Handbook of

Fundamentals
Technology
and Applications
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VOLUME 1
Fundamentals and
Survey of Systems
Editors
Wolf Vielstich
IQSC, Sao Car/os, Universidade de Sao
Paulo, Brazil
Arnold Lomm
DaimlerChrysler Research and Technology,
Ulm, Germany
Hubert A. Gosteiger
Fuel Cell Activities, General Motors
Corporation, Honeoye Falls, NY, USA
GQ
WILEY
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Cover Images
Foreground: Cutaway view of General Electric PEM fuel cell system for Gemini spacecraft, 3 stacks of
32 cc1is in parallel. (Reproduced by permission of Schenectady Museum.)
Background: Scheme of a H2/02 fuel cell.
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British Library Cataloguing ill Publication Data
A catalogue record for this book is available from the British Library
ISBN: 0-471-49926-9
Typeset in 101l2.5pt Times by Laserwords Private Limited, Chennai, India
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Contents
VOLUME 1: Fundamentals and Survey of Systems
Contributors to Volume 1 vii
FOreWOl"d ix
Preface xiii
Abbreviations and Acronyms xv
Pal"t 1: Thermodynamics and kinetics offuel
cell reactions 1
The components of an electrochemical cell 3
A. H(lmllell
2 The electrode-electrolyte interface 13
A. Hamlletl
3 Thermodynamics of electrodes and cells 21
A. Hamllelt
4 Ideal and effective efficiencies of cell reactions and comparison to
carnal cycles 26
W. Vie/stich
5 Kinetics of electrochemical reactions
A. HOl1/11etl
6 Introduction to fuel-cell types
A. Hall/neft
Part 2: Mass transfer in fuel cells
7 Mass tram;fer at two-phase and three-phase interfaces
A. Weber/R. Darling/f. Meyers/J. NelVman
8 Mass transfer in flow fields
K. Scott
Part 3: Heat transfer in fuel cells
9 Low temperature fuel cells
J. Divisek
10 High temperature fuel cells
J. Dh'isek
I I Air-cooled PEM fuel cells
R. VOl' flelmoltlW. Lehner!
31
36
45
47
70
97
99
115
134
Pal"t 4: Fuel cell principles, systems and
applications
12 History of low temperature fuel cells
c. SalldstedelE. J. CairnslV. s. Bago/sky/K. Wieseller
13 History of high temperature fuel cell development
H. Yokokawa/N. Sakai
14 Hydrogen/oxygen (Air) fuel cells with alkaline electrolytes
M. CiJraill/K. Korde.w:h
15 Hydrazine fuel cells
H. Kohllke
16 Phosphoric acid electrolyte fuel cells
J. M. Killg/H. R. KUllz
17 Aqueous carbonate electrolyte fuel cells
E. J. Cairns
18 Direct methanol fuel cells (DMFC)
A. Hal/mel(
19 Other direct-alcohol fuel cells
C. Willy/E. M. Belgsir
20 Solid oxide fuel cells (SO Fe)
P. Holtappe!sIU. StilllllJillg
21 Biochemical fuel cells
E. Katz/A. N. Shipway//' Willner
22 Metal/air batteries: The zinc/air case
O. Haas/F. Ho/zer/K. Miiller/S. Miiller
23 Seawater aluminum/air cells
J. P. ludice de SouzaiW. Vie/stich
24 Energy storage via electrolysis/fuel cells
J. Divisek/B. Emollls
Contents for Volumes 2, 3 and 4
Subject Index
143
145
219
267
281
287
301
305
323
335
355
382
409
416
433
439
Chapter 2
The electrode-electrolyte interface
A. Hamnett
University of Strathclyde, Glasgow, UK
1 THE ELECTRIFIED DOUBLE LAYER
Once an electrode, which for our purposes may initially
be treated as a conducting plane, is introduced into an
electrolyte solution, several things change. There is a sub-
stantial loss of symmetry, the potential experienced by
an ion will now be not only the screened potential of
the other ions but will contain a term arising from the
field due to the electrode and a term due to the image
charge in the electrode. The structure of the solvent is
also perturbed: ncxt to the electrode, the oricntation of
the molecules of solvent will be affccted by the elec,
tric field at the electrode surrace, and the net orientation
will derive from both the interaction with the electrode
and with neighboring molecules and ions. Finally, there
may be a sufficiently strong interaction between ions and
the electrode surface that the ions lose at least some of
their inner solvation sheath and adsorb on the electrode
surface.
