CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr.

Eld Gyenge

1.1-1.5

Chapter 1: Basic Concepts

Electrochemical processes can be classified as either electric power consuming (i.e.,
power sinks) or electric power generating (i.e., power sources or galvanic cells). The
first basic requirement for electrochemical power sources (batteries, fuel cells) is that
the electrochemical transformations taking place in the system must be
thermodynamically spontaneous, i.e., the Gibbs free energy of the power source
(Gcell) must be negative. In case of power sinks on the other hand, (e.g.,
electrosynthesis (inorganic and organic), electrodeposition of metals) the cell reaction
thermodynamically is not spontaneous, the Gibbs free energy is positive, hence, an
external dc electricity source is required to carry out the electrochemical reactions.

Anode:
Power Source
electrode where oxidation occurs Thermodynamically

Power Sink
Thermodynamically
not spontaneous system
Gcell > 0

spontaneous system
Gcell < 0

Cathode:
electrode where reduction occurs
occurs

(DC power supply)

Load
(+)

()

Electrolyte

Anode

R2 O2 + ne

()

Cathode

Electrolysis
Electrodeposition
Electrosynthesis

Ecell

()

Porous
Separator

(+)

Electrolyte

Anode

R2 O2 + ne

Ecell

R1 O1 + ne

(+)
R1 O1 + ne

Cathode

Batteries, Fuel Cells

Fig. 1.1 Conceptual representation of electrochemical systems.

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1.1-1.5

1.1 Thermodynamic considerations using Voltas pile as an example

A
V

Load
ad

Aerated salt water soaked in a porous material

(Note in Voltas days a cheese cloth or wood
bark was used. Now various porous polymeric
materials are employed as separators).

Zn: electrode
Ag (or Cu): + electrode
Chemical species: Zn, Ag, O2, N2, H2O, Na+, Cl
Fig. 1.2 Schematic diagram of Voltas pile comprised of two cells connected in series.
Features of Voltas pile:
1. Zn anode
2. O2 (or air) cathode
3. Separator (electronic insulator, ionic conductor)
4. Electrolyte (salt water)
5. Bipolar plate stacking to increase the cell voltage (observe how the two cells are
connected in series in Fig. 1.2).
Table 1.1 Potential electrochemical reactions involving chemical species present in
Voltas pile and the corresponding standard Gibbs free energies of reactions.
Nr.
1
2
3
4
5

Potential electrochemical reactions

Zn Zn2+ + 2e
1/2O2 + H2O + 2e 2OH
Ag Ag+ + e
Na+ + e Na
2Cl Cl2 + 2e

G0 (kJ) [at 298 K]

147.1
77.4
77.1
261.9
262.6

In Table 1.1 the standard Gibbs free energies for the reactions were calculated from
the tabulated standard Gibbs free energies of formation (fG0) of the chemical species
(Langes Handbook 15th edition Table 6.3). Elements in their most basic, natural, form
have fG0 = 0.

1.1-1.5

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

Based on Table 1.1 there is only one combination of two electrochemical reactions
(oxidation and reduction) that could lead to a thermodynamically spontaneous Volta pile
characterized by a very negative standard Gibbs free energy:
Anode (): Zn Zn2+ + 2e
Cathode (+): 1/2O2 + H2O + 2e 2OH
Volta cell: Zn + 1/2O2 + H2O Zn(OH)2
0
0
G0cell Goxid
Gred
G[01.1] G[01.2] 0 .

oxidation
reduction

(1.1)
(1.2)
(1.3)
(1.4)

G0cell = -147.1-77.4 = 224.5 kJ molZn-1.

Since G0cell < 0, it means thermodynamically SPONTANEOUS system. Thus,
theoretically, the combination of reactions (1.1) and (1.2) could function as an
electrochemical power source. Whether it is a practical system, it is a more complex
question and it depends on a number of factors such as rate of electrochemical reactions,
electrolyte employed, cell design and cost.
Based on thermodynamic considerations it can be shown that the Gibbs free energy of
the cell (for either standard G0cell or non-standard (actual) states Gcell) is equal to the
useful non pressure-volume work exerted or received by the system at equilibrium.

