Accepted Manuscript

BaCo0.4Fe0.4Zr0.2O3-δ: Evaluation as a cathode for ceria-based electrolyte IT-

SOFCs

Limin Zhang, Jun Shan, Qing Wang

PII: S0925-8388(18)33120-7
DOI: 10.1016/j.jallcom.2018.08.232
Reference: JALCOM 47320

To appear in: Journal of Alloys and Compounds

Received Date: 17 May 2018

Revised Date: 17 August 2018
Accepted Date: 24 August 2018

Please cite this article as: L. Zhang, J. Shan, Q. Wang, BaCo0.4Fe0.4Zr0.2O3-δ: Evaluation as a
cathode for ceria-based electrolyte IT-SOFCs, Journal of Alloys and Compounds (2018), doi: 10.1016/
j.jallcom.2018.08.232.

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 ACCEPTED MANUSCRIPT

BaCo0.4Fe0.4Zr0.2O3-δδ: evaluation as a cathode for ceria-based

electrolyte IT-SOFCs

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Limin Zhang*, Jun Shan, Qing Wang

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Key Laboratory of Magnetic Molecules, Magnetic Information Materials Ministry of

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Education, the School of Chemical and Material Science, Shanxi Normal University,
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Linfen 041004, China
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Corresponding author, Tel.:+86 357 2051192;

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E-mail: [email protected]

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Abstract

Zr-doped perovskite-type material BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) is prepared and

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systematically studied via X-ray diffraction (XRD) analysis, dilatometry and

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temperature-programmed desorption (TPD) of oxygen. The electrochemical

performance of the BCFZ is characterized using electrochemical impedance

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spectroscopy (EIS) with symmetric cell configurations. BCFZ not only shows high

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oxygen reduction reaction (ORR) electro catalytic activity but also exhibits excellent
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compatibility with ceria-based (Ce0.8Sm0.2O1.9, SDC) electrolyte. They have a similar

thermal expansion coefficient and no chemical reaction. With a BCFZ cathode, the
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SDC-based SOFC (Ni-SDC|SDC|BCFZ) shows high power densities (879 and 669
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mW cm-2 at 650 and 600 °C, respectively). Moreover, it shows favorable stability in
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CO2-containing environment under SOFCs operating conditions.

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Keywords: Electrochemical performance; Solid oxide fuel cells; Cathode; Barium

cobalt iron zirconium oxide; CO2-Poisoning resistance;

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1. Introduction

At present, societal grand challenges include the global warming and the tightening

supplies of energy, clean water and food, which make the development and utilization

of clean energy resource and technology highly urgent subjects [1]. Solid oxide fuel

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cells (SOFCs) have become the promising alternative energy source because of their

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intrinsic simplicity and over 50 % efficiency in converting fuel to electricity with

negligible pollutant emission and very low noise. Potential application of SOFCs is to

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provide power to residential quarters and shops, and as auxiliary power equipment for

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vehicles [2-4]. Although the up-and-coming technology has been investigated for
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many decades, there has not yet been a commercial application in our daily life due to

issues in cost and durability. The major obstacle to large-scale commercialization is

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high system capital cost, poor thermal cycling capability, and poor system reliability
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and lifetime [5]. All these issues can be solved effectively by lowering the operating
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temperature of SOFC, and therefore, decreasing SOFC operating temperature is the

major targets in current SOFC research.

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In reducing the high operating temperatures of SOFCs, use of CeO2- or LaGaO3-

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based oxides as an alternative electrolyte material is attractive due to their high

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conductivity in an intermediate-temperature regime (IT, 500–750 °C) [6].

Furthermore, the advanced ultrathin-film deposition technologies have been used

fabricating thin (hundreds nm – several µm) electrolytes for reduced temperature

operation [7-9]. For example, the Kim group recently reported fabrication of SOFCs

with a 180 nm-thick yttria-stabilized zirconia (YSZ) electrolyte via atomic layer

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deposition (ALD) method, demonstrating a maximum power density of 380 mW cm-2

at 450 °C [10]. Meanwhile, the cathode polarization can be minimized through

creation of novel architecture/microstructure at the electrode/electrolyte interface to

reduce the operating temperature [11, 12]. Of course, cathode performance can also

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be greatly improved by developing new materials. Consequently, significant efforts

