FUEL CELLS

Mass transport or concentration polar-
ization can be expressed mathematically
by
where il is a limiting current dependent
on mass transport properties of the sys-
tem. For example, for a fuel gas diffus-
ing through a fine pore electrode to reach
a reaction site, a pressure drop will exist
along the pores. When the pressure
drop equals the initial gas pressure then
the maximum possible mass transport
and hence current, is occurring. As i
closely approaches il mass transport
polarization increases rapidly. For a
good diffusion electrode a highly de-
veloped interior area is required but at
the same time the pores must not be so
fine as to give excessive concentration
polarization by making il small.
Ohmic polarization is, of course, ex-
pressed in the form = ir where r is the
internal resistance between the elec-
trodes. For high temperature cells us-
ing molten electrolytes much of the polar-
ization is often caused by low conduc-
tivity of the melt and by insulating layers
forming on the electrodes.
Another form of polarization, which is
actually a case of activation polarization,
is that occurring a t air or oxygen-carbon-
alkali electrodes. The reaction which
occurs is
0 2 (adsorbed) + H z O 4-
2eeHOz’ + OH’
instead of
0 2 (adsorbed) -I- H z O 2 OH’
Since the standard state free energy
change of Reaction 5 is less than that of
Reaction 6 the voltage, even a t open
circuit, is less than theoretical. If the
peroxide ion could be catalytically de-
composed to reach a HOz’-OH’-Oz
equilibrium the potential would rise to
that of Reaction 6. With catalysts
known at present, however, the peroxide
decomposition is not sufficiently rapid for
this equilibrium to be reached and a loss
of ideal potential occurs.
References
(1) Berzius, T., Delahay, P., J. Am. Chem.
SOC.77, 6448 (1955).
(2) Frumkin, A. N., Trans. Faraday SOC.
(London) 5 5 , 156 (1959).
(3) Parsons, R., Trans. Faraday SOC. (Lon-
don) 54, 1053 (1958).
(4) Potter, E. C., “Electrochemistry,”
Cleaver-Hume Press Ltd., p. 133, Lon-
(5) don, 1956.
(5) Kordesch, K., Marko, A., Oesterr.
Chem. Ztg. 52, 125 (1951).
(6) Kortum, G., Bockris, J. O’M., “Text-
(6) book of Electrochemistry,” vol. 11,
Elsevier Pub. Co., New York, 1951.
RECEIVED
for review January 4, 1960
ACCEPTED January 15, 1960
Division of Gas and Fuel Chemistry, Sym-
posium on Fuel Cells, 136th Meeting, ACS,
Atlantic City, N. J., September 13-18,1959.
1. G. AUSTIN
College of Mineral Industries,
Pennsylvania State University,
University Park, Pa.

The High Pressure Hydrogen-Oxygen Fuel Cell

IN THE CELL used for this work, the
main cell parts are of nickel plated
about ‘/le inch thick; this provides
adequate strength, and serves also to
were made previously without a backing
plate of solid metal, but it was considered
steel or pure nickel, and the electrodes conduct away the current generated. unlikely that larger ones would be satis-
are of porous sintered nickel. The Electrodes up to 5 inches in diameter factory without adequate support. Sep-
electrolyte is strong potassium hydroxide
solution, with a concentration between
37 and SO%, and normal operating con- This Is the Best Performance of the 10-Inch Cell
ditions are 200’ C. and 300 to 600 p.s.i. (200’ C. at 400 P.s.i.)
At present 400 p.s.i. is normally used. Current density
The nickel electrodes are about ‘/I6 Amp./sq. ft. 0’ 10 50 100 200 300 440
inch thick. A small pressure difference Ma./sq. cm. 0 11 54 107.6 215 323 473
is set up across each electrode so that Voltage, v. 1.04 1.005 0.93 0.885 0.82 0.755 0.68
liquid is expelled from the large pores
on the gas side but gas cannot bubble
through the small pores on the liquid side
because of liquid surface tension. The
interior of the 30-micron pores (Figure
POROUS NICKEL 16 MICRONS DIA.PORES (MAX)
1) presents a large surface for gas absorp- ELECTROLYTE
CIRCULATION
tion. The oxygen electrodes are given
a high temperature preoxidation treat-
1 ,/ ,POROUS NICKEL 30 MICRONS DIA.PORES (APPROX)

ment in air to protect them from corro- 02 FROM CYLINDER- 4 .Hp FROM CYLINDER
sion by the high pressure oxygen and
* and electrolyte. Lithium atoms incor-
porated into the crystal lattice of the COOLING FINS
nickel oxide convert the green nickel
oxide, which is a good insulator, into a
black double oxide of nickel and lithium
which is a good semiconductor.
CIRCULATOR
Electrode Design
The largest electrodes made so far are
10 inches, in effective diameter, though
this does not by any means represent
the limit in size. They are sintered Figure 1. The hydrogen-oxygen cell. Because a small pressure difference i s
directly onto a flat circular perforated set up across each electrode, liquid i s expelled from the large pores on the gas
sheet of nickel or nickel-plated steel, side, but gas cannot bubble through the smaller pores on the liquid side

