CHEE 470

Fuel Cells Lecture

Outline
1. Definition
2. Principles of Operation
3. Components of a Single Fuel Cell
4. Fuel Cell Stack and System Components
5. Types of Fuel Cells
6. Fuel-Oxidant Combinations
7. Fuel Cell Performance
8. Fuel Cell Efficiencies
9. Applications
10. Direct Methanol Fuel Cells (DMFCs)
11. Direct Methanol Fuel Impurities
12. Methanol as a Direct Feed to Fuel Cells Issues

Purpose
A tidy and linear overview of fuel cell science and technology,
which leads to a discussion of the issues arising in developing an approach
to providing high purity methanol as a direct fuel cell feed.

Definition
Galvanic cells are devices which convert the intrinsic chemical free
energy of a fuel directly into direct-current electrical energy in a continuous
catalytic process.
Fuel cells are steady-state reactors to which reactants are continuously
supplied and from which products are continuously withdrawn
The fuel cell itself should not itself undergo change; that is, unlike the electrodes of
a battery, its electrodes ideally remain invariant.

1.1 Batteries
As so-called Primary cells, batteries are unsteady-state devices containing initial
fixed amounts of reactants
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Secondary cells function as galvanic cells in use and are regenerated by

reversing the cell reaction through the addition of electrical energy
- a lead-acid automotive battery is a series-connected device

1.2 Electrolytic cells

Electrochemical cells in which chemical reactions are forced by the application of
electrical energy

Principle of operation
An ionic mechanism produces and consumes electrons at two isolated
phases of the cell the electrodes.
The electrochemical reaction occurs at the interface between the
electrodes and an electrolyte the third essential phase in an
electrochemical cell.
Electrocatalysis drives the power generation process.
A transfer of charge occurs by the flow of the electrons between the
electrodes through an external circuit.

2.1 Electrodes are good electron conductors

An electrochemical cell may be considered to consist of two half cells
- each is associated with one of the cell electrode reactions

2.1.1 Anode
the electrode at which an electron-producing ionic reaction dominates
M M e

the electrode potential, anode, ascribed to this reaction is referred to as

the oxidation potential

2.1.2 Cathode
the electrode at which an electron-consuming ionic reaction dominates
N e N

the electrode potential, cathode, ascribed to this reaction is referred to as

the reduction potential

2.1.3 Cell potential

The magnitude of the potentials in each of the half cells is quite arbitrary
It is the difference between the potentials the cell potential which
drives the flow of current.
For a galvanic cell cathode anode positive
- the cathode is positive with respect to the anode
The direction of electron flow in the external circuit is always from anode
to cathode.
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Both oxidation and reduction reactions occur at an electrode, even if one

direction dominates when a net current is produced.
When the electrodes exist at thermodynamic (internal) equilibrium, and
when the cell and the external circuit are in equilibrium, so that there is
no net current flow, the electrodes are at their reversible potential, and
the potential difference between them is the electromotive force (emf) of
the cell.
To produce a net current flow, the electrodes are moved away from their
reversible potentials
- the extent to which the electrodes become polarized away from their
respective reversible potentials is referred to as their overpolarization.
The cell potential when current is drawn is the cell voltage.
The cell potential when the external current is zero, but the electrodes are
not in the thermodynamic equilibrium condition is referred to as the open
circuit voltage.

2.2 Electrolyte
Internal charge transfer by ionic conduction is needed to complete the
circuit
Electrolytes need to be poor electronic conductors in order to avoid internal
short-circuiting
Depending upon the electrolyte, either:
protons are produced by reaction at the catalytic anode-electrolyte
interface; or,
oxide ions are produced by reaction at the catalytic cathode-electrolyte
interface
These are transported through an ion-conducting but electronically insulating
electrolyte to combine with oxide or protons at the other electrode to generate water
and electric power.
The electrolyte must limit the crossover of fuel from the anode to the cathode in
order to avoid creating mixed potential
- that is, some electrochemical oxidation of fuel competes with oxygen reduction at
the cathode, and as a consequence the cathode potential is drawn towards the
equilibrium oxidation potential, reducing the cell potential difference.

