wt%) (0.53 mg cm¡2) MEA-B (Solvay AAEM) 50 25 202
2000 sccm O2 (RH = 100%) XC-72 (2.1 mg cm¡2) XC-72 (2.1 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.56 mg cm¡2) Pt/C (20 wt%) (0.56 mg cm¡2) MEA-C (Solvay AAEM) 50 34 202
2000 sccm O2 (RH = 100%) XC-72 (2.2 mg cm¡2) XC-72 (2.2 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.55 mg cm¡2) Pt/C (20 wt%) (0.55 mg cm¡2) MEA-D (Solvay AAEM) 50 32 202
2000 sccm O2 (RH = 100%) XC-72 (2.2 mg cm¡2) XC-72 (2.2 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.57 mg cm¡2) Pt/C (20 wt%) (0.57 mg cm¡2) MEA-E (Solvay AAEM) 50 35 202
2000 sccm O2 (RH = 100%) XC-72 (2.3 mg cm¡2) XC-72 (2.3 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.55 mg cm¡2) Pt/C (20 wt%) (0.55 mg cm¡2) MEA-F (Solvay AAEM) 50 80 202
2000 sccm O2 (RH = 100%) XC-72 (2.2 mg cm¡2) XC-72 (2.2 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.57 mg cm¡2) Pt/C (20 wt%) (0.57 mg cm¡2) MEA-G (Solvay AAEM) 50 75 202
2000 sccm O2 (RH = 100%) XC-72 (2.3 mg cm¡2) XC-72 (2.3 mg cm¡2)
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.49 mg cm¡2) Pt/C (20 wt%) (0.49 mg cm¡2) MEA-H (Solvay AAEM) 50 61 202
2000 sccm O2 (RH = 100%) XC-72 (2.0 mg cm¡2) XC-72 (2.0 mg cm¡2)
2000 sccm H2 (RH = 100%) / XC-72 (2.2 mg cm¡2) XC-72 (2.2 mg cm¡2) MEA-I (Solvay AAEM) 50 22 202
2000 sccm O2 (RH = 100%)
¡2 ¡2
2000 sccm H2 (RH = 100%) / Pt/C (20 wt%) (0.55 mg cm ) Pt/C (20 wt%) (0.55 mg cm ) MEA-J (Surrey AAEM) 50 104 202
2000 O2 (RH = 100%) XC-72 (2.2 mg cm¡2) XC-72 (2.2 mg cm¡2)
H2 (RH = 100%) / air (RH = 100%) Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) 57 um LDPE-VBC membrane 50 255 203
H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) 57 um LDPE-VBC membrane 50 300 203
air (1 bar gauge) (RH = 100%)
H2 (RH = 100%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) 57 um LDPE-VBC membrane 60 337 203
air (1 bar gauge) (RH = 100%)
¡2 ¡2
H2 (RH = 100%) / O2 (RH = 100%) Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) 57 um LDPE-VBC membrane 60 390 203
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) FAA-3 membrane (0.6 activated) 50 71 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) FAA-3 membrane (0.1 activated) 50 75 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) FAA-3 membrane (VI activated) 50 110 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) FAA-3 membrane (VI activated) 40 41 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) FAA-3 membrane (VI activated) 50 112 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) FAA-3 membrane (VI activated) 60 176 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) FAA-3 membrane (VI activated) 60 140 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) FAA-3 membrane (VI activated) 60 178 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.6 mg cm¡2) Pt/C (0.6 mg cm¡2) FAA-3 membrane (VI activated) 60 181 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm ) Pt/C (0.8 mg cm ) FAA-3 membrane (VI activated) 60 201 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (1.0 mg cm ) Pt/C (1.0 mg cm ) FAA-3 membrane (VI activated) 60 194 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm¡2) Pt/C (0.8 mg cm¡2) FAA-3 membrane (VI activated) 60 77 209
200 sccm O2 (RH = 100%) (15% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm¡2) Pt/C (0.8 mg cm¡2) FAA-3 membrane (VI activated) 60 176 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm ) Pt/C (0.8 mg cm ) FAA-3 membrane (VI activated) 60 153 209
200 sccm O2 (RH = 100%) (45% FAA ionomer) (150 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm¡2) Pt/C (0.8 mg cm¡2) FAA-3 membrane (VI activated) 60 150 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (100 cN m)
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm¡2) Pt/C (0.8 mg cm¡2) FAA-3 membrane (VI activated) 60 199 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (150 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm ) Pt/C (0.8 mg cm ) FAA-3 membrane (VI activated) 60 223 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (200 cN m)
¡2 ¡2
200 sccm H2 (RH = 100%) / Pt/C (0.8 mg cm ) Pt/C (0.8 mg cm ) FAA-3 membrane (VI activated) 60 177 209
200 sccm O2 (RH = 100%) (25% FAA ionomer) (250 cN m)
6 sccm H2 (RH = 0%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) AEM/PEM(Nafion)/AEM 60 78.3 211
8 sccm O2 (RH = 0%)
6 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) AEM/PEM(Nafion)/AEM 60 55.6 211
8 sccm O2 (RH = 100%)
¡2 ¡2
12 sccm H2 (RH = 100%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) HMEA-II (a high-pH cathode with a 50 22 214
6 sccm O2 (RH = 100%) Nafion core membrane)
12 sccm H2 (RH = 80%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) HMEA-II (a high-pH cathode with a 50 35 214
6 sccm O2 (RH = 80%) Nafion core membrane)

(continued)
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 167

Table 4 (Continued)

Fuel/Oxidant Anode Cathode Membrane T (°C) Power density Ref.

(mW cm¡2)

12 sccm H2 (RH = 37%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) HMEA-II (a high-pH cathode with a 50 63 214
6 sccm O2 (RH = 37%) Nafion core membrane)
12 sccm H2 (RH = 0%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) HMEA-II (a high-pH cathode with a 50 52 214
6 sccm O2 (RH = 0%) Nafion core membrane)
1000 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) A901 50 »330 216
2000 sccm air (RH = 95%)
¡2 ¡2
500 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) A201 50 »260 216
1000 sccm air (RH = 95%)
500 sccm H2 (RH = 95%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) A201 (Pt/C:AS-4 = 6:4) 50 »20 216
1000 sccm air (RH = 95%)
500 sccm H2 (RH = 95%) / Pt/C (0.4 mg cm¡2) Pt/C (0.4 mg cm¡2) A201 (Pt/C:AS-4 = 7:3) 50 »275 216
1000 sccm air (RH = 95%)
¡2 ¡2
500 sccm H2 (RH = 95%) / Pt/C (0.4 mg cm ) Pt/C (0.4 mg cm ) A201 (Pt/C:AS-4 = 8:2) 50 »140 216
1000 sccm air (RH = 95%)
¡2 ¡2
500 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) A201 (Pt/C:AS-4 = 7:3) 50 »260 216
1000 sccm air (RH = 95%)
500 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) A201 (Pt/C:AS-X = 7:3) 50 »295 216
1000 sccm air (RH = 95%)
1000 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm¡2) Pt/C (0.5 mg cm¡2) A901 (Pt/C:AS-X = 7:3) 50 340 216
2000 sccm air (RH = 95%)
¡2 ¡2
1000 sccm H2 (RH = 95%) / Pt/C (0.5 mg cm ) Pt/C (0.5 mg cm ) A901 (Pt/C:AS-X = 7:3) 50 450 216
2000 sccm O2 (RH = 95%)

TagedPanode electrocatalyst and cathode electrocatalyst, respectively, as 7. Innovative system designs

well as an AAEM (Tokuyama A201). Yang et al. [194] fabricated high-
performance electrodes with fine microstructure by changing the 7.1. Hybrid fuel cells
content of the ionomer and selecting the appropriate dispersion sol-
vent. A maximum power density of 358 mW cm¡2 was achieved TagedPRecently, some innovative structures have been proposed with
when the ionomer content is 20 wt% (CCM-I20) with humidified H2 the purpose of improving the fuel cell performance [211
216]. Unl € u€
in the anode at a rate of 100 sccm and humidified O2 in the cathode et al. [211] developed a novel hybrid polymer electrolyte fuel cell, as
at a rate of 200 sccm at 50°C, which is three and five times of CCM- shown in Fig. 10(a), in which the hybrid membrane was composed
I25 and CCM I10, respectively. Importantly, the peak power density of a proton exchange membrane sandwiched by two AAEMs,
increased remarkably to 407 mW cm¡2 when the dispersion solution denoted as AAEM/PEM/AAEM fuel cell, simplifying water manage-
changed to NBA. Recently, Wang et al. [210] found that the highest ment and avoiding CO poisoning. The hybrid fuel cell fabricated with
power density of 1000 mW cm¡2 was obtained when Pt
Ru Pt (0.5 mg cm¡2) both at anode and cathode exhibited a peak power
(0.4 mg cm¡2) is utilized as anode electrocatalyst, Pt (0.4 mg cm¡2) density of 55.6 mW cm¡2 with H2 (RH = 100%) and O2 (RH = 100%)
is used as cathode electrocatalyst, and H2 and O2 were fed at flow supplied at a rate of 360 and 480 sccm, respectively. The peak power
rates at 400 sccm at 60°C, which was 400 mW cm¡2 higher than the density increased to 78.3 mW cm¡2 at 0% RH under the same condi-
performance of a fuel cell running under the same conditions apart tions. They claimed that the unpredictable phenomenon was attrib-
from the unitary anode electrocatalyst Pt as shown in Fig. 9(c). It has uted to the superior water management configuration. However,
been revealed that the enhancement in the kinetics of the HOR was Shen et al. [212] developed a type of non-flooding hybrid polymer
attributed to weakening the Pt
Had interaction rather than the ever fuel cell, in which a PEM and an AAEM were pressed together. They
reported oxophilic effect. Breakthroughs in power output has been found that the performance was improved with increasing the tem-
reported vary recently [190,191,205], as shown in Fig. 9(d) (e) and perature and relative humidity, which was opposed to the results
(f). A peak power density of 1.4 Wcm¡2 was achieved with hydro- reported by Unl € u€ et al. [211]. Zhang et al. [213] developed a hybrid
gen and oxygen both at a flow rate of 1000 sccm at 60°C, when system consisting of an alkaline fuel cell and a heat-driven cycle as
PtRu (0.67 mg cm¡2) and Pt (0.53 mg cm¡2) were employed as shown in Fig. 10(b), which reused the waste heat to improve the
anode electrocatalyst and cathode electrocatalyst, respectively maximum equivalent power output. The hybrid system showed
[205]. More importantly, the dew points for the electrode configu- superior performance, which was 1.4 times higher than that
ration was optimized to 54/57°C, which was the same thing as RHs achieved by a single AAEMFC. Unl € u
€ et al. [214] proposed a novel
equal to 75%/85%. The spectacular performance was primarily hybrid anion and proton exchange membrane fuel cell, denoted as
attributed to the optimal balance between necessary membrane AAEM cathode/PEM anode and PEM anode/AAEM cathode, as shown
hydration and electrode flooding/dry-out. To date, 1.4 W cm¡2 was in Fig. 10(c), which exploited the electrochemical advantages of the
the highest peak power density at 60°C. As Wang et al. [191] devel- high-pH operation due to at least one electrode being at high pH.
oped a LDPE-AAEM that possessed the ability to be routinely evalu- They illustrated that the AAEM cathode/PEM anode junction failed
ated in fuel cells at 80°C, the H2/O2 AAEMFC fabricated with at high current densities resulting from the inadequate flux of water
this AAEM, a PtRu/C anode (0.4 mg cm¡2), and a Pt/C cathode to the AAEM/PEM interface where water dissociated into hydrogen
(0.4 mg cm¡2) exhibited a peak power density as high as ions (which migrates to the cathode) and hydroxide ions (which
1.45 W cm¡2. It was claimed that avoiding anode flooding and migrates to the anode). On the contrary, the PEM anode/AAEM cath-
enhancing supply of H2O to the cathode reaction sites contributed ode junction was shown to be an available configuration. Despite
to the splendid power output. Since the reactant diffusion limita- the modest power density, the type of structure exhibited steady
tions in anode and cathode at high current densities were more performance with 0% relative humidity at 65°C for a three-day con-
serious at 80°C than 60°C, the effects of the water management on tinuous operation, whereas the conventional fuel cell experienced
the performance were more significant. severe degradation over the same time without humidification. They
168 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Fig. 10. (a) Schematic of a hybrid fuel cell comprising high pH AEM electrodes and a PEM [211]. Reproduced with permission from Wiley. (b) Schematic of an AFC/heat-driven
cycle hybrid system [213]. Reproduced with permission from Elsevier. (c) Schematic of the depletion region at the junction of the AEM and PEM in contact [214]. Reproduced
with permission from American Chemical Society. (d) Schematic of hybrid fuel cells comprising low pH anode/high pH cathode [215]. Reproduced with permission from Wiley.