VOL. 52, NO. 4 APRIL 1960 301

 arators, in the form of narrow vertical
strips of Teflon or polytetrafluoroethyl-
ene, have to be used with IO-inch
diameter electrodes, to prevent internal
short circuits when the pressure dif-
erence is applied.
The alternative electrode is a bipolar
structure with recesses, machined on
either side of a solid metal plate, which
arc than filled with porous sintered
nickel for a hydrogen and oxygen elec-
trode. A thin dimpled perforated plate
is first sintered into each recess, and this
leaves a narrow space for leading the gas
from ports in the rim to all parts of the
porous metal. When bipolar electrodes
of this type are assembled in series,
with gaskets of insulating material
between each, they form a series of
cells which do not require an external
current connection except a t each end of
the battery. This electrode construc-
tion leads to a very compact battery,
but, mainly because of difficulties in
manufacture, it has temporarily been
abandoned in favor of the simple uni-
polar design.
Hydrogen electrodes are activated
by impregnation with a strong solution
of nickel nitrate, followed by roasting in
air a t 400’ C., and finally reduction in
hydrogen at about the same temperature.
M‘ork is proceeding on the activation
of oxygen electrodes, but a standard
treatment has not yet been derived.
Cell Performance
Performance of the cell improves
with both temperature and pressure,
but to attain a long life the lvorking
temperature will probably have to be
limited to 200’ C. or slightly higher.
Diameter of the sinter is somewhat less
than 10 inches (about 9 5 / * inches),
but it is believed more precise to base
thc figure for current density on internal
diameter of the cell body.
These figures were taken from one cell
in a 3 0-cell battery, using 37% potassium
hydroxide as the electrolyte; both
these factors contribute to the rather
low open-circuit voltage obtained.
Using 0.68 volt and 440 amperes per
square foot, the power output per unit
of internal volume corresponds to 8.2
kw. per cubic foot. At the maximum
output so far obtained-namely 0.62
volt and 585 amperes per square foot
at 200’ C. and 600 p.s.i.-power output
per unit of internal volume was 10
kw. per cubic foot.
The current efficiency, measured over
a period of some hundreds of hours in a
5-inch diameter unit with two cells in
series, is 98%. This means that energy
efficiency, based on free energy of the
reaction at any useful current density,
approximates voltage efficiency-e.g.,
at 0.9 volt and 200’ C. a t 600 p.s.i.,
energy efficiency will be 0.9/1.20 X
100 = 75y0,;at 0.8 volt it will be 6670,
and at 0.6 volt it will be 5070.
302 INDUSTRIAL AND ENGINEERING CHEMISTRY
Up to 40 cells such as the one shown here have been operated in series without
special difficulty
When the cell is on load, losses which
appear as heat, are caused mainly by
irreversibility of the electrode reactions,
or what is called activation polarization.
O n open circuit and at low current
densities, there will also be a “lost current”
caused by diffusion of the two gases in
solution through the electrolyte, fol-
lowed by combination on the opposite
electrode.
Present Design
I n 1957, the National Research De-
velopment Corp. of Great Britain agreed
to finance the development and construc-
tion of a unit developing 5 to 10 kw.,
complete with automatic controls. A
contract for this work was placed with
Marshall of Cambridge, England.
I t was decided that a 10-inch diameter
cell should be constructed, and this has
been in operation since March 1958.
The present electrode design has already
been described; axial ports for the
admission of the two gases and the elec-
trolyte are drilled in the rim. When
these electrodes are bolted together in
the correct order, with rings to provide
space for the electrolyte and with flat
disks of metal to separate the hydrogen
from the oxygen in the adjacent cell, they
form a battery, the voltage of which
depends upon the number of cells con-
nected in series. Radial ports for ad-
mitting gas or electrolyte from the axial
ports to each cell are provided simply
by slotting the gaskets. A distributor
plate for leading the gases and electro-
lyte into and out of the battery is pro-
vided either a t one end, or in the center
of the cell pack. The whole assembly
is bolted between two ribbed end plates,
and electrical insulation is placed be-
tween the ends of the pack and end
plates. Electrical connections are sil-
ver-soldered onto each electrode, and
the intercell connections are made
externally; the main connections are, of
course, made to the electrodes at each
end of the pack..
U p to 40 cells in series have been
operated and no special difficulties have
been encountered-e.g., in sealing the
joints, excessive shunt current between
cells, or excessive electrolysis in the elec-
trolyte ports.
Development of Control Gear
Control of gas admission has always
been a problem, because a delicate
pressure balance has to be maintaincd
between the two gases in the battery.
A system has now been worked out
whereby. as a basis, pressure of the
oxygen remains constant under all
conditions of load; this is achieved
with a standard two-stage reducing valve.
The hydrogen then has to be admitted
at precisely the correct rate, so that the
two gas pressures are balanced to within
a few inches water gage. This is done by
fitting an accurate differential pressure
meter, which actuates a power-operated
valve and admits hydrogen ; the valve-
opening is controlled by a servo mech-
anism operating with compressed air.
A fair amount of experience has been
obtained with this gear which works
extremely d l .
Removing water at the same rate at
which it is formed, is also a problem.
Previously this has been achieved by
circulating the hydrogen-steam mixture
by thermosyphonic action, the steam
being condensed out in a small vessel
outside the lagging. For a large battery,
large hydrogen-circulating pipcs and
ports would be needed ; therefore, a