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have been devoted to searching for new cathode materials that can operate with high

performance at intermediate temperatures. In the last decade, new cathode materials

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for SOFCs operating in the IT regime have been explored, including simple

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perovskite type oxides, such as La1-xSrxCo1-yFeyO3-δ (LSCF), Sm0.5Sr0.5CoO3-δ (SSC),
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and Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), etc., and layered perovskite oxides, notably

LnBaM2O5+δ , (Ln = Pr, Nd, and Gd, M=Co, Fe, etc.) [13-19]. However, the activation
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energies for the well-known cathode are in range of 100-200 kJ mol-1, indicating the
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cathode polarization resistances will increase steeply with decreasing temperature.

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The activation energy of the cathode material BSCF, for instance, is about 120 kJ

mol-1 [14]. In addition, the phase instability of the perovskite-type oxides containing
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alkaline-earth species under CO2-containing atmosphere also restricts its practical

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application for SOFCs cathodes [20-22]. It has been demonstrated that reducing the
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oxygen vacancy (V Ogg ) concentration can decrease the basicity of perovskite oxides and

improve their resistivity to CO2 [23, 24]. The oxygen vacancy (V Ogg ) concentration in

perovskite oxides can be reduced by partial substitution of B-site cation with high

valence, less reducible metal cations (such as Zr4+, Nb5+, Ti4+ or W6+), and then their

resistance against CO2 could be significantly improved [25, 26]. Recently, Zr-doped

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perovskite-type material BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) as the candidate cathode for

proton-conducting SOFCs has been investigated and exhibits the good

electrochemical performance [27, 28]. However, more detailed knowledge about

electrochemical properties, thermal expansion behavior and stability in

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CO2-containing environment under operating conditions is still very limited. The

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electrochemical activity of a cathode for IT-SOFCs is determined primarily by the

cathode/electrolyte interface [29, 30], suggesting that the performances of the cathode

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is closely related to the electrolyte in contacts [31, 32]. There has been no information

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on the performance of BCFZ as cathode material for ceria-based IT-SOFCs.
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In present study, Zr-doped perovskite-type material BCFZ was prepared by sol-gel

method, and systematically characterized as a cathode for ceria-based IT-SOFCs.

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Cathode performance of BCFZ on ceria-based electrolyte (Ce0.8Sm0.2O1.9, SDC) was

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firstly investigated and its CO2-poisoning resistance under operating conditions was
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emphasized.

2. Experimental
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2.1 Materials synthesis

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BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) powders were prepared by sol-gel method combining

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ethylenediamine tetraacetic acid (EDTA) and citric acid complexes [28]. Briefly, the

stoichiometric amount of BaCO3 (Sinopharm Chemical Reagent Co., Ltd.), Zr(NO3)4 ⋅

4H2O (Sinopharm Chemical Reagent Co., Ltd.), Co (NO3)2 ⋅ 6H2O (Sinopharm

Chemical Reagent Co., Ltd.) and Fe (NO3)3 ⋅ 9H2O (Sinopharm Chemical Reagent Co.,

Ltd.) were mixed in EDTA-ammonium hydroxide aqueous solution accompanied with

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heating and stirring continuously, and then a right amount of citric acid in a solid state

was added to the solution. When the molar ratio of total metal ions: EDTA: citric acid

was controlled to be around 1: 1: 1.5, the stable sol was obtained. Evaporating

gradually excess water from the solution, a dark purple gel was formed. Further

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heating caused the precursor gel to autoignite, obtaining primary black powder

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material. The resultant powder was ball-milled, followed by calcining at 1050 °C in

air for 5 h for getting phase pure perovskite oxide with the desired composition.

