Historical Pathways for Fuel Cells

The New Electric Century

Patrick Grimes
Grimes Associales. 241 I Hill Road, Scotch Plains, NJ 07076-4517

ABSTRACT

With the turn of the century, we are entering a new era of personal electricity. It will be created at our command to power
our cars, our homes and apartments. Electricity will be the response to the drivers of: environmental factors, toxic emissions and
greenhouse gases, improved efficiency, decentralization. But telecommunication, Internet and satellites increasingly globally tie
people together. Fuel cells and batteries are the principle systems to develop this age of personal electricity. History of the
pathways of fuel cells will help guide the development of the present and the future electrical systems.

Introduction
We are entering a century of personal electricity, PE,
century. This century will be driven by many forces: -
environmental concerns, toxic emissions, greenhouse gasses,
efficiency improvements, decentralization, distributed
electricity production, stationary and mobile power
production. Fuel cells will be in the basements; Fuel cell and
battery electric vehicles will bc in garages.
Telecomunicarions, sensors, electronics, personal
computers, Internet and technofogy advances, wired and
wireless will be our companions. Each person will be
controlling his or her production and use of electricity, We,
however, are increasingly tied together by electron flow .We
arc leaving the age of combustion and thermal engines.
Electricity will no longer be controlled heat - enthalpy, AH,
and it will enter the electric age of Gibbs function, free
energy, AG. Electricity production will be brought closer to
the electricity user-another decentrz’ization process-changing
ovr daily lives
to rise out af the multitude of systems into the race for the
commercial world. Applications, personalities and
technology / science have bccn the drivers . It may be time to
look at other candidates for today’s specific applications.
History
Sir William Robert Grove (1811-1896) is generally
considered to be the father of the fucl cell for his work 1839
- 1849 in England. He used his own moncy together with
large amounts of platinum supplied by Johnson Mathey
Company, London to build his cclls and laboratory. His
electrolysis I fuel cell system using piatinum electrodes is
shown it? the figure below.

