Chapter 3

Electrochemical
Energy Storage (fuel
cell)
 Outline
 Electrochemical reaction
 Fuel cell Performance
 Thermodynamics of fuel cell
 Types of fuel cell
Electrochemical reactions
 Redox (oxidation-reduction) reaction in which electrons are
transferred from a donor (reducing agent) to an accepter
(oxidant).
 Redox reactions take place by movement of electrons or ions
across the interface of metal electrode.
 Each of the reaction is known as half-reaction and system of an
electrode with electrolyte is called half-cell.
 A half cell is a structure that contains a conductive electrode
and a surrounding conductive electrolyte separated by a
natural occurring Helmholtz electrical double layer.
 Both half-reaction must always go side by side to sustain the
electrochemical reaction.
Fuel cell Performance
 Fuel cell can operate at higher efficiencies than combustion
engines and can convert the chemical energy in the fuel directly
to electrical energy with efficiencies of capable of exceeding
60%.
 Fuel cell
A fuel cell is an electrochemical cell that converts chemical
energy from a fuel into electricity through an
electrochemical reaction of hydrogen fuel with oxygen or
another oxidizing agent.
Ordinary combustion process of fuel
Fuel + oxygen = combustion product +heat
The process of fuel cell
Fuel + oxygen = Oxidation products + Electricity
Parts of a fuel cell
Anode
 Negative post of the fuel cell
 Conducts the electrons that are freed from the hydrogen molecules so that they can be
used an external circuit.
 Etched channels disperse hydrogen gas over the surface of the catalyst.
Cathode
 Positive post of the fuel cell
 Etched channels distribute oxygen to the surface of the catalyst.
 Conducts electrons back from the external circuit to the catalyst.
 Recombine with the hydrogen ions and oxygen to form water.
Electrolyte
 Proton exchange membrane
 Specially treated material, only conducts positively charged ions.
 Membrane block electron.
 Cont…
Catalyst
 Special material that facilitates the reaction of oxygen and hydrogen.
 Usually, palatinum powder very thinly coated onto carbon paper or
cloth.
 Rough and porous maximizes surface area exposed to hydrogen or
oxygen.
 The platinum-coated side of the catalyst face the PEM.
Principle of operation
Pressurized hydrogen gas (H2) enters cells on anode side.
 Gas is forced through the catalyst by pressure.
 When H2 molecule comes contacts platinum catalyst, it splits into two
H+ ions and two electrons (e-).
Electrons are conducted through the anode
 Make their way through the external circuit( doing useful work such as
turning a motor) and return to the cathode side of the fuel cell.
On the cathode side, oxygen gas (O2) is forced through catalyst.
 Forms two oxygen atom, each with strong negative charge.
 Negative charge attracts the two H+ ion through the membrane.
 Combine with an oxygen atom and two electrons from the external
circuit to form a water molecule (H2O).
 Fuel cells operation
• Example: PEMFC
• The hydrogen atom’s electron and proton are separated at
the anode.
• Only the protons can go through the membrane (thus, the
name proton exchange membrane fuel cell).
dc current
Heat
Oxygen
Hydrogen

Water
Membrane
Catalyst (Pt) (Nafion) Catalyst (Pt)
Anode (-) Cathode (+)

H 2  2 H   2e  1/ 2O2  2 H   2e   1H 2O

O2  2 H 2  2 H 2O (Er 1.23 V )
Reaction in fuel cell
 At anode
2H2 4H+ + 4e-
 At cathode
O2 + 4H+ + 4e- 2H2O
 Over all
2H2 + O2 2H2O
Fuel cell representation
Fuel cell thermodynamics
 The study of the transformation of energy from one form to other.
 Predict the upper bound limit on the maximum electrical potential
that can be generated in a reaction, or the ideal performance of a fuel
cell under ideal condition.
 Predict weather a candidate fuel cell reaction is energetically
Spontaneous.
 Thermodynamics yields the theoretical boundaries of what is possible
with a fuel cell; it gives the “ideal case.”
 Any real fuel cell will perform at or below its thermodynamic limit.
Understanding real fuel cell performance requires a knowledge of
kinetics in addition to thermodynamics.
 Internal energy: it associated with microscopic movement and
interaction particles at atomic and molecular levels.
 Internal energy is also associated with the chemical bonds between
the hydrogen atoms.
 For example, a tank of H2 gas sitting on a table has no apparent
energy. However, the H2 gas actually has significant internal energy.
on the microscopic scale it is a whirlwind of molecules traveling
hundreds of meters per second.
 Internal energy is also associated with the chemical bonds between
the hydrogen atoms. A fuel cell can convert only a portion of the
internal energy associated with a tank of H2 gas into electrical energy.
First law of thermodynamics
 The Energy of a system is conserved
δQ – δW = ∆E
 For a closed system (control mass system), such as a piston
∆E = UE + ∆KE + ∆P
 The total energy change equals the sum of the change internal energy,
the change in kinetic energy and the change in potential energy.
U = ∆Q - ∆W
∆W = pdV (mechanical work done).
Second Law
The concept of entropy. Entropy is determined by the number of possible
microstates accessible to a system, or, in other words, the number of
possible ways of configuring a system.
 A system’s entropy is usually inferred based on how heat transfer causes
the entropy of the system to change. For a reversible transfer of heat at
constant pressure, the entropy of a system will change as

