Ashok K.

Vijh Electrochemical Principles Involved

Hydro-Quebec Institute of Research
Varennes, P.Q., Canada
in a Fuel Cell

The electrochemical energy converter,
popularly known as “fuel cell/’ is an interesting modern
modification of the primary cell (e.g., Leclanche cell)
and it has had wide application in space exploration.
Fuel cells were an important source of auxiliary power
in the Gemini and Apollo spacecrafts. The fuel cell
is also being studied very carefully for possible use for a
type of electric automobile to partially or possibly com-
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e.g., a hydrogen-oxygen fuel cell. In this fuel cell, the
process that results in the production of electricity is
exactly the converse of the electrolysis of water. In the
electrolysis of water, we force the decomposition of
water into hydrogen and oxygen by supplying electrical
energy to the system, i.e., by passage of current. Since
electrolysis of water into gaseous hydrogen and oxygen
proceeds by a transfer of electrons from the OH- to the

pletely replace the gasoline engine in order to minimize H+ to form H2 and 02 as the electric current is forced
air pollution and noise. through the solution, it is logical to assume that the
A fuel cell is thus related to the two major problems process, i.e., the combination of gaseous hydro-
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reverse
of today, namely, conquest of space and elimination of gen and oxygen should result in the reverse transfer of
air pollution. electrons. This is indeed observed. Hence the com-
The purpose of this article is to present an elementary bination of gaseous hydrogen and oxygen to produce
discussion of the electrochemical principles involved in water may also be carried out in an electrochemical cell
the operation of a fuel cell. and energy released may be tapped as the useful electri-
Importance of fuel cells, and the scientific and tech- cal energy. The device that accomplishes this is called
nological problems involved in it, may be indicated by a hydrogen-oxygen fuel cell.
stating that the development of the fuel cell is one of In its simplest form (see the figure), it consists of a
the three major areas of energy research today, namely container holding a suitable electrolyte solution (e.g.,
Direct conversion of fuel to electrical energy (viz. fuel cell) sulfuric acid, potassium hydroxide) and two inert elec-
Direct conversion of solar energy to electrical energy trodes, the anode (A) and the cathode (C). Gaseous
Direct conversion of nuclear energy to atomic energy hydrogen is admitted at the anode and gaseous oxygen
is admitted at the cathode. On joining the anode and
Definition of a Fuel Cell cathode externally by means of a conducting wire, the
The term “fuel cell” usually refers to a family of current flows in the circuit, which may be made to do
devices used for generating electricity electrochemically. useful work, e.g., to light an electric bulb. The elec-
In this sense, a fuel cell is very similar to the conven- trochemical reactions involved at the two electrodes are
tional batteries. There are important differences, how- as follows
ever. Firstly, a fuel cell is similar to a primary battery Anode + H2 Anode + 2H+ + 2e~ (1)
in that it consumes the chemical substances fed into it. Cathode + V202 + H20 + 2e~ Cathode + 20H~ (2)
On the other hand, the fuel cell differs from a primary
H2 + V202 — H20 (3)
battery in that it is not discarded after the chemical
reactants put in it initially have been consumed. In- If we combine the cathodic and anodic half cell re-
stead, some more chemicals are fed into it to produce
more electricity and the process can be made continu-
ous. A fuel cell hence is a continuous-feed primary
battery which will, ideally, go on producing electricity
as long as suitable reactants are being fed into it. The
other major requirement is the continuous removal of 2e 2e
products (wastes) which are produced as a result of
electrochemical reactions within the fuel cells.
The similarity between a primary battery and a fuel
cell may be illustrated by comparing the Leclanche
cell with the hydrogen-oxygen fuel cell: in the former,
the zinc provides the electrons for the outside circuit,
while in the latter it is the hydrogen gas (fuel); again,
in the former, the manganese dioxide accepts the elec-
trons from the outside circuit, whereas in the latter,
the oxygen gas is the electron acceptor.
Fuel Cells: Electrochemical Principles
To illustrate the electrochemical principles in- A diagramatic representation of reactions involved in a simple hydrogen-
volved in a fuel cell is to discuss the simplest example, oxygen fuel cell, after Gregory (7 6).

