CH5013: Principles of Fuel Cells

Basics of Fuel Cells

Prof. Raghuram Chetty

Department of Chemical Engineering
Indian Institute of Technology Madras
 PEM Fuel Cells
❑ Proton exchange
membrane or polymer
electrolyte membrane
(PEM) fuel cell consists
of an anode and
cathode separated by
an electrolyte
membrane.

❑ Both the anode and

the cathode contain a
catalyst to speed up
the electrochemical
processes.
Half Cell Reactions
❑ Hydrogen is oxidised at the anode and oxygen/air is
reduced at the cathode.
❑ Protons are transported from the anode to the cathode
through the electrolyte membrane and electrons are
carried to the cathode over an external circuit.
❑ On the cathode, oxygen/air reacts with protons and
electrons forming water and producing heat.

Anode
2H2→ 4H+ + 4e- (Ea = 0.0 V)
Cathode
O2+ 4H+ + 4e- → 2H2O (Ec= 1.229 V)

Net reaction
O2+ 2H2 →2H2O + Heat (Ecell= 1.229 V)
Components of Fuel Cells
❑ Electrolyte Membrane
❑ Electrodes (Anode & Cathode)
❑ Membrane Electrode Assembly (MEA)
❑ Gas Diffusion Layer (GDL) / Microporous
Layer (MPL) / Backing Layer
❑ Bipolar Plates / End Plates
❑ Flow Channels
❑ Single or Unit Fuel Cell
❑ Fuel Cells Stack
Components of Fuel Cells
Electrolyte membrane
❑ The electrolyte has three main functions in a fuel
cell; to conduct ions, act as an electric insulator
and physically separate the anode and cathode
reactants.
❑ Separates the two electrode reactions
❑ Prevents the mix up of reactants
❑ Allows the treatment of reactions as separate processes–
no mixed kinetics
❑ Ions have to pass through the membrane to
maintain charge equilibrium between the anode
and cathode.
❑ As the abbreviation PEMFC implies, a proton
conducting polymer member is used as the
electrolyte in this fuel cell type.
Electrolyte membrane
❑ The membrane remain hydrated in order to be
proton conductive, which makes water
management a central issue in PEMFC
development. The requirement to keep the
membrane hydrated also restricts the operation
of the cell to temperatures under the boiling
point of water.
❑ The benefits of a thin solid electrolyte include
high power density and the lack of corrosion and
stability problems of liquid electrolytes.
❑ Membrane thickness ranges from ∼10–250 μm,
e.g. 18 μm for Gore 18 and 175 μm for Nafion®
117.
PEM Requirements
❑ High ionic conductivity (and zero electronic
conductivity)
❑ Good chemical stability in oxidizing and
reducing environments
❑ Good thermal stability in operating range –
Temperature and Relative Humidity
❑ Good mechanical strength - resistance to
swelling
❑ Low porosity – effective barrier to gases (cross
over)
❑ Easy scale-up and ready availability
 Early PEM Development
❑ During 1962–1965, GE developed partially
sulfonated polystyrene sulfonic acid membranes
(prepared by dissolving polystyrene sulfonic acid in
ethanol stabilized chloroform followed by sulfonation
at room temperature). Used in NASA’s Gemini space
shuttle programme. However, this membrane
exhibited brittleness in the dry state.
❑ In the late sixties, cross-linked polystyrene-
divinylbenzene sulfonic acid membrane/polymer
was prepared in an inert matrix by GE. The life of the
membrane ranged from 1000 to 10,000 h.
❑ In 1970s, DuPont developed a perfluorosulfonic acid
called “Nafion®” that not only showed a two-fold
increase in the specific conductivity of the membrane
but also extended the lifetime.
Early PEM Development

Grubb and Neidrach at GE Russell Hodgdon at GE

Early PEMFC ~ 1963 Early PEM ~ 1965

Nafion was developed by Dr. Walther Grot at DuPont in the late

1960’s prepared by modifying Teflon®.
Electrolyte membrane
❑ Nafion® has a backbone structure of
polytetrafluoroethylene (PTFE, known by the
trade name Teflon), which provides membrane
with physical strength. The sulfonic acid
functional groups in Nafion® provide charge sites
for proton transport.

