Fuel Cells

FUEL CELL BASED ENERGY STORAGE AND ITS

ANALYSIS
• In contrast to a chemical battery, the fuel cell generates electric
energy rather than storing it and continues to do so as long as a fuel
supply is maintained.
• Compared with the battery-powered electric vehicles (EVs), the fuel
cell-powered vehicle has the advantages of a longer driving range
without a long battery charging time.
• Compared with the internal combustion engine (ICE) vehicles, it has
the advantages of high energy efficiency and much lower emissions
due to the direct conversion of free energy in the fuel into electric
energy, without undergoing combustion
OPERATING PRINCIPLES OF FUEL CELLS
• A fuel cell is an electrochemical device that produces electricity by means of a chemical reaction, much like a
battery.
• The major difference between batteries and fuel cells is that the latter can produce electricity as long as fuel
is supplied, while batteries produce electricity from stored chemical energy and, hence, require frequent
recharging.
• The basic structure of a fuel cell consists of an anode and a cathode, similar to a battery.
• The fuel supplied to the cell is hydrogen and oxygen.
• The concept of fuel cell is the opposite of electrolysis of water, where hydrogen and oxygen are combined to
form electricity and water.
• The hydrogen fuel supplied to the fuel cell consists of two hydrogen atoms per molecule chemically bonded
together in the form H2.
• This molecule includes two separate nuclei, each containing one proton,
while sharing two electrons.
• The fuel cell breaks apart these hydrogen molecules to produce electricity.
• The exact nature of accomplishing the task depends on the fuel cell type,
although what remains the same for all fuel cells is that this reaction takes
place at the anode.
• The hydrogen molecule breaks into four parts at the anode due to the
chemical reaction, releasing hydrogen ions and electrons.
• A catalyst speeds the reaction, and an electrolyte allows the two hydrogen
ions, which essentially are two single protons, to move to the cathode
through the electrolyte placed between the two electrodes.
• The flow of electrons from the anode to the cathode through the external
circuit is what produces electricity.
• For the overall cell reaction to complete, oxygen or air must be passed over
the cathode. The cathode reaction takes place in two stages.
• First, the bond between the two oxygen atoms in the molecule breaks and
then each ionized oxygen atom grabs two electrons coming from the anode
through the external circuit to become negatively charged.
• The negatively charged oxygen atoms are balanced by the positively
charged hydrogen atoms at the cathode, and the combination produces
H2O commonly known as water.
Fuel Cell Types
• Alkaline Fuel Cell
• Proton Exchange Membrane
• Direct Methnol
• Phosphoric Acid FC
• Molten Carbonate FC
• Solid Oxide FC
Operating Data of Various Fuel Cell Systems
Alkaline Fuel Cell
• AFCs use an aqueous solution of potassium hydroxide (KOH) as the
electrolyte to conduct ions between electrodes.
• Potassium hydroxide is alkaline.
• Because the electrolyte is alkaline, the ion conduction mechanism is
different from PEM fuel cells. The ion carried by the alkaline
electrolyte is a hydroxide ion (OH-).
• This affects several other aspects of the fuel cell. The half reactions
are:
• Unlike in acidic fuel cells, water is formed on the hydrogen electrode.
• In addition, water is needed at the cathode by the oxygen reduction.
Water management becomes an issue, which is sometimes resolved
by making the electrodes waterproof and keeping the water in the
electrolyte.
• The cathode reaction consumes water from the electrolyte where the
anode reaction rejects its product water.
• The excess water (2 mol per reaction) is evaporated outside the stack.
• AFCs are capable of achieving very high efficiencies because of the fast kinetics
allowed by the hydroxide electrolyte.
• The oxygen reaction (O2→OH-) in particular is much easier than the oxygen
reduction in acidic fuel cells. As a result, the activation losses are very low.
• The fast kinetics in AFCs allow using silver or nickel as catalysts instead of
platinum. The cost of the fuel cell stack is thus greatly reduced.