2.3 Electrocatalysis
Charge moving across the electrode/electrolyte interface must overcome an
activation energy barrier.
This is accomplished by the overpolarization of the electrodes.
The degree of activation polarization required is determined by the activity
of the catalyst.
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2.3.1 Generic requirements of hetereogeneous catalysts

(e.g.,) a large number of sites
high intrinsic activity (turnover frequency)
chemical stability
cost and quality of manufacture

2.3.2 Specific requirements

porous catalytic materials with high surface areas
- to ensure a large contact area between electrolyte and gas
good electrochemical contact with the membrane to ensure low resistance
to the interfacial transport of charge.
high electrical conductivity
- to minimize resistive losses in the layer
2.4

The H2/O2 Cell

The conduction or, carrier - ion is the hydrogen ion, produced from hydrogen
at the anode and consumed to give water at the cathode.
R

Anode

Cathode

H2 2e-+ 2H+

+ 2e-

Proton flow
.

2.4.1 Anode:

H2O
2H+ + O2

Membran
e

The fuel hydrogen is catalytically oxidized into electrons and protons.

H 2 2 H 2e

When operating on pure hydrogen, the anode stays at a potential close to the
theoretical reversible potential of a hydrogen electrode of zero
- indicative of the hydrogen oxidation being a kinetically facile reaction
- a low activation reaction

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By convention, the standard hydrogen electrode is assigned a potential

of zero. The hydrogen electrode is said to have zero overpotential

2.4.2 Cathode:
Oxygen is reduced to oxide species in a series of complex reactions
taking place at the catalyst layer
1
O2 2 H 2 e H 2 O
2

The oxygen reduction reaction requires the breaking of a double bond with
transfer of four electrons per molecule in a complex series of reactions.
As an activated reaction, high overpotential contributes to the losses in
fuel cell voltage at a given current in low-temperature fuel cells
In high-temperature systems, oxygen reduction contributions to voltage
efficiency losses are less significant, since the reaction rate increases with
temperature.

2.4.3 Net Reaction:

H2 g

1
O2 g H 2 O l
2

Components of a single fuel cell

flow field plate and gas porous

anode substrate
electrolyt
e

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thin gas porous catalyst

layer

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3.1 Electrode materials

The type of electrolyte employed strongly influences electrode material and
structure requirements
- (e.g.,) corrosion effects, interfacial phenomena
Carbon fibre papers or woven cloths may serve as substrate materials

3.2 Catalyst materials

3.2.1 Noble metals
Platinum affords excellent activity and stability
catalyst loading of platinum minimized
- supported catalyst technology employed in gas phase kinetics adopted
- (e.g.,) highly dispersed particles in specialized carbon substrates
highly susceptible to poisoning by carbon monoxide

3.2.2 Other materials

Nickel alloys is a good anode material for hydrogen
- nickel oxide cathode
Specialized carbon materials and structures
solid oxide materials are employed in cells operating at high temperature
(~ 1000C)

3.3 Electrolyte
Anisotropic structures
- solid/solid or molten liquid /solid

3.4 Cell internal impedance

Ohmic losses occur during transport of electrons and ions (protons)
Electrolyte materials, structures and thickness chosen to balance high
conductivity against low porosity

3.4.1 Geometry and resistance

The electrode substrate layer is designed to balance achieving low ohmic
losses high land area in contact with the catalyst layer - against
achieving effective fuel distribution through having a high open area
Thin catalyst layers in good ionic contact with thin electrolyte sections

3.5 Mass transfer effects

Macroscopic flooding of the electrode at which the product water is
formed, or of the anode when a liquid fuel is used, must be avoided.
Blocking of gas access to the catalyst pores by water droplets can lead to
reduced oxygen partial pressure, due to nitrogen blanketing, when air is the
oxidant
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Composites structures impregnated with Telfon may be used for

controlled wetting of electrodes

Fuel cell stack and system components

Planar stack design generally favoured
- mechanical stability and sealing
- minimization of the contribution of stack components to ohmic losses
Tubular bundle configuration may be employed with a solid electrolyte

4.1 Membrane Exchange Assembly (MEA)

Catalysts form thin (several microns to several tens of microns) gas-porous
layers on either side of a membrane electrolyte to create a compact cell
core
- ionomer coating of the electrodes may be employed to enhance ionic
contact with the MEA
- applied (for example) by hot-pressing techniques