Fuel cells
Fuel cell is two four-letter words - fuel and cell. The majority
of the research had been focused at thc cells but fucl is now
first and the foremost concern. The complete fuel cell system
- fuel in and electricity out - is the primary focus today with
increased attention to the fuel “well to wheel” overall
processes.
There are tens - bundreds and fuel cells and their chemistries.
The essentials of a fuel cell are
Fuel /anode electrode I Electrolyre I
/cathode electrode / Oxidant.
Many components and reactants have been proposed. The
permutations and combinations arc large. Only a few fuel
cell systems have had sufficient attention and proper funding
. When electriciiy was first applied to the system the sulfuric
acidiwater elcctrolyte was electrolyzed to hydrogen and
oxygen and stored at the appropriate electrodes of the series
connected cells. Disconnccthg the electric power stopped
the electrolysis. When a single elcctrolysis cell (an electrical
resistancc load) is connected (0 the terminals of (he series
cells, hydrogen and oxygen were converted back to water by
the electrochcmical reactions at the platinum electrodes.
Hydrogen and oxygen were made in the single electrolysis
cell. Grove further made more fuel cells with ethylene and
carbon monoxide as fuels. Later he made hydrogenfair
(oxygen) series cells with a glass manifold hydrogen supply
to the anodes. The hydrogen fuel was made by reacting zinc
with acid. The concepts of fuel cells were demonstrated
morc than 150 years ago. Grove went on to make
contributions to electric lights.
In 1889 Ludwig Mond and Carl Langer extended Grove’s
work to a gas-powered battery and called their system a fuel
-
cell. They found that while platinum black is a very good gas
absorber, it loses i!s condensing power (activity) when it gets
wet. They used thin diaphragms of nonconducting matrixes
impregnated with electrolyte and then sandwiched them
between metallic electrodes for their cells. The capillary
action of the matrix kept the electrolyte contained. Currents
of 2 A with a voltage of 0.73 were seen. The high platinum
cost. Limited the further work to who could afford platinum
well-to-do researchers.
Antoine Becquerel of France i n 1855 made a new type of
battery. He melted niter (potassium nitrate) in a platinum
vessel and then inserted a carbon rod. He measured electric
current passage when wires were attached to the rod and the
vessel.
In 1896, Dr. William W. Jacques, a Boston entrepreneur,
further explored the carbon approach. These fuel cetls
became the new Hot Technology. At that time, the average
efficiency of coal fired central station systems was 2.6%.
Jacques’ system approached IS%. Jacques’ fuel cells had a
carbon rod central anode in the electrolyte of potassium
hydroxide molten at 400 - 500 C. Circular iron containers
were used to contain the molten electrolyte. The walls of the
iron containers were also the cathode catalysts for the
oxygen (air) bubbled on ;nd past the oxidized iron surfaces.
Performance was very good. There were reports of 100
makm2 at 1 volt for cells operating for extended periods. A
fuel cell system of 100 cylindrical cells built on top of an
oven flat hot plate was demonstrated periodically for about a
half year, It produced as much as 1500 watts. ScaIed up
modules as tall as a man, were built for a larger system. The
anticipated output was projected to be 15 “electrical horse
power”. Costs and lack of easy process to regenerate of
carbonates together with rapid improvements i n steam
engine/electric generation slowed the work on the Jacques
cell to a standstill.
In 1898 W, Nernst suggested that a redox fuel cell system
could have more flexibility and more choices of reactants. In
the 195O’s, Professor Posner at University of Florida, in the
pre-Sputnik days, made redox Nernst systems using tin
bromide solutions.
Tin has two oxidize states - stanoust2 , Sn” and
stannic+“, ~ n + “
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Bromine has two states bromine, Br3 -’ and bromide,
2 Br -’-I- 3 r - ’
Posner circulated the anode solution from the anode
compartment through a tank of powdered coal reductively
converting Sn+2 to Sn+4. The Sn+4 was pumped back
through the bottom of the anode compartment. There, Sn-t.4
was then oxidized to Sn+2 releasing two electrons to the
terminal eleclrodes. The cycle continues. At thc same time,
the cathode solution was sprayed over a glass bead bed
sweep by a rising bubbling stream of air. The bromide ions
were reduced with two electrons from the load circuit. NOx
was found to be a good reactant catalyst. These systems
operated at near ambient temperatures. Posner was abIc to
convert up to 70% of the coal to electricity. General Electric,
who supported the work, [hen used its money to go for space
age fuel cells for NASA. Unfortunately, the redox fuel cell
system was not suitable for space travel because of the
difficulty of pumping solutions in zero gravity. Perhaps now
is a good time to rcexamine the redox cells of Posner and
others.
Starting in early 1930’s, Francis Bacon while at Cambridge
University in England worked on fuel cells. His approach
was to use alkaline systems that did not use noble metal
catalysts. He found that at 2OO+C nickel electrodes were
good catalysts for the hydrogen and oxygen reactions and
improved performance by raising the pressure to 40 atm
(increasing gas solubilily). To maintain low pressure
differential for larger diameter celts, double porosity
electrodes were used. Larger diameter pores faced toward
the liquid electrolyte (highly fluidic KOH at cell
temperatures) limiting the penctration of the liquid
elcctrolyte into the electrode. On [he gas s;?e, the pores are
smaller al!owing the gases to penetrate into the porous
electrode ‘and permitting an intermediate region in the
electrode for gas/dectrolyte boundaries.
Francis Bacon announced in August 1959 that a 6 kW
alkaline hydrogen/ oxygen system had been developed, built
and demonstrated to power a welding machine, a circular
saw and a forklift truck.
At the same time, October 1959, Dr Harry Ihrig, Allis-
Chalmers Manufacturing Company Milwaukee, Wisconsin,
introduced the first fueI cell tractor in the figure below. Jean
Manion and others used hydrogen and oxygen to operate an
ambient temperature, matrix held, alkaIine eIectrolyte 15 kW
(20-hp) fuel cell developed the system. There were over a
thousand cells in the system. After displays at county and
and state fairs the fuel cell tractor was retired to the
Smithsonian Institute in Washington