• The AFC kinetics is further improved by the eventual circulation of the electrolyte.
When the electrolyte is circulated, the fuel cell is said to be a “mobile electrolyte
fuel cell.” The advantages of such an architecture are:
• An easy thermal management because the electrolyte is used as coolant;
• More homogeneous electrolyte concentration, which solves problems of
concentration around the cathode;
• The possibility of using the electrolyte for water management;
• The possibility of replacing the electrolyte if it has been too polluted by
carbon dioxide; and
• finally there is the possibility of removing the electrolyte from the fuel cell
when it is turned off, which has the potential to greatly lengthen the lifetime
of the stack.
• The greatest problem is the increased risk of leakage: potassium hydroxide is
highly corrosive and has a natural tendency to leak even through the tightest
seals. The construction of the circulation pump and heat exchanger and
eventual evaporator is further complicated. Another problem
• The risk of internal electrolytic short-circuit between two cells if the
electrolyte is circulated too violently or if the cells are not isolated enough.
• The greatest problem with AFCs is the poisoning by carbon dioxide. The
alkaline electrolyte has a great affinity for carbon dioxide and together they
form carbonate ions. These ions do not participate in the fuel cell reaction
and diminish its performance.
• There is also a risk that the carbonate will precipitate and obstruct the
electrodes.
• The advantages of AFCs are that they require cheap catalysts, cheap
electrolytes, high efficiency, and low-temperature operation.
• However, they also have some disadvantages such as impaired durability due
to corrosive electrolyte, water produced on fuel electrode, and poisoning by
carbon dioxides.
Proton Exchange Membrane Fuel Cell
• Electrolyte- Solid Polymer membrane
• Perfluorosulfonic acid, which is also referred to as Nafion
• This polymer membrane is acidic; therefore, the ions transported are hydrogen ions (H+) or
protons.
• The PEMFC is fueled with pure hydrogen and oxygen or air as oxidant.
• The polymer electrolyte membrane is coated with a carbon-supported catalyst.
• The catalyst is in direct contact with both the diffusion layer and the electrolyte
for a maximized interface.
• The catalyst constitutes the electrode.
• Directly above the catalyst layer is the diffusion layer.
• The assembly of the electrolyte, catalyst layers, and gas diffusion layers is referred
to as the membrane–electrode assembly
• Because of the low operating temperature of the fuel cell and the acidic
nature of the electrolyte, noble metals are required for the catalyst layer.
• The cathode is the most critical electrode because the catalytic reduction of
oxygen is more difficult than the catalytic oxidation of hydrogen.
• In order to operate properly, the polymer membrane needs to be kept humid.
Indeed, the conduction of ions in polymer membranes requires humidity. If
the membrane is too dry, there will not be enough acid ions to carry the
protons. If it is too wet (flooded), the pores of the diffusion layer will be
blocked and the reactant gases will not be able to reach the catalyst.
• In PEM fuel cells, water is formed on the cathode. It can be removed by
keeping the fuel cell at a certain temperature and flowing enough to
evaporate the water and carry it out of the fuel cell as a vapor.
• However, this approach is difficult because the margin of error is narrow.
Some fuel cell stacks run on a large excess of air that would normally dry the
fuel cell, and use an external humidifier to supply water by the anode.
• The last major critical issue in PEM fuel cells is poisoning.
• The platinum catalyst is extremely active and thus provides great
performance. The trade-off of this great activity is a greater affinity for
carbon monoxide (CO) and sulfur products than oxygen.
• The poisons bind strongly to the catalyst and prevent hydrogen or oxygen
from reaching it.
• The electrode reactions cannot take place on the poisoned sites and the
fuel cell performance is diminished.
• If hydrogen is fed from a reformer the stream will contain some carbon
monoxide. The carbon monoxide may also enter the fuel cell in the air
stream if the air is pumped from the atmosphere of a polluted city.
