POLYMER ELECTROLYTIC FUEL CELL

-A CONVENTIONAL ENERGY

ABSTRACT

Fuel cell is an electro chemical device which will produces electrical energy by using
chemical energy. Polymer electrolyte fuel cells have attracted enormous interest as a
primary power source for electric vehicles. Water management in the electrolyte is one
of the complicated problems to be overcome. A new self-humidifying electrolyte
membrane is proposed to solve this problem. Self humidification allows the use of very
hin membranes, simultaneously allowing high performance of the cell. Use of the new,
thin membranes makes the system very simple and ready for cold starts and also
amenable to abrupt load changes. The electrolyte is comprised of polymer membrane
containing platinum catalyst particles and a few weight percent of a hygroscopic material
such as silica or titanium. The platinum particles catalyze the oxidation of cross over
hydrogen with oxygen to generate water, which in turn is adsorbed by the oxide particles.
The cell shows exceptionally stable and high performance even under ambient pressure
conditions when operated with hydrogen saturated with water at 20 0c and dry oxygen.
Operation under the non-humidified conditions was demonstrated with a membrane
electrode assembly (MEA) for a proton exchange membrane cell. The platinum catalyst
was coated with a gradient on the active area of a MEA. The MEA with the gradient
coating method produced more water than with uniform coating method. And the water
was used to mitigate the dryness of the MEA. The polymer electrolyte fuel cell (PEFC’s)
powered vehicles has the potential for zero emission high energy conversion efficiency
and extended range compared to present day battery powered EV’s.

BACKGROUND

Fuel cells convert the chemical energy of fuels directly into electricity. The principle
of the fuel cell was developed by William Grove in 1839. Already around 1900 scientists
and engineers were predicting that fuel cells would be common for producing electricity
and motive power within a few years. That was roughly 100 years ago. Contrast this with
the roughly 2 years that it took Nikolaus Otto to bring his Otto cycle 4-stroke internal
combustion engine from the invention stage to a commercial success.

HOW A FUEL CELL WORKS:

A fuel cell works similar to a battery. In a battery there are two electrodes which are
separated by an electrolyte. At least one of the electrodes is generally made of a solid
metal. This metal is converted to another chemical compound during the production of
electricity in the battery. The energy that the battery can produce in one cycle is limited
by the amount of this solid metal that can be converted. In the fuel cell the solid metal is
replaced by an electrode that is not consumed and a fuel that continuously replenishes
the fuel cell. This fuel reacts with an oxidant such as oxygen from the other electrode. A
fuel cell can produce electricity as long as more fuel and oxidant is pumped through it.

Fig 1: Alkaline fuel cell often uses hydrogen and oxygen as fuel

The alkaline fuel cell as shown in Fig 1 is one of the oldest and most simple type of
fuel cell. This is the type of fuel cell that has been used in space missions for some time.
Hydrogen and oxygen are commonly used as the fuel and oxidant. The electrodes are
made of porous carbon plates which are laced with a catalyst...which is a substance that
accelerates chemical reactions. The electrolyte is potassium hydroxide. At the anode, the
hydrogen gas combines with hydroxide ions to produce water vapor. This reaction results
in electrons that are left over. These electrons are forced out of the anode and produce the
electric current. At the cathode, oxygen and water plus returning electrons from the
circuit form hydroxide ions which are again recycled back to the anode. The basic core of
the fuel cell consisting of the manifolds, anode, cathode and electrolyte is generally
called the stack.
Proton exchange membrane fuel cell:

Diagram of a PEM fuel cell

Proton exchange membrane fuel cells, also known as polymer electrolyte membrane
fuel cells (PEMFC), are a type of fuel cell being developed for transport applications as
well as for stationary and portable applications. Their distinguishing features include
lower temperature/pressure ranges and a special polymer electrolyte membrane.

Reactions:

A proton exchange membrane fuel cell transforms the chemical energy liberated during
the electrochemical reaction of hydrogen and oxygen to electrical energy, as opposed to
the direct combustion of hydrogen and oxygen gases to produce thermal energy.

A stream of hydrogen is delivered to the anode side of the membrane-electrode assembly

(MEA). At the anode side it is catalytically split into protons and electrons. This
oxidation half-cell reaction is represented by:

Eo = 0VSHE

The newly formed protons permeate through the polymer electrolyte membrane to the
cathode side. The electrons travel along an external load circuit to the cathode side of the
MEA, thus creating the current output of the fuel cell.

