Nanomaterials for Fuel Cells

1)The importance of Fuel Cells and their Simulation.

2)The major Drawback for large-scale production. Carbon
nanomaterials as metal-free catalysts (to replace Pt).
3)CNFs vs CNTs. Importance of large Active Area.
4)Other limitations.

1)The importance of Fuel Cells and their Simulation.

The rapid increase in the global energy consumption and the

environmental impact of traditional energy resources pose serious
challenges to human health, energy security, and environmental
protection.
One promising solution, providing clean and sustainable power, is fuel
cells.
High energy conversion efficiency (typically, 4060% or up to 85%
efficiency if waste heat is captured for use) and high energy density,
virtually no pollution, and potential large-scale applications.
Fuel cells may have their greatest environmental impact in motor vehicles.
In most automotive engines, gasoline is converted into mechanical energy
through heat produced during combustion. The efficacy of this process is
limited by the efficiency formula for the Carnot cycle, which describes the
thermomechanical operation that takes place in a gasoline engine.

Efficiency is fixed for a fixed T (~20% for an automobile).

To bypass limitations of Carnot Cycle:

Fuel cell: U(chem.)---> U(elect.); Motor: U(elect.)--->U(mech)

Efficiency increases to almost 90% (theo), 50% (exp).

Consequently, carbondioxide emissions are lower, and the lower operating
temperatures of fuel cells all but eliminate the production of nitrogen
oxides (NOx) and sulfuric oxides (SOx).
The electronics industry is pursuing miniature fuel cells. Motorola has
demonstrated a cellular telephone powered by a fuel cell whose operating
time with one fuel cartridge is five times longer than that of a conventional
battery with one recharge. Other likely applications include power
supplies in laptop computers and portable video, audio, and entertainment
equipment.
Fuel cells also provide an uninterrupted power supply because there is no
self-dis charge, as occurs with batteries, an advantage that minimizes
maintenance and maximizes the systems reliability. In addition, fuel cells
have a higher energy density and therefore a higher power capacity per
unit of weight.

Technology development is an important weapon at this stage, and small

companies with technical skills in fuel-cell processes have become
important partners to the large electronic and automotive companies.
In this rapidly developing and highly competitive market, the time from
idea to prototype has shrunk. Therefore, tools for developing virtual
prototypes have become exceptionally important.
Optimizing a fuel cells performance in combination with its auxiliary
equipment and operation of the electric motor requires a lot of
mathematical puzzling. A combination of modeling and experimentation
has reduced the cost and accelerated the pace of building and
understanding prototype systems.
Modeling provides valuable insights into the electro-chemistry of the fuel
cell and the processes that take place in the heart of the fuel-cell system
(the electrodes and electrolyte in the fuel-cell stack).
These processes are described at the microlevel: single catalyst
agglomerates; a unit cell consisting of an anode, a cathode, and the
electrolyte between them; and as reactor models of the fuel processor in
fuel cells for cars.

Schematic drawing of
a fuel cell unit cell
and the structure of
one of the GDEs. It
represents a fuel cell
unit cell and a
magnified section of
the cathode GDE and
its contact with the
electrolyte.

Oxygen and hydrogen are supplied to the cell through the gas channels
in the current collector and current feeder, respectively. The current
collector and the current feeder are usually made of electronic
conducting materials and are equipped with grooves that form the gas
channels. These grooves are open channels with the open side facing
the surface of the GDEs.
The current collectors and feeders also conduct the current to the wires
connected to the load. They can also supply cooling required during
operation and heating required during star t-up of the cell.
The GDE magnified in Last Figure is an oxygen-reducing cathode in a
fuel cell with acidic electrolyte, for example the PEMFC. In the PEMFC,
the active GDE is confined to a thin active layer supported by a pure gas
diffusion layer (GDL).
From the free electrolyte, current enters the electrolyte contained in the
GDE (also called pore electrolyte) as protons, and is transferred to
electron current in the charge transfer reaction at the reaction sites.
These reaction sites are situated at the interface between the
electrocatalyst in the electrode material and the pore electrolyte.