❑ Other perfluorinated polymer materials are also

adopted for PEM fuel cell applications such as:
❑ Neosepta-F (Tokuyama)
❑ Gore-Select (W.L. Gore and Associates, Inc.)
❑ Flemion (Asahi Glass Company)
❑ Asiplex (Asahi Chemical Industry).
Development of PFSA Backbones

PTFE backbone with perfluorovinyl ether pendant

chains with sulfonic acid groups at the end
Structure of Nafion
❑ Hydrophobic region – Teflon-like backbone chains,
side chains
❑ Hydrophilic regions – sulfonic acid moieties +
attached water + counter ions
❑ these regions come together to form aggregates of ~30-
50 nm in diameter.

Chemical structure of Nafion

Structure of Nafion

Excellent proton conductor (0.07-0.23 S cm-1 at 100% RH)

1 M H2SO4  = 0.08 S cm-1.

Nafion is stable in both oxidative and reductive environments.

Electrical conductivity of common solutions
 Nafion & Water content
❑ Dry membrane is characterized
by the presence of isolated
spherical ionic clusters
❑ As water is absorbed in the
membrane, its hydrophilic
domain size increases (swells in
water)
❑ As more water is absorbed in the
PFSA membrane, the cluster size
is connected to each other
through the water passage
❑ Water and hydrophilic solvents
can penetrate the membrane
through water channel and it can
also provide the passage of
protons (percolation).
Conductivity Mechanisms
Vehicular Grotthuss mechanism
mechanism
❑ Also called “hopping”
❑ Proton attached to mechanism
solvent (“vehicle”)
molecule – e.g. ❑ Stationary vehicles
H3O+ (only local motion)
❑ Proton “hops” from
vehicle to vehicle
❑ Moves at rate of
vehicular diffusion ❑ Always within H bond
environment
❑ Solvent reorientation –
❑ Net proton transport provides H+ pathway
– governed by
vehicle diffusion ❑ Continuous motion
rates
Thickness of Nafion membrane
❑ Nafion solution as well as membrane are
available commercially.
❑ Nafion115 and Nafion117 are widely used as fuel
cell membranes. The various important
nomenclature of the Nafion is given below.
❑ For example, Nafion115, the first two digits
multiplied by 100 gives the equivalent weight of
the polymer. For e.g. it will be 11x100=1100
g/mol.
❑ The remaining digit gives us the thickness of the
membrane in mil. One mill is 1000 part of an
inch. Thus, in this case, the thickness of the
Nafion115 membrane would be 5/1000 inch (or
around 127 micrometer).
Thickness of Nafion membrane

Typical
Membrane Basis Weight
Thickness Conductivity
Type (g/m2)
(microns) (S cm-1)

N112 51 100 0.16

N117 178 360 0.08

N1110 254 500 -

Respiratory System
 Respiratory System

The exchange of gases (O2 & CO2) between the alveoli & the blood
occurs by simple diffusion: O2 diffusing from the alveoli into the blood &
CO2 from the blood.
Gas Diffusion Layer (GDL)
❑ The thin catalyst layer is usually supported by a
thicker electrode layer referred to as gas diffusion
layer.
❑ A thicker gas diffusion layer provides increased
protection and mechanical strength for the catalyst
layer and enhanced reactant gas diffusion or
transport to reaction sites, but with increased ohmic
resistance.
❑ The GDL is made of sufficiently porous, electrically
conductive materials. The GDL is usually made of
carbon cloth or carbon paper coated with a mixture
of carbon black and PTFE.
❑ Since PTFE is hydrophobic, it can prevent the
electrode from flooding.
❑ Some popular brands are Toray, CARBEL and
SIGRACET.
Gas Diffusion Layer (GDL)
❑ The GDL provides electric contact between the electrode
and the flow field plate.The gas diffusion layer provides
uniform distribution of the reactant over the catalyst
layer. Moreover, it also helps to remove the reaction
products efficiently from the reaction sites. It captures
the electrons and transport them to the bipolar plate as
well as remove the water formed.
❑ The GDL are characterised by their thickness, the
presence of hydrophobic and hydrophilic regions, dry
resistance to flow and electric properties.
❑ Both the liquid and the gaseous phase coexist in the pore
system of the GDL, therefore, the GDL should have the
following properties. It should have
❑ excellent electrical conductivity
❑ optimum porosity, and
❑ Optimum wetting and de-wetting properties.
Properties of Carbon Paper
Properties of Toray Paper 30
Thickness (m) 110 microns
Bulk Density 0.40 g/cm3
Through-Plane Resistance
80
(mΩcm2)
Porosity 80%
Flexural Strength (GPa) 40
PTFE Treated Yes
Micro Porous Layer (MPL) No