Meanwhile, a stream of oxygen is delivered to the cathode side of the MEA. At the
cathode side oxygen molecules react with the protons permeating through the polymer
electrolyte membrane and the electrons arriving through the external circuit to form water
molecules. This reduction half-cell reaction is represented by:

Eo=1.229VSHE
PARTS OF FUEL CELL:

Polymer electrolyte membrane (PEM) fuel cells are the current focus of research for fuel
cell vehicle applications. PEM fuel cells are made from several layers of different
materials, as shown in the diagram. The three key layers in a PEM fuel cell include:

• Membrane electrode assembly

• Catalyst
• Hardware

Other layers of materials are designed to help draw fuel and air into the cell and to
conduct electrical current through the cell.

MEMBRANE ELECTRODE ASSEMBLY:

The electrodes (anode and cathode), catalyst, and polymer electrolyte membrane
together form the membrane electrode assembly (MEA) of a PEM fuel cell.
• Anode. The anode, the negative side of the fuel cell, has several jobs. It conducts
the electrons that are freed from the hydrogen molecules so that they can be used
in an external circuit. Channels etched into the anode disperse the hydrogen gas
equally over the surface of the catalyst.
• Cathode. The cathode, the positive side of the fuel cell, also contains channels
that distribute the oxygen to the surface of the catalyst. It conducts the electrons
back from the external circuit to the catalyst, where they can recombine with the
hydrogen ions and oxygen to form water.
• Polymer electrolyte membrane. The polymer electrolyte membrane (PEM)—a
specially treated material that looks something like ordinary kitchen plastic wrap
—conducts only positively charged ions and blocks the electrons. The PEM is the
key to the fuel cell technology; it must permit only the necessary ions to pass
between the anode and cathode. Other substances passing through the electrolyte
would disrupt the chemical reaction.

Types of Fuel Cells

Fuel cells are classified primarily by the kind of electrolyte they employ. This
determines the kind of chemical reactions that take place in the cell, the kind of catalysts
required, the temperature range in which the cell operates, the fuel required, and other
factors. These characteristics, in turn, affect the applications for which these cells are
most suitable. There are several types of fuel cells currently under development, each
with its own advantages, limitations, and potential applications. Learn more about:

• Polymer Electrolyte Membrane (PEM) Fuel Cells

• Direct Methanol Fuel Cells
• Alkaline Fuel Cells
• Phosphoric Acid Fuel Cells
• Molten Carbonate Fuel Cells
 • Solid Oxide Fuel Cells
• Regenerative Fuel Cells
• Comparison of Fuel Cell Technologies

1. POLYMER ELECTROLYTE MEMBRANE (PEM) FUEL CELLS:

Polymer electrolyte membrane (PEM) fuel cells—also called proton exchange

membrane fuel cells—deliver high power density and offer the advantages of low weight
and volume, compared to other fuel cells. PEM fuel cells use a solid polymer as an
electrolyte and porous carbon electrodes containing a platinum catalyst. They need only
hydrogen, oxygen from the air, and water to operate and do not require corrosive fluids
like some fuel cells. They are typically fueled with pure hydrogen supplied from storage
tanks or onboard reformers.

Polymer electrolyte membrane fuel cells operate at relatively low temperatures,

around 80°C (176°F). Low temperature operation allows them to start quickly (less
warm-up time) and results in less wear on system components, resulting in better
durability. However, it requires that a noble-metal catalyst (typically platinum) be used to
separate the hydrogen's electrons and protons, adding to system cost. The platinum
catalyst is also extremely sensitive to CO poisoning, making it necessary to employ an
additional reactor to reduce CO in the fuel gas if the hydrogen is derived from an alcohol
or hydrocarbon fuel. This also adds cost. Developers are currently exploring
platinum/ruthenium catalysts that are more resistant to CO.