Principle of the
oxygen reduction
process in the
electrode --------->
Transport of oxygen,
water, protons, and
electrons to and from
the reaction site in an
oxygen reducing
GDE.

Description of the schematic path of the current in the electrode. The

current in the pore electrolyte decreases as a function of the distance
from the free electrolyte as it is transferred to electron current in the
electrode. The direction of the current in the electrode is opposite to that
of the electrons, by definition. The supply of oxygen takes place in
conjunction with the charge transfer reaction and can be subject to mass
transport resistance both in the gas phase and in the thin layer of pore
electrolyte that covers the reaction site.

The water balance in the electrode is maintained through evaporation and

transport through the gas pores.
The pore electrolyte has to form an unbroken path from the free electrolyte,
between the anode and the cathode, to the reaction site. Also, the electrode
material and the gas pores must each form an unbroken path to the reaction
site or to the pore electrolyte covering the reaction site.
The processes described above including fluid flow, chemical species
transport, heat transfer, current conduction in the collectors, feeders,
electrodes and electrolytes, and the electrochemical reactions are all
coupled together, and determine the characteristics of a unit cell.
Several important design parameters can be investigated by modeling these
processes. Among these parameters are:
*Porosity, active surface area, and pore electrolyte content of the GDEs

* Geometry of the GDEs (active layer and GDL for the PEMFC) and
electrolyte in relation to the gas channels, the current collectors, and feeders
* Geometry of the grooves that form the gas channels and dimensions of the
current collectors and feeders

Different simulations can be performed

Mass Transport and Electrochemical Reaction in a Fuel Cell

Cathode: One of the most importantand most difficult
parameters to model in a fuel cell is the mass transport
through gas diffusion and reactive layers. Gas concentrations
are often quite large and are significantly affected by the
reactions that take place. This makes Fickian diffusion an
inappropriate assumption to model the mass transport.
Model Geometry:

Results:

Oxygen concentration at a total potential drop over the modeled domain of

190 mV. The figure shows that concentration variations are small along
the thickness of the cathode for this relatively small current density, while
they are substantially larger along the electrodes width.

There is a significant velocity peak at the edge of the inlet orifice. This is
caused by the contributions of the reactive layer underneath the current
collector because in this region the convective flux dominates the mass
transport. Thus it is important to model the velocity field properly.

The local overvoltage is rather even throughout the cathode. This is

caused by the high electronic conductivity in the porous material. Another
observation is that the maximum overvoltage is -180 mV. This means that
there is a voltage loss of 10 mV in the electrolyte layer. Although the local
overvoltage distribution is rather even, the concentration of oxygen is not.
This means that the reaction rate is nonuniform in the reactive layer. One
way to study the distribution of the reaction rate is to plot the ionic current
density at the bottom boundary of the free electrolyte.

The current-density distribution shows that the variations are rather

large. The reaction rate and the current production are higher
beneath the orifice and decrease as the distance to the gas inlet
increases. This means that the mass transport of reactant

dictates the electrodes efficiency for this design at these

particular conditions.

Another example....
Species Transport in the Gas Diffusion layers of a PEM

Current distribution in the PEM fuel cell. There are significant

current spikes present at the corners of the current collectors.

To further analyze the cells behavior, plot the current density at the active
layer as a function of cell height (y). The current density is uneven with the
highest density in the cells upper region. This means that the oxygenreduction reaction rate in the cathode determines the current-density
distribution. The maximum current density arises close to the air inlet.

The convective fluxes generally dominate mass transport in the

cell. To study the convective effects, plot the velocity field. The flowvelocity magnitude attains its highest values at the current collector
corners.

Reactant (oxygen and hydrogen) weight fractions in the cathode and

anode gases. Surprisingly, the hydrogen fraction increases as the anode
gas flows from the inlet (at the bottom) to the outlet (at the top). This is the
result of the electroosmotic drag of water through the membrane, which
results in a higher flux than the consumption of hydrogen. This means that
the resulting convective flux of anode gas towards the membrane causes
the weight fraction of hydrogen to go up. In the cathode gas, there is an
expected decrease in oxygen content along the flow direction.