Toray Carbon Paper

Toray Paper 30 - THP-H-030 - thickness of 110 m
Toray Paper 60 - TGP-H-060 190 m
Toray Paper 90 - TGP-H-090 - 280 m
Toray Paper 120 - TGP-H-120 - 370 m
Carbon Paper & Cloth

Scanning Electron Microscope images of (left) carbon paper

(Toray 060), and (right) carbon cloth (E-Tek).
 Electrodes
❑ The electro-catalysts have a central part in the fuel cell
and impact the efficiency, durability, and cost of the cell to
a large extent.
❑ All electrochemical reaction takes place on the electrode
surfaces. Low operating temperature and low pH makes
the use of catalysts necessary, especially oxygen
reduction reaction on the cathode is very slow in the
absence of noble metal catalysts.
❑ Platinum is used as an active catalyst for H2 electro-
oxidation at anode and also for oxygen electro-reduction
at cathode of PEMFC.
❑ The use of bulk platinum (e.g. Pt-sheet or foil) neither
yields good performance of the PEMFC nor it is economical
due to low surface area per unit weight of platinum. In
order to increase the surface area per unit weight, the
nanoscale Pt particles are dispersed on supporting
materials.
Electrocatalysts

❑ H2-PEM fuel cells adopt Pt as anode and cathode

catalyst.
❑ In order to reduce the cost, platinum alloys are
considered as a plausible alternative.
❑ Ru, W, Sn , Os, Pd , Co, Ir, Mn, Cr, Au, Ag, Rh, in
the form of binary and ternary alloys were
investigated as anode material.
❑ Binary alloys of Pt-Cu, Pt-Co, Pt-Ni and Pt-Cr were
investigated as alternative oxygen reduction
catalyst to Pt.
Basic Pt-based heterogeneous electrocatalyst approaches

Mark Debe, Nature 486 (2012) 43–51

 Aspect Ratio of Carbon Materials

Because of their smaller

diameter, CNTs typically
have a higher length-to-
diameter ratio.

CNTs are high aspect

ratio materials, with
lengths typically ˃100
times diameter or even
higher.

Their application and

performance depends
not only on aspect ratio,
but also on the
dimensions and degree
of defects in the tubes.
High aspect ratio
(length-to-diameter ratio)
 Aspect Ratio
A high aspect
ratio wing is
a wing that is
long and
narrow. A low
aspect ratio
wing is a
short and
wide wing

Common aspect ratios for

different video uses
Different Shapes of Pd Nanocrystals

Pd nanocrystals were
synthesized in a variety
of shapes, which can be
divided into five groups
according to the types of
facets exposed on the
surface.

Palladium nanocrystals with different shapes reported in literature.

Zhang et al. Acc. Chem. Res 46 (2013) 1783

SEM Images of Nanostructured Materials

Scientific Reports 3 (2013) 1526 J Colloid Interf. Sci. 367 (2012) 342

Angew. Chem. Int. Ed. 49 (2010) 4962 J. Phys. Chem. C 113 (2009) 7200
Structural Dependence of Activity

Anodic polarization curves for the oxygen reduction reaction (ORR) on

Pd cubes and octahedra supported on carbon black in 0.1 M HClO4.
Shao et al. Chem. Commun. 47 (2011) 6566
Catalyst Support
❑ In order to achieve fine dispersion, high utilization and stable metallic
particles, catalyst-supporting strategies have been explored.

❑ Compared to bulk metal catalysts, supported catalysts show higher

activity and stability.

❑ Carbon is used as catalyst supports because of their relative stability

in both acidic and basic media, good electric conductivity and high
specific surface area.