The classical model of the electrified interface is shown
in Figure 1,[1
1
and the following features are apparent:
I. There is an ordered layer of solvent dipoles next to
the electrode surface, the extent of whose orientation
is expected to depcnd on the charge on the electrode.
2. There is, or may be, an inner layer of specifically
adsorbed anions on the surface; these anions have
displaced one or more solvent molecules and have lost
part of their inner solvation sheath. An imaginary plane
can be drawn through the centers of these anions to
form the inner Helmholtz plane (lHP).
3. The layer of solvent molecules not directly adja,
cent to the metal is the closest distance of approach
of solvated catiolls. Since the enthalpy of solvation
of cations is usually substantially larger than that
of anions, it is normally expected that there will
be insufficient energy to strip the cations of their
inner solvation sheaths, and a second imaginary plane
can be drawn through the centers of the solvated
cations: this second plane is termed the outer Helmholtz
plane (OHP).
4. Outside the OHP, there may still be an electric field and
hence an imbalance of anions and cations extending in
the form of a diffuse layer into the solution.
5. The potential distribution in this model obviously can,
sists of two parts: a quasi-linear potential drop between
the metal electrode and the IHP or OHP depending
on the charge on the electrode sUIt"ace and the corre-
sponding planar ionic density, and a second part cor-
responding to the diffuse layer; as we shall see below,
in this part, the potential decays roughly exponen,
tially through screening" However, there arc subtleties
about what can actually be measured that need some
attention.
2 THE ELECTRODE POTENTIAL
Any measurement of' potential must describe a reference
point, and we will take as this point the potential of
an electron well separated from the metal and at rest
in vacuo. By reference to Figure 2Yl we can define the
following quantities:
Handbook of FIIel Cells - Fundamentals, TechnoLogy alld Applications, Edited by Wolf Vielslich, Hubert A. Gasteiger, Arnold Lamm.
Volume I: Fundamentals and Survey of Systems. 2003 John Wiley & Sons, Ltd. ISBN: 0-471-49926-9.
14 Part J: Thermodynamics and kinetics of fuel cell reactions
Metal
Metal
plane
Inner Outer
Helmholtz Helmholtz
plane
cations
anions
Normal
water
structure
Primary
water
layer
Secondary
water
layer
Figure 1. Hypothetical structure of the electrolyte double layer.
I. The Fermi energy cr which is thc difference in energy
between the bottom of the conduction band and the
Fermi levcl; it is positive and in the simple Sommerfeld
theory of metals [3] c = h
2
k
2
/2m = h2(3rrn )2/3/2m
'F Fe'
where nc is the number density of electrons.
2. The work function q,M which is the energy rcquired
to remove an electron from the inner Fermi level
to vacuum.
3. The surface potential of the electrode, X M, due to
the presence of surface dipoles. At the metal-vacuum
interface, these dipoles arise from the fact that the
Vacuum
level----- T ----- --
Figure 2. Potential energy profile at the metal-vacuum boundary.
Bulk and surface contributions to V are separately shown. (Repro-
duced from Trassatti (1980)[2] with permission from Kluwer
Academic/Plenum Publishers.)
electrons in the metal can relax at the surface to some
degrcc, extending outwards by a distance of the order
of I A, and giving rise to a spatial imbalance of charge
at the surface.
4. The chemical potential of the electrons in the metal,
a negative quantity.