Water mass fraction in the anode and cathode gases as well as the
diffusive flux of water in the anode. It is apparent that water is transported
through both diffusion and convection to the membrane on the anode side.
The results show a minimum occurring in the upper corner of the
membrane on the anode side. This is known to limit fuel cell performance.
If the anode gas becomes too dry, the membrane dries out, resulting in
decreasing ionic conductivity and the cell subsequently fails.

On the other hand, on the

cathode side water levels
increase with the direction
of flow, and a local
maximum in water current
occurs in the lower corner
to the membrane. This
might also be critical
because water droplets
can clog the pores and
effectively hinder gas
transport to the active
layer.

Let's return to materials for Fuel-Cells

In order to perform simulations we have to specify physical

parameters that are going to enter the PDE that govern the physical
processes described before.
The PEM fuel cell electrodes are of the gas diffusion type. They
consist of a supporting carbon structure with gas-filled pores
(denoted gas backing) and a porous active layer that also contains
the polymer electrolyte. The electrochemical reactions take place in
the active layer, which contains a platinum catalyst. The gas
diffusion electrodes are designed to maximize the specific area
available for the reaction, maximize the distribution of reactant (that
is, achieve a low gas-transport resistance), and minimize the
resistance for the proton transport to and from the active sites at
the electrodes.
So I decided to find out more information about Nanomaterials for
Fuel Cells........

2)The major Drawback for commercial applications. Carbon

nanomaterials as metal-free catalysts (to replace Pt).

While the very facile H2 oxidation kinetics greatly reduces the

amount of catalyst (e.g., platinum) at the anode, the slow oxygen
reduction reaction (ORR) on the cathode is a key step to limit the
energy conversion efficiency of a fuel cell and requires a substantial
amount of platinum catalyst (representing at least a quarter of the
fuel cell cost).
Although platinum nanoparticles have long been regarded as the
best catalyst for the ORR, the Pt-based electrode suffers multiple
drawbacks, including its time-dependent drift, methanol crossover,
and CO deactivation.
This, together with the high cost of platinum and its scarcity, has
made these catalysts the primary barrier to mass market fuel cells
for commercial applications. Thus, the large-scale practical
application of fuel cells has not been realized, though alkaline fuel
cells with platinum as an ORR electrocatalyst were developed for
the Apollo lunar mission in the 1960s.

Even though the amount of platinum needed for the desired

catalytic effect could be reduced using Pt alloys, most non-noble
metal catalysts still remain too low in efficiency when compared to
Pt or too expensive as commercial mass production would still
require large amounts of platinum. The large-scale practical
application of fuel cells will be difficult to realize if the expensive
platinum-based electrocatalysts for ORR cannot be replaced by
other efficient, low cost, and stable electrodes.
Along with the intensive research efforts in reducing or replacing Ptbased electrode in fuel cells, a new class of carbon nanomaterials
has been discovered, which, as alternative ORR catalysts, could
dramatically reduce the cost and increase the efficiency of fuel
cells.
Their research has found that vertically-aligned nitrogen-doped
carbon nanotube (VA-NCNT) arrays can act as a metal-free
electrode to catalyze an ORR process free from CO poisoning
with a 3-times higher electrocatalytic activity, much smaller
crossover effect, and better long-term operational stability than that
of the commercial platinum-based electrode (C2-20, 20% platinum
on Vulcan XC-72R; E-TEK) in alkaline fuel cells.

Based on the experimental observations and quantum mechanics

calculations by B3LYP hybrid density functional theory, they attributed
the improved catalytic performance to the electron-accepting ability of
the nitrogen atoms, which creates net positive charge on adjacent
carbon atoms in the nanotube carbon plane of VA-NCNTs to readily
attract electrons from the anode for facilitating the ORR.
The nitrogen-induced charge delocalization can also change the
chemisorption mode of O2 from the usual end-on adsorption (Pauling
model) at the nitrogen free CNT (CCNT) surface (top right) to a side-on
adsorption (Yeager model) onto the NCNT electrode.