PEM fuel cells are used primarily for transportation applications and some stationary
applications. Due to their fast startup time, low sensitivity to orientation, and favorable
power-to-weight ratio, PEM fuel cells are particularly suitable for use in passenger
vehicles, such as cars and buses.
 A significant barrier to using these fuel cells in vehicles is hydrogen storage. Most fuel
cell vehicles (FCVs) powered by pure hydrogen must store the hydrogen onboard as a
compressed gas in pressurized tanks. Due to the low energy density of hydrogen, it is
difficult to store enough hydrogen onboard to allow vehicles to travel the same distance
as gasoline-powered vehicles before refueling, typically 300-400 miles. Higher-density
liquid fuels such as methanol, ethanol, natural gas, liquefied petroleum gas, and gasoline
can be used for fuel, but the vehicles must have an onboard fuel processor to reform the
methanol to hydrogen. This increases costs and maintenance requirements. The reformer
also releases carbon dioxide (a greenhouse gas), though less than that emitted from
current gasoline-powered engines.

The most commonly used membrane is Nafion® by DuPont®, which relies on liquid
water humidification of the membrane to transport protons. This implies that it is not
feasible to use temperatures above 80–90˚C, since the membrane would dry. Other, more
recent membrane types, based on Polybenzimidazole (PBI) OR phosphoric acid, can
reach up to 220˚C without using any water management: higher temperature allow for
better efficiencies, power densities, ease of cooling (because of larger allowable
temperature differences), reduced sensitivity to carbon monoxide poisoning and better
controllability (because of absence of water management issues in the membrane);
however, these recent types are not as common and most research labs and papers still
use Nafion. Companies producing PBI membranes include Celanese and PEMEAS, and
there is an EU research project regarding these membranes.

2. DIRECT ALCOHOL FUEL CELL (DAFC):

FIG 2.A small simple 30 KW Direct Methanol Fuel Cell

Several companies around the world are presently working on DAFC. In 1999 there
was a marked shift away from developing the PEFC in favor of the DAFC [5]. ]. In this
type of fuel cell, either methyl DMFC or ethyl DEFC alcohol is not reformed into
hydrogen gas but is used directly in a very simple type of fuel cell. Its operating
temperature of 50-100°C is low and so is ideal for tiny to midsize applications. Its
electrolyte is a polymer or a liquid alkaline. This type of fuel cell was largely overlooked
in the early 1990s because its efficiency was below 25%. Most companies rather pursued
the PEFC because of its higher efficiency and power density. There has been tremendous
progress made in the last 7 years. Efficiencies of the DMFC are much higher and
predicted efficiencies in the future may be as high as 40% [6] for a DC automobile power
plant. Power densities are over 20 times as high now as in the early 1990s. It is expected
that the DMFC will be more efficient than the PEFC for automobiles that use methanol as
fuel. Presently the power density of the DEFC is only 50% of the DMFC but hopefully
this can be improved in the future.

Fuel crossing over from the anode to the cathode without producing electricity is one
problem that has restricted this technology from its inception. One company, Energy
Ventures Inc claimed in Dec1999 that it has completely solved this cross-over problem.
Another problem however is that there are often chemical compounds formed during
operation that poisons the catalyst.

There are already working DMFC prototypes used by the military for powering
electronic equipment in the field.

Figure 2 illustrates a type of DMFC that could be used in a 30 kW system. Even

smaller ones for use as battery replacements do away with the air blower and the separate
methanol water tank and pump. Such fuel cells are not much different than batteries in
construction.
Recently there has been much concern about the poisonous aspects of methanol--
methyl alcohol. As of 2001 methanol is "out" and ethanol is "in". Already several
companies are now working on DEFC. Presently the power density is only 50% of the
DMFC but hopefully this can be improved.

3. SOLID OXIDE FUEL CELL (SOFC):

Fig 3. Simple type [2] SOFC suitable for 1-30 kW power plants
 The Solid Oxide Fuel Cell is considered to be the most desirable fuel cell for
generating electricity from hydrocarbon fuels. This is because it is simple, highly
efficient, tolerant to impurities, and can at least partially internally reform hydrocarbon
fuels.