small hydrogen blower was used, and to
prevent hydrogen leakage, a glandless
drive was also used. A magnetically
driven pump using a sealing shroud of
thin nonmagnetic metal has been
successfully employed for some time; it
can be seen mounted underneath the
battery (figure, page 302). T h e rate at
which the condensate is removed from the
system is controlled by switching the
blower on and off at intervals. The
switch is controlled by a second differ-
ential pressure meter which operates on
the difference between the hydrogen in
the system and the electrolyte. I n this
way, the removal of water is controlled
by the total volume of electrolyte which
should, of course, be kept approximately
constant. The condensate collects in a
small vessel, from which it is released
periodically by a level-sensing device
High Temperature Fuel Cells
E X P E R I M E N T A L WORK in these labora-
tories on high temperature fuel cells was
initiated by a thorough investigation of
the type of cells described by Davtyan
(7). Because neither the electrodes nor
electrolyte were found to be stable, these
cells are not suitable for long term opera-
tion. Therefore, work was directed
toward developing a cell that would ful-
fill stability requirements over long pe-
riods in the presence of reacting gases and
their combustion products.
The electrolyte selected was a mixture
of lithium, sodium, and/or potassium
carbonate, impregnated in a porous sin-
tered disk of commercial magnesium
oxide. After a presintering stage a t
1200' C., sintering was carried out at the
Same temperature. Because of the low
firing temperature, the disks were not very
hard. They had a volume porosity of
40 to 5oy0. After impregnation, the al-
kali carbonate content was usually about
4oy0 by weight, which indicates that not
all pores of the magnesium oxide were
filled with electrolyte.
The cell construction is illustrated in
Figure 1. The impregnated disk (4)was
covered on both sides with thin laycrs of
metal powders (5) prepared by reducing
the corresponding oxides in a hydrogen or
carbon monoxide atmosphere. To pre-
vent sintering during operation, the re-
duction temperature selected was equal
to or slightly above operating ternpera-
ture.
Because electrode reactions are con-
fined to areas close to the geometrical
three-phase lines bordering the metal,
.electrolyte and gas phases, powder lay-
such as a capacitance probe. The main
parts of this gear have been in operation
and appear to work perfectly well.
Until more experience is obtained, the
main level gages will be retained, but
eventually it should be possible to remove
them.
The initial heating of the battery is
accomplished by electrical heaters
mounted on the end plates and round
the main body of the battery inside the
lagging.
I t is difficult to prevent some genera-
tion of hydrogen and oxygen by electrol-
ysis in the common electrolyte ports,
although insulation with p.t.f.e. helps
considerably. Moreover, there is al-
ways the possibility that an electrode may
leak and allow gas to get into the
electrolyte system. This is taken care of
by a level-sensing device, which by
ers must be kept thin as possible and yet
permit electrical contact and prevent
flooding. These layers can be made less
than 1 mm. thick if they are covered with
silver wire gauze (O), or a t the anode with
iron, nickel, or copper gauze. To pre-
vent deformation, the gauze in turn is
covered with firm pekforated stainless-
steel disks (7), 1 mm. thick. Terminal
wires (9) of silver were screwed (10) into
the steel disks, and the assembly was com-
pleted by gaskets of mica (8) and asbestos
(3), together with steel covers (2) and
pipes (11, 13) for circulating the gases.
Screws (1) with appropriate mica isolat-
ing rings held the cell parts together.
Figure 1 . The high temperature cell. The electrolyte is a mixture of lithium,
sodium and/or potassium carbonates impregnated in a sintered disk of magnesium
oxide
FUEL CELLS
means of a solenoid operated valve,
will release any gas which may collect
at the top of the electrolyte system.
These controls may seem somewhat
complicated and expensive, but they
will work. With a larger battery they
should be no more complex and there-
fore would represent only a small
proportion of the cost for the whole
plant.
RECEIVED for review September 15, 1959
ACCEPTED December 28, 1959
Division of Gas and Fuel Chemistry, Sym-
posium on Fuel Cells, 136th Meeting, ACS,
Atlantic City, N. J., September 13-18, 1959.
F. T. BACON'
National Research Development Corp.,
London, England
Present address, Marshall's Flying
School, Ltd., Cambridge, England.
Cells of this type can be run contin-
uously for several months, operating be-
tween 550' and 700' C. on town gas,
hydrogen, carbon monoxide, and natural
gas. T h e best cell had a life of 6 months
without an appreciable decrease in gal-
vanic activity. However, slow deteriora-
tion was caused by a gradual loss of car-
bonate melt, both by direct vaporization
of carbon dioxide, lithium oxide, and so-
dium and potassium monoxides and by
chemical reactions with the gasket.
The increasing loss of fused salts led to
increasing gas leakage across the disks,
thus lowering cell voltage. Therefore,
conclusions about performance of elec-
VOL. 52, NO. 4 APRIL 1960 303