TagedPalso evaluated the effect of RH, ionomer content in the anion-con- TagedPHence, Eq. (16) and Eq. (17) result in the overall reaction:
ductive electrode and the inlet gas flow rates on the performance of
2H2 O ! 2H2 þ O2 ð18Þ
the hybrid fuel cells, as shown in Fig. 10(d) [215]. The results showed
that the ionomer fraction of the high-pH cathode played an impor- T he produced hydrogen is stored on site after the electrolysis,
agedPT
tant role in the performance, which was limited by the availability of and can be used as fuel in the fuel cell anode subsequently when the
oxygen in the active sites resulting from the flooding in the cathode. electricity is needed. The reactions of the fuel cell mode have been
When the gases were fed at high flow rates, the water removal from mentioned earlier take place. Though the RFC is a particular candi-
cathode was enhanced and the flooding problem was eliminated. date for storing renewable electricity, the high cost still is the pri-
Fukuta et al. [216] tested the optimization of MEA construction mary impediment for the commercialization. The main reason for
employing newly developed membrane and ionomer by Tokuyama, the high cost is ascribed to the use of platinum group metal catalysts.
which was one of the leading developers of electrolyte materials for Ng et al. [217] developed a bifunctional Ni based on carbon black (Ni/
AAEMFCs, to improve the power density. They suggested that the C) electrocatalyst for the H2 electrode because the Ni possessed cata-
optimized MEA was fabricated with ionomer: AS-X (Pt/C: AS- lytical activity for the hydrogen evolution reaction (HER) and the
X = 70:30), membrane: A901, and Pt (0.5 mg cm¡2) both at the anode HOR. It was shown that the Ni/C electrocatalyst exhibited compara-
and cathode, exhibiting a peak power density of 450 mW cm¡2 with ble activity to the Pt/C electrocatalyst at low potentials, while the
humidified hydrogen at a flow rate of 1000 sccm and pure oxygen at activity began to decrease at high potential due to the Ni oxidation.
a flow rate of 2000 sccm. In summary, several novel structure Meanwhile, they synthesized a precious-metal free and carbon-free
designs that are mainly associated with the MEA construction have O2 electrode via electrodeposition of manganese oxide (MnOx) on a
been proposed. As a result, the performance is promoted due to the stainless steel (SS) substrate followed by high-temperature calcina-
superior water management, the use of preferable pH value, and the tion at 480°C [218]. It was revealed that the fabricated electrode pos-
low degradation rate of membrane. sessed comparable oxygen reduction and water oxidation activities
and durability to the precious-metal based electrode, which was
attributed to avoiding the carbon corrosion. Wu et al. [219] prepared
7.2. Regenerative fuel cells four nanometer size CuxMn0.9¡xCo2.1O4 samples (x = 0, 0.3, 0.6, and
0.9) as a non-precious metal based bifunctional oxygen electrode for
TagedPRegenerative fuel cell (RFC) is not only an energy conversion the use in regenerative fuel cells and studied their characteristics
device, but an energy storage machine, which typically employs with XRD, SEM, TEM, and cyclic voltammetry. It was indicated that
hydrogen as a flexible energy carrier, as shown in Fig. 11. It is the the CuxMn0.9¡xCo2.1O4 electrode exhibited promising ORR activity
concept that the fabricated electrodes, which exhibit catalytic activi- which was similar to Pt/C electrode and a peak power density of
ties for both ORR and oxygen evolution reaction (OER), can be used 80 mW cm¡2 was obtained. Meanwhile, in electrolyzer mode, the
as either electrolyzer or a fuel cell. When the AAEM-RFC is working prepared electrode showed better OER catalytic activity, with
as an electrolyzer, water reacts with electrons to produce hydrogen 100 mV more negative onset potentials. Matsushima et al. [220]
and hydroxide ions at the cathode according to: investigated the three-phase interfacial phenomena in alkaline
4H2 O þ 4e
! 4OH
þ 2H2 ð16Þ regenerative fuel cell by a charge-coupled device (CCD) and confocal
laser microscopy. It was shown from the results that the hydroxide
TagedPThe hydroxide ions are transported through the AAEM to the
ions reduced the surface tension, resulting in the spread of the
anode catalyst layer where the hydroxide ions are oxidized to
three-phase interface. Consequently, the ORR was promoted as a
release electrons, oxygen and water according to:
result of the obvious enlargement of the reaction surface and the
4OH
! 2H2 O þ 4e
þ O2 ð17Þ short diffusion path of dissolved oxygen. On the other hand, the OER
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 169

Fig. 11. Schematic of an AEM-URFC as an energy storage device for grid applications [217]. Reproduced with permission from Wiley.

TagedPwas enhanced by the convectional factor of gas evolution. In sum- TagedP ecrease of the membrane thickness due to the reduction of the
d
mary, to develop a cost-effective energy storage technology that is mass transport loss between the anode and the cathode. Deng et al.
for grid-scale applications, it is crucial to realize the utilization of [226] developed a 3-D multiphase non-isothermal model for the
renewable energy sources such as wind and solar. Undoubtedly, the whole hydrogen-fed AAEMFC. It was shown from the results that the
RFCs using solar and wind are composed the idea of circulation and insertion of anode MPL, increment of anode back pressure and dec-
the concept of sustainable. Although great progress has been made, rement of membrane thickness generally improved the cell perfor-
one issue needs to be addressed. Currently, the precious metals are mance. In addition, the water behavior was also studied and it was
mainly the electrocatalysts both in anode and cathode, leading to found that at high current densities, no water was observed in the
the high cost of the RFCs. As a result, the commercialization is shad- cathode due to the electro-osmotic drag by ion transport and con-
owed. Hence, it is urgent to develop non-precious metal electrocata- sumption as the reactant; while, at low current densities, liquid
lysts to reduce the cost. However, the non-precious metal water may exist in cathode arising from improving the anode back
electrocatalysts in one electrode are generally not effective enough diffusion or reducing the membrane thickness. When anode back
to catalyze the two reactions. Hence, future direction is to synthesize pressure increased and membrane thickness decreased, the water
cost-efficient electrocatalysts with highly catalytic activity. transport from anode to cathode was changed from diffusion domi-
nated to diffusion/hydraulic permeation dominated. Huo et al. [227]
8. Mathematical modeling developed a numerical model to investigate the water transport in
the anode. Fig. 12(a) depicted the distributions of liquid water in
TagedPAs an economical and useful tool, mathematical modeling can anode catalyst layer and gas diffusion layer. It was indicated that the
play a significant role in the quantification of the intricate physico- current density and temperature were two crucial parameters influ-
chemical processes in AAEMFCs. Hence, various models have been encing the liquid water transport. Since the current density
conducted on predicting the hydroxyl anion conductivity [221], ana- increased from 0.05 to 1.45 A cm¡2, the liquid water volume fraction
lyzing the concentration profile of carbonate ions [222], and study- in the anode increased due to more water produced and dragged to
ing the effect of design and operating parameters on the fuel cell the anode. In addition, the liquid water volume fraction in the anode
performance [223
232]. Jiao et al. [223] developed a three-dimen- decreased with the temperature due to more water evaporated, sug-
sional multiphase model to investigate the effect of design and oper- gesting that the anode flooding was suppressed. Shiau et al. [228]
ating parameters on the heat and mass transfer characteristics and developed a two-dimensional nonisothermal multiphase model to
performance. It was indicated the power output was improved investigate the effects of operation condition on the performance.
sharply with more anode humidification at the range of 50
80%, When the gases were fully humidified, the current density was
whereas the enhancement was less significant at higher humidifica- higher than that of partially humidified, which was ascribed to
tion levels. Moreover, the cathode humidification played a more enhanced ORR kinetics and ion/water transport through the mem-
important role than that of anode, showing a positive effect on per- brane. The performance was also improved with increasing temper-
formance, especially at high current densities. When the liquid ature due to the same reasons. A theoretical analysis conducted by
water volume fraction on the cathode reached 0.02, the liquid water Deng et al. [229] showed that a higher ionomer content resulted in a
began to move from channels to the CL. With the liquid water vol- better performance under various gas relative humidity due to the
ume fraction increasing to 0.08, a balance was formed between the improved membrane hydration and enhanced ionic conductivity. As
anode and the cathode. The performance was promoted with the the cathode might suffer from large performance losses resulting
170 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

Fig. 12. (a) Distributions of liquid water in anode catalyst layer and gas diffusion layer at different current densities [227]. (b) Effect of MPL configurations on (I) cell voltage and
power density and (II) activation and ohmic overpotential with 100% cathode inlet humidification [230]. (c) Phase boundary of the water droplet in the DNS model of turbulent
two-phase flow at different time instances [231]. (d) Iso-surface of the water phase fraction for two-droplet case and three-droplet case at different time instances [232]. Repro-
duced with permission from Elsevier.