dS = dQrev/T
Based on the first and second laws of thermodynamics, we can write down
“rules” to specify how energy can be transferred from one form to another.
These rules are called thermodynamic potentials.
U = ∆Q - ∆W
= dST – pdV
Internal energy a function of entropy and volume.
U = U(S, V)
We can also derive the following useful relations, which show how the
dependent variables T and p are related to variations in the
independent variables (S and V):
Unfortunately, S and V are not easily measurable in most experiments.
(There is no such thing as an “entropy meter.”) Therefore, a new
thermodynamic potential is needed equivalent to U but depending on
quantities that are more readily measured than S and V. Temperature T and
pressure p fall into this category
Types of fuel cell
 Fuel
cells are classified primarily by the kind of electrolyte
they employ.
 This
classification determines the kind of electro-chemical
reaction that takes place in the cell, the kind of catalysts
required, the temperature range in which the cell
operates, the fuel required, and the other factors.
 These characteristics affect, in turn, affect the applications
for which these cell are most suitable.
 There are several types of fuel cells currently under
development, each with its own advantages, limitations,
and potential application.
 Prominent Types
 Polymer electrolyte membrane fuel cell (PEMFC).
 Direct methanol fuel cell (DMFC).
 Alkaline fuel cell (AFC).
 Phosphoric acid fuel cell (PAFC).
 Molten-carbonate fuel cell (MCFC).
 Solid-oxide fuel cell (SOFC).
 Reversible fuel cells
 Polymer electrolyte membrane fuel cell (PEMFC).

 Polymer electrolyte membrane (PEM) fuel cells also called proton

exchange membrane fuel cells: deliver high power density and offer the
advantage of low weight and volume compared with the fuel cells.
 PEM fuel cells uses a solid polymer as an electrolyte and porous carbon
electrode containing a platinum or platinum alloy catalysts. They need only
hydrogen and oxygen from the air and water to operate.
 Operate relatively low temperature, around 800 C. the low temperature
operations allows them to start quickly (less warm-up time) and results in
the less wear on the system components, resulting better durability.
 PEM fuel cells have a practical efficiency of 60%. Power output is in the
range of 5-200kw. They are ideal for transportation and portable power.
 PEM fuel cells are particularly suitable for use in passenger vehicles, such
as cars and buses.
Diagram of PEM
Electrochemical reaction occurring in PEMFC

 At anode
H2 2H+ + 2e-
 At cathode
1/2O2 + 2H+ + 2e- H2 O
 Over all
H2 + 1/2O2 H2 O
 Direct methanol fuel cells
 Directmethanol fuel cells (DMFCs), are powered by pure
methanol, which is usually mixed with water and fed directly
to the fuel cell anode.
 Direct
methanol fuel cells do not have many of the fuel
storage problems typical of some of the fuel systems
because methanol has a higher energy density than
hydrogen- though less than gasoline or diesel fuel.
 DMFCs are often used to provide power for portable fuel cell
applications such as cell phones or laptop computer.
 DMFC: Electrochemical equation
Anode (oxidation)
CH3OH + 6OH- 5H2O + 6e- + CO2
Cathode (Reduction)
3/2O2 + 3H2O + 6e- 6OH-
Overall reaction
CH3OH + 3/2O2 2H2O + CO2
AFC
 Alkaline fuel cells (AFCs) were one of the first fuel cell technologies
developed, and they were the first type widely used in the U.S. space
program to produce electrical energy and water on-board spacecraft.
 These fuel cells use a solution potassium hydroxide in water as the
electrolyte and can use a variety of non-precious metals as a catalyst at
the anode and cathode.
 A key challenge for this fuel cell is type is that it is susceptible to
poisoning by carbon dioxide (CO2)
 The operating temperature of AFCs is about 700 C and their power
output is 10 – 100 kW.
 They have been widely used for space and defense applications, where
pure hydrogen is used.
 Their excessive cost and sensitive to CO2, have restricted their research
and development, no matter their high efficiency and power density.
AFC electrochemical equation

Anode (oxidation)
H2 + 2(OH)- 2H2O + 2e-
Cathode (reduction)
1/2O2 + OH2 + 2e- 2(OH)-
Overall reaction
H2 + 1/2O2 + CO2 H2O

1.Hydrogen, 2. electron flow, 3. load

4. oxygen, 5. cathode, 6. electrolyte
7. Anode, 8. water, 9. Hydrogen ion
Phosphoric acid fuel cell (PAFC).