4.2 Bipolar plates

The substrate layer may be linked to adjacent cells of a stack
High conductivity balanced against gas access
Machined flow fields with high large-scale porosity
- (e.g.,) Serpentine flow channels
Gas distribution design must account for two-phase flow
- at the anode when water is added for humidification of membrane
electrolytes
- at the cathode for product water removal
Graphite-based materials are expensive
Corrosion resistance is a concern with metallic plates

4.3 Heat management

Closed-loop circulation of fuel or antioxidant flows in excess of the
stoichiometric requirements may be employed for cooling
Endothermic fuel reforming chemical reactions may provide a heat sink for
removal of heat generated by the exothermic electrochemical reactions
within the cell
Cooling plates may be employed between bipolar plates in high power
output stacks
Cooling jackets or air cooling may be employed
The heat generated can be used in cogeneration heating
- offering enhanced overall process efficiency
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(and the generated water may be useful)

4.4 Other stack components

4.4.1 Current collector plates
4.4.2 End plates

Fuel Cell types

Fuel cells are classified by the nature of the electrolyte
- as this defines chemical environment
The other significant feature defining fuel cell classification is the temperature
of operation

Table 1 Currently Developed Types of Fuel Cells

Fuel Cell

Acronym

Temp.
range
(C)

Alkaline

AFC

H 2 2OH 2 H 2 O 2e

Solid
Polymer

SPFC,

60
90
70
90

PAFC

~220

H 2 2H

MCFC

~650

2
H 2 CO
H 2 O CO 2 2e
3

SOFC

~1000

H2 O
H 2 O 2e

PEMFC

Phosphoric
acid
Molten
Carbonate
Solid Oxide

Anode Reaction
(1)

H 2 2H

2e

2e

Cathode Reaction
(1)
1

O 2 H 2 O 2e

2OH

1 O 2H 2e H O
2
2 2

1 O 2H 2e H O
2
2 2
1 O CO 2e CO2
2
3
2 2
1 O 2e O2
2 2

Notes:
(1) The charge carrier in the case of each of the fuel cell types is shown in bold
letters.
(2) Proton Exchange Membrane Fuel Cell

5.1. Sulphuric acid

- Groves experiments (1842)
Two platinum electrodes were half-way submerged into a beaker of
sulphuric acid
Two tubes containing hydrogen and oxygen gas, respectively, were inverted
and lowered over each of the electrodes
the gases displaced the electrolyte
- leaving only a thin film
flow of electrons between the electrodes indicated by galvanometer
deflection
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after the initial deflection, the current decreased the reaction rate could be
restored by recreating the electrolyte layer
- thin enough to allow gas to diffuse to the solid electrode
Shell employed sulphuric acid in their experiments on Direct Methanol Fuel
Cells (DMFC) in the 1960s
- when they were looking for an inexpensive, less complex alternative to
their demonstration hydrogen-air system

5.2.

Strong alkalis (NaOH, KOH)

absorption of carbon dioxide reduces electrolyte conductivity
used in space program Apollo - with cryogenic hydrogen and oxygen
- operating at 260C, with sintered nickel oxide cathodes
allowed the use of electrode materials besides noble metals (platinum)
The space shuttle orbiter: PTFE-bonded low-loading platinum-based electrodes and
graphite intercell separator plates.

5.3. Molten phosphoric acid

Developed to use natural gas
- steam reformed to produce hydrogen
Higher temperature of operation chosen to:
- assist the removal of carbon monoxide produced in the reforming
operation
- improve heat management by meeting the heat requirements of the
endothermic reforming reaction by burning excess fuel from the anode
reaction
Held in some form of matrix
- solidification at 45C

5.4. Molten Bases

Mixture of alkali carbonates
- typically Li2CO3 and K2CO3
Sealing of the two gas compartments from each other by using nanoporous
materials with tightly controlled pore size
Operate on CO as a fuel
Nickel-based anode catalyst allows direct internal processing of fuels such
as natural gas
High temperature corrosion a concern

5.5. Solid Oxides

Entirely solid-state design
Tube bundle design attempts to deal with sealing problems associated with the
conventional planar design
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Choice of materials governed by thermal stress and corrosion resistance requirements