TagedPfrom the lack of water, properly increasing the water amount in TagedPwere merged and the finally merged droplet was higher in the lami-
cathode could effectively reduce mass transport and ohmic losses. nar flow. Since the liquid films formed on the GDL surface moved
Moreover, slight anode pressurization and insertion of MPL were slowly, a hydrophobic GDL surface was required for water removal
preferred. However, Huo et al. [230] argued that the best configura- enhancement.
tion was only inserting MPL in anode rather than placing MPLs both TagedPIn summary, along with the experiments, modeling and simula-
in anode and cathode as shown in Fig. 12(b). It was explained that tion play a critical role in providing detailed insights concerning the
the MPL implemented in anode forced the liquid water to back-dif- complex mass, heat and charged particle transport in an AAEMFC.
fuse to the cathode and MPL eliminated in cathode enhanced the Modeling is especially important when an experiment is either too
water transport to the cathode CL, both of which led to a high reac- expensive to conduct or unable to capture the detailed underlying
tion rate and membrane conductivity. Besides, decreasing the cath- physics. As the modeling studies are conducted on investigating the
ode CL contact angle improves the performance because more water mass transport phenomenon in the AAEMFCs, particularly on the
could be kept in the cathode CL decreasing polarization losses. Nev- water management, the results can be expressed: anode flooding
ertheless, attention should be paid into the possibility of cathode can be a critical issue at 100% RH, whereas at lower RH high ionic
flooding problem. Recently, Niu et al. [231] took the two-phase tur- transport resistance in the cathode dominates due to dehydrated
bulent flow in fuel cell flow channel into consideration, which was ionomer phase at high current, where the impact of water-consum-
largely ignored in previous studies. They developed a direct numeri- ing ORR kinetic polarization is also crucial.
cal simulation (DNS) model with modified volume-of-fluid (VOF)
approach for tracking the air/water interface. It could be seen from
Fig. 12(c) that the water droplet was deformed asymmetrically and 9. Remaining challenges and perspectives
became water films spreading on the GDL surface, which was advan-
tageous for reducing the flow resistance. Whereas such water films TagedPPlatinum has been widely used as electrocatalyst both in anode
were difficult to be removed, therefore, the reactant supply was sup- and cathode due to its desirable electrochemical activities. However,
pressed. Subsequently, the DNS model was used to investigate the the high cost becomes the main constraint, which makes the
behavior of two droplets and three droplets in turbulent and laminar AAEMFC less attractive.
flows [232]. Fig. 12(d) depicted the proccess. In the two-droplet case, TagedPFor the anode electrocatalysts, although the HOR is the simplest
the front droplet firstly became flat and moved towards the other electrochemical reaction, high activity catalysts are in urgent need
one. Eventually, they were merged in turbulent flow. In the laminar due to the less active HOR in basic media than that in acid media.
flow, the two droplets were also merged and the finally merged Thus, the Pt alloys and hybrid structures with high activity and low
droplet was higher. In the three-droplet case, the two droplets cost have been proposed. However, there are still several problems
downstream were merged firstly, followed by combining with the needed for further investigation, which can be concluded as fol-
front droplet in turbulent flow. It was similar that the three droplets lows: (1) synthesizing highly active non-PGM electrocatalysts;
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 171