(left) The calculated

charge density
distribution and (right)
schematic
representations of
possible adsorption
modes of an oxygen
molecule.

The N-induced charge-transfer from adjacent carbon atoms could

lower the ORR potential while the parallel diatomic adsorption could
effectively weaken the OO bonding, facilitating ORR at the VANCNT electrode. Uncovering this new ORR mechanism in the
nitrogen-doped carbon nanotube electrode is significant as that the
same principle could be applied to the development of various other
metal-free efficient ORR catalysts for fuel cell applications.
Although it is still a challenge to determine the exact locations of
nitrogen atoms in the carbon nanotube structures and chemical
nature of the catalytic sites, recent research activities carried out in
many laboratories, including our own one, have not only confirmed
the above findings but also further proved that the doping-induced
charge transfer has large impact on the design/development of new
metal-free catalytic materials for fuel cell and many other
applications.

For instance, Yang et al. have recently extended the doping

atoms to include Boron with a lower electronegativity than that
of carbon.

These authors found that the doping-induced charge redistribution,

regardless whether the dopants have a higher (as N) or lower (as
B) electronegativity than that of carbon, could create charged sites
(C + or B + ) favorable for O2 adsorption to facilitate the ORR
process.
This work suggests further exploration of the metal-free
electrocatalysts based on carbon nanotubes doped by atoms (other
than N and B) with electronegativities different from that of carbon
atom.
By extension, they have successfully prepared vertically-aligned
BCN (VA-BCN) nanotubes containing both nitrogen and boron
heteroatoms. Due to a synergetic effect arising from the co-doping
of carbon nanotubes with boron and nitrogen, the resultant VA-BCN
nanotubes were demonstrated to show a higher electrocatalytic
activity for ORR in alkaline medium than VA-CNTs doped with either
boron or nitrogen only.

The observed superior ORR performance with a good methanol

and CO tolerance and excellent durability for the VA-BCN nanotube
electrode than the commercial Pt/C electrode opens up avenues
for the development of novel efficient metal-free ORR catalysts by
co-doping carbon nanotubes with more than one heteroatom of
electro-negativities different from that of carbon atom.
As a building block for carbon nanotubes, graphene is an
alternative candidate for potential uses as the metal-free ORR
catalyst. Indeed, N-doped graphene (N-graphene) films produced
by chemical vapor deposition (CVD) in the presence of ammonia
have recently been demonstrated to show a superb ORR
performance similar to that of VA-NCNTs with the same nitrogen
content in alkaline medium.
The ease with which graphene materials and their N-doped
derivatives can be produced by various low-cost, large-scale
methods, ranging from the CVD to solution exfoliation of graphite,
suggests considerable room for cost effective preparation of metalfree efficient graphene-based catalysts for oxygen reduction.

In addition, Liu et al. have reported the ORR electrocatalytic

performance better than platinum for nitrogen-doped ordered
mesoporous graphitic arrays (NOMGAs) prepared by a metal-free
nanocasting technology using a nitrogen-containing aromatic
dyestuff, N,N0 -bis(2,6-diisopropyphenyl)-3,4,9,10perylenetetracarboxylic diimide (PDI), as the carbon precursor.
Owing to the metal-free preparation procedure, the reported
electrocatalytic activity can be attributed exclusively to the
incorporation of nitrogen in PDI-NOMGAs.
In a somewhat related, but independent study, Liu et al. have
demonstrated phosphorus-doped graphite layers with high
electrocatalytic activity for ORR in an alkaline medium.
Metal-freeN-doped MWCNTs or ordered mesoporous carbons
(OMCS) have also been produced through carbonization of a
MWCNT-supported polyaniline (PANI) coating or via NH3
activation.