Allis-Chalmers continued to make fuel cell systems. A low
temperature, hydrogen oxygen fuel cell wits demonstrated in
zero gravity and Allis-Chalmers became the backup for
space programs. Ammonia fuel and cryogenic oxygen fuel
cells were used to power a forklift. The lead acid battery was
removed and additional cast steel was added to the rear to as
a counter weight. A one-man submarine was powered with a
hydrazine and compressed oxygen fuel cell. Hydrazine and
hydrogen peroxide fuel cell was used to operatc a golf cart.
Alcohol and hydrogen peroxide fuel cell kits were sold.
These systems used matrix held alkaline solution or flowing
alkaIine electrolyte. Problems of reducing costs and thus a
limited market stopped the projects
Fuel Cells as Electrochemical Reactors
Circulating electrolyte cells were used to separate and
pressurize oxygen from air electrochemically. Air was
supplied to an alkaline matrix electrolyte fuel cell stack
without a fuel supply. A power supply was attached to the
terminals o f the system. Oxygen is activated at the air
cathode into hydroxyl ic.:s !hen migrated through the
electrolyte to thc anode where they are was converted back
[o separated out the oxygen. A multi cell oxygen generator
was operated in the laborntory for 17,000 hours at ambient
temperature with periodic electrolyte replacement.
Modern Era of Fuel Cell Development
Space fuel cells
With the launch of Russia's Sputnik in 1957, the modern era
of fuel development began. Thc space race was on. It soon
became obvious to NASA that fuel cells using cryogenic
hydrogen and oxygen fuel and oxidant would be the lowest
weight power plant for the manned flights. Even the water
product would be useful.
General Electric Company proposed work on fuel cells with
solid colymer membrane, SPE, electrolyte. The initial
membranes were electrodialysis membranes from Ionics of
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Cambridge, MA. Later perflora ionic membranes from
DuPont more stable to oxidization by oxygen and peroxide
ions in the presence of high surface area platinum were used.
The cells operated at temperatures less 100 C. These fuel
cells were used on the Mercury space missions. Three
modules of 32 cells, operating with low temperature SPE
etectrolytc produced 1 kW at a current density of 36
mdcm2. Present PBM cells with proton exchange
membrane trace their lineage to the space projects.
The requirements for ApoIto mission to land a man on the
moon (and bring him back) required more power. The Bacon
fuel ccll technology above was selected for the Apollo
missions. Early missions were powdered with three 1.42 kW
high temperature, high-pressure fuel cell modules at 68 ma
cm2 current density. The Orbiter shuttle required even more
power. Pratt & Whitney is now United Technologies
Company, UTC. used hydrogen and oxygen alkaline
capillary matrix electrolyte fuel cells. The first Orbitor fuel
cell system operated at low temperatures (80-9OC)at
pressures of 4-4.4 aim. Two parallel stacks produced 12 kW.
As the demands increased, the systems have grown to higher
power capability at reduced weight.
Earth fuel cells
Phosphoric Acid Fuel Cells, PAFC
The success of fuel cells in space lead to dreams of the future
fuel cells on earth. Alkaline space fuel cells difficulties with
CO2 however lead to a search for a CO2 rejecting electrolyte
for use on earth with hydrocarbons as the precursor fuel and
air as the source of oxygen. The major work has lead to 200
C, 85% phosphoric acid electrolyte with hydrogen rich gas
reformates as fuels. At these temperatures, carbon monoxide
even at one to two % does not compete strongly with
hydrogen for the platinum catalysts. Above 230 C
pressurization i s needed io retain water in the electrolyte.
Silicon carbide is added to the phosphoric acid to bind the
acid into a tile. The acid units form inorganic polymers that
have hydrogen ion migration. Phosphoric acid is a non-
oxidizing acid. Many materials of construction are stable at
200 C acid.
UTC now through ONSI Division markets PAFC's as PC25
units. which have D. 200 kW output. The systems steam
reform methane (natural gas propane) to a hydrogen rich gas,
which is then water gas, shifted on the way to the cclls to
incrcase hydrogen content and to reduce thc carbon
monoxide to a one to two % level. There are many PC25C
units installed around the world. good. According CO ONSI,
the performance has been very good. However, while the
price now at $4000 per kW is acceptable for demonstrations.
It is loo high for bulk commercial sales.