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Ce0.8Sm0.2O1.9 (SDC) solid electrolyte powder was synthesized by using the same

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process.
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2.2 Basic characterization of materials
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Crystal structure of BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) powder was examined by X-ray

diffraction (XRD) using a Rigaku X-ray diffractometer (Rigaku Ultima IV) with Cu
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Kα radiation (λ = 1.5418 Å), tube voltage 40 kV, and tube current 40 mA. Diffraction
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data were collected by step scanning 2θ from 10 o to 130o with interval of 0.02o and 2
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s swept time at each step at room temperature. The quantitative Rietveld refinements

of the XRD patterns were performed by using the FullProf 2015 refinement software.
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The effect of CO2 poisoning on structural stability of BCFZ material was also

investigated by using XRD. Samples were poisoned with pure CO2 atmosphere in a

tubular furnace at different temperatures for 1 h. The temperature was then gradually

reduced to room temperature in pure CO2 atmosphere. The poisoned samples were

determined by room temperature XRD. Any detrimental chemical interaction of

different components had to be avoided during fuel cell fabrication. The chemical
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compatibility between electrode (BCFZ) and electrolyte (SDC) was also investigated

with the XRD. Powders of BCFZ and SDC with a weight ratio 1:1 were mixed

thoroughly in a ball mill firstly. Secondly, the mixture were calcined at 1100 °C in air

for 5 h, and then the final sintered powders were ball milled and examined by XRD.

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A standard four-probe DC technique was used to measure electrical conductivities

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of BCFZ material in ambient air using Keithley 2420-C digital source-meter. The

Arrhenius equation (1) and Arrhenius plots were used to determine activation energy

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(Ea) for conducting process, which is generally expressed as follows:

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- Ea
ln( s T ) = A+ (1)
RT
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where A is the pre-exponential constant, R is the ideal gas constant, σ is electrical
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conductivity, and Ea is the activation energy. Thermal expansion data of BCFZ were

collected using a PCY high temperature dilatometer from room temperature to

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1000 °C with a heating rate of 10 °C min-1. The specimens used for these
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measurements were sintered at 1280 °C in air for 3 h. The monolithic bar-shaped

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specimens were ground to their final dimension (2 mm×5 mm×30 mm).

O2-temperature programmed desorption (O2-TPD) was studied on a chemical

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adsorption instrument (PCA-1200, Beijing Builder) with a thermal conductivity

detector (TCD) to study the O2 desorption properties, and the reducibility of

transitional metal in perovskite material BCFZ. Typically, the sample (200 mg) was

loaded in a U-type quartz tube, and after that pretreated in pure O2 (50 mL min-1)

under 450 °C for 0.5 h. After cooling to room temperature in pure O2, pure He (20 mL

min-1) was introduced into the U-type quartz tube to get stable TCD signal baseline,
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and then temperature was programmatically increased to 950 °C with the heating rate

of 5 °C min-1.

2.3 Fabrication of symmetric cell and fuel cell

The symmetric cell BCFZ|SDC|BCFZ was fabricated to assess the electrochemical

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properties of the cathode material BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) using electrochemical

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impedance spectroscopy (EIS). Dense electrolyte SDC pellets were prepared by using

dry pressing method, and subsequently sintered in air under 1450 °C for 5 h. Both

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sides of pellet were ground to a 360-grit SiC polishing paper. Cathode slurry, which

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containing the cathode BCFZ powder, methyl cellulose, and terpinol solvent, was
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printed on both sides of the pellet and then calcined in air at 1050 °C for 3 h. Effective

electrode area was 0.33 cm2. Silver (Ag) paste was brushed onto the electrode
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surfaces as the current collector and then heated at 700 °C for 0.5 h.
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Anode-supported planar SOFCs (Ni-SDC|SDC|BCFZ) were fabricated according to

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the procedure based on previous literature reports [33]. In brief, NiO and SDC (0.6:

0.4 by weight) powders were mixed using ball milling in ethanol for 4 h. After drying,
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the NiO-SDC mixture was pre-pressed into a pellet (~ 0.8 mm thick and 22 mm
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diameter) in a stainless-steel die at 200 MPa. Then loose SDC powder was uniformly
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distributed on the anode substrate, co-pressed at 300 MPa and co-sintered

subsequently at 1450 °C for 5 h in air. The BCFZ cathode slurry was screen-printed

on the SDC-coated surface and co-fired at 1050 °C in air for 3 h to form a single cell.