TagedP(2) improving the durability of the electrocatalysts in hash alkaline TagedPheavy blocking of surface pores, which impedes the H2 and O2 in the
media; (3) studying the HOR process on electrocatalysts. process of diffusing to the electrocatalyst particles for carrying out
TagedPFor the cathode electrocatalysts, considerable improvements the electrode reactions. Within an appropriate range, increasing
have been made to synthesize novel ORR electrocatalysts to replace electrocatalyst loading is beneficial for promoting peak power den-
the Pt recently, but there are still remaining some problems sity, but too much loading will cause the agglomeration of electroca-
unsolved, i.e. the low stability, the high overpotential, and the low talyst and decrease of active sites. Notably, humidifying both
reactivity. The proposed alternative non-PGM electrocatalysts are hydrogen and oxygen is obligatory. Considering the best perfor-
supposed to enhance the direct four-electron pathway and inhibit mance to date, the RHs are 75% on anode and 85% on cathode. Too
the formation of hydrogen peroxide, resulting in the promotion of high RHs will result in electrode flooding problem, and too low RHs
the catalytic activity. Although many non-platinum electrocatalysts will result in low ORR kinetics and sluggish OH¡ conductivity.
showing comparable activity to Pt have been prepared, as men- TagedPThis review provides an overview of the recent development on
tioned earlier, the durability and stability problems still should be the AAEMFC, in terms of the physical and chemical processes, the
addressed. electrocatalysts toward the HOR and ORR, the system designs and
TagedPAs the key component of the MEA, the AAEM is directly related to performance, as well as the remaining challenges and perspectives.
the fuel cell performance. Hence, it should be pointed out the future Although promising, there is still plenty room for substantially
research direction for the synthesis of the membrane as well as the increasing the power output before the widespread application. Fur-
ionomer. Tang et al. [233] and Slade et al. [206] have indicated that ther development of the AAEMFC may concentrate on, but not be
the dissoluble ionomer is essential because the ionomer can be limited to the following: (1) synthesize high activity, high durability,
impregnated into the pores of the porous electrodes, working as a and non-PGM electrocatalysts for both hydrogen oxidation reaction
binder that can significantly decrease the interfacial resistance. Zeng and oxygen reduction reaction; (2) identify the active sites of the
et al. [234] found that the fundamental improvement of the fuel cell electrocatalysts, which is critical for understanding the catalytic
performance was attributed to the water removal from the surface mechanism and designing new electrocatalysts; (3) develop the high
of catalyst. Hence, a low swelling ionomer film with a highly hydro- hydroxide-ion conductivity, low water uptake, and high durability
philic surface is recommended. In addition, for the application of the polymer electrolyte membrane; (4) optimize the electrode design
AAEMFCs, the AAEM is expected to work normally at a wider range for high transport rates of mass, ions and electrons, including the
of temperature. Consequently, the AAEMs are required to be ther- ionomers and structures; (5) optimize the operating conditions for
mally stable. On the other hand, the thin films also need to be the maximum power output.
mechanically stable, being both flexible and strong.
TagedPAs an economical and useful tool, mathematical modeling can
play a significant role in the quantification of the intricate physico- Acknowledgments
chemical processes in AAEMFCs. However, as composed to the
extensive experiment research on the AAEMFCs, mathematical TagedPThis work was supported by a grant from the Research Grants
modeling has not received similar attention. Moreover, the limited Council of the Hong Kong Special Administrative Region, China
modeling studies are conducted on investigating the mass transport (HKUST9/CRF/11 G) and a grant from the Natural Science Foundation
phenomenon in the AAEMFCs, particularly on the water manage- of China (No. 51506039).
ment. Although water management has been verified to have vital
effects on the fuel cell performance, the modeling research on the
References
electrochemical process on the CLs is still deficient. Herein, we sug-
gest that more attention should be focused on the modeling and TagedP [1] An L, Zhao TS, Xu JB. A bi-functional cathode structure for alkaline-acid direct
mathematical analysis. ethanol fuel cells. Int J Hydrogen Energy 2011;36:13089–95.
TagedP [2] An L, Zhao TS, Shen SY, Wu QX, Chen R. An alkaline direct oxidation fuel cell
with non-platinum catalysts capable of converting glucose to electricity at high
10. Concluding remarks
power output. J Power Sources 2011;196:186–90.
TagedP [3] Mamlouk M, Horsfall JA, Williams C, Scott K. Radiation grafted membranes for
T s the promising emerging energy technology, the AAEMFC has
agedPA superior anion exchange polymer membrane fuel cells performance. Int J
Hydrogen Energy 2012;37:11912–20.
attracted worldwide attention recently due to the significant reduc-
TagedP [4] An L, Zhao TS, Zhou XL, Yan XH, Jung CY. A low-cost, high-performance zinc-
tion of the cost. Consequently, great progress has been made in pro- hydrogen peroxide fuel cell. J Power Sources 2015;275:831–4.
moting the power density, enhancing the durability, as well as TagedP [5] An L, Zhao TS, Zhou XL, Wei L, Yan XH. A high-performance ethanol-hydrogen
reducing the cost. Generally, the peak power density is related to peroxide fuel cell. RSC Adv 2014;4:65031–4.
TagedP [6] Varcoe JR, Atanassov P, Dekel DR, Herring AM, Hickner MA, Kohl PA, Kucernak
temperature, DL porosity, tuned ionomer carbon ratios, electrocata- AR, Mustain WE, Nijmeijer K, Scott K, Xu TW, Zhuang L. Anion-exchange mem-
lyst loadings, and carefully controlled RHs. Typically, the perfor- branes in electrochemical energy systems. Energy Environ Sci 2014;7:3135–91.
mance increases with the increasing temperature due to the TagedP [7] An L, Chen R. Mathematical modeling of direct formate fuel cells. Appl Therm
Eng 2017;124:232–40.
enhanced electrode reaction kinetics. Whereas, too high tempera- TagedP [8] Li YS, Zhao TS. Ultra-low catalyst loading cathode electrode for anion exchange
ture is harmful to those components that are not stable enough, membrane fuel cells. Int J Hydrogen Energy 2012;37:15334–8.
resulting in the performance degradation. Besides, higher DL poros- TagedP [9] Varcoe JR, Beillard M, Halepoto DM, Kizewski JP, Poynton SD, Slade RCT. Mem-
brane and electrode materials for alkaline membrane fuel cells. ECS Trans
ity a lower mass/charge transport resistance, which is advantageous 2008;16:1819–34.
for improving power output. Nevertheless, a DL also functions as an TagedP [10] Yu EH, Wang X, Krewer U, Li L, Scott K. Direct oxidation alkaline fuel cells: from
electron transmitter and a CL supporter. Too high porosity is unfa- materials to systems. Energy Environ Sci 2012;5:5668–80.
TagedP [11] An L, Zhao TS, Chai ZH, Zeng L, Tan P. Modeling of the mixed potential in hydro-
vorable for electron transport and mechanical support. Hence, an gen peroxide-based fuel cells. Int J Hydrogen Energy 2014;39:7407–16.
optimal DL porosity can be determined by taking these three aspects TagedP [12] Li YS, He YL. Layer reduction method for fabricating Pd-coated Ni foams as
into consideration. The ionomer content has synergetic effects on high-performance ethanol electrode for anion-exchange membrane fuel cells.
RSC Adv 2014;4:16879–84.
the electrode microstructure and kinetic properties in terms of the
TagedP [13] Duan CC, Hook D, Chen YC, Tong JH, O'Hayre R. Zr and Y co-doped perovskite as
active, ohmic, and mass diffusion polarizations. A deficient ionomer a stable, high performance cathode for solid oxide fuel cells operating below
content in the CLs leads to non-continuous network for aiding the 500 °C. Energy Environ Sci 2017;10:176–82.
hydroxide transport, correspondingly lessening the reactive TPBs, TagedP [14] An L, Zhao TS, Zeng L, Yan XH. Performance of an alkaline direct ethanol fuel cell
with hydrogen peroxide as oxidant. Int. J. Hydrogen Energy 2014;39:2320–4.
and reducing the electrocatalyst utilization. However, an overload- TagedP [15] An L, Zhao TS. Performance of an alkaline-acid direct ethanol fuel cell. Int J
ing ionomer content results in high shielding of electrocatalysts and Hydrogen Energy 2011;36:9994–9.
172 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedP [16] Zhang H, Ohashi H, Tamaki T, Yamaguchi T. Direction and management of TagedP [52] Zakaria Z, Kamarudin SK, Timmiati SN. Membranes for direct ethanol fuel cells:
water movement in solid-state alkaline fuel cells. J Phys Chem C an overview. Appl Energy 2016;163:334–42.
2012;116:7650–7. TagedP [53] Bakosa I, Paszterna k A, Zitoun D. Pd/Ni synergestic activity for hydrogen oxida-
TagedP [17] An L, Zhao TS, Zeng L. Agar chemical hydrogel electrode binder for fuel-electro- tion reaction in alkaline conditions. Electrochim Acta 2015;176:1074–82.
lyte-fed fuel cells. Appl Energy 2013;109:67–71. TagedP [54] Lu SF, Pan J, Huang AB, Zhuang L, Lu JT. Alkaline polymer electrolyte fuel cells
TagedP [18] An L, Jung CY. Transport phenomena in direct borohydride fuel cells. Appl completely free from noble metal catalysts. Proc Natl Acad Sci
Energy 2017;205:1270–82. 2008;105:20611–4.
TagedP [19] Gunasekara I, Lee M, Abbott D, Mukerjee S. Mass transport and oxygen reduc- TagedP [55] Vinodh R, Sangeetha D. Carbon supported silver (Ag/C) electrocatalysts for alka-
tion kinetics at an anion exchange membrane interface: microelectrode studies line membrane fuel cells. J Mater Sci 2012;47:852–9.
on effect of carbonate exchange. ECS Electrochem Lett 2012;1:F16–9. TagedP [56] Mamlouk M, Kumar SMS, Gouerec P, Scott K. Electrochemical and fuel cell eval-
TagedP [20] An L, Chen R. Recent progress in alkaline direct ethylene glycol fuel cells for uation of Co based catalyst for oxygen reduction in anion exchange polymer