Poisoning by carbon monoxide is reversible but it comes at a cost and
requires the individual treatment of each cell.
• Low-temperature operation and hence its fast start-up are desirable
for an EV and HEV.
• The power density is the highest among all the available types of fuel
cells. The higher the power density, the smaller the size of the fuel
cell that needs to be installed for the desired power demand.
• Its solid electrolyte does not change, move, or vaporize from the cell.
• Since the only liquid in the cell is water, the possibility of any
corrosion is essentially delimited.
• Disadvantages- The expensive noble metal needed, expensive
membrane, and easily poisoned catalyst and membrane.
Phosphoric Acid Fuel Cells
• PAFCs rely on an acidic electrolyte
• The anode and cathode reactions are the same as PEM fuel cell
reactions.
• Phosphoric acid (H3PO4) is a viscous liquid that is contained by
capillarity in the fuel cell in a porous silicon carbide matrix.
• PAFC is the first fuel cell technology to be marketed.
• Many hospitals, hotels, and military bases make use of a PAFC to
cover part or a totality of their electricity and heat needs.
• The phosphoric acid electrolyte temperature must be kept above 42°C, which is its
freezing point.
• Freezing and rethawing the acid unacceptably stresses the stack. Keeping the stack
above this temperature requires extra hardware, which adds to its cost, complexity,
weight, and volume.
• Most of these issues are minor in the case of a stationary application but are
incompatible with a vehicular application.
• Another problem arising from the high operating temperature (above 150°C) is the
energy consumption associated with warming up the stack. Every time the fuel cell is
started, some energy (i.e., fuel) must be spent to heat it up to operating temperature
and every time the fuel cell is turned off, the heat (i.e., energy) is wasted.
• The loss is significant for short travel time, which is a common occurrence for city
drivers. However, this issue seems to be minor in the case of mass transportation
such as buses.
• The advantages of PAFC are its use of a cheap electrolyte, low operating
temperature, and reasonable start-up time.
• The disadvantages are expensive catalyst (platinum), corrosion by acidic electrolyte,
CO2 poisoning, and low efficiency.
Molten Carbonate Fuel Cells
• MCFCs are high-temperature fuel cells (500 to 800°C).
• They rely on a molten carbonate salt to conduct ions, usually lithium–
potassium carbonate or lithium–sodium carbonate.
• The ions conducted are carbonate ions (CO32-).
• The ion conduction mechanism is that of a molten salt like in PAFC or
highly concentrated alkaline fuel cells.
• The electrode reactions are different from other fuel cells:
• The major difference from other fuel cells is the necessity to provide carbon
• dioxide at the cathode. It is not necessary to have an external source
• since it can be recycled from the anode. MCFCs are never used with pure
• hydrogen but rather with hydrocarbons. Indeed, the major advantage of
• high-temperature fuel cells is their capability to, almost, directly process
• hydrocarbon fuels because the high temperature allows decomposing
• them to hydrogen on the electrodes. This would be a tremendous
advantage
• for automotive applications because of the present availability of
• hydrocarbon fuels. In addition, the high temperatures enhance the kinetics
• to the point that cheap catalysts may be used.
 Molten Carbonate Fuel Cells
• MCFCs are high-temperature fuel cells (500 to 800°C).
• They rely on a molten carbonate salt to conduct ions, usually lithium–potassium carbonate or
lithium–sodium carbonate. The ions conducted are carbonate ions (CO32-).
• The ion conduction mechanism is that of a molten salt like in PAFC or highly concentrated alkaline
fuel cells.
• The major difference from other fuel cells is the necessity to provide
carbon dioxide at the cathode.
• It is not necessary to have an external source since it can be recycled
from the anode.
• MCFCs are never used with pure hydrogen but rather with
hydrocarbons. Indeed, the major advantage of high-temperature fuel
cells is their capability to, almost, directly process hydrocarbon fuels
because the high temperature allows decomposing them to
hydrogen on the electrodes. This would be a tremendous advantage
• for automotive applications because of the present availability of
hydrocarbon fuels. In addition, the high temperatures enhance the
kinetics to the point that cheap catalysts may be used.