❑ Several carbon materials have been tested as catalyst supports for

fuel cells. Carbon material has a strong influence on the properties of
supported noble metal catalysts, such as metal particle size,
morphology, size distribution, alloyed degree, stability and
dispersion.
Support Surface area
Vulcan XC-72R 237 m2 g-1
Ketjen black 800 m2 g-1
Black pearls 2000 475 m2 g-1
Denka Black 65 m2 g-1
Vulcan Carbon

(a) Scanning Electron Microscope (SEM) and Transmission Electron

Microscopy (TEM) images of Vulcan.
 Platinum on Vulcan Carbon

(a) Transmission Electron Microscopy (TEM). and (b) Scanning Electron

Microscope (SEM) images of Platinum on Vulcan (Pt/C).
 Carbon Nanotubes (CNTs)

SEM micrograph of CNT

TEM Images: Carbon nanotube with

various layer numbers: (a) single
walled carbon nanotube, (b) double
wall carbon nanotube, (c) triple wall
carbon nanotube, and (d) quadruple
wall carbon nanotube.
Other Carbon Support
❑ Ordered mesoporous carbon
❑ Carbon gels
❑ Carbon nanotubes (CNT)
❑ Carbon nanofibers
❑ Graphene
❑ Boron doped diamond
 Ordered Mesoporous Carbon

(a–d) SEM images of the ordered mesoporous carbon

nanospheres prepared by hydrothermal method.

Ref. Advanced Materials

DOI: 10.1002/adma.202004654
Non-Carbon Support
Polymer based catalyst support
❑ Conducting polymer (CP) such as
❑ polyaniline (PAni)
❑ polypyrrole (PPy)
❑ polythiophene (PTh)
❑ and their derivatives fulfill the requirements of a suitable fuel
cell catalyst support

Ceramic based catalyst support

❑ Metal oxides: SnO2, WO3, RuO2, ZrO2, SiO2, In2O3, TiO2,
Titania nanotubes
❑ Metal carbides: SiC, B4C, WC
 PEMFC with Different Layers

Schematic of a PEMFC showing the different layers, their compositions, and

reactant transport pathways. Black structures indicate carbon support, purple
the ionomer, red the PTFE, and green the catalysts.

Advanced Energy Materials,

DOI: (10.1002/aenm.202101025)
Membrane Electrode Assembly (MEA)
❑ The MEA consists of a membrane and two electrodes (anode
and cathode), one on each side.
❑ In order to be able to catalyse the cell reactions, the catalyst
particles are to be located in such a way that they form a
there-phase boundary. Catalyst particles must be in contact
with both electronic and protonic conductors. Passage must
be left for reactants to reach the catalyst sites as well as
passages for reaction products to exit. An essential goal in
electrode developments is thus to maximise the utilisation of
catalysts.
❑ There are two approaches to apply the catalyst layer for the
MEA fabrication. One is the combination of the catalyst layer
and the gas diffusion layer that forms an electrode. Another
is coating catalyst layer on the surface of polymer electrolyte
membrane (a polymer electrolyte membrane is sandwiched
between two electrodes) which is also referred as catalyst-
coated membranes (CCMs). The CCM is then sandwiched
between 2 GDL’s.
Fuel Cell Reactant Flow
Membrane Electrode Assembly
Porous Gas Diffusion
Layer
Teflonised Carbon
Particle

Porous Catalyst Layer

Active Catalyst Particle
Bipolar / Inactive Catalyst Particle
End plates Ionomer Strand
Carbon Support

Carbon cloth
microporous
layer
Catalyst layer

Polymer electrolyte membrane

Triple Phase Boundary (TPB)
The TPB concept holds that
the hydrogen oxidation
reaction (HOR) and the
oxygen reduction reaction
(ORR) can only occur at
confined spatial sites, called
‘‘triple phase boundaries’’
where electrolyte, gas, and
electrically connected
catalyst regions contact. A simplified schematic diagram of the
electrode/electrolyte interface
in a fuel cell, illustrating the TPB
On the technology side, reaction zones where the catalytically
efforts to increase the active electrode particles, electrolyte
amount of TPB in phase, and gas pores intersect.
fuel cells by using
nanostructured catalyst
layers have Ref: Journal of The Electrochemical
proven highly successful. Society, 152 (2005) A439-A444.
Membrane Electrode Assembly (MEA)
Commercial MEA