sustainable energy production. J. Power Sources 2016;329:484–501. membrane fuel cells. J Power Sources 2011;196:7594–600.
TagedP [21] An L, Zhao TS, Yan XH, Zhou XL, Tan P. The dual role of hydrogen peroxide in TagedP [57] Ogihara Y, Yano H, Matsumoto T, Tryk DA, Liyama A, Uchida H. In situ FTIR anal-
fuel cells. Sci Bull 2015;60:55–64. ysis of co-tolerance of a Pt
Fe alloy with stabilized Pt skin layers as a hydrogen
TagedP [22] Li YS, Lv JH, He YL. A monolithic carbon foam-supported pd-based catalyst anode catalyst for polymer electrolyte fuel cells. Catalysts 2017;7:8.
towards ethanol electro-oxidation in alkaline media. J Electrochem Soc TagedP [58] Fu J, Qiao JL, Wang XZ, Ma JX, Okada T. Alkali doped poly(vinyl alcohol) for
2016;163:F424–7. potential fuel cell applications. Synth Met 2010;160:193–9.
TagedP [23] Hou HY. Recent research progress in alkaline polymer electrolyte membranes TagedP [59] Tanaka M, Fukasawa K, Nishino E, Yamaguchi S, Yamada K, Tanaka H, Bae B,
for alkaline solid fuel cells. Acta Phys -Chim Sin 2014;30:1393–407. Miyatake K, Watanabe M. Anion conductive block poly(arylene ether)s: synthe-
TagedP [24] An L, Zeng L, Zhao TS. An alkaline direct ethylene glycol fuel cell with an alkali- sis, properties, and application in alkaline fuel cells. J Am Chem Soc
doped polybenzimidazole membrane. Int J Hydrogen Energy 2013;38:10602–6. 2011;133:10646–54.
TagedP [25] An L, Zhao TS. An alkaline direct ethanol fuel cell with a cation exchange mem- TagedP [60] Yan JL, Zhu L, Chaloux BL, Hickner MA. Anion exchange membranes by bro-
brane. Energy Environ Sci 2011;4:2213–7. mination of tetramethylbiphenol-based poly(sulfone)s. Polym Chem
TagedP [26] Merle G, Wessling M, Nijmeijer K. Anion exchange membranes for alkaline fuel 2017;8:2442–9.
cells: a review. J Membrane Sci 2011;377:1–35. TagedP [61] Wang X, Li MQ, Golding BT, Sadeghi M, Cao YC, Yu EH, Scott K. A polytetra-
TagedP [27] Gu € lzow E, Schulze M. Long-term operation of AFC electrodes with CO2 contain- fluoroethylene-quaternary 1,4-diazabicyclo- [2.2.2]-octane polysulfone com-
ing gases. J Power Sources 2004;127:243–51. posite membrane for alkaline anion exchange membrane fuel cells. Int J
TagedP [28] McLean GF, Niet T, Prince-Richard S, Djilali N. An assessment of alkaline fuel cell Hydrogen Energy 2011;36:10022–6.
technology. Int J Hydrogen Energy 2002;27:507–26. TagedP [62] Li XH, Tao JX, Nie GH, Wang LC, Li LH, Liao SJ. Cross-linked multiblock copoly
TagedP [29] Goue rec P, Poletto L, Denizot J, Sanchez-Cortezon E, Miners JH. The evolution of (arylene ether sulfone) ionomer/nano-ZrO2 composite anion exchange mem-
the performance of alkaline fuel cells with circulating electrolyte. J Power Sour- branes for alkaline fuel cells. RSC Adv 2014;4:41398–410.
ces 2004;129:193–204. TagedP [63] Cha MS, Lee JY, Kim TH, Jeong HY, Shin HY, Oh SG, Hong YT. Preparation and
TagedP [30] Wang YJ, Qiao JL, Baker R, Zhang JJ. Alkaline polymer electrolyte membranes for characterization of crosslinked anion exchange membrane (AAEM) materials
fuel cell applications. Chem Soc Rev 2013;42:5768–87. with poly(phenylene ether)-based short hydrophilic block for use in electro-
TagedP [31] Li YS, Zhao TS, Chen R. Cathode flooding behaviour in alkaline direct ethanol chemical applications. J Membrane Sci 2017;530.
fuel cells. J Power Sources 2011;196:133–9. TagedP [64] Li YS, He YL. An all-in-one electrode for high-performance liquid-feed micro
TagedP [32] An L, Zhao TS, Li YS. Carbon-neutral sustainable energy technology: direct etha- polymer electrolyte membrane fuel cells. J Electrochem Soc 2016;163:F663–7.
nol fuel cells. Renew Sustain Energy Rev 2015;50:1462–8. TagedP [65] Sheng WC, Gasteiger HA, Shao-Horn Y. Hydrogen oxidation and evolution reac-
TagedP [33] An L, Zhao TS, Li YS, Wu QX. Charge carriers in alkaline direct oxidation fuel tion kinetics on platinum: acid vs alkaline electrolytes. J Electrochem Soc
cells. Energy Environ Sci 2012;5:7536–8. 2010;157:B1529–36.
TagedP [34] An L, Zhao TS. Transport phenomena in alkaline direct ethanol fuel cells for sus- TagedP [66] Durst J, Siebel A, Simon C, Hasche F, Herranz J, Gasteiger HA. New insights into
tainable energy production. J Power Sources 2017;341:199–211. the electrochemical hydrogen oxidation and evolution reaction mechanism.
TagedP [35] Yang DL, Yu HM, Li GF, Song W, Liu YX, Shao ZG. Effect of gas diffusion electrode Energy Environ Sci 2014;7:2255–60.
parameters on anion exchange membrane fuel cell performance. Chin J Catal TagedP [67] Sheng WC, Zhuang ZB, Gao MR, Zheng J, Chen JGG, Yan YS. Correlating hydro-
2014;35:1091–7. gen oxidation and evolution activity on platinum at different pH with mea-
TagedP [36] Li YS, He YL, Yang WW. Performance characteristics of air-breathing anion- sured hydrogen binding energy. Nat Commun 2015;6:5848–53.
exchange membrane direct ethanol fuel cells. Int J Hydrogen Energy TagedP [68] Ledezma-Yanez I, Wallace WDZ, Sebastia n-Pascual P, Climent V, Feliu JM, Koper
2013;38:13427–33. MTM. Interfacial water reorganization as a pH-dependent descriptor of the
TagedP [37] An L, Zhao TS, Wu QX, Zeng L. Comparison of different types of membrane in hydrogen evolution rate on platinum electrodes. Nat Energy 2017;2:17031–7.
alkaline direct ethanol fuel cells. Int J Hydrogen Energy 2012;37:14536–42. TagedP [69] Alesker M, Page M, Shviro M, Paska Y, Gershinsky G, Dekel DR, Zitoun D. Palla-
TagedP [38] An L, Chen R. Direct formate fuel cells: a review. J Power Sources dium/nickel bifunctional electrocatalyst for hydrogen oxidation reaction in
2016;320:127–39. alkaline membrane fuel cell. J Power Sources 2016;304:332–9.
TagedP [39] Follain N, Roualdes S, Marais S, Frugier J, Reinholdt M, Durand J. Water trans- TagedP [70] Ohyama J, Sato T, Satsuma A. High performance of Ru nanoparticles supported
port properties of plasma-modified commercial anion-exchange membrane for on carbon for anode electrocatalyst of alkaline anion exchange membrane fuel
solid alkaline fuel cells. J Phys Chem C 2012;116:8510–22. cell. J Power Sources 2013;225:311–5.
TagedP [40] Li YS. A liquid-electrolyte-free anion-exchange membrane direct formate-per- TagedP [71] Lu SF, Pan J, Huang AB, Zhuang L, Lu JT. Alkaline polymer electrolyte fuel cells
oxide fuel cell. Int J Hydrogen Energy 2016;41:3600–4. completely free from noble metal catalysts. Proc Natl Acad Sci
TagedP [41] Li YS, Zhao TS. Understanding the performance degradation of anion-exchange 2008;105:20611–4.
membrane direct ethanol fuel cells. Int J Hydrogen Energy 2012;37:4413–21. TagedP [72] Lu SQ, Zhuang ZB. Electrocatalysts for hydrogen oxidation and evolution reac-
TagedP [42] Kabir S, Lemire K, Artyushkova K, Roy A, Odgaard M, Schlueter D, Oshchepkov tions. Sci China Mater 2016;59:217–38.
A, Bonnefont A, Savinova E, Sabarirajan DC, Mandal P, Crumlin EJ, Zenyuk IV, TagedP [73] Miller HA, Lavacchi A, Vizza F, Marelli M, Benedetto FD, D'Acapito F, Paska Y,
Atanassov P, Serov A. Platinum group metal-free NiMo hydrogen oxidation cat- Page M, Dekel DR. A Pd/C-CeO2 anode catalyst for high-performance platinum-
alysts: high performance and durability in alkaline exchange membrane fuel free anion exchange membrane fuel cells. Angew Chem Int Ed 2016;55:6004–
cells. J Mater Chem A 2017;5:24433–43. 7.
TagedP [43] Holby EF, Zelenay P. Linking structure to function: the search for active sites in TagedP [74] Hu QP, Li GW, Pan J, Tan LS, Lu JT, Zhuang L. Alkaline polymer electrolyte fuel
non-platinum group metal oxygen reduction reaction catalysts. Nano Energy cell with Ni-based anode and Co-based cathode. Int J Hydrogen Energy
2016;29:54–64. 2013;38:16264–8.
TagedP [44] Li YS, Wu H, He YL, Liu Y, Jin L. Performance of direct formate-peroxide fuel TagedP [75] Sheng WC, Bivens AP, Myint M, Zhuang ZB, Forest RV, Fang QR, Chen JiGG, Yan
cells. J Power Sources 2015;287:75–80. YS. Non-precious metal electrocatalysts with high activity for hydrogen oxida-
TagedP [45] Li YS, Zhao TS, Liang ZX. Performance of alkaline electrolyte-membrane-based tion reaction in alkaline electrolytes. Energy Environ Sci 2014;7:1719–24.
direct ethanol fuel cells. J Power Sources 2009;187:387–92. TagedP [76] Zhuang ZB, Giles SA, Zhang J, Jenness GR, Caratzoulas S, Vlachos DG, Yan YS.
TagedP [46] Pan ZF, Chen R, An L, Li YS. Alkaline anion exchange membrane fuel cells for Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation
cogeneration of electricity and valuable chemicals. J Power Sources reaction catalyst in alkaline electrolyte. Nat Commun 2016;7:10141–8.
2017;365:430–45. TagedP [77] Alia SM, Pivovar BS, Yan YS. Platinum-coated copper nanowires with high activ-
TagedP [47] Li YS, Feng Y, Sun XD, He YL. A sodium-ion-conducting direct formate fuel cell: ity for hydrogen oxidation reaction in base. J Am Chem Soc 2013;135:13473–8.
generating electricity and producing base. Angew Chem 2017;129:5828–31. TagedP [78] Maiorova NA, Mikhailova AA, Khazova OA, Grinberg VA. Thin-film rotating disk
TagedP [48] Li YS, Sun XD, Feng Y. Hydroxide self-feeding high-temperature alkaline direct electrode as a tool for comparing the activity of catalysts in the hydrogen oxida-
formate fuel cells. ChemSusChem 2017;10:2135–9. tion reaction. Russ J Electrochem 2006;42:331–8.
TagedP [49] Chen XY, Li TC, Shen JN, Hu ZL. From structures, packaging to application: a sys- TagedP [79] Gabrielli C, Grand PP, Lasia A, Perrot H. Investigation of hydrogen adsorption
tem-level review for micro direct methanol fuel cell. Renew Sustain Energy Rev and absorption in palladium thin films II. Cyclic voltammetry. J Electrochem
2017;80:669–78. Soc 2004;151:A1937–42.
TagedP [50] Li YS, Zhao TS. A passive anion-exchange membrane direct ethanol fuel cell TagedP [80] Bartlett PN, Gollas B, Guerin S, Marwan J. The preparation and characterisation
stack and its applications. Int J Hydrogen Energy 2016;41:20336–42. of H1-e palladium films with a regular hexagonal nanostructure formed by
TagedP [51] Li YS, He YL, Yang WW. A high-performance direct formate-peroxide fuel cell electrochemical deposition from lyotropic liquid crystalline phases. Phys Chem
with palladium-gold alloy coated foam electrodes. J Power Sources Chem Phys 2002;4:3835–42.
2015;278:569–73.
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 173