5.6. Solid polymer electrolyte

A membrane electrolyte must form a sound electronic insulator and gas
barrier, while allowing rapid proton transport
Nafion displays high dimensional stability and chemical inertness
It consists of a Polytetrafluoroethylene (PTFE) backbone with a
perfluorinated vinyl polyether ether side chain
- attached via oxygen atoms
|
OCF2CF2SO3H
The sulphonic acid groups at the end of the side chain impart the cation
exchange functionality to the polymer
The membrane relies on the presence of liquid water for effective proton
conduction
- this limits the temperature of operation
vehicle (H3O+) mechanism of proton transport proposed
- other principal mechanisms involve reorganization of the proton
environment to create uninterrupted pathways for proton migration
Proton conductivity versus fuel permeability becomes the key concern in
material selection
The current high cost of Nafion is a barrier to its commercial use

6. Fuel-oxidant combinations
6.1. Oxidants
Oxygen from air for economic reasons
or as a cryogenic liquid for example, for use in space craft

6.1.1. oxidant utilization

the Utilization factor is usually in the range of 50 to 60%

6.2. Fuels
6.2.1. Hydrogen
Hydrogen fuel is generated from fuels such as natural gas, propane,
methanol, or other petroleum products
In the high-temperature cells, internal steam reforming of simple
hydrocarbons and alcohols for example, methane and methanol can
take place by the injection of the fuel with steam.

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Typically reformed gas contains approximately 80% hydrogen, 20%

carbon dioxide
CO consumed directly via the internal water-gas shift process
Storage technologies: high pressure gas; cryogenic liquid; metal hydride
matrix
Practical hydrogen-bearing fuels which have reactivities in lowtemperature cells provided that suitable anode catalysts are used include:
hydrocarbons << ammonia < methanol << hydrazine < hydrogen
Indirect methanol fuel
- reforming to hydrogen, carbon dioxide and carbon monoxide takes place
at 250C

6.2.2.

Renewable fuel sources

water electrolysis, biomass

6.2.3. High Temperature Fuel Cell direct fuel options

hydrogen, carbon monoxide, small hydrocarbons gas mixtures
- off-process gas streams?

6.2.4. Low temperature fuel cell Direct methanol fuel

Liquid fuel methanol water mixture and air

7. Fuel cell performance

7.1. Energy generation by electrochemical reaction
Electrical work is done by charge moving in an electric field.
When a differential quantity of electricity dq is transferred between two
points between which the electrical potential difference is , the work done
is expressed in differential form as:
dWe dq

in terms of the cell voltage V cathode anode

dWe V dq

When the charge transfer is due to electrochemical reaction, then dq is the

electronic charge transferred between the terminals via the external circuit
per dni mole of component i produced.
By Faradays Law, a given amount of electricity is always produced by, or
would produce, the same amount of chemical reaction.
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The amount of electricity associated with one chemical equivalent of

reaction is equal to 96, 519 coulombs, the Faraday, .
dq Nd
dn
d i

where
i stoichometric coefficient of i in the overall cell reaction

The rate at which charge is transferred under the influence of the cell
voltage determines the power output of the cell.
That is:
where
circuit

Power = V I
I is the measured current through the external

The DC power produced is either applied directly to a DC load or converted

to AC power by an inverter

7.2. Electromotive Force (EMF) of a fuel cell

When the electrochemical reaction is carried out within the fuel cell
reversibly, the energy available for work is at its maximum.
Practical reversibility can be accomplished in electrochemical systems by
the Compensation Method for measuring the voltage of a cell without
drawing current from it
Rshunt

Vshunt

N
Rcell

Vcell

The terminal voltage of the cell is balanced by an opposing external voltage

to create a state of external equilibrium.
The terminal voltage is equal to the open-circuit voltage of the cell.
When a cell is displaced from a state of internal equilibrium by an
infinitesimal amount, in a way that the external and internal equilibrium
states are maintained, then the process may be considered for all practical
purposes to have taken place reversibly.
The characteristic cell voltage under conditions where internal and external
equilibrium exist is called the electromotive force (emf).
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The reversible electrical work done by an electrochemical cell, or the

available free energy, is given by the product of the emf of the cell and the
amount of electricity flowing through it
dWe , rev E mf dq

application of the First and Second Laws of Thermodynamics leads to the

result
G nFE r

The maximum net work obtainable from the cell is given by the free energy
at unit activity:
G 0 nFE r0
where :
G 0 standard free energy change
E r0 standard emf of the reaction

Under the standard conditions, the oxidation of hydrogen electrochemical

reaction takes place with a free-energy change of
G0 = -237.3 kilojoules per mole of water
Since the formation of water involves two electrons, at 1 eV = 23.06
kcal/equivalent,
E r0 1.23 electronvo lts

At thermodynamic equilibrium (zero current) the effective reversible

potential should be 1.23 V.