2.4 Electrochemical characterization

The cathode polarization resistance measurements were performed on a Zahner

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Zennium electrochemical workstation (Zahner Instument, Germany) using a

symmetric cell with the configuration of BCFZ|SDC|BCFZ. Electrochemical

impedance spectroscopy (EIS) of the fuel cells was performed under open circuit

voltage (OCV) conditions over the frequency from 0.1 Hz to 106 Hz and AC signal

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amplitude of 10 mV was used. EIS was characterized at 500 – 700 °C. For single cell

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testing, silver paste was coated onto the electrode surface (both anode and cathode) as

the current collector. The performance and electrochemical properties of the fuel cells

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were determined in an alumina supporting tube (10-mm-inner diameter) placed within

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a vertical tube furnace. Humidified (~ 3 vol. % H2O) hydrogen (150 mL min-1) was
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used as fuel and the air (100 mL min-1) as the oxidant. Current-voltage (I-V)

polarization data were collected using digital multi-meters (XIELI, DPM) over range
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of temperatures from 500-650 °C. The microscopic morphologies of the tested cells
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were revealed using scanning electron microscopy (SEM, JEOL JSM-7500F).

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3. Results and discussion

In order to identify the structural information of BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ)

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material, BCFZ pattern was refined, using FullProf 2015 program integrated in
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WinPlotr refinement software, in a symmetric cubic system with space groups Pm3തm
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(No 221). Fig. S1 displays the XRD pattern and the refinement profile of BCFZ

powders sintered at 1050 °C for 5 h in air. The cubic phase structural parameters

obtained based on this model are a = b = c= 4.10175 ± 0.00021 Å. The low reliability

factors (e. g. Rwp = 6.96 %, Rp = 5.46 %, see the Supporting Information, Table S1)

indicates that the observed XRD pattern coincides well with the calculated one.

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The chemical compatibility between components is crucial for SOFCs, because the

formation of any impurity phases at the interface under the operation and fabrication

conditions might adversely affect the performance for SOFCs. Fig. 1 shows the XRD

patterns of BCFZ, SDC and their mixed powder co-sintered in air at 1100 °C for 5 h.

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The diffraction peaks of all the samples (BCFZ, SDC) are matched with the single

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phase (JCPDS 75-0227, JCPDS 75-0158) with no distinct extra peaks. The XRD

pattern of the BCFZ-SDC system shows that no impurities forms due to reaction

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between BCFZ and SDC at this heating temperature, suggesting BCFZ cathode and

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SDC electrolyte have good chemical compatibility with each other at 1100 °C.
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The electrical conductivity of the as-synthesized BCFZ is measured from 300 to

800 °C using the four-terminal DC technique. Fig. 2 shows the natural logarithm of
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the electrical conductivity (ln σ) as the function of temperature. The data exhibit
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semiconducting nature for the studied temperature range (300-800 °C). The result
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shows that the electrical conductivity of BCFZ oxide gradually increases with

increasing temperature (p-type semi-conductor behavior). This p-type semi-conductor

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behavior can be depicted using a thermally activated p-type small polaron hopping
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mechanism [34, 35]. The electrical conductivity of BCFZ oxide firstly increases
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rapidly (Ea = 0.37 eV), then increases slowly with low activation energy (Ea = 0.24

eV). This inflection of electrical conductivity is generally attributed to a lattice

expansion and a reduction of the concentration of electronic charge carriers due to the

loss of lattice oxygen at high temperatures (above 450 °C) [36-38].

The thermal expansion properties are an important parameter for SOFCs. The

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electrodes must match well with the electrolyte in thermal expansion coefficient

(TEC), otherwise unmatched TECs between the SOFCs components may cause

internal stresses, which negatively affect the SOFCs lifetime. TECs of BCFZ and

SDC in the range of temperatures 150-1000 °C were measured by the dilatometer.

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Based on the dL/L0 vs. temperature curve (Fig. 3), the BCFZ exhibits almost linear

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thermal expansion. However, there are two obvious inflections on the thermal

expansion curve, one between 400 °C and 600 °C and the other between 850°C and

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1000 °C. The occurrence of these inflections for BCFZ are corresponding to the

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absence of lattice oxygen and the formation of oxygen vacancies at elevated
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temperatures [39, 40]. TEC of BCFZ in the range of temperatures (150-1000 °C) is

1.44×10-7 K-1, which is close to that of SDC electrolyte (~1.26×10-7 K-1) [41, 42]. The
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thermal expansion behavior of BCFZ is similar to SDC electrolyte, which enables high
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thermal stability and good thermal compatibility with the electrolyte.