680 / Journal of Chemical Education

actions, we obtain the total fuel cell reaction, namely,
reaction (3). This reaction is simply the combination
of gaseous hydrogen and oxygen to produce water and
is accompanied by release of electrical energy. The
anode and cathode in the fuel cell (Fig. 1) will assume,
as a result of reaction (3), a difference of potential de-
rived from the free energy change of the overall reaction
(3). Both the intensity (reversible potential, 1E, in
volts V) and the quantity (faradays, F, or coulombs,
C) of the total cell output are contained in the molar
free energy, AG, of the overall cell reaction (3). This
may be represented as
AG =
-nFE =
-E X I X t =
VC (4)
Here, n is the number of electrons per molecule of the
anodic fuel (hydrogen is the present example; hence n
is two) that is being oxidized and I is the average cur-
rent in amperes derived for t seconds. The total quan-
tity of electricity (/ X t C) derived from such a fuel
=
cell (Fig. 1) is proportional to the weight of chemicals
consumed. One Faraday or 26.8 A-hr/g-equivalent
weight of the fuel is the electricity released assuming
complete oxidation and absence of a variety of possible
power losses. The nature of some of these power losses
will be outlined in the following discussion.
It is important to note in above reactions (l)-(3) that
anode and cathode are not consumed in the respective
anodic oxidation (reaction (1)) and cathodic reduction
(reaction (2)), What, then, is the function of these
electrodes? The first and the most obvious function of
these electrodes is that they act as source (anode) or
sink (cathode) of electrons in the electrochemical reac-
tions involved in the fuel cell. Since this function can
be performed by any good metallic conductor, it follows
that several of the metals or graphite material should be
suitable as electrodes in the fuel cell. In actual prac-
tice, it is observed, however, that among metals, plati-
num and related metals like iridium, rhodium, etc.,
are the only ones which act as suitable electrodes or as
suitable coating of electrodes in the fuel cells since they
are needed as catalytic agents. The electrodes in a
fuel cell, as in all electrochemical reactions, act not only
as sources or as sinks of electrons, but also as specific
catalysts for the two electrode reactions. Platinum is
a good anode catalyst for reaction (1) in a fuel cell, be-
cause it provides a path of low activation energy for
reaction (1) to occur, and the rate of reaction will be
higher in the presence of platinum than without it. If
platinum is replaced by a noncatalytic metal, reaction
(1) would still occur; however, the activation energy for
reaction (1) on a non-catalytic metal will be very high
and the rate will be very low. Since heterogeneous
catalysis in electrode reactions is accompanied by
charge transfer at the metal-electrolyte interface (e.g.,
in reaction (1)), platinum, which has been chosen as an
anodic catalyst in our example here, is called an electro-
catalyst. An important requirement, therefore, for a
suitable electrode in a fuel cell is that it behave as a
good electrocatalyst for the particular electrode reaction
to be carried out on it. If one performs reaction (1),
for example, on a poor electrocatalyst, the charge trans-
fer in reaction (1) will assume significant rates only if it
is driven by a high field at the metal-solution interface.
Application of such a field results in electrode polariza-
tion, i.e., the applied field forces the electrode away
from its reversible potential. In terms of fuel cell
terminology, this polarization amounts to a power loss.
In other words, in the absence of a good electrocatalyst,
the fuel cell provides lesser amounts of useful power out-
put since a part of the power is “wasted” on driving
reactions (1) and (2) at significant rates. The theoreti-
cal aspects of polarization at the metal-solution inter-
face and its relation to the rates of electrode reactions
have been discussed in previous recent articles (1, 2)
and will not be dealt with here. Other elementary
(3, 4) or advanced accounts {5-8) of these matters are
also available in the literature.
From the foregoing introduction and Figure 1, it is
obvious that the four most important parts of a fuel cell
e.g., a hydrogen-oxygen fuel cell, are as follows
Anodic electrocatalyst
Cathodic electrocatalyst
Anodic fuel, e.g., for the electron producing reaction (1)
Cathodic fuel, e.g., for the electron consuming reaction (2)
As regards the question of a good anodic electro-
catalyst, platinum and related metals are more or less
satisfactory. On grounds of high cost and limited
world supply, however, these metals must be excluded
as attractive electrocatalysts for fuel cells meant to
compete with other power sources (e.g., internal com-
bustion engines, hydroelectric power, etc.) for a variety
of terrestrial uses. For very restricted uses (e.g.,
supplying power to remote regions, military uses, etc.),
fuel cells employing very small quantities of platinum
metals are within the realm of commercial possibility.
The situation for the case of cathodic electrocatalysts
is less encouraging. Even though platinum metals are
one of the best available electrocatalysts for reduction
of oxygen (i.e., reaction (2)), the power losses are still
excessive. Recently, it has been claimed that some
phthalocyanines adsorbed on active charcoal and some
tungsten bronzes approach platinum in electrocatalytic
activity for reaction (2), i.e., reduction of oxygen gas to
hydroxyl ions. These claims have yet to be corrobo-
rated under rigorous conditions of experimentation.
The best claimed cathodic electrocatalysts to date are
far from being excellent since polarization (i.e., power
loss) involved is still of appreciable magnitude. There
is urgent need, therefore, for discovering a good ca-
thodic electrocatalyst before fuel cells could become eco-
nomically competitive sources of power. It is also clear
that some cheaper anodic electrocatalysts approaching
platinum metals in their activity would be very desir-
able.
Regarding fuel for the anodic reaction (1), hydrogen
gas is, of course, very attractive from the point of view