These metal-free N-doped nanocarbons have also been

demonstrated to exhibit high ORR activities even in acidic
electrolytes. Good ORR activities in the acidic media have also
been observed for NCNTs produced by both metal catalyzed and
metal-free nanotube growth processes.
However, the catalytic performance of these reported N-doped
carbon nanomaterials in acidic medium still needs to be further
improved to meet the requirement for practical applications.
In addition to the intramolecular charge-transfer that impart ORR
electrocatalytic activities to heteroatom-doped carbon nanotubes,
graphene and graphite described above, they have recently
demonstrated that certain polyelectrolyte (e.g.,
poly(diallyldimethylammonium chloride)) adsorbed pure carbon
CNTs or graphene, either in an aligned or nonaligned form, could
also act as metal-free electrocatalysts for ORR through the
intermolecular charge-transfer from the all-carbon CNTs or
graphene to the adsorbed PDDA.

It is notable that the PDDA adsorbed vertically aligned CNT

electrode possesses remarkable electrocatalytic properties for
ORR; similar to that of commercially available Pt/C electrode.
These results clearly indicate that the important role of
intermolecular charge-transfer to ORR can be applied to carbon
nanomaterials in general for the development of various other
metal-free efficient ORR catalysts for fuel cell applications, even
new catalytic materials for applications beyond fuel cells (e.g.,
metalair batteries, electrochemical biosensors).
However, further study on the catalytic mechanism and kinetics is
still needed in order to design and develop functionalized carbonbased catalysts with a desirable activity and durability. The longterm performance evaluation of these nanocarbon catalysts in
actual fuel cells should also be performed.

They firmly believe that heteroatom-doping of

carbonnanomaterials (e.g., nanotube, graphene, mesoporous
carbon)to induce the intramolecular charge transfer has been
shown to be a promising approach to the development of
metal-free, carbon-based catalysts with even a higher
electrocatalytic activity and better long-term operation stability
than that of commercially available platinum-based electrodes
for oxygen reduction in fuel cells.
Furthermore, intermolecular charge transfer has also been
demonstrated to impart ORR activities to all-carbon carbon
nanomaterials for fuel cell applications, even new catalytic
materials for applications beyond fuel cells.

Although the ORR catalytic performance of N-doped carbon

nanomaterials in acidic media is still relatively poor with
respect to that in alkaline electrolytes, judicious application of
the intramolecular (intermolecular) charge transfer processes
with various dopant atoms of different electronegativities
(charged absorption moieties) to different carbon
nanomaterials has opened up the rich field of metal-free ORR
electrocatalysts with vast opportunities.
Further development in this exciting field will surely
revolutionize the way in which future energy systems are
developed, and should result in a better fuel economy, a
decrease in harmful emissions, and a reduced reliance on
petroleum sources.

3)CNFs vs CNTs. Importance of large Active

Area.

Current PEFC still face significant technological critical points which

must be overcome before becoming economically viable. The high
cost of platinum, together with its limited reserves in nature, has
been shown to be the major drawback to mass market fuel cell for
commercial applications.
Moreover, PEFC suffer from insufficient performance stability, due
mainly to catalyst oxidation, migration and CO induced poisoning,
loss of electrode active surface area and corrosion of the carbon
support. An overview will be given on the applications of carbon
nanomaterials as electrocatalyst support for PEFC and on the
replacement of traditional chemical reduction method for catalyst
dispersion with electrodeposition (ELD) and sputtering deposition
(PVD). Both these techniques offer the advantage of easy catalyst
preparation (absence of reducing and de-flocculating agents, no
heat treatment in hydrogen) and easy transfer of the process to the
industrial level.

Nanomaterials can hold new prospects in the effort to increase the

catalyst activity and utilization. Nanostructured materials are
intrinsically materials with very high specific surface, which is a
basic requirement for enhanced catalytic activity.
Recently, the use of carbon nanotubes (CNT) has been proposed to
this purpose but it has been reported that CNT has relative small
specific surface areas and weak interactions with the supported
metals.
Carbon nanofibers (CNF) with larger specific surface area and
more available edge atoms are thought to be more efficient from
this point of view.
CNF can have different morphology depending on the angle of
graphene layers with respect to the fiber axis. Graphene layers are
perpendicular to the filament axis in platelet CNF and parallel to the
fiber axis in the tubular CNF.