Gcell wcell thermo

(1.5)

For an electrochemical power source (Gcell < 0), eq. (1.5) means that the Gibbs free
energy of the cell is equal to the thermodynamic maximum electric work the system
could produce, wcell-thermo. The latter can never be achieved in practice since eq. (1.5)
implies an ideal reversible systems, where there is no net flow of electrons in either
direction, hence there is no net consumption of reactants. In other words eq. (1.5)
describes the electrochemical equilibrium case and in practice, when the cell is operating,
the generated electric work is always smaller than the thermodynamically determined
maximum value due to various losses that will be discussed in detail in upcoming
chapters. Thus, for a practical electrochemical power source the actual electric work
produced wcell is:

wcell wcell thermo .

(1.6)

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1.1-1.5

Note: for electric energy and work is common to use [Wh] or [kWh] as unit. 1 kWh =
3.6 MJ =3.6x106 J
For an electric power consuming cell Gcell > 0 (e.g., electrolysis reactor), the
reaction is NOT spontaneous, hence, electric work in the form of electric charge flow
needs to be provided to the reactor to carry out the reaction. In this case, eq. (1.5)
expresses the minimum electric work that has to be provided by the external power
supply in order to drive the electrochemical reactions. In practice, more work has to be
provided than that expressed by (1.5) in order to overcome the various losses in the
system:
wcell wcell thermo.

(1.7)

1.2 The electrochemical equilibrium

Consider the electrode interface where an electronic conductor (or in some cases a
semi-conductor) is in contact with an ionic conductor phase (e.g., liquid or solid
electrolyte). The chemical species from the ionic conductor phase can be in equilibrium
with the electrons or vacancies from the conduction band of the electronic conductor.
Thermodynamics dictates that at equilibrium the Gibbs free energy change across the
electrode interface (better referred to as the electrochemical Gibbs free energy change

across the electrode interface, G ) must be zero.

For any electrochemical (half-cell) reaction (see for example Table 1.1), separating
conceptually the electrons and the chemical species at the electrode interface, the general
stoichiometry can be written as:
ne s j M j j ;
z

(1.8)

electronic conductor (phase ) ionic conductor (electrolyte, phase ) .

Where: zj = 0, and/or, +, and/or

z s

j j

n .

(1.9)

n- nr. of electrons exchanged in the half-cell reaction, sj stoichiometric coefficient, zj

oxidation state. Mj symbolizes a chemical species. The electrode material itself might or
might not be a chemically active participant in the electrochemical reaction.

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1.1-1.5

Note: eq. (1.8) implicitly is written in the reduction direction, with the electrons on
the left-hand side. This means that sj is taken as negative if species j in the reaction
stoichiometry was on the electron side (i.e., reactant oxidized species) and positive if
species j in the reaction stoichiometry is situated on the opposite side vs. electrons
(product reduced species).
Under electrochemical equilibrium conditions there is no net flow of electrons at any
temperature. In other words, the rates of the half-cell oxidation and reduction reactions
are equal. Hence, the net electrode reaction rate is zero. Thermodynamically the
electrochemical equilibrium is defined as the Gibbs free energy change between phases
(electrolyte ionic conductor) and (electronic conductor) is zero:

G 0 s j f G j n f Ge ,

(1.10)

where f Ge is the Gibbs free energy of formation per mole of electron in the conduction
band, f G j is the Gibbs free energy of formation of the chemical species Mj involved in
the half-cell electrode reaction.
The Gibbs free energy of formation of the electrons (J mole--1) can be expressed in
terms of the equilibrium electrode potential Ee multiplied by the charges carried:
f Ge FEe

(1.11)

where Ee is the equilibrium electrode potential at any temperature the system is at, and F
is Faradays constant, expresses the charge carried by one mole of electrons (~96,500 C
mole--1). The negative sign in eq. (1.11) corresponds to the electron charge.
Note the units: [Joule] = [Coulomb] x [Volt].
Combining eqns. (1.10) and (1.11) for electrochemical equilibrium at any temperature
we obtain:

G s j f G j nFEe 0 ,

(1.12)

or
G s j f G j nFE e .
j

(1.13)