7.3. Electrochemical kinetics

Whereas thermodynamic considerations describe the theoretical maximum
performance of an energy conversion device, kinetic considerations account
for the actual performance.
Current is produced from the reactants that reach the surface of the
electrode and lose and gain electrons. The net flux of reactants is the
difference between the rate of conversion of the reactants by the competing
oxidation and reduction reactions.
i = nF(jf jb) = n (Fkf[Ox]0 Fkb[Red]0)
When the electrodes are in equilibrium at their reverse potential and the
cell voltage is at its maximum voltage theoretically obtainable its emf the
forward and backward reactions are in balance.
The current density at this condition is the exchange current density.
In low-temperature fuel cells, in particular, because of the difficulties in
attaining internal equilibrium due to kinetic factors, the open-circuit voltage
is not in general equal to the emf.
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In a thermodynamic sense, irreversibilities have been introduced, degrading

the work that can be done by the cell through electrochemical conversion of
the fuel energy input.
Various factors contribute intrinsically to the open-circuit voltage not
reaching the theoretical value of the reversible cathode potential
At a net (nonzero) current, the cell will show further losses in cell voltage.
Cell voltage falls with increasing current per unit area
- due to the cumulative effects of irreversibilities
These irreversibilities differ in nature for different ranges of current.
At low load, kinetic effects result from chemical changes taking place which
do not produce current; that is, flow of electrons through the external circuit
Within the normal operating range of the cell, these chemical reactions are
dominated by the electrochemistry, the voltage current relationship reflects
the internal resistances of the cell.
At high loads, mass transfer effects take control.

7.3.1. Characteristic Performance Curve

The dashed line corresponds to the cell emf
- attained when internal and external equilibrium is attained
Vc is the open-circuit voltage
- measured when external equilibrium is attained

E0mf
0
Vc
mfthe
- V actual cell voltage is related to
The difference between the emf Eand
the irreversible heat generated
Voltag
7.4. Cell Performance Characteristics
e
Cell voltage

Current density: current divided by the superficial electrode area

perpendicular
to the current within the cell
Current
Power density - product of voltage and current density

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Fuel Cell

Temp.
C

Alkaline
70
Phosphoric 190
acid
Phosphoric 205
acid
Molten
650
carbonate
Solid oxide 1000
Notes: Internal reforming

Pressure
atm
(kPa)
1 (101)
1 (101)

Current
density
A/cm 2
0.2
0.324

Voltage
V

8 (808)

0.216

0.73

1 (101)

0.16

0.78

1 (101)

.2

0.66

0.8
0.62

7.5. Cell lifetime

Time at which output voltage at rated current has decreased by 10% of the initial
value
Factors affecting electrode lifetime
- platinum agglomeration and corrosion of carbon support

Fuel cell efficiencies

The efficiency of a fuel cell under a given load may be related simply to its
voltage output at that current density.
The open-circuit efficiency may be estimated from consideration of the
theoretical thermodynamic efficiency of the cell
and its intrinsic electrochemical efficiency, reflected by its open-circuit
voltage.
An overall system efficiency can be estimated through multiplication of
various system component efficiencies.

6.1 Fuel Cell efficiency

Basis: utilized hydrogen
- assuming all utilized hydrogen is converted into electricity
The rate of generation of electrical energy in the cell is given by VI
So that, the fuel cell efficiency, expressed by the ratio of the electrical
energy generation rate to the hydrogen consumption rate in the cell, is given
by:

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E FC

3.6 VI
M H U

where
M hydrogen flow rate in (mole / hr )
H hydrogen heating value (kJ / mole)
U hydrogen utilization factor at the anode

the output current is given by: I M U 2 26.81

so that E FC

192V
H

the Higher Heating Value of hydrogen is 285.84 kJ/mole

so that the fuel cell efficiency is given by E FC .675V

6.2 Thermodynamic efficiency

For most fuel-oxidant combinations, the maximum available free energy is
somewhat less than the heat of combustion.
For the oxidation of hydrogen, the heat of formation of H2O(l), under
standard conditions of temperature and pressure, 25C and 1 atm, is
-H0 = 286.0 kJ/mole, corresponding to -1.48 eV