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The oxygen vacancy (V Ogg ) plays a very important role for examining the oxygen

reduction reaction (ORR) catalytic activity of the cathode [43, 44]. Thus, oxygen
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vacancy distributions and dynamics directly control the operation of SOFCs [45, 46].
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The generation of oxygen vacancies was determined by the temperature-programmed

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O2 desorption (O2-TPD) using TCD. The O2-TPD profile (Fig. 4) of the BCFZ

material shows two ranges of temperature-related oxygen desorption peaks. The low

temperature feature is observed between 346 and 509 °C with a peak at 422 °C, while

the other high temperature one at ~ 845 °C, implying that the oxygen species may

exist in different matrices in the BCFZ. The low temperature for the onset temperature

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of oxygen desorption peak of BCZF indicates that the bonding of adsorbed oxygen in

the lattice is weak, and that the oxygen ions are more mobile [32, 43]. It is popularly

believed that the lower temperature region (between 346 and 509 °C) desorption peak

is accompanied by the partial reduction of the transition metal in the B-site (Fe4+ to

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Fe3+, Co4+ to Co3+) and the elevated temperature range (from 800 °C to 897°C)

desorption peak at ~ 845 °C is corresponding to the partial reduction of Co3+ to Co2+

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[47]. The temperature range of two oxygen desorption peaks in O2-TPD

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chromatogram consistent well with that displayed in the thermal expansion curve (Fig.

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3).
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The electrocatalytic activity of BCFZ for oxygen reduction reaction (ORR) on

oxygen-ion electrolyte SDC was first evaluated by electrochemical impedance

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spectroscopy (EIS) in a symmetrical cell configuration between 500 and 700 °C in

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different atmospheres. The area-specific resistance (ASR) for the BCFZ cathode
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measured by two-probe electrode impedance using the BCFZ|SDC|BCFZ symmetric

cell is shown in Fig. 5. The cathode ASR increases with the decrease of the operating
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temperature, typically from 0.035 Ω cm2 at 700 °C to 0.081 Ω cm2 at 600 °C in

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oxygen atmosphere (from 0.068 Ω cm2 at 700 °C to 0.205 Ω cm2 at 600 °C in air),
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respectively. Compared to the other cathode composition (see the Supporting

Information, Table S2), the lower the ASR of the cathode indicates the higher

electrocatalytic activity [32]. The apparent activation energy (Ea) for ASRs, counted

by Arrhenius curve, is 87.8 kJ mol-1 (in ambient air), 75.1 kJ mol-1 (in pure oxygen).

The active energy is substantially lower than that for the well-known BSCF cathode

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material (120 kJ mol-1[14]), and comparable to BaCo0.4Fe0.4Zr0.1Y0.1O3-δ cathode

material (79.2 kJ mol-1[48]). The smaller is the activation energy, the more benefit is

it to reduce the operating temperature for SOFCs [32]. It demonstrates that the BCFZ

material is an excellent electrocatalyst for ORR in ceria-based IT-SOFCs.

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The electrochemical performance of the BCFZ cathode fired at 1050 °C was further

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characterized in single fuel cell. A three-layered single fuel cell, Ni-SDC|SDC|BCFZ

(for an SEM image, see Fig. S2 a), was adopted. Fig. S2 a shows the cross-sectional

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views of the as-prepared anode | electrolyte | cathode sandwich structure after testing.

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It can be seen that the SDC membrane is completely dense. There are no obvious
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pores and cracks on the cross-section of SDC membrane. Moreover, there is no

obvious grain coarsening of BCFZ after testing (see Fig. S2 b, c). It can be observed
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that the adhesion of the BCFZ cathode to the SDC electrolyte seems to be excellent
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(see Fig. S2 d, e). The current-voltage characteristics and the corresponding power
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densities are expressed in Fig. 6(a), measured at temperatures from 500 to 650 °C

using wet H2 (~ 3 % H2O) as the fuel and air as the oxidant. As can be seen from Fig.
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6(a), the fuel cells with BCFZ cathode delivered a very attractive power output with
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peak power densities of 879, 669, 434 and 243 mW cm-2 at 650, 600, 550 and 500 °C,
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respectively. With BCFZ cathode, the fuel cell offered a better electro-performance

than those by applying typical cobalt-based mixed conducting oxides like LSCF [49]

and SSC [50] as cathodes. This result further suggest the excellent electrocatalytic

activity of BCFZ for oxygen reduction reaction (ORR) within the intermediate

temperature range of 500 - 650 °C. Nyquist EIS plots of the BCFZ cells under open

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circuit conditions are shown in Fig. 6(b). The total polarization resistances of the

single cell, determined from the arc length of the impedance spectra, decrease with

the increasing operating temperatures, typically from 0.096 Ω cm2 measured at

550 °C to 0.035 Ω cm2 at 650 °C, which is lower than that using well-known LSCF

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and SSC.