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

1.1-1.5

Eq. (1.13) is fundamental for electrochemical thermodynamics because it allows the

calculation of the equilibrium electrode potential from thermodynamic data with respect
to the free energy change of the reaction (G).
For the particular case when the activities of the chemical species are all equal to one,
(i.e. for ideal cases this means molar concentrations of 1 M and/or pressure = 1 bar (
1atm), see also further Chapter 2), eq. (1.13) becomes:
G 0 s j f G j nFE 0 .
0

(1.14)

E0 is the standard electrode potential at any temperature. In Chapter 2 the temperature

dependence of E0 is further discussed in detail.
Furthermore, it is of interest to note the thermodynamic relationship between the
equilibrium constant K and the standard potential E0 at any temperature, using the wellknown thermodynamic equation:
G0 RT ln K

E0

(1.15 I)

RT
ln K .
nF

(1.15 II)

Combining now two half-cell electrode reactions of general form (1.8) into a
stoichiometrically balanced cell reaction (i.e., n is the same for both half-cell reactions):
cathode

ne s j , c M j , c j ,
z

Gc nFEe,c

(1.16 I)

zj

Ga nFEe, a

(1.16 II)

ne s j , a M j , a

anode

----------------------------------[Cell] = [Cathode] [Anode]

0 s j ,c M j ,c
j

zj

s j,a M j,a j .
z

At any temperature, at equilibrium:

Gcell Gc Ga nFEe,cell

(1.16 III)

or similarly, under standard conditions (i.e. activities equal to one):

0
0
Gcell
Gc Ga nFEcell
.

(1.16 IV)

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CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

From eqns. (1.16 I) (1.16 IV) the cell potential at equilibrium under non-standard
(actual) conditions (Ee,cell) and under standard equilibrium conditions (E0cell) is expressed
as:
Ee,cell Ee, c Ee, a ,

(1.17 I)

E 0cell E 0c E 0 a .

(1.17 II)

At this point is important to note the IUPAC (International Union of Pure and
Applied Chemistry) electrochemical convention. Accordingly, the electrode reactions are
always considered in the reduction direction (i.e., with the electrons as reactants on the
left hand side of the stoichiometric equation), irrespective of the actual direction in an
electrochemical system. Thus, all the electrode potentials are expressed for reductions.
Ered Ecathode Ec ,

(cathode is the electrode where reduction occurs)

Eoxid Eanode Ea , (anode is the electrode where oxidation takes place).

(1.18 I)
(1.18 II)

From (1.16 III and 1.6 IV):

-

for electrochemical power sources (and galvanic corrosion): Ee,cell and E0cell > 0.

for electrolysis (power consuming systems): Ee,cell and E0cell < 0.

Standard electrode potentials E0 for inorganic and organic electrochemical reactions

are listed at 298 K in many databases such as Langes and CRC Handbook of Chemistry.
According to convention, E0 is given for the reduction direction (i.e., electrochemical
reactions are written with electrons on the left hand side).
For the H+/H2 redox couple E0 = 0 V at 298 K because G0 = 0 at 298 K, due to zero
standard Gibbs energies of formation for both H+ and H2 (see Langes Handbook 15th ed.
p. 6.93). Hence, the standard hydrogen electrode (SHE) is used as primary reference
electrode for measurement of the electrode potentials (see Chapter 2). Table 1.2 lists
selected standard electrode potentials for inorganic and organic reactions.

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1.1-1.5

Table 1.2 Selected standard electrode potentials at 298 K (source CRC Handbook
of Chemistry and Physics 75th ed. and Langes Handbook 15th ed.)
Electrochemical Reaction

E0 at 298 K (V vs. SHE)

Co3+ + 1e- Co2+

1.92

Ce4+ + 1e- Ce3+

1.72

N2O + 2H+ +2e- N2 + H2O

1.77

PbO2 +SO42- +4H+ + 2e- PbSO4 + 2H2O 1.69

O2 + 4H+ + 4e- 2H2O

1.23

2H+ + 2e- H2

O2 + H2O + 2e- HO2- + OH-

-0.076

CO2 + 2H+ +2e- HCOOH

-0.20

Ni(OH)2 + 2e- Ni + 2OH-

-0.72

Zn2+ + 2e- Zn

-0.76

Li+ + e- Li

-3.04

Example:
A) for O2 electroreduction under neutral or alkaline conditions, written under the
form of eq. (1.8):
2e 2OH - 1/2O2 - H2O.