of ease of electrochemical oxidation. Because of
hazard and high cost (at site) involved in the use of
hydrogen gas, substitute sources of electrochemically
available hydrogen are being explored, e.g., methanol,
hydrazine, hydrocarbons, etc. For example, the elec-
trons released in the anodic reaction (1) could also be
obtained, instead, by reactions of the type
Anode + C2H2 + 4H20 -> 2C02 + 10H~ + lOe" (5)
In other words, electrons may be released by oxida-
tion of hydrogen-containing compounds. This ap-
proach has achieved some success even though an ideal
fuel which meets all the scientific, technological, and
Volume 47, Number 10, October 1970 / 681
economic requirements for a commercially attractive
fuel cell has yet to be found.
The various requirements desired in a commercially
attractive anodic fuel, briefly enumerated, are: low
cost at the site of fuel consumption; ease of electro-
chemical oxidation; high energy density (i.e., available
electrons in a reaction of type (5) above) per unit weight
of the fuel; adequate world reserves; ease of handling
and transportation; lack of hazard and toxicity; chemi-
cal stability in a wide range of temperature, etc. It is
believed that an ideal fuel cell would be a device which
accepts conventional fuels such as coal, crude oil, or
gasoline as anodic fuels. These fuels, when oxidized
directly, have very low electrochemical activity, how-
ever. To circumvent this problem, these fuels are
sometimes first decomposed by a chemical-thermal
treatment in a “reformer,” to yield hydrogen or hydro-
gen containing low molecular weight hydrocarbons,
which are then fed to a fuel cell. This procedure is
called indirect oxidation of these fuels. This, however,
is not an entirely satisfactory procedure since it raises
the cost of energy production by fuel cells and intro-
duces other problems, e.g., catalyst poisoning by traces
of CO present in the gases produced by the reformer
(9-11). It may be mentioned here that a great deal of
electrochemical research effort has been devoted in re-
cent years to the problem of elucidation of the mecha-
nisms of anodic oxidation of organic compounds (12-15)
with a view to understanding the nature of interfacial
problems involved in the oxidation of fuels.
The final problem involved in a fuel cell is that of a
suitable cathodic fuel (reaction (2) in the foregoing
discussion) and the solution is rather straightforward
for the case of hydrogen-oxygen fuel cell. The oxygen
which is contained in air, after suitable purification, is
quite acceptable as a cathodic fuel. This is the source
of oxygen in the present commercially used “air cell.”
In applications where storage space and weight of a fuel
are paramount considerations, pure oxygen in liquefied
form is to be preferred, e.g., in the space missions in the
USA.
Other Types of Fuel Cells
The preceding discussion of fuel cells was centered
around hydrogen-oxygen fuel cell. However, there are
several other types of fuel cells (9-11) which essentially
involve similar principles; i.e., the basic requirement in
these cells is an electron producing reaction (i.e., re-
action (1)) and electron consuming reaction (i.e., re-
action (2)).1 Since many of these fuel cells do not
involve any completely novel principles, it is not nec-
essary to discuss them here. The possible exception
are the biological fuel cells, also referred to by the
following names: bio-fuel cells; biochemical fuel cells;
biobatteries; biosolar cells.
The most important aspect of these fuel cells is
involvement of living organisms, e.g., bacteria in
extracting electricity from low cost or abundant fuels.
Use of even household sewage has been suggested as the
1
One such cell that has been studied for electrical auto use is
the sodium (anode)-sulfur (cathode) cell; another that has re-
ceived some attention for an easily regenerative system is the
H2-lithium cell.
682 / Journal of Chemical Education
possible fuel thus indicating that some fuel cells offer
the possibility of achieving simultaneously two impor-
tant goals, namely producing electricity and fighting
water pollution. The role of these living organisms in
the production of electricity may take one of the follow-
ing forms
1) The bacteria may be used for breaking complex organic mat-
ter contained, e.g., in sewage or cellulose into simpler organic
molecules (e.g., hydrogen sulfide, methane) that show electro-
chemical activity as anode fuels in conventional fuel cells.
This type of bacterial decomposition is indeed frequently found in
nature.
2) Some living organisms can convert complex organic wastes
into oxygen which may then be used at the cathode of a fuel cell.
This particular phenomenon will have only limited application,
however, since oxygen is already easily and cheaply available from
the atmosphere.
3) Enzymes produced by some bacteria may act as catalysts or
promotors for anodic oxidation of organic fuels.
Until now, the biochemical fuel cells (9-11) are no-
where near the stage of commercial feasibility. The
possibilities, however, are enormous. For example,
it has been suggested that biochemical fuel cells may
provide the possibility of converting the entire Black
Sea into a gigantic fuel cell. At the bottom of Black
Sea, Disulfovibrio bacteria obtain oxygen from sulfates
in water and in the process create large amounts of hy-
drogen sulfide which can, of course, be used as an
anodic fuel. Sewage ponds in every community may
be converted into huge fuel cells. These rather specu-
lative possibilities have already been demonstrated to
be valid at the test tube level. At the present time, the
commercial exploitation of biochemical fuel cells is
prohibited by, among other factors, the rather low con-
centrations of the electroactive materials produced by
the bacterial decomposition. Notwithstanding the
lack of present commercial feasibility of biochemical
fuel cells, the intellectual fascination of the problems
involved cannot be disputed.
Acknowledgment
The author is indebted to the reviewer of this paper
for several suggestions for improvement of the manu-
script.
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