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The physical and chemical properties of cathode materials are critical to the

performance of SOFCs. The cathode must have high electronic conductivity, excellent

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electrochemical activity for oxygen reduction and compatibility with the electrolyte

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and interconnection. Finally, high CO2 tolerance is also especially important for the
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cathode materials that work in the air. Many perovskite cathodes containing

alkaline-earth elements (Ba, Sr, etc.) are very sensitive to CO2-rich atmospheres at
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operating temperatures. Facile carbonate formation on the surface of the perovskites

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can destroy the phase structure. Although some strategies against CO2 poisoning have
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been proposed during recent years [24, 51, 52], a single-phase cathode material with

anti-CO2-poisoning capability is still limited. The phase stability of BCFZ cathode in

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pure CO2 atmosphere was investigated. The XRD spectrums (shown in Fig. S3)
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suggest that the carbonates (BaCO3) have been formed at 500 °C for 1h. CO2
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poisoning can greatly deteriorate the performance of cathodes and then affect the

long-term durability of the SOFCs [20]. In this present study, in order to investigate

the CO2 resistivity of the BCFZ cathode, fuel cells of Ni-SDC|SDC|BCFZ was also

operated in 5 vol %-CO2 containing oxygen (Fig. 7). Based on the fuel cell

performance shown in Fig. 7 (a), in the range of temperature 550 to 650 °C, both the

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OCVs and the output power densities show similar values before and after

introduction of CO2. As can be seen from Fig. 7 (a), the peak power densities of the

cell are slightly lower in CO2-containing oxygen than that in pure oxygen, which can

be attributed to the dilution effect of the CO2 [24, 53]. To determine the tolerance

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towards CO2, the polarization resistances of the single fuel cell were also monitored

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under open circuit conditions after the introduction of oxygen containing a

concentration of CO2 (5 vol %). As can be seen from Fig. 7 (b), the polarization

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resistances were only slightly higher after having been subjected to CO2. The effect of

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CO2 on BCFZ cathode was further studied at 600 °C. The BCFZ cathode of the fuel
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cell was subjected to cycling between pure oxygen and oxygen containing 5 % CO2

while operating at V = 0.4 V at 600 °C (Fig. 7 c). When CO2 is introduced into
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oxygen, the current density of the fuel cell rapidly drops from ~ 1130 mA cm-2 to
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1015 mA cm-2. Nevertheless, after pure oxygen replaces CO2/O2 mixture, the current
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density recovers in about 20 min. As can be seen from Fig. 7 (c), the recovery of

current density is reversible during the six CO2 exposure cycles of the stability test
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over a period of about 5 h. The value of the current density recovers completely after
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removing the CO2, illustrating that the poisoning effect of CO2 is nearly reversible in
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relatively short-term cycles at 600 °C under the fuel cell operating conditions.

4. Conclusions

In this study, we report a perovskite-type BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) cathode,

which is a promising, active and stable cathode material for ceria-based IT-SOFCs.

BCFZ exhibits high stability, good electrochemical performance, and low activation

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energy for oxygen reduction. The catalytic activity for oxygen reduction reaction

(ORR) was identified by symmetric cell and single-cell tests. The cathode ARS is as

low as 0.081 Ω cm2 at 600 °C, underscoring the high oxygen reduction reactivity for

BCFZ cathode. The apparent activation energy of area specific resistances for BCFZ

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cathode is ~ 80 kJ mol-1, which is relatively lower than that for the BSCF (117 kJ

mol-1), indicating its potential in low-temperature SOFCs applications. Moreover, the

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BCFZ cathode also has some other advantages, such as a low TEC value, and

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adequate stability with CO2. With BCFZ as the cathode, the fuel cells produce a peak

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power density of 879 mW cm-2 at 650 °C. These results illustrate that BCFZ is a
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potential cathode material for IT-SOFCs.
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Acknowledgments:

This work was supported by the Shanxi Provincial Natural Science Foundation of
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China (Grant No. 201601D011024).