• MCFCs, however, pose many problems due to the nature of their electrolytes and the operating
temperatures that they require.
• The carbonate is an alkali, and is extremely corrosive especially at high temperatures. Not only is this
unsafe, there is also the problem of corrosion on the electrodes.
• It is unsafe to have a large device at 500 to 800°C under the hood of a vehicle.
• While it is true that temperatures in internal combustion engines do reach above 1000°C, these
temperatures are restricted to the gases themselves and most parts of the engine are kept cool
(around 100°C) by the cooling system.
• The fuel consumption associated with heating up the fuel cell is also a problem, worsened by the
very high operating temperature, and latent heat necessary to melt the electrolyte. These problems
are likely to confine molten carbonate fuel cells to stationary or steady power applications such as
ships.
• The major advantages of MCFCs are that they are fueled with hydrocarbon fuels, require a low-cost
catalyst, have improved efficiency due to fast kinetics, and low sensitivity to poisoning.
• The major disadvantages are slow start-up and reduced material choice due to high temperature,
complex fuel cell system due to CO2 cycling, corrosive electrolyte, and slow power response.
Solid Oxide Fuel Cells
• SOFCs conduct ions in a ceramic membrane at high temperature (1000 to 1200°C).
• Usually, the ceramic is a yttrium stabilized zirconia (YSZ) that will conduct oxygen ions (O2), but
other ceramics conduct hydrogen ions.
• The conduction mechanism is similar to that observed in semiconductors, often called solid-state
devices. The name of the fuel cell is derived from that similarity.
• Here again, water is produced at the fuel electrode.
• The greatest advantage of SOFCs is this static electrolyte. There is no moving part, except perhaps in
the ancillaries.
• The very high operating temperature allows the use of hydrocarbon fuels as in MCFCs.
• SOFCs are not poisoned by carbon monoxide and that they process it about as efficiently as hydrogen.
• The anode reaction is then
• SOFCs also benefit from reduced activation losses due to their high operating temperature.
• The losses are dominated by the ohmic component.
• SOFCs may be of two kinds: planar or tubular.
• The planar type is a bipolar stack similar to other fuel cell technologies.
• The major advantages of tubular technologies include easier sealing and reduced constraints on the
ceramics. Disadvantages include lower efficiency and power density.

Tubular solid oxide fuel cell

• Like MCFCs, the disadvantages of SOFCs are mostly associated with
their high operating temperature (safety, fuel economy).
• Supplementary problems arise because the ceramic electrolyte and
electrodes are extremely brittle.
• This is a major disadvantage for vehicular applications where
vibrations are a common occurrence. Thermal cycling further stresses
the ceramics and is a major concern for planar fuel cells.
Direct Methanol Fuel Cells
• Instead of using hydrogen, methanol can be directly used as the fuel for a fuel
cell; this is the so-called DMFC.
• There are some definite motivations for applying DMFC to vehicles. First,
methanol is a liquid fuel that can be stored easily, distributed, and marketed for
vehicle application; hence, the current infrastructure of fuel supply can be used
without too much further investment.
• Second, methanol is the simplest organic fuel, which can be most economically
and efficiently produced on a large scale from relatively abundant fossil fuel,
namely coal and natural gas.
• Furthermore, methanol can be produced from agriculture products, such as
sugar cane.
• In the DMFC, both the anode and cathode adopt platinum or platinum alloys as
electrocatalyst.
• The electrolyte can be trifluoromethane sulfonic acid or PEM.
• The chemical reaction in a DMFC is:

• The DMFC is relatively immature among the aforementioned fuel cells.

• At the present status of DMFC technology, it generally operates at 50 to
100°C.
• Compared with direct hydrogen fuel cells, DMFC has low power density,
• slow power response, and low efficiency.