TagedP [81] Rau MS, Quiano PM, Gennero de Chialvo MR, Chialvo AC. Hydrogen oxidation TagedP[109] Ding W, Wei ZD, Chen SG, Qi XQ, Yang T, Hu JS, Wang D, Wan LJ, Alvi SF, Li L.
reaction: evidences of different electrocatalytic activity between a and b Pd-H. Space-confinement-induced synthesis of pyridinic- and pyrrolic-nitrogen-
Electrochem Commun 2008;10:208–12. doped graphene for the catalysis of oxygen reduction. Angew Chem Int Ed
TagedP [82] Feng ZLA, Gabaly EE, Ye XF, Shen ZX, Chueh WC. Fast vacancy-mediated oxygen 2013;52:11755–9.
ion incorporation across the ceria-gas electrochemical interface. Nat Commun TagedP[110] Shui JL, Wang M, Du F, Dai LM. N-doped carbon nanomaterials are durable cata-
2014;5:4374. lysts for oxygen reduction reaction in acidic fuel cells. Sci Adv 2015;1:
TagedP [83] Ska 
la T, Sutara 
F, Skoda M, Prince KC, Matolín V. Palladium interaction with e1400129.
CeO2, Sn-Ce-O and Ga-Ce-O layers. J Phys Condens Matter 2009;21:055005. TagedP[111] Xu B, Hou SS, Cao GP, Wu F, Yang YS. Sustainable nitrogen-doped porous carbon
TagedP [84] Miller HA, Vizza F, Marelli M, Zadick A, Dubau L, Chatenet M, Geiger S, Cherevko with high surface areas prepared from gelatin for supercapacitors. J Mater
S, Doan H, Pavlicek RK, Mukerjee S, Dekel DR. Highly active nanostructured pal- Chem 2012;22:19088–93.
ladium-ceria electrocatalysts for the hydrogen oxidation reaction in alkaline TagedP[112] Liang HW, Wu ZY, Chen LF, Li C, Yu SH. Bacterial cellulose derived nitrogen-
medium. Nano Energy 2017;33:293–305. doped carbon nanofiber aerogel: an efficient metal-free oxygen reduction elec-
TagedP [85] Anastasijevic NA, Vesovic V, Adzic RR. Determination of the kinetic parameters trocatalyst for zinc-air battery. Nano Energy 2015;11:366–76.
of the oxygen reduction reaction using the rotating ring-disk electrode. J Elec- TagedP[113] Lu ZJ, Xu MW, Bao SJ, Tan K, Chai H, Cai CJ, Ji CC, Zhang Q. Facile preparation of
troanal Chem 1987;229:305–16. nitrogen-doped reduced graphene oxide as a metal-free catalyst for oxygen
TagedP [86] He QG, Cairns EJ. Review-recent progress in electrocatalysts for oxygen reduc- reduction reaction. J Mater Sci 2013;48:8101–7.
tion suitable for alkaline anion exchange membrane fuel cells. J Electrochem TagedP[114] Merle G, Hosseiny SS, Wessling M, Nijmeijer K. New cross-linked PVA based
Soc 2015;162:F1504–39. polymer electrolyte membranes for alkaline fuel cells. J Membrane Sci
TagedP [87] Varcoe JR, Slade RCT, Wright GL, Chen YL. Steady-state dc and impedance inves- 2012;409-410:191–9.
tigations of H2/O2 alkaline membrane fuel cells with commercial Pt/C, Ag/C, and TagedP[115] Zhang J, Zhou TC, Qiao JL, Liu YY, Zhang JJ. Hydroxyl anion conducting mem-
Au/C cathodes. J Phys Chem B 2006;110:21041–9. branes poly(vinyl alcohol)/poly(diallyldimethylammonium chloride) for alka-
TagedP [88] Dai LM, Xue YH, Qu LT, Choi HJ, Baek JB. Metal-free catalysts for oxygen reduc- line fuel cellapplications: effect of molecular weight. Electrochim Acta
tion reaction. Chem Rev 2015;115:4823–92. 2013;111:351–8.
TagedP [89] Poynton SD, Kizewski JP, Slade RCT, Varcoe JR. Novel electrolyte membranes TagedP[116] Jasti A, Shahi VK. A facile synthesis of highly stable multiblock poly(arylene
and non-Pt catalysts for low temperature fuel cells. Solid State Ion ether)s based alkaline membranes for fuel cells. J Power Sources
2010;181:219–22. 2014;267:714–22.
TagedP [90] Maheswari S, Selvarani G, Sridhar P, Pitchumani S, Shukla A. Oxygen reduction TagedP[117] Li XH, Cheng SS, Wang LC, Long Q, Tao JX, Nie GH, Liao SJ. Anion exchange
catalysts for alkaline polymer electrolyte fuel cells. ECS Trans 2010;33:1795– membranes by bromination of benzylmethyl-containing poly(arylene ether)s
807. for alkaline membrane fuel cells. RSC Adv 2014;4:29682–93.
TagedP [91] Maheswari S, Karthikeyan S, Murugan P, Sridhar P, Pitchumani S. Carbon-sup- TagedP[118] Li YS, Zhao TS, Yang WW. Measurements of water uptake and transport proper-
ported Pd
Co as cathode catalyst for APEMFCs and validation by DFT. Phys ties in anion-exchange membranes. Int J Hydrogen Energy 2010;35:5656–65.
Chem Chem Phys 2012;14:9683–95. TagedP[119] Qiao JL, Fu J, Liu LL, Zhang J, Xie J, Li G. Synthesis and properties of chemically
TagedP [92] Zhang Q, Feng JX, Wang AJ, Wei J, Feng JJ. Simple synthesis of bimetallic alloyed cross-linked poly(vinyl alcohol)
poly(acrylamide-co-diallyldimethylammo-
Pd
Au nanochain networks supported on reduced graphene oxide for nium chloride) (PVA
PAADDA) for anion-exchange membranes. Solid State Ion
enhanced oxygen reduction reaction. Rsc Adv 2014;4:52640–6. 2012;214:6–12.
TagedP [93] Fu GT, Liu ZY, Chen Y, Lin J, Tang YW, Lu TH. Synthesis and electrocatalytic TagedP[120] Qiao JL, Zhang J, Zhang JJ. Anion conducting poly(vinyl alcohol)/poly(diallyldi-
activity of Au@Pd core-shell nanothorns for the oxygen reduction reaction. methylammonium chloride) membranes with high durable alkaline stability
Nano Res 2014;7:1205–14. for polymer electrolyte membrane fuel cells. J Power Sources 2013;237:1–4.
TagedP [94] Kruusenberg I, Matisen L, Shah Q, Kannan AM, Tammeveski K. Non-platinum TagedP[121] Zhang J, Qiao JL, Jiang GP, Liu LL, Liu YY. Cross-linked poly(vinyl alcohol)/poly
cathode catalysts for alkaline membrane fuel cells. Int J Hydrogen Energy (diallyldimethylammonium chloride) as anion-exchange membrane for fuel
2012;37:4406–12. cell applications. J Power Sources 2013;240:359–67.
TagedP [95] Li XG, Popov BN, Kawahara T, Yanagi H. Non-precious metal catalysts synthe- TagedP[122] Lu WT, Shao ZG, Zhang G, Zhao Y, Yi BL. Crosslinked poly(vinylbenzyl chloride)
sized from precursors of carbon, nitrogen, and transition metal for oxygen with a macromolecular crosslinker for anion exchange membrane fuel cells. J
reduction in alkaline fuel cells. J Power Sources 2011;196:1717–22. Power Sources 2014;248:905–14.
TagedP [96] Song P, Zhang YW, Pan J, Zhuang L, Xu WL. Cheap carbon black-based high-per- TagedP[123] Tanaka M, Fukasawa K, Nishino E, Yamaguchi S, Yamada K, Tanaka H, Bae B,
formance electrocatalysts for oxygen reduction reaction. Chem Commun Miyatake K, Watanabe M. Anion conductive block poly(arylene ether)s: synthe-
2015;51:1972–5. sis, properties, and application in alkaline fuel cells. J Am Chem Soc
TagedP [97] He QG, Li Q, Khene S, Ren XM, Ló pez-Suá rez FE, Lozano-Castelló D, Bueno-Ló pez 2011;133:10646–54.
A, Wu G. High-loading cobalt oxide coupled with nitrogen-doped graphene for TagedP[124] Ong AL, Saad S, Lan R, Goodfellow RJ, Tao SW. Anionic membrane and ionomer
oxygen reduction in anion-exchange-membrane alkaline fuel cells. J Phys based on poly(2,6-dimethyl-1,4-phenylene oxide) for alkaline membrane fuel
Chem C 2013;117:8697–707. cells. J Power Sources 2011;196:8272–9.
TagedP [98] Suntivich J, Gasteiger HA, Yabuuchi N, Nakanishi H, Goodenough JB, Shao-Horn TagedP[125] Lin XC, Wu L, Liu YB, Ong AL, Poynton SD, Varcoe JR, Xu TW. Alkali resistant and
Y. Design principles for oxygen-reduction activity on perovskite oxide catalysts conductive guanidinium-based anion-exchange membranes for alkaline poly-
for fuel cells and metal
air batteries. Nat Chem 2011;3:546–50. mer electrolyte fuel cells. J Power Sources 2012;217:373–80.
TagedP [99] Sunarso J, Torriero AAJ, Zhou W, Howlett PC, Forsyth M. Oxygen reduction reac- TagedP[126] Lin XC, Liang XH, Poynton SD, Varcoe JR, Ong AL, Ran J, Li Y, Li QH, Xu TW. Novel
tion activity of la-based perovskite oxides in alkaline medium: a thin-film alkaline anion exchange membranes containing pendant benzimidazolium
rotating ring-disk electrode study. J Phys Chem C 2012;116:5827–34. groups for alkaline fuel cells. J Membrane Sci 2013;443:193–200.
TagedP[100] Jin C, Cao XC, Zhang LY, Zhang C, Yang RZ. Preparation and electrochemical TagedP[127] Lin XC, Varcoe JR, Poynton SD, Liang XH, Ong AL, Ran J, Li Y, Xu TW. Alkaline
properties of urchin-like La0.8Sr0.2MnO3 perovskite oxide as a bifunctional cata- polymer electrolytes containing pendant dimethylimidazolium groups for alka-
lyst for oxygen reduction and oxygen evolution reaction. J Power Sources line membrane fuel cells. J Mater Chem A 2013;1:7262–9.
2013;241:225–30. TagedP[128] Li NW, Guiver MD, Binder WH. Towards high conductivity in anion-exchange
TagedP[101] Stoerzinger KA, Risch M, Suntivich J, Lu WM, Zhou JG, Biegalski MD, Christen membranes for alkaline fuel cells. ChemSusChem 2013;6:1376–83.
HM, Ariando, Venkatesan T, Shao-Horn Y. Oxygen electrocatalysis on (001)-ori- TagedP[129] Dang HS, Jannasch P. A comparative study of anion-exchange membranes teth-
ented manganese perovskite films: Mn valency and charge transfer at the ered with different hetero-cycloaliphatic quaternary ammonium hydroxides. J
nanoscale. Energy Environ Sci 2013;6:1582–8. Mater Chem A 2017;5:21965–78.
TagedP[102] Risch M, Stoerzinger KA, Maruyama S, Hong WT, Takeuchi I, Shao-Horn Y. TagedP[130] Wang XJ, Wang P, Sun YY, Wang JL, Fang HG, Yang SZ, Wei HB, Ding YS. A
La0.8Sr0.2MnO3-d decorated with Ba0.5Sr0.5Co0.8Fe0.2O3-d: a bifunctional surface mechanically strong and tough anion exchange membrane engineered with
for oxygen electrocatalysis with enhanced stability and activity. J Am Chem Soc non-covalent modalities. Chem Commun 2017;53:12369–72.
2014;136:5229–32. TagedP[131] Benipal N, Qi J, Gentile JC, Li WZ. Direct glycerol fuel cell with polytetrafluoro-
TagedP[103] Pendashteh A, Palma J, Anderson M, Marcilla R. NiCoMnO4 nanoparticles on N- ethylene (PTFE) thin film separator. Renew Energy 2017;105:647–55.
doped graphene: highly efficient bifunctional electrocatalyst for oxygen reduc- TagedP[132] Zhao Y, Yu HM, Yang DL, Li J, Shao ZG, Yi BL. High-performance alkaline fuel
tion/evolution reactions. Appl Catal B 2017;201:241–52. cells using crosslinked composite anion exchange membrane. J Power Sources
TagedP[104] Gupta S, Kellogg W, Xu H, Liu XE, Cho J, Wu G. Bifunctional perovskite oxide 2013;221:247–51.
catalysts for oxygen reduction and evolution in alkaline media. Chem Asian J TagedP[133] Zhao Y, Pan J, Yu HM, Yang DL, Li J, Zhuang L, Shao ZG, Yi BL. Quaternary ammo-
2016;11:10–21. nia polysulfone-PTFE composite alkaline anion exchange membrane for fuel
TagedP[105] Nie Y, Li L, Wei ZD. Recent advancements in Pt and Pt-free catalysts for oxygen cells application. Int J Hydrogen Energy 2013;38:1983–7.
reduction reaction. Chem Soc Rev 2015;44:2168–201. TagedP[134] Li GW, Pan J, Han JJ, Chen C, Lu JT, Zhuang L. Ultrathin composite membrane of
TagedP[106] Zhang YQ, Tao HB, Liu J, Sun YF, Chen J, Hua B, Thundat T, Luo JL. A rational alkaline polymer electrolyte for fuel cell applications. J Mater Chem A
design for enhanced oxygen reduction: strongly coupled silver nanoparticles 2013;1:12497–502.
and engineered perovskite nanofibers. Nano Energy 2017;38:392–400. TagedP[135] Zhou JF, Unlu M, Vega JA, Kohl PA. Anionic polysulfone ionomers and mem-
TagedP[107] Higgins DC, Chen ZW. Nitrogen doped carbon nanotube thin films as efficient branes containing fluorenyl groups for anionic fuel cells. J Power Sources
oxygen reduction catalyst for alkaline anion exchange membrane fuel cell. ECS 2009;190:285–92.
Trans 2010;28:63–8. TagedP[136] Yang YQ, Wang J, Zheng JF, Li SH, Zhang SB. A stable anion exchange membrane
TagedP[108] Rao CV, Ishikawa Y. Activity, selectivity, and anion-exchange membrane fuel based on imidazolium salt for alkaline fuel cell. J Membrane Sci 2014;467:48–
cell performance of virtually metal-free nitrogen-doped carbon nanotube elec- 55.
trodes for oxygen reduction reaction. J Phys Chem C 2012;116:4340–6.
174 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175