(1.19)

Using eq. (1.14):

G0 2FEO0

/ OH

0
0
0
2 f GOH
1 / 2 f GO f GH O .
2
2

(1.20)

Substituting the Gibbs free energies of formation at 298 K in J mol-1 (e.g., data from
Langes Handbook 15th ed., Table 6.3):
2FEO0

EO0

/ OH

/ OH

2(157.28x103 ) 1/ 2 x0 (237.14 x103 ).

0.4 V vs. SHE (at 298 K).

B) The standard cell potential for Voltas battery at 298 K is calculated using eq.
(1.16 I) (1.16 IV).
() [anode]: Zn2+ + 2e Zn

o
GZn
147.1 kJ; E0a = 0.76 V vs. SHE
2
/ Zn

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

1.1-1.5

(+) [cathode]: 1/2O2 + H2O + 2e 2OH GOo

/ OH

77.4 kJ ; E0c = 0.40 V vs. SHE

Cell = [cathode] [anode]

Standard cell potential at 298 K:
E0cell = E0c E0a = 0.40-(-0.76) = 1.16 V.

(1.21)

1.3 The rate of electrochemical transformation and Faradays law

A fundamental question for electrochemical processes is the correlation between the
electric current and the consumption/production of chemical species. Faradays constant
expresses that 1 mol of e carries a charge of F = 96,500 Coulombs = 26.8 Ah.

F N A e 6.023x1023 1.6 x1019 96,488 C,

(1.22)

where NA is Avogadros number, and e is the elementary charge.

In other words, Faradays law states that 1 equivalent-gram of any species if undergoes
electrochemical transformation with 100% current efficiency, involves F = 96,500
Coulombs of charge.
Consider the general electrochemical stoichiometry given by eq. (1.8). The rate of
consumption or production of a species Mj in the electrode reaction normalized per
electrode area A, can be related to the current density across the electrode interface i, by:
rj

i
1 dn j
,

s j Adt nF

(1.23)

where nj is the number of moles of species Mj.

Note: the units for the reaction rate
[rj] = [mol m-2 s-1], just like for any heterogeneous reaction.
The current density i, in SI units is expressed in [A m-2] (where A Amperes).
However, units such as [mA cm-2] are also very common in the literature. The current
density is defined in terms of the current I, as:

I
.
A

A is the geometric electrode area, than i is referred to as the superficial current

(1.24)

If:

density;

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10

A is the electrocatalytically active area, than i is referred to as the real (or

actual or effective) current density. The electrocatalytically (or electrochemically)
active area can be determined using special techniques such as H2 underpotential
deposition and stripping, COad voltammetric stripping or Cu underpotential
deposition and stripping

By convention the following sign rules apply:

at the cathode, i and I < 0,

at the anode, i and I > 0.

For the cell (composed of the anode and cathode):

I cell I a I c .

(1.25)

Example:
For a 5 cm2 geometric area anode of the Volta pile, how much Zn is consumed to produce
100 mA cm-2 current density for 20 minutes?
Writing the anode reaction in terms of eq. (1.8) (see also Table 1.1):
2e Zn Zn2 ,

(1.26)

sZn = +1, sZn(2+) = -1, n = 2.

From eq. (1.24):
rZn

dnZn
i
.

(1) Adt 2 F

(1.27)

Since it is an anode: i > 0, Zn is consumed thus, dnZn < 0.

Substituting the numerical values, gives a Zn consumption of: 0.2 g.
Example:
For a 5 cm2 geometric Ag cathode area of the Volta pile, how much O2 is consumed and
how much hydroxide is produced when the cell operates at 100 mA cm-2 current density
for 20 minutes?
Based on eq. (1.22): sO2 = -1/2, sOH(-) = 2, n = 2

rO2

dnO2
(1/ 2) Adt

i
.
2F

(1.28)

Since it is a cathode: i < 0, and O2 is consumed thus, dnO2 < 0.

rOH

dnOH
(2) Adt

i
.
2F

(1.29)

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1.1-1.5

11

At the cathode: i < 0, and OH is produced thus, dnOH(-) >0.