PAFC have been used in transportation. H Power in
Bloomfield, NJ has used PAFC’s to power three buses.
Methanol liquid fuel was reformed to hydrogen rich gases.
Fuji of Japan made the phosphoric acid stacks under license
from Englehard, Edison NJ. These systems worked well.
Software glitches were a problem controlling the flame
temperatures in the reformer. Japanese and Italians
ScientistsLengineers and industries have shown considerable
continuing interest in PAFC’s.
High temperature fuel cells
High temperature cells are not affected by carbon dioxide.
They can use conventional fuels. The fuels are generally
natural gas, gasified coal and other gasified solids fuels.
They are converted to hydrogen and carbon monoxide.
Molten Carbonate Fuel Cells, MCFC
Molten carbonate fuel cells operate at about 600 C. This
temperature, molten Carbonate electrolyte has good
conductivity. Carbon dioxide is not a problem for these cells.
It is a necessity. Carbon dioxide is added to the incoming air
stream. Carbon dioxide and oxygen from air, together with
electrons from the cathode electrode are converted to
carbonate ions,
2 e + C 0 2 + 0 2 3 C03=
Migrated carbonate ions react with the fuel (hydrogen and
carbon monoxide) at the anode electrodes reIeasing electrons
and producing carbon dioxide and water.
MC Power in Buy-Ridge IL, feeds cells reformate from an
external reformer. ERC in Danbury CN, puts reforming
catalysts in
The anode compartments and reforms the fuel locally.
Several MCFC systems have reached the megawatt stages.
Solid Oxide Fuei Cells, SOFC
Solid oxide fuel cells use oxide ion migration through
ionically conducting ceramics for ihe electrolyte. Calcium
oxide stabilized with zirconia has adequate conductivity
approaching 1OOOC. At the cathode electrode, there i s a
conversion of oxygen (02) to two oxide ions, 0-. These ions
migrate through the ceramic electrolyte to the anode
electrode. At the anode electrode, the oxide ions unite with
the fuel releasing electrons and producing carbon dioxide
and water. Solid oxide cells have bcen under investigation
for aboui four decades. Seimens recently bought
Westinghouse and affirmed their tubular design by dropping
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the Seimens planar approach - problem with planar sealing.
Systems operating in the 100 kW have been demonstrated.
Zetec. Polydyne and others are concentrating on smaller
sizes.
Alkaline Electrolyte Fuel Cells, AFC
AFC arc now receiving more attention. The pathways
charted by Allis-Chalmers, Union Carbide and others are
being followed in this alkaline work. These systems are
ambient temperature systems, circulation the electrolyte for
heat transfer and water and carbonate removal. The systems
have been operated below wro C to above 100 C. The
construction is molded plastics and non-noble and noble
metal catalysts. Zevco of Belgium and London recently
showed alkaline fuel cell powered London Taxi in London
and New York.
Summary
The development pathway of electrochemical devices toward
fuel cell began over 150 years ago with Sir William Grove
through Francis Bacon’s power plant and the fuel cell
powered tractor to the Space Race. Multi-kW fuel cells
could be used in our daily Iives to power electric vehicles,
power our homes, apartments, offices, hospitaIs and small
malls. Additionally we want to use fractional kW fuel cells
could be used for powering portable computers, cell phones
and wireless connections. I n this new electric century fuel
cells and batteries will give us personal electricity for
personal and dispersed electricity.
There are 10’s of fud cell possibilities. A fuel cell can be
selecrcd from lists of fuels, oxidants, electrolytes,
temperatures, pressures and sizes, plus numerous other
factors. Presently only a handful of fuel cells are at the stage
of deveIopment involving muIti kW systems. The cvolution
of these js a function of applications, appropriate technology,
available money, system costs and personalities of the people
driven to succeed. These and other systems will emerge from
the many systems, waiting and wanting to more fully meet
the needs, requirements and the specifications for
commercial success.
The turn of the century to 1900’s brought an etectric century
with central station generation of electricity with alternating
current, ac, and the grid with motors and electric lights. The
turn of a new century to 2000’s will bring a decentralization
of electric power and a move to personal electricity. Our
lives will be changed beyond our present dreams.
 Suggested Reading for history
of fuel cells
Fuel Cells: Gregory D.P.; M & B Monographs, Chemical
Engineering - Mills & Boon Limited, London, England
1972.

Fuel Cells; Mitchell, Will, Jr.,Ed; Academic Press, New

York, NY 1963,

Fuel Cells An Introduction to Electrochemistry; Klein, H.

Arthur; I.3. Lippincott Company, Philadelphia, PA 1966.

Fuel Cells and Batteries; Eiebhafsky, H.A. and Cairns, E.J.;

John Wiley & Sans, New York, NY 1968.

-
Fuel Cells Energy Alternatives Series; McDougalI Angus;
John Wiley & Sons, New York, NY 1976.

Fuel Cells Power for Tomorrow; Halacy, D.S..Jr.; Thc

World Publishing Company, Cleveland, OH 1966.

Fuel Cells: Their Electrochemistry; Bockris, John, O’M. and

Srinivasan, S.; McGraw-Bill, Inc., New York, NY 1969.

Handbook of Batteries & Fuel Cells; Linden, David;

McGraw-Hill, Inc., New York, NY 1969.

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