TagedP[137] Li XH, Tao JX, Nie GH, Wang LC, Li LH, Liao SJ. Cross-linked multiblock copoly TagedP[167] Wang GG, Weng YM, Zhao J, Chu D, Xie D, Chen RR. Developing a novel alkaline
(arylene ether sulfone) ionomer/nano-ZrO2 composite anion exchange mem- anion exchange membrane derived from poly(ether-imide) for improved ionic
branes for alkaline fuel cells. RSC Adv 2014;4:41398–410. conductivity. Polym Adv Technol 2010;21:554–60.
TagedP[138] Zhang XH, Tay SW, Liu ZL, Hong L. Alkaline anion-exchange polymer membrane TagedP[168] Luo YT, Guo JC, Liu YH, Shao Q, Wang CS, Chu D. Copolymerization of methyl
with grid-plug microstructure for hydrogen fuel cell application. J Power Sour- methacrylate and vinylbenzyl chloride towards alkaline anion exchange mem-
ces 2011;196:5494–8. brane for fuel cell applications. J Membrane Sci 2012;423-424:209–14.
TagedP[139] He SS, Frank CW. Facilitating hydroxide transport in anion exchange mem- TagedP[169] Pan J, Chen C, Zhuang L, Lu JT. Designing advanced alkaline polymer electrolytes
branes via hydrophilic grafts. J Mater Chem A 2014;2:16489–97. for fuel cell applications. Acc Chem Res 2012;45:473–81.
TagedP[140] Vinodh R, Purushothaman M, Sangeetha D. Novel quaternized polysulfone/ZrO2 TagedP[170] Li W, Fang J, Lv M, Chen CX, Chi XJ, Yang YX, Zhang YM. Novel anion exchange
composite membranes for solid alkaline fuel cell applications. Int J Hydrogen membranes based on polymerizable imidazolium salt for alkaline fuel cell
Energy 2011;36:7291–302. applications. J Mater Chem 2011;21:11340–6.
TagedP[141] Varcoe JR, Slade RCT, Yee ELH. An alkaline polymer electrochemical interface: a TagedP[171] Mamlouk M, Scott K. Effect of anion functional groups on the conductivity and
breakthrough in application of alkaline anion-exchange membranes in fuel performance of anion exchange polymer membrane fuel cells. J Power Sources
cells. Chem Commun 2006;13:1428–9. 2012;211:140–6.
TagedP[142] Pan J, Li Y, Zhuang L, Lu JT. Self-crosslinked alkaline polymer electrolyte excep- TagedP[172] Jiang RZ, Chu D. An air-breathing H2/air cell design suitable for fast screening of
tionally stable at 90 °C. Chem Commun 2010;46:8597–9. electrolytes. Electrochim Acta 2011;56:8365–70.
TagedP[143] Zhou J, Guo JS, Chu D, Chen RR. Impacts of anion-exchange-membranes with TagedP[173] Yan JL, Hickner MA. Anion exchange membranes by bromination of benzyl-
various ionic exchange capacities on the performance of H2/O2 fuel cells. J methyl-containing poly(sulfone)s. Macromolecules 2010;43:2349–56.
Power Sources 2012;219:272–9. TagedP[174] Zhou JF, Unl € u€ M, Vega JA, Kohl PA. Anionic polysulfone ionomers and mem-
TagedP[144] Li N, Leng Y, Hickner MA, Wang CY. Highly stable, anion conductive, comb- branes containing fluorenyl groups for anionic fuel cells. J Power Sources
shaped copolymers for alkaline fuel cells. J Am Chem Soc 2013;135:10124–33. 2009;190:285–92.
TagedP[145] Ren XM, Price SC, Jackson AC, Pomerantz N, Beyer FL. Highly conductive anion TagedP[175] Fukuta K, Inoue H, Watanabe S, Yanagi H. In-situ observation of CO2 through
exchange membrane for high power density fuel-cell performance. ACS Appl the self-purging in alkaline membrane fuel cell (AMFC). ECS Trans 2009;19:23–
Mater Interfaces 2014;6:13330–3. 7.
TagedP[146] Lu WT, Shao ZG, Zhang G, Zhao Y, Li J, Yi BL. Preparation and characterization of TagedP[176] Vega JA, Smith S, Chartier C, Mustain WE. Effect of carbonate on anion exchange
imidazoliumfunctionalized poly (ether sulfone) as anion exchange membrane membrane conductivity and hydrogen oxidation for AAEMFCs. ECS Trans
and ionomer for fuel cell application. Int J Hydrogen Energy 2013;38:9285–96. 2010;28:103–9.
TagedP[147] Zhang FX, Zhang HM, Qu C. Imidazolium functionalized polysulfone anion TagedP[177] Vega JA, Chartier C, Smith S, Mustain WE. Effect of carbonate on oxygen reduc-
exchange membrane for fuel cell application. J Mater Chem 2011;21:12744– tion, hydrogen oxidation and anion exchange membrane chemical stability.
52. ECS Trans 2010;33:1735–49.
TagedP[148] Ran J, Wu L, Varcoe JR, Ong AL, Poynton SD, Xu TW. Development of imidazo- TagedP[178] Vega JA, Mustain WE. Effect of CO2, HCO3- and CO3-2 on oxygen reduction in
lium-type alkaline anion exchange membranes for fuel cell application. J Mem- anion exchange membrane fuel cells. Electrochim Acta 2010;55:1638–44.
brane Sci 2012;415-416:242–9. TagedP[179] Vega JA, Chartier C, Mustain WE. Effect of hydroxide and carbonate alkaline
TagedP[149] Xing B, Savadogo O. Hydrogenroxygen polymer electrolyte membrane fuel cells media on anion exchange membranes. J. Power Sources 2010;195:7176–80.
(PEMFCs) based on alkaline-doped polybenzimidazole (PBI). Electrochem Com- TagedP[180] Inaba M, Matsui Y, Saito M, Tasaka A, Fukuta K, Watanabe S, Yanagi H. Effects of
mun 2000;2:697–702. carbon dioxide on the performance of anion-exchange membrane fuel cells.
TagedP[150] Li S, Zhu XL, Liu DZ, Sun F. A highly durable long side-chain polybenzimidazole Electrochemistry 2011;79:322–5.
anion exchange membrane for AEMFC. J Membrane Sci 2018;546:15–21. TagedP[181] Matsui Y, Saito M, Tasaka A, Inaba M. Influence of carbon dioxide on the perfor-
TagedP[151] Wan Y, Creber KAM, Peppley B, Bui VT, Halliop E. New solid polymer electrolyte mance of anion-exchange membrane fuel cells. ECS Trans 2010;25:105–10.
membranes for alkaline fuel cells. Polym. Int 2005;54:5–10. TagedP[182] Suzuki S, Muroyama H, Matsui T, Eguchi K. Influence of CO2 dissolution into
TagedP[152] Wan Y, Peppley B, Creber KAM, Bui VT, Halliop E. Preliminary evaluation of an anion exchange membrane on fuel cell performance. Electrochim Acta
alkaline chitosan-based membrane fuel cell. J Power Sources 2006;162:105– 2013;88:552–8.
13. TagedP[183] Gubler L. Polymer design strategies for radiation-grafted fuel cell membranes.
TagedP[153] Luo YT, Guo JC, Wang CS, Chu D. Quaternized poly(methyl methacrylate-co- Adv Energy Mater 2014;4:1300827.
butyl acrylate-co-vinylbenzyl chloride) membrane for alkaline fuel cells. J TagedP[184] Nasef MM. Radiation-grafted membranes for polymer electrolyte fuel cells:
Power Sources 2010;195:3765–71. current trends and future directions. Chem Rev 2014;114:12278–329.
TagedP[154] Luo YT, Guo JC, Wang CS, Chu D. An acrylate-polymer-based electrolyte mem- TagedP[185] Varcoe JR, Slade RCT. An electron-beam-grafted ETFE alkaline anion-exchange
brane for alkaline fuel cell applications. ChemSusChem 2011;4:1557–60. membrane in metal-cation-free solid-state alkaline fuel cells. Electrochem
TagedP[155] Luo Y, Guo J, Wang C, Choi KY, Chu D. High molecular weight copolymer alka- Commun 2006;8:839–43.
line fuel cell membrane via miniemulsion polymerization. ECS Trans TagedP[186] Poynton SD, Kizewski JP, Slade RCT, Varcoe JR. Novel electrolyte membranes
2010;33:1893–902. and non-Pt catalysts for low temperature fuel cells. Solid State Ion
TagedP[156] Luo YT, Guo JC, Wang CS, Chu D. Tunable high-molecular-weight anion- 2010;181:219–22.
exchange membranes for alkaline fuel cells, Macromol Chem Phys 212 (20110) TagedP[187] Nikolic VM, Zugic DL, Maksic AD, Saponjic DP, Kaninski MPM. Performance
2094
2102. comparison of modified poly(vinyl alcohol) based membranes in alkaline fuel
TagedP[157] Wu GM, Lin SJ, Yang CC. Preparation and characterization of high ionic conduct- cells. Int J Hydrogen Energy 2011;36:11004–10.
ing alkaline non-woven membranes by sulfonation. J Membrane Sci TagedP[188] Deavin OI, Murphy S, Ong AL, Poynton SD, Zeng R, Herman H, Varcoe JR. Anion-
2006;284:120–7. exchange membranes for alkaline polymer electrolyte fuel cells: comparison of
TagedP[158] Sollogouba C, Guinault A, Bonnebat C, Bennjima M, Akrour L, Fauvarque JF, pendent benzyltrimethylammonium- and benzylmethylimidazolium-head-
Ogier L. Formation and characterization of crosslinked membranes for alkaline groups. Energy Environ Sci 2012;5:8584–97.
fuel cells. J Membrane Sci 2009;335:37–42. TagedP[189] Fang J, Yang YX, Lu XH, Ye ML, Li W, Zhang YM. Cross-linked, ETFE-derived and
TagedP[159] Hibino T, Shen Y, Nishida M, Nagao M. Hydroxide ion conducting antimony(v)- radiation grafted membranes for anion exchange membrane fuel cell applica-
doped tin pyrophosphate electrolyte for intermediate-temperature alkaline tions. Int J Hydrogen Energy 2012;37:594–602.
fuel cells. Angew Chem Int Ed 2012;51:10786–90. TagedP[190] Wang LQ, Magliocca E, Cunningham EL, Mustain WE, Poynton SD, Escudero-Cid
TagedP[160] Hibino T, Kobayashi K. An intermediate-temperature alkaline fuel cell using an R, Nasef MM, Ponce-Gonza lez J, Bance-Souahli R, Slade RCT, Whelligan DK, Var-
Sn0.92Sb0.08P2O7-based hydroxide-ion-conducting electrolyte and electrodes. J coe JR. An optimised synthesis of high performance radiation-grafted anion-
Mater Chem A 2013;1:1134–40. exchange membranes. Green Chem 2017;19:831–43.
TagedP[161] Zhao Y, Yu HM, Xie F, Liu YX, Shao ZG, Yi BL. High durability and hydroxide ion TagedP[191] Wang LQ, Brink JJ, Liu Y, Herring AM, Ponce-Gonza lez J, Whelligan DK, Varcoe
conducting pore-filled anion exchange membranes for alkaline fuel cell appli- JR. Non-fluorinated pre-irradiation-grafted (peroxidated) LDPE-based anion-
cations. J Power Sources 2014;269:1–6. exchange membranes with high performance and stability. Energy Environ Sci
TagedP[162] Kim DS, Fujimoto CH, Hibbs MR, Labouriau A, Choe YK, Kim YS. Resonance sta- 2017;10:2154–67.
bilized perfluorinated ionomers for alkaline membrane fuel cells. Macromole- TagedP[192] Sun L, Guo JS, Zhou J, Xu QM, Chu D, Chen RR. Novel nanostructured high-per-
cules 2013;46:7826–33. formance anion exchange ionomers for anion exchange membrane fuel cells. J
TagedP[163] Chen YN, Li ZM, Chen NJ, Li R, Zhang YJ, Li K, Wang FH, Zhu H. A new method for Power Sources 2012;202:70–7.
improving the conductivity of alkaline membrane by incorporating TiO2- ionic TagedP[193] Matsumoto K, Fujigaya T, Yanagi H, Nakashima N. Very high performance alkali
liquid composite particles. Electrochim Acta 2017;255:335–46. anion-exchange membrane fuel cells. Adv Funct Mater 2011;21:1089–94.
TagedP[164] Einsla BR, Chempath S, Pratt LR, Boncella JM, Rau J, Macomber C, Pivovar BS. TagedP[194] Yang DL, Yu HM, Li GF, Zhao Y, Liu YX, Zhang CK, Song W, Shao ZG. Fine micro-
Stability of cations for anion exchange membrane fuel cells. ECS Trans structure of high performance electrode in alkaline anion exchange membrane
2007;11:1173–80. fuel cells. J Power Sources 2014;267:39–47.
TagedP[165] Arges CG, Parrondo J, Johnson G, Nadhan A, Ramani V. Assessing the influence TagedP[195] Ewing SJ, Lan R, Xu XX, Tao SW. Synthesis of dendritic nano-sized nickel for use
of different cation chemistries on ionic conductivity and alkaline stability of as anodematerial in an alkaline membrane fuel cell. Fuel Cells 2010;10:72–6.
anion exchange membranes. J Mater Chem 2012;22:3733–44. TagedP[196] Kucernak A, Bidault F, Smith G. Membrane electrode assemblies based on
TagedP[166] Park JS, Park SH, Yim SD, Yoon YG, Lee WY, Kim CS. Performance of solid alka- porous silver electrodes for alkaline anion exchange membrane fuel cells. Elec-
line fuel cells employing anion-exchange membranes. J Power Sources trochim Acta 2012;82:284–90.
2008;178:620–6. € u
TagedP[197] Unl € M, Zhou JF, Anestis-Richard I, Kohl PA. Characterization of anion exchange
ionomers in hybrid polymer electrolyte fuel cells. ChemSusChem
2010;3:1398–402.
 Z.F. Pan et al. / Progress in Energy and Combustion Science 66 (2018) 141
175 175