5. The electrochemical potential the electrons in
metal M is defined as - eo 1JrM - eo X M, where 1JrM
is the mean electrostatic potential just outside the metal,
which will tend to zero as the free-charge density, (J,
on the metal tends to zero; as (J --+ 0, then --+
- eox
M
== _q,M from Figure 2. Hence, for (J # 0,
= _q,M - eo1JrM
6. The potcntial energy of the elcctrons, V, which is a
negative quantity that can be partitioned into bulk and
surface contributions as shown. Clearly, from Figure 2,
= E
F
+ Vir
Of the quantities shown in Figure 2, <pM is measurable, as is
cr, but the remainder are not, and must be calculated. Valucs
of 1-2 e V have been obtained for X M, though smaller
values are found for the alkali metals.
If two metals with diffcrcnt work functions are placcd
in contact, there will be a flow of electrons from the
metal with the lowcr work function to one with the higher
work function; this will continue until the electrochemical
potentials of the electrons in the two phases are equal.
This change gives rise to a measurable potential difference
between the two metals tenned the contact potential or
Volta potential difference. Clearly q, = where
is the Volta potential difference between a point
close to the surface of M
J
and one closc to the surface
of M
2
, both points bcing in the vacuum phase; this is
an experimentally measurable quantity. The actual number
of electrons transferred is very small, so that the electron
densities of the two phases will be unaltered, and only the
value of the potential V will have changed, If we assume
that, on putting the metals together, the X
M
vanish, and we
define the potential inside the metal as <j>, then the equality
of electrochemical potentials also leads to
(1)
This internal potential, <1>, is not directly measurable; it is
termed the Galvani potential, and is the target of most of
the modeling discussed below, Clearly, if the electrons are
transferred across the free surfaces and vacuum between
the two metals, we have <I> = <j> +
Once a metal is immersed in a solvent, a second dipolar
layer will form at the metal surface due to the alignment of
the solvent dipoles, Again, this contribution to the poten-
tial is not directly measurable, and, in addition, the mctal
dipole contribution itself will change since the distribution
of the electron cloud will be modified by the presence of
the solvent. Finally, there will be a contribution from free
charges both on the metal and in the electrolyte. The over-
all contribution to the Galvani potential difference bctween
metal and solution then consists of thesc four quantities, as
shown in Figure 3.[21 If the potential due to dipoles at thc
metal-vacuum interface for the metal is X M and for the
solvent-vacuum interface is X s, then the Galvani poten-
tial difference between metal and solvent can be written
either as
(2)
or as
(3)
where OX M, OX s, are the changes in surface dipole for metal
and solvent on forming the interface. In equation (2) we
pass across the interface, and in equation (3) we pass into
the vacuum from both metal and solvent. As bcfore, the
value of the Volta potcntial differcnce, is measurable
experimentally, but it is evident that we cannot associate
this potential difference with that due to free charges at
the interface, since there are changes in dipole contribution
on both sides as wcll. Evcn if there are no free charges
at the interface (at the point of zero charge (PZC)), the
Volta potential difference is not zero unless oXM = oXs i.e.,
the free surfaces of the two phases will still be charged
unless the changes in surface dipole of solvent and metal
balance exactly. In practice, this is not the case: careful
measurements[41 show that >V = -O.26V at the PZC,
showing that the dipole changes do not, in fact, compensate.
Historically, this discussion is of considerable interest, since
The electrode-electrolyte ilUe1face 15
M
O(e)
\---,-,,- - -I
+1
1

1
1
1
1
()
1
1
1
1
o
1
1
1
0)
s
Figure 3. Components of the Galvani potential difference at a
metal-solution interface. (Reproduced from Trassatti (1980)121
with permission from Kluwer Academic/Plenum Publishers.)
a bitter dispute between Galvani and Volta over the origin
of the electromotive force (EMF) when two different metals
are immersed in the same solution could, in principle, be
due just to the Volta potential difference between the metals.
In fact, it is easy to see that if conditions arc such thaL
there are no free charges on either metal, the difference
in potential between them, again a measurable quantity, is
given by
(4)
showing that the difference in work functions would only
account for the difference in electrode potentials if the two
Volta terms were actually zero.
3 INTERFACIAL STATISTICAL
THERMODYNAMICS OF THE
DIFFUSE LAYER
Development of a self-consistent theory for the double layer
has proven extremely difficult, since the presence of an
electrode introduces an essentially non-isotropic element
into the equations. This manifests itself in the need for