Since the properties of graphite are anisotropic, its orientation

strongly affects the resulting material properties, thus
exercising control over the morphology and layers stacking of
CNF is of considerable importance for applications.
Depending on the morphology, CNF can exhibit larger specific
surface area larger and more available edge atoms than CNT.
CNF with different controlled morphology have been grown on
carbon paper by methane decomposition over Ni clusters
through plasma enhanced CVD.

In conventionally prepared electrodes, Pt is usually deposited onto

the carbon support electrodes, using the impregnation-reduction
method, where the reduction is chemically performed. The
minimum platinum load obtained by this method is 0.1 mg cm-2.
Even though low, this value still raises the cost of the fuel cell
production.
In the last years, to reduce the platinum load and increasing at the
same time the utilization, techniques able to localize the metal on
the surface of the electrode have been employed.
By electrodeposition metal particles are deposited by means of an
electric field that ensures the catalyst will be located only in regions
that have access to electrons and protons.

With this method the catalyst loading has been highly reduced.
More recently sputter deposition technique has been examined as
a means to obtain ultra low levels of catalyst loading. Electrodes
ultra-low catalyzed with this technique have shown electrochemical
performance comparable with that of the conventionally prepared
catalyst, combined with an outstanding decrease of the Pt load
down to 0.06 mg cm-2.
A considerable reduction of the catalyst load has been also
achieved by the electrodeposition of Pt clusters onto CNF.
Moreover, it was found that electrochemical performance and
stability of Pt/CNF electrodes was strongly related to the graphene
related sheets arrangement.
The platelet CNF showed the highest activity attributed to the
higher ratio of edge to basal atoms and, as a consequence, larger
number of active sites for electron transfer, a very large working
surface area, a more uniform dispersion of Pt particles with more
smaller size and a higher performance for the methanol oxidation
reaction. Therefore, the platelet CNF are good candidate for
catalyst support in PEFC with better performances with respect to
commercial supports.

4)Other limitations.

An additional problem hindering the real penetration of PEFC into

the market is the CO induced poisoning of the platinum, which
implies the need of high platinum load in order to obtain reasonable
performances. The development of more tolerant catalysts is
required and the research is focused on the development of binary
alloys, where the second component is thought to inhibit the CO
adsorption on the catalyst surface.
To this aim, electrodes have been catalyzed with sputtered PtAu
clusters. The catalyst resulted localized only on the uppermost
surface, combining low loading levels with higher electrochemical
performance and stability compared to PtAu deposited onto
commercial carbon supports.

Although hydrogen has a high energy density by weight, it has a

low energy density by volume as compared to hydrocarbon-based
fuel cells. Thus, hydrogen storage is one of the bottlenecks for
hydrogen fuel cell development since high-pressure compressed
gas tanks are large and heavy. In addition, compressing hydrogen
to high pressures require energy as well, defeating some of the
cost benefits with fuel cells. Liquid hydrogen storage, which does
not have a great energy density by volume as compared to
hydrocarbon, also requires cryogenic storage a bulky and
expensive option.
Hydrogen fuel cell technologies will not be adopted unless the
hydrogen gas storage tanks can be improved to decrease size and
weight.
Nanotechnologies have potential for use in advancing hydrogen
storage technologies to create breakthroughs in weight and size.
They are exploring nanomaterials and microscale designs that may
help improve hydrogen storage.

The nanomaterials provides large surfaces areas to which

hydrogen adsorbs; consequently, the materials improve the
energy density by volume. Other researchers have
investigated activated carbon, carbon nanotubes, and metal
organic frameworks. We are extending the range of materials
to other carbon-based structures and sources. We will also
investigate the effect of doping of the materials to improve
adsorption.