Substituting the numerical values gives: 1.55x10-3 mole O2 consumed and 6.22x10-3
mole OH produced.
In cases when more than one electrochemical reaction can occur at the same
electrode, the current efficiency must be taken into account. The current efficiency
indicates the fraction of the total current consumed by a particular electrochemical
reaction.

ik k i,

(1.30)

where ik is the current density corresponding to reaction k occurring at the electrode

surface, k is the current efficiency for reaction k (0 k 1) and I is the total current
density at a particular electrode (anode or cathode).

i ik ,

(1.31)

Therefore,

1.

(1.32)

For virtually all practical electrolysis systems the current efficiency for the main (or
desired) electrode reaction is below 100%. During electrolysis in aqueous solutions at the
cathode, the electrochemical generation of H2 is a ubiquitous secondary reaction
competing with the main (or principal) reaction. Similarly, during electrolysis in aqueous
solutions at the anode oxygen evolution is a common secondary reaction.
As an example, during electrodeposition of Cu from aqueous acidic solutions, at the
cathode (negative electrode in this case) the following reactions can take place: 1.
electroreduction of Cu2+, 2. evolution of H2,(g) from the hydronium ions in the acidic
solution, and 3. reduction of dissolved O2. Thus, k in eq. (1.31), (1.32) is k =1, 2, 3.
1. Cu2+ + 2e Cu
2. 2H+ + 2e H2,(g)
3. O2 + 2e +2H+ H2O
In case of efficient Cu electrodeposition plants the current efficiency for Cu deposition
(option 1, main reaction) is typically between 90-95% (i.e., 1 = 0.9 0.95). The current
efficiency is a function of a large number of factors that must be engineered for optimal

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1.1-1.5

12

performance such as electrolyte composition, hydrodynamics, electrode and cell design.

The total current density is expressed as the sum of the partial current densities for each
reaction. In case of Cu electrodeposition:
i i1 i2 i3 .

(1.33)

Including the current efficiency the general rate equation is expressed as:
rj

1 dn j k i
.

s j Adt nF

(1.34)

Integrating eq. (1.34) with I = const. (galvanostatic condition):

n j n j ,0 n j

sj
nF

iA k dt .

(1.35)

Assuming k = const. over time (which is not always the case because due to electrode
fouling and under factors, the current efficiency is likely to change over time), eq. (1.35)
can be easily integrated, generating in essence the mathematical form of Faradays law:
n j

sj
nF

k iA t.

(1.36)

Note index k refers to a particular reaction on the surface which involves a number of
species j.
If the concentration is expressed instead of moles,
C j

sj
nF

ki

s
A
t j k i as t ,
V
nF

(1.37)

where as - specific surface area of the electrode, it is the area per volume of the electrodic
compartment (either anodic or cathodic compartment) or total cell volume, depending
where the concentration of species j is defined:

as

A
.
V

(1.38)

In order to increase the conversion of species j, it follows from eq. (1.37) that as
should be increased. Therefore, porous electrodes have been introduced with specific
surface areas between 100 to 20,000 m2 m3. Porous electrodes can have various
configurations such as bed of particles, metal meshes, fibrous materials. Fig. 1.3 presents
the diagram of an electrochemical cell equipped with a porous cathode.

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

1.1-1.5

Ecell

anode

Fig. 1.3 Schematic of a divided electrochemical cell

(reactor) equipped with a porous cathode. O
indicates oxidized species which are reactants at the
cathode; R indicates reduced species which are the
products at the cathode. The anode could have
either a separate line of reactants or products or it
could be fed from the cathode side with the same
species. The anode and cathode are electronically
separated but ionically connected using a porous
separator material which is filled with electrolyte.

cathode
separator

1.4 Polarization curves, power and energy density

Directly related to the rate of the electrode processes is the polarization phenomena,
which in essence is responsible for the deviation of the electrode and cell potentials under
operating current density conditions from the values given by thermodynamics. In other
words, the dependence of the electrode or cell potentials on the current density is referred
to as polarization.
At the cathode: Ec (i) Ee,c ; at the anode: Ea (i) Ee,a .
The cell potential - current density profile for an electrochemical power source is
expressed by polarization curves such as those shown in Fig. 1.4. The open circuit cell
potential Eoc (defined at i = 0) is typically somewhat lower than the equilibrium
(reversible) cell potential Ee,cell. The dependence of the operating cell potential on current
density depends on a number of phenomena such as electrode kinetics, ionic conductivity
and mass transfer.