The SOFC runs at a red-hot temperature of 700-1000°C. Westinghouse has worked at

developing a tubular style of SOFC for many years which operates at 1000°C.One of the
big advantages of the SOFC over the MCFC is that the electrolyte is a solid. This means
that no pumps are required to circulate hot electrolyte. Small planar SOFC of 1 kW could
be constructed with very thin sheets and result in a very compact package.
A big advantage of the SOFC is that both hydrogen and carbon monoxide are used in
the cell [3]. In the PEFC the carbon monoxide is a poison, while in the SOFC it is a fuel.
This means that the SOFC can readily and safely use many common hydrocarbons fuels
such as natural gas, diesel, gasoline, alcohol and coal gas. In the PEFC an external
reformer is required to produce hydrogen gas while the SOFC can reform these fuels into
hydrogen and carbon monoxide inside the cell. This results in some of the high
temperature waste thermal energy being recycled back into the fuel.
Because the chemical reactions in the SOFC are good at the high operating
temperatures, air compression is not required. Especially on smaller systems this results
in a simpler system, quiet operation, and high efficiencies..
Many fuel cells such as the PEFC require an expensive liquid cooling system but the
SOFC requires none. In fact insulation must be used to maintain the cell temperature on
small systems. The cell is cooled internally by the reforming action of the fuel and by the
cool outside air that is drawn into the fuel cell.
Because the SOFC does not produce any power below 650°C, a few minutes of fuel
burning is required to reach operating temperature. While the SOFC is also being
proposed as an automotive power plant, this time delay is considered to be a
disadvantage.

FUELS:

The hydrogen economy which was popularized in the 1970s was based on producing
hydrogen using nuclear power plants. Now that nuclear power is unpopular, we have
eliminated any present method of making large amounts of hydrogen for a reasonable
price. Society has however held on to the wonders of having a hydrogen economy, where
hydrogen would be used for everything from generating electric power to heating homes
and powering industry.

Hydrogen is admittedly a wonderful fuel because only water is produced in operating

the fuel cell. Hydrogen is however a difficult fuel to store. It is difficult and costly to
liquefy. It has lower energy content than natural gas when pressurized in tanks. There has
been increasing success in storing hydrogen gas in metal hydrides and carbon compounds
but many of these techniques require either pressure or temperature swings during storage
and extraction. Many require cryogenic refrigeration.
Fuel Cell Systems:

The design of fuel cell systems is complex and can vary significantly depending upon
fuel cell type and application. However, most fuel cell systems consist of four basic
components:

• Fuel cell stack

• Fuel processor
• Current converter
• Heat recovery system

Most fuel cell systems also include other components and subsystems to control fuel cell
humidity, temperature, gas pressure, and wastewater.

Fuel Cell Stack:

The fuel cell stack is the heart of a fuel cell power system. It generates electricity in the
form of direct current (DC) from chemical reactions that take place in the fuel cell. A
single fuel cell produces enough electricity for only the smallest applications. Therefore,
individual fuel cells are typically combined in series into a fuel cell stack. A typical fuel
cell stack may consist of hundreds of fuel cells. The amount of power produced by a fuel
cell depends upon several factors, such as fuel cell type, cell size, the temperature at
which it operates, and the pressure at which the gases are supplied to the cell. Learn more
about the parts of a fuel cell.

Fuel Processor:

The fuel processor converts fuel into a form useable by the fuel cell. If hydrogen is fed to
the system, a processor may not be required or it may only be needed to filter impurities
out of the hydrogen gas.

If the system is powered by a hydrogen-rich conventional fuel such as methanol,

gasoline, diesel, or gasified coal, a reformer is typically used to convert hydrocarbons
into a gas mixture of hydrogen and carbon compounds called "reformate." In many cases,
the reformate is then sent to another reactor to remove impurities, such as carbon oxides
or sulfur, before it is sent to the fuel cell stack. This prevents impurities in the gas from
binding with the fuel cell catalysts. This binding process is also called "poisoning" since
it reduces the efficiency and life expectancy of the fuel cell.

Some fuel cells, such as molten carbonate and solid oxide fuel cells, operate at
temperatures high enough that the fuel can be reformed in the fuel cell itself. This is
called internal reforming. Fuel cells that use internal reforming still need traps to remove
impurities from the unreformed fuel before it reaches the fuel cell.
Current Inverters and Conditioners:

Current inverters and conditioners adapt the electrical current from the fuel cell to suit the
electrical needs of the application, whether it is a simple electrical motor or a complex
utility power grid.

Fuel cells produce electricity in the form of direct current (DC). In a direct current circuit,
electricity flows in only one direction. The electricity in your home and work place is in
the form of alternating current (AC), which flows in both directions on alternating cycles.
If the fuel cell is used to power equipment using AC, the direct current will have to be
converted to alternating current.