G 0 lim Q R 237.3 kJ / mole

R

Lim Qc Qrev TS 0
R

the working cell has reversibly furnished heat to the environment

Qrev H 0 G 0 286.0 237.3 48.7 kJ / mole

the theoretical thermodynamic First Law efficiency is th

1.23
0.83
1.48

6.3 Electrochemical efficiency

The actual open circuit voltage is typically in the range of 0.9 to 1.1V.
At an open-circuit voltage of 1.0 V, the maximum Second Law
electrochemical efficiency is
el , max

We , actual
We , rev

1
0.80
1.23

Under open-circuit no load conditions, approximately two-thirds of the

chemical energy in the hydrogen is available to do electrical work.
In high-temperature systems, the major contribution to efficiency loss is
thermodynamic: the irreversible oxygen electrode losses diminish with the
increase in reaction rate. The available free energy decreases to a value
corresponding to about 1.0 V at 1000C, so that approximately two-thirds of
the chemical energy in the hydrogen is available to do electrical work.
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6.4 System efficiency

The overall plant efficiency of a fuel cell power generating system is given
by
ET E FP E FC E P
where
E FP fuel process efficiency
E P power efficiencies

Fuel Cell

(e.g ., ) HHV H 2 / HHV Methane

(e.g ., ) E inverter E Power Factor

Temp.
70
190

Cell
thermal
efficiency
54
42

System
thermal
efficiency
32
36

205

49

42

650

53

54

1000

45

45

Alkaline
Phosphoric
acid
Phosphoric
acid
Molten
carbonate
Solid oxide

Notes: Internal reforming

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6.5 Heat engine efficiencies

A fuel cell extracts the chemical energy electrochemically, converting it
directly to electricity rather than the intermediate form of heat, as is done in
the combustion process of a heat engine to which a rotating electrical
generator is coupled.
Chemical Energy of the
Fuels

Heat
Engine:

Electrochemical
reaction

Thermal Energy
Conversion

Electrical Energy
Conversion

Mechanical
Energy
Conversion

6.5.1 Generic heat engine cycle

Receives heat from a high-temperature source
Converts part of this heat to work
- (e.g.,) by a turbine
Rejects the remaining heat to a low-temperature sink
- (e.g.,) atmosphere, river)
Operates on a thermodynamic cycle
Steam power plant, for example, receives heat from an external
combustion chamber, extracts work by a turbine, and rejects heat to a
condenser

6.5.2 The maximum conversion efficiency

for any heat engine is that associated with the reversible Carnot Cycle
E Carnot 1

TLow
THigh

The state of the surroundings to which the reversible heat engine

discharges its heat is conventionally a temperature of 25C at atmospheric
pressure.
The heat engine has the potential to match the theoretical maximum fuel
cell thermodynamic efficiency of 83.% if it draws its heat from a high
temperature source (of work), which is available at a temperature of
1480K. At this temperature the maximum available energy in a fuel cell
process has dropped to a state having a Gibbs Free energy of 164.4
kJ/mole.
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At a temperature of 950K, the theoretical maximum thermodynamic

efficiencies of the heat engine and the fuel cell are equivalent.
Fuel cells are not limited by Carnot cycle efficiency

Applications
Fuel cells promise more power for less fuel
The economic potential is driven by demand for reliable, inexpensive,
environmentally sound energy sources.
Commercialization has moved from niche opportunities (e.g., alkaline cells
found application in the space program) to widespread application

Currently Developed Types of Fuel Cells

- after Gregor Hoogers, (ed.,) Fuel Cell Technology Handbook, CRC Press, 2002
Fuel Cell

Fuel

Electrolyte

Electric
Efficiency
(system) (%)