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Intensity (a. u.)

SDC

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BCFZ-SDC

BCFZ

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PDF#75-0158 PDF#75-0227

20 40 60 80 100
θ (Degree)
2θ

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Fig. 1 XRD patterns of BCFZ, SDC and BCFZ-SDC mixed powder sintered at
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1100 °C for 5 h
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Temperature (oC)
800 700 600 500 400 300
8
Ea = 0.24 eV

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7
lnσ T (S cm -1 K )

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6
Ea = 0.37 eV

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5

1.0 1.2 1.4 1.6 1.8

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1000/T (K-1)
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Fig. 2 Temperature dependence of electrical conductivity of the BCFZ between 300

and 800 °C
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1.6
BCFZ
1.4
SDC

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1.2
dL/L0 /%

1.0

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0.8

0.6

0.4

0.2

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0.0
200 400 600 800 1000
Temperature (°C)
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Fig. 3 Thermal expansion curve of the BCFZ sample between room temperature and
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1000 °C in air
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Oxygen Signal

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0
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300 400 500 600 700 800 900

Temperature (°C)
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Fig. 4 O2-TPD profiles of the BCFZ sample

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Temperature (oC)
500 550 600 650 700

0.0
Ea=87.8 kJ mol-1

-0.4 O2
lg (ASR) (Ω cm2)

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Air

-0.8

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Ea=75.1 kJ mol-1
-1.2

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-1.6
1.30 1.25 1.20 1.15 1.10 1.05 1.00
-1
1000/T(K )

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Fig. 5 Cathode ASR values for the symmetric cell BCFZ|SDC|BCFZ in an Arrhenius
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diagram as a function of temperature.

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1.0 1000
(a)
0.8 800

Power density(mW cm-2)

650 oC
0.6 600 oC 600

Voltage(V)
550 oC
500 oC
0.4 400

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0.2 200

0.0 0

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0 500 1000 1500 2000 2500 3000
Current density (mA cm-2)

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0.6
(b)
0.5

0.4

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o
650 C
-Z (Ω cm2)

o
0.3 600 C
o
550 C
''

o
0.2 500 C
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0.1
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0.0
0.1 0.2 0.3 0.4 0.5 0.6
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'
Z (Ω cm2)

Fig. 6 (a) I-V and I-P curves for the complete cell based on Ni-SDC|SDC|BCFZ and
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(b) the corresponding impedance spectra under open circuit conditions at different

temperatures.
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1.0 o
650 C 700
(a) o
600 C
o
0.8 550 C 600

Power density(mW cm-2)

500
0.6

Voltage(V)
400

0.4 300

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200
0.2
100

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0.0 0
0 500 1000 1500 2000
Current density (mA cm-2)

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0.5
(b)

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0.4
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0.3
-Z (Ω cm2)

o
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0.2 550 C
''

o
600 C
o
650 C
0.1
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0.0
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0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

'
Z (Ω cm2)
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1300
C

(c)
1250
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Current density (mA cm-2)

1200

1150

1100

1050

1000

950

900
0 60 120 180 240 300
Elapsed time (min)

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Fig. 7 (a) I-V and I-P curves of the single fuel cell were tested using oxygen in the

cathode side at 550-650 °C (purple curves). After introduction of 5 vol % CO2 for 1 h,

the fuel cell was tested again in CO2 containing oxygen (blue curves). (b) The

corresponding impedance spectra under open circuit conditions. (c) Stability

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measurement of the single fuel cell at a constant 1130 mA cm-2 at 600 °C while

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cycling between pure oxygen and oxygen + 5 vol % CO2

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Highlights

BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) is firstly investigated as a cathode for ceria-based

IT-SOFC.

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BCFZ presents good ORR activity with low activation energy on SDC

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electrolyte.

BCFZ exhibits a low thermal expansion coefficient.

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BCFZ has good CO2-poisoning resistance.

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Fuel cell with BCFZ cathode gives excellent performances.
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