13

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

Cell potential, Ecell (V)

1.1-1.5

14

Ee,cell
Eoc
A
B
0

Current density, i (A m2)

Fig. 1.4 Cell potential as a function of superficial current density for an electrochemical
power source (polarization curve). A and B represent two different performance
characteristics, such as beginning of life and end of life performance, respectively.
Ee,cell is the equilibrium cell potential, Eoc is the open circuit cell potential (at i = 0).
The electric power output for a power source (Ecell > 0) or the power consumption for
an electrolysis unit (Ecell < 0) per cell (or reactor) volume Vcell:
PDV

I cell Ecell
.
Vcell

(1.39)

where PDV is the volume based power density (W m3).

If the anode and cathode geometric areas are equal (i.e., Ac = Aa = A), than it is common
to use the current density ( i ia ic ) and to calculate an area-specific power density:
PDA

I cell Ecell
i Ecell ,
A

(1.40)

where PDA is the area-specific power density (W m2).

A major issue in the design and operation of electrochemical power sources is to
increase the power density, while for electrolysis the goal is to lower the power
consumption.
The polarization curves of the type shown by Fig. 1.4, when converted to power
density generate a parabolic function with respect to current density (Fig. 1.5).

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

PDA (W m-2)

1.1-1.5

Current density, i (A m-2)

Fig. 1.5 Power density for an electrochemical power source as a function of

superficial current density.

1.5 Review and classification of fuel cell systems

(+)

Fuel (e.g. H2 )

Oxidant (e.g. O2 )

~ 3 mm

and
Separator

(contains a catalyst layer, gas diffusion

region and flow field-current collector plate)

()
(contains a catalyst layer, gas diffusion region
and flow field-current collector plate)

Fig. 1.6 Basic components of a generic fuel cell [modified after Larminie and Dicks,
2001].

15

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CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

16

Table 1.3 Examples of oxidant choices for fuel cells and the standard cathode potentials
at 298 K
Oxidant
Half-cell cathode reaction
Eoc (VSHE)

Oxygen

In acid: O2 + 4H+ + 4e 2H2O

In alkali: O2 + 2H2O +4e 4OH

1.23
0.40

Hydrogen peroxide

H2O2 + 2H+ + 2e 2H2O

1.78

Ozone

O3 + 2H+ + 2e O2 + H2O

2.08

Table 1.4 Possible fuel choices for fuel cells and the respective standard anode potentials
at 298 K.
Fuel
Half-cell anode reaction
Eoa (VSHE)
(Note:
indicates the actual direction of the
reaction in the fuel cell)
H2
0
2H+ + 2e H2
Methanol

CO2 + 6H+ + 6e CH3OH + H2O

0.04

Ethanol

2CO2 + 12H+ + 12e C2H5OH + 3H2O

0.08

Formic Acid

CO2 + 2H+ + 2e HCOOH

0.20

Hydrocarbons

nCO2+ (6n+2)H+ + (6n+2)e CnH2n+2+ 2nH2O(g)

0.17
(for n=1 CH4)

Coal

CO2 + 4H+ + 4e C + 2H2O(g)

0.21

Carbon monoxide

CO2 + 2H+ +2e CO + H2O(g)

0.11

Hydrazine

N2 + 4H+ + 4e N2H4

0.33

+ 2H+ + 2e SH2

Biomass
rich in sugars
(e.g. glucose, maltose)

(gluconate)

Borohydride

BO2 + 6H2O + 8e BH4 + 8OH

0.47

enzyme (glucose)

1.24

1.1-1.5

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

17

Table 1.5 Classification of fuel cells based on the type of ionic conductor (electrolyte)
No. Fuel Cell
Typical Electrolyte and Symbol
separator
1

2
3
4
5

Solid polymer electrolyte

(or polymer electrolyte-membrane)
< 90 oC
(occasionally up to ~130 oC)

Proton-exchange
membrane

Alkaline
80 200 oC

KOH (or NaOH)

Phosphoric acid
200 oC

H3PO4

Molten carbonate (or molten salt)

600 800 oC

mix. of LiCO3 K2CO3

Solid oxide
600 1000 oC

ZrO2 stabilized with Y2O3

SPE
PEM

(fluorinated organic polymer

scaffold with acidic (-SO3H)
groups)
functions as both electrolyte
and separator

AFC

asbestos matrix

PAFC

silicon carbide matrix

MCFC

ceramic matrix of LiAlO2

functions as both electrolyte

and separator

SOFC

1.1-1.5

CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

PEM and

Fig. 1.7 Schematic representation of the ion-conduction through electrolyte for solid
oxide (SOFC), proton exchange membrane (PEM), phosphoric acid (PAFC) and molten
carbonate fuel cells (MCFC) [Kinoshita, 1992].