Heat Recovery System:

Fuel cell systems are not primarily used to generate heat. However, since significant
amounts of heat are generated by some fuel cell systems—especially those that operate at
high temperatures such as solid oxide and molten carbonate systems—this excess energy
can be used to produce steam or hot water or converted to electricity via a gas turbine or
other technology. This increases the overall energy efficiency of the systems

FUEL CELL PROBLEMS:

Fuel cells might be the answer to our power problems, but first scientists will have to sort
out a few major issues:
Cost:
Chief among the problems associated with fuel cells is how expensive they are. Many
of the component pieces of a fuel cell are costly. For PEMFC systems, proton exchange
membranes, precious metal catalysts (usually platinum), gas diffusion layers, and bipolar
plates make up 70 percent of a system's cost
Durability:
Researchers must develop PEMFC membranes that are durable and can operate at
temperatures greater than 100 degrees Celsius and still function at sub-zero ambient
temperatures. A 100 degrees Celsius temperature target is required in order for a fuel cell
to have a higher tolerance to impurities in fuel. Because you start and stop a car relatively
frequently, it is important for the membrane to remain stable under cycling conditions.
Currently membranes tend to degrade while fuel cells cycle on and off, particularly as
operating temperatures rise.
Hydration:
Because PEMFC membranes must by hydrated in order to transfer hydrogen protons,
researches must find a way to develop fuel cell systems that can continue to operate in
sub-zero temperatures, low humidity environments and high operating temperatures. At
around 80 degrees Celsius, hydration is lost without a high-pressure hydration system.
The SOFC has a related problem with durability. Solid oxide systems have issues with
material corrosion. Seal integrity is also a major concern. The cost goal for SOFC’s is
less restrictive than for PEMFC systems at $400 per kilowatt, but there are no obvious
means of achieving that goal due to high material costs. SOFC durability suffers after the
cell repeatedly heats up to operating temperature and then cools down to room
temperature.
Delivery:
The Department of Energy’s Technical Plan for Fuel Cells states that the air
compressor technologies currently available are not suitable for vehicle use, which makes
designing hydrogen fuel delivery system problematic.
Infrastructure:
In order for PEMFC vehicles to become a viable alternative for consumers, there must
be a hydrogen generation and delivery infrastructure. This infrastructure might include
pipelines, truck transport, fueling stations and hydrogen generation plants. The DOE
hopes that development of a marketable vehicle model will drive the development of an
infrastructure to support it.
Storage and Other Considerations:
Three hundred miles is a conventional driving range (the distance you can drive in a
car with a full tank of gas). In order to create a comparable result with a fuel cell vehicle,
researchers must overcome hydrogen storage considerations, vehicle weight and volume,
cost, and safety.
There is also safety concerns related to fuel cell use. Legislators will have to create new
processes for first responders to follow when they must handle an incident involving a
fuel cell vehicle or generator. Engineers will have to design safe, reliable hydrogen
delivery systems.

CONCLUSIONS:
Fuel cells are still a few years away from commercialization on a large scale. It is very
difficult to tell which fuel and which technology will be predominant in the future. There
are some problems to be solved in the SOFC and the DAFC. If these can be solved then
these will become the predominant fuel cells being developed in the future.

REFERENCES:
Buswell, Clause, Cohen, Louie, Watkins 1994 Ballard US Patent 5,360,679
...Hydrocarbon Fueled Solid Polymer Fuel Cell Electric Power Generation System
Kordesch, K., Simader, G. 1996 Fuel Cells and their Applications VCH Press NY USA
Stimming, U. et all 1997 Proceedings of the fifth International Symposium on Solid
Oxide Fuel Cells Vol 97-40 pg 69 The Electrochemical Society NJ USA.
Minh, Nguyen Quang, Takahashi, Takehiko 1995 Science and Technology of Ceramic
Fuel Cells Elesevier Science B.V. Amsterdam, Netherlands
Comline News Service 09Feb1999 Nissan, Suzuki Join Effort for Direct Methanol Fuel
Cell
Nowell, G.P. 1998 The Promise of Methanol Fuel Cell Vehicles American Methanol
Institute Washington DC USA.