Power Range
and
Application

Alkaline

Pure H2

35 50% KOH

35 - 55

< 5 kW
military,
space

Proton
Exchange
Membrane

Pure H2

(e.g.,)
NAFION

35 - 45

Phosphoric acid

Pure H2

Concentrated
phosphoric acid

40

Molten
carbonate

H2, CO, CH4,

other
hydrocarbons

Lithium and
potassium
carbonate

> 50

Solid oxide

H2, CO, CH4,

other
hydrocarbons

Yttriumstabilized
zirconium
dioxide

Methanol

> 50

5 250 kW
portable, CHP,
transportation
200 kW
CHP

More Power
for less Fuel

200 kW-MW
CHP, gridindependent
power
2 kW MW
CHP, gridindependent
power

CHP: combined heat and power

generation

Direct Methanol Fuel Cell (DMFC)

8.1 Benefits
Liquid fuel
- high energy density per unit volume
Current distribution network

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direct electrochemical conversion alleviates the need for fuel processing

- methanol reforming

8.2 Operating principle

Methanol and water react stoichiometrically at the anode to form carbon
dioxide, protons and electrons
- multi-electron transfer to form carbon dioxide
Dilute methanol solution feed (<10%) due to the high solubility of methanol
in electrolyte materials
The thermodynamics of electro-oxidation of methanol compares favourably
compared with hydrogen electro-oxidation
- methanol should be oxidized spontaneously when the oxidation potential
of the anode exceeds 0.046V with respect to the reversible hydrogen
electrode (RHE)
- this implies a reversible cell potential of 1.18 V at 100% voltage efficiency,
independent of current density
Proton Exchange Membrane (PEM) favoured as the electrolyte
- acidic electrolyte rejects CO2
Low temperature operation
Platinum-based systems are the most effective anode and cathode catalysts

8.3 Technical limitations

8.3.1 Poor electrode kinetics
It is highly unlikely that the transfer of the six electrons involved in the
electro-oxidation of methanol will occur simultaneously to form stable
solution intermediates
- surface-absorbed species likely to partially cover the platinum catalyst
surface
kinetic limitations lead to large anode overpotentials
- cell voltage reduced by 400 to 600 mV at practical current densities
- strong focus on achieving higher electrocatalyst activity

8.3.2 Mass transport limitations

CO2 rejection through the liquid feed diffusing to the reactive zone of the
anode
- similar to the problem of rejection of the water of reaction and dilution at
the anode through the air feed
methanol crossover through the PEM
- mixed overpotentials at the cathode
- corruption of the cathode structure as methanol wets the hydrophobic
surface
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8.4 Methanol Purity Requirements

The published allowable limits for impurities in commodity methanol are not
directly applicable to fuel cell requirements.
Species that are quite harmless in normal applications of methanol limit the activity
of the fuel cell catalyst.
Some impurities will be ignored by the fuel cell.

8.4.1 Carbon monoxide

CO has been shown to have a dramatic effect on the performance of
H2/PEMFC cells
- reduction of the cell voltage by approximately 50% at a current density of
0.5 Acm-2 at concentrations as low as 10 ppm
CO binds strongly to platinum sites
- as an inert adsorbate at anode potentials
- electrochemical oxidation of CO is thermodynamically favourable, but
high overpotential required
Coverage at PEMFC operating temperatures is very high
- this drops dramatically with temperature
The number of sites available for H2 adsorption and oxidation is reduced

8.4.2 Carbon dioxide

Poisoning of Pt catalysts is modest compared with CO
The product of the electrochemical reverse water-gas shift reaction both
is CO
- similar to the gas phase reaction

8.4.3 Higher alcohols and Aldehydes

Ethanol and aldehydes are both electrochemical fuels

8.4.4 Nitrogen
diluent

8.4.5 Trace impurities

Sulphur, halogens, silicon compounds strongly influence Pt catalysts

Geoff Whitfield

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A set of specifications are tabulated in the Kirk-Othmer Encyclopedia of Chemical

Technology, 4th edition, Volume 16, page 554, for:
a) solvent grade A; b) hydrogen and carbon dioxide feedstock grade AA;
and, c) ASTM D1152.
The stated target fuel cell methanol requirements are compared with the ASTM
specifications in the Table below.
ASTM
carbon monoxide
Methane
Acetone + aldehydes
Acetone
Ethanol
Acidity
Water

Geoff Whitfield

wt %, max
wt %, max
wt %, max
wt %, max
wt %, max
wt %, max
wt %, max

0.003
0.003
0.01

Page 22

Fuel cell (ppm)

0.0001
0.005

1
50

0.001
0.01

10
100

2.0

23/05/2015