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CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

Schematic representation of a fuel cell gas diffusion electrode

Cb
Reactant conc.
Profile (e.g. O2)

Cs

H+; H2O

Macro-porous
material, e.g.
carbon cloth or
carbon paper
Pore diameter:
~ 3 50 m
and Electronic Separator

Catalyst
layer,
Reaction
sites
Meso-pores filled with
electrolyte between the
catalyst particles and
particle agglomerates
Pore diameter: 2- 50 nm
~ 100-200 m

~ 5-20
m

~50 - 200 m

Fig. 1.8 Schematic of the electrolyte-electrode interface for fuel cells.

Note: in the case of PEM fuel cells a polymer electrolyte membrane is used and the
electrode/electrolyte system is referred to as membrane-electrode assembly (MEA)
[modified after Larminie and Dicks, 2001].

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CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

Enlarged view of the catalyst layer: The importance of ionic conductivity of

the catalyst layer

Gas
O2 or H2

~ 2-10 nm

~ 0.1 2 m

Fig. 1.9 The interaction between the electrolyte and electrode in a low-temperature fuel
cell (e.g. PEM) [modified after Larminie and Dicks, 2001].

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CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

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1.6 The Specific Power and Energy Relationship: The Ragone Plot

Specific Power, SP

Electric Power
;
Total weight of the fuel cell (or battery)

[W kg1]

Electric Energy E cell I t ; [W h]

Specific Energy, SE

(1.41)

(1.42)

Electric Energy
; [Wh kg1]
Total weight of the fuel cell (or battery)

(1.43)

Rule of thumb: a 50% increase of specific energy for an electrochemical power

source device provides approximately a 74% increase in driving range for a
vehicle.

battery

Specific Power (W/kg)

Sodium sulfur
battery

Typical
transportation
PEM fuel cell

AgO - Zn

Specific energy (Wh/kg)

Figure 1.7 Ragone plot: Specific power vs. specific energy for various electrochemical
power sources.

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CHBE 477/577: Fuel Cells and Electrochemical Engineering-Dr. Eld Gyenge

battery discharge reaction; battery charge reaction

Thermal battery (molten salt):
4LiAl + FeS2 2Li2S + 4Al + Fe;
T: 400-700 0C,
Electrolyte: LiCl-Li2SO4-KCl (molten salt);
Ecell (i.e. operating cell potential range) = 2 1.6 V
Sodium-sulfur battery:
2Na(l) + 4S(l) Na2S4;
T: 200 - 400 0C,
Electrolyte: sodium beta-alumina (solid porous electrolyte)
Ecell (i.e. operating cell potential range) = 2 1.75 V
Lead-acid battery:
PbO2 + Pb + 2H2SO4 2PbSO4 + 2H2O;
T: between 40 and + 60 0C,
Electrolyte: H2SO4 ~ 38% by weight
Ecell = 2 1.7 V
Nickel-Cadmium battery:
2NiOOH + Cd + 2H2O 2Ni(OH)2 + Cd(OH)2;
T: between 40 and + 85 oC,
Electrolyte: KOH ~24% LiOH ~5% by weight
Ecell = 1.3 0.9 V
Zinc-Silver Oxide battery: (satellites, button cell for photocamera),
2AgO + Zn + H2O Ag2O + Zn(OH)2;
T: between 20 and + 55 oC,
Electrolyte: KOH conc. immobilized
Ecell = 1.5 1.2 V.
Primary lithium-thionyl chloride battery: (button cell for electronic devices, military)
4Li + 2SOCl2 4LiCl + SO2 + S;
T: between 20 and + 55 oC,
Electrolyte: propylene carbonate-LiAlCl4;
Ecell = 3.6 2.9 V.

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