 Phosphoric acid fuel cells(PAFCs) use a liquid phosphoric acid as an

electrolyte- the acid is contained a Teflon –bonded silicon carbide matrix
and porous carbon electrodes contain platinum catalyst.
 The PAFC is considered the “first generation” of modern fuel cells.
 PAFCs have an operating temperature of 200 0 C. the power output varies
from 200kW to 20 MW.
 The main disadvantage is that it has no self-starting capability, because
of the lower temperature (400 C – 500 C) freezing of concentrated
phosphoric acid occurred.
 PAFCs are more than 85% efficient when used for co-generation of
electricity and heat but they are less efficient at generating electricity
alone (37% - 42%).
 PAFCs are also less powerful than other fuel cells, given the same weight
and volume. As a result, this fuel cells are typically large and heavy.
PAFC are also expensive.
Electro chemical equation
Anode reaction (oxidation)
2H2(g) 4H+ + 4e-
Cathode (reduction)
O2(g)+4H+ + 4e- 2H2O
Overall reaction
2H2 + O2 2H2O
Molten carbonate fuel cell
 Molten carbonate fuel cells (MCFCs) are currently being developed for a
natural gas and coal-based power plants for electrical utility, industrial and
military application.
 MCFCs are a high temperature fuel cells that use an electrolyte composed
of a molten carbonate salt mixture suspended in a porous, chemically inert
ceramic lithium aluminum oxide matrix
 As they operate at high temperatures of 650ºC (1200 ºF), non-precious
metals can be used as catalyst at the anode and cathode, reducing costs.
 Molten carbonate fuel cells when coupled with a turbine, can reach efficiencies
approaching 65%, considerable higher than the 37% - 42% efficiencies of a
phosphoric acid fuel cell plant.
 When the waste heat is captured and used, overall fuel efficiencies can be over
85%.
 The primary disadvantage of current MCFC technology is durability. The high
temperature at which these cells operate and the corrosive electrolyte used
accelerate component breakdown and corrosion, decreasing cell life.
Electrochemical equation
Anode (oxidation)
H2 + CO32- H2O + CO2 + 2e-
Cathode (reduction)
1/2O2 + CO2 + 2e- CO32-
Cell reaction
H2 + O2 + CO2 H2O + CO2
Solid oxide fuel cell
 Solid oxide fuel cell (SOFCs) use a hard, non- porous ceramic compound as the
electrolyte.
 SOFCs are around 60% efficient at converting fuel to electricity and operate at
very high temperature- as high as 1000 ºC (1830 ºF ).
 High temperature operation removes the need for precious-metal catalyst,
thereby reducing cost.
 It also allows SOFCs to reform fuels internally, which enables the use of a
variety of fuels and reduces the cost associated with adding a reformer to the
system.
 In addition, they are not poisoned by carbon, which can even be used as a fuel.
These property allows SOFCs to use a natural gas, biogas and gases made from
coal.
 High temperature operation has disadvantage. It results in a slow start up and
require significant thermal shielding to retain heat and protect personnel,
which may be acceptable for utility application but not for transportation.
SOFC electrochemical reaction
Anode (oxidation)
H2 + O2 H2O + 2e-
Cathode (reduction)
½ O2 + 2e- O2-
Cell reaction
H2 + ½ O2 H2O
Reversible fuel cell
 Reversible fuel cells produce electricity from hydrogen and oxygen
and generate heat and water as a byproduct, just like other fuel cells.
However, reversible fuel cell systems can also use electricity from
solar power, wind power or other sources to split water into oxygen
and hydrogen fuel through a process called electrolysis.
 Reversible fuel cells can provide power when needed, but during
times of high production from other technologies (such as when high
winds lead to an excess of available wind power), reversible fuel cells
can store excess energy in the form of hydrogen.
 This energy storage capability could be a key enable for intermittent
renewable energy technologies.
 Advantage of fuel cell
 High efficiency : when utilizing co-generation, fuel cells can attain
over 80% energy efficiency
 Good reliability: Quality of power provided does not degrade over
time.
 Noise: offer a much more silent and smoother alternative to
conventional energy production.
 Environmentally beneficial: greatly reduces CO2 and harmful
pollutant emissions.
 Size reduction: fuel cells are significantly lighter more compact.
Disadvantage of fuel cell
 Expensive to manufacture due the high cost of catalysts
(platinum).
 Lack of infrastructure to support the distribution of hydrogen.
 A lot of the currently available fuel cell technology is in the
prototype stage and not yet validated.
 Hydrogen is expensive to produce and not widely available.