TagedP[198] Gu S, Sheng WC, Cai R, Alia SM, Song SQ, Jensen KO, Yan YS. An efficient Ag-ion- TagedP[215] Unl € u € M, Zhou JF, Kohl PA. Self-humidifying hybrid anion-cation membrane fuel
omer interface for hydroxide exchange membrane fuel cells. Chem Commun cell operated under dry conditions. Fuel Cells 2010;10:54–63.
2013;49:131–4. TagedP[216] Fukuta K, Inoue H, Chikashige Y, Yanagi H. Improved maximum power density
TagedP[199] Unl € u € M, Zhou JF, Anestis-Richard I, Kim H, Kohl PA. Improved gas diffusion elec- of alkaline membrane fuel cells (AMFCs) by the optimization of mea construc-
trodes for hybrid polymer electrolyte fuel cells. Electrochim Acta tion. ECS Trans 2010;28:221–5.
2011;56:4439–44. TagedP[217] Ng JWD, Gorlin Y, Hatsukade T, Jaramillo TF. A precious-metal-free regenerative
TagedP[200] Zhou JF, Unl € u€ M, Anestis-Richard I, Kim H, Kohl PA. Solvent processible, high- fuel cell for storing renewable electricity. Adv Energy Mater 2013;3:1545–50.
performance partially fluorinated copoly(arylene ether) alkaline ionomers for TagedP[218] Ng JWD, Tang M, Jaramillo TF. A carbon-free, precious-metal-free, high perfor-
alkaline electrodes. J Power Sources 2011;196:7924–30. mance O2 electrode for regenerative fuel cells and metal-air batteries. Energy
TagedP[201] Kubo D, Tadanaga K, Hayashi A, Tatsumisago M. Improvement of electrochemi- Environ Sci 2014;7:2017–24.
cal performance in alkaline fuel cell by hydroxide ion conducting Ni
Al layered TagedP[219] Wu X, Scott K. A non-precious metal bifunctional oxygen electrode for alkaline
double hydroxide. J Power Sources 2013;222:493–7. anion exchange membrane cells. J Power Sources 2012;206:14–9.
TagedP[202] Tamain C, Poynton SD, Slade RCT, Carroll B, Varcoe JR. Development of cathode TagedP[220] Matsushima H, Majima W, Fukunaka Y. Three-phase interfacial phenomena in
architectures customized for H2/O2 metal-cation-free alkaline membrane fuel alkaline unitized regenerative fuel cell. Electrochim Acta 2013;114:509–13.
cells. J Phys Chem C 2007;111:18423–30. TagedP[221] Grew KN, Chiu WKS. A dusty fluid model for predicting hydroxyl anion conduc-
TagedP[203] Mamlouk M, Scott K, Horsfall JA, Williams C. The effect of electrode parameters tivity in alkaline anion exchange membranes. J Electrochem Soc 2010;157:
on the performance of anion exchange polymer membrane fuel cells. Int J B327–37.
Hydrogen Energy 2011;36:7191–8. TagedP[222] Siroma Z, Watanabe S, Yasuda K, Fukuta K, Yanagib H. Mathematical modeling
TagedP[204] Oshiba Y, Hiura J, Suzuki Y, Yamaguchi T. Improvement in the solid-state alka- of the concentration profile of carbonate ions in an anion exchange membrane
line fuel cell performance through efficient water management strategies. J fuel cell. J Electrochem Soc 2011;158:B682–9.
Power Sources 2017;345:221–6. TagedP[223] Jiao K, He P, Du Q, Yin Y. Three-dimensional multiphase modeling of alkaline
TagedP[205] Omasta TJ, Wang L, Peng X, Lewis CA, Varcoe JR, Mustain WE. Importance of anion exchange membrane fuel cell. Int J Hydrogen Energy 2014;39:5981–95.
balancing membrane and electrode water in anion exchange membrane fuel TagedP[224] Deng H, Chen JX, Jiao K, Huang XR. An analytical model for alkaline membrane
cells. J Power Sources 2018;375:205–13. direct methanol fuel cell. Int J Heat Mass Transf 2014;74:376–90.
TagedP[206] Slade RCT, Kizewski JP, Poynton SD, Zeng R, Varcoe JR. Fuel cells: selected TagedP[225] Feng ZLA, Gabaly EE, Ye XF, Shen ZX, Chueh WC. Fast vacancy-mediated oxygen
entries from the encyclopedia of sustainability science. Springer; 2012 ion incorporation across the ceria-gas electrochemical interface. Nat Commun
(Chapter 2). 2014;5:4374.
TagedP[207] Luo YT, Guo JC, Wang CS, Chu D. Fuel cell durability enhancement by crosslink- TagedP[226] Deng H, Wang DW, Xie X, Zhou YB, Yin Y, Du Q, Jiao K. Modeling of hydrogen
ing alkaline anion exchange membrane electrolyte. Electrochem Commun alkaline membrane fuel cell with interfacial effect and water management opti-
2012;16:65–8. mization. Renew Energy 2016;91:166–77.
TagedP[208] Fujimoto C, Kim DS, Hibbs M, Wrobleski D, Kim YS. Backbone stability of qua- TagedP[227] Huo S, Deng H, Chang YF, Jiao K. Water management in alkaline anion exchange
ternized polyaromatics for alkaline membrane fuel cells. J Membrane Sci membrane fuel cell anode. Int J Hydrogen Energy 2012;37:18389–402.
2012;423-424:438–49. TagedP[228] Shiau HS, Zenyuk IV, Weber AZ. Water management in an alkaline-exchange-
TagedP[209] Carmo M, Doubek G, Sekol RC, Linardi M, Taylor AD. Development and electro- membrane fuel cell. ECS Trans 2015;69:985–94.
chemical studies of membrane electrode assemblies for polymer electrolyte TagedP[229] Deng H, Wang DW, Wang RF, Xie X, Yin Y, Du Q, Jiao K. Effect of electrode
alkaline fuel cells using FAA membrane and ionomer. J Power Sources design and operating condition on performance of hydrogen alkaline mem-
2013;230:169–75. brane fuel cell. Appl Energy 2016;183:1272–8.
TagedP[210] Wang Y, Wang GW, Li GW, Huang B, Pan J, Liu Q, Han JJ, Xiao L, Lu JT, Zhuang L. TagedP[230] Huo S, Park JW, Hu P, Wang DW, Jiao K. Analytical modeling of liquid saturation
Pt
Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or elec- jump effect for hydrogen alkaline anion exchange membrane fuel cell. Int J
tronic effect? Energy Environ Sci 2014;8:177–81. Heat Mass Transf 2017;112:891–902.
TagedP[211] Unl € u € M, Zhou JF, Kohl PA. Hybrid polymer electrolyte fuel cells: alkaline elec- TagedP[231] Niu ZQ, Jiao K, Zhang F, Du Q, Yin Y. Direct numerical simulation of two-phase
trodes with proton conducting membrane. Angew Chem Int Ed 2010;49:1299– turbulent flow in fuel cell flow channel. Int J Hydrogen Energy 2016;41:3147–
301. 52.
TagedP[212] Shen WD, Zhang FY, Prasad A, Hertz J. Non-flooding hybrid polymer fuel cell. TagedP[232] Niu ZQ, Wang RF, Jiao K, Du Q, Yin Y. Direct numerical simulation of low Rey-
ECS Trans 2010;33:2011–6. nolds number turbulent air
water transport in fuel cell flow channel. Sci Bull
TagedP[213] Zhang XQ, Chen JC. Maximum equivalent power output and performance opti- 2017;62:31–9.
mization analysis of an alkaline fuel cell/heat-driven cycle hybrid system. J TagedP[233] Tang DP, Pan J, Lu SF, Zhuang L, Lu JT. Alkaline polymer electrolyte fuel cells:
Power Sources 2011;196:10088–93. principle, challenges, and recent progress. Sci China Chem 2010;53:357–64.
€ u
TagedP[214] Unl € M, Zhou JF, Kohl PA. Hybrid anion and proton exchange membrane fuel TagedP[234] Zeng R, Handsel J, Poynton SD, Roberts AJ, Slade RCT, Herman H, Apperley DC,
cells. J Phys Chem C 2009;113:11416–23. Varcoe JR. Alkaline ionomer with tuneable water uptakes for electrochemical
energy technologies. Energy Environ Sci 2011;4:4925–8.