Unit 1 - 2

SRM Institute of Science and Technology
Unit 1
Introduction to Fuel Cells
And Fuel Cell
Thermodynamics
Dr Balaji S
Assistant Professor
1
Department of Mechanical Engineering
Introduction
• The principle of fuel cell was discovered by
German scientist “CHRISTIAN FRIEDRICH
SCHONBEIN”
• Based on this principle the first fuel cell was
demonstrated by “SIR WILLIAM ROBERT
GROOVE”
• A fuel cell is a device that converts the chemical
energy from a fuel into electricity through
chemical reaction with oxygen or any other
oxidising agent
• Fuel cells require a constant supply of fuel and
oxygen so that they can produce electricity
continuously
2
Cont..
• They produce zero or very low emissions,
especially Green House Gases (GHGs)
depending on the fuel used.
• Have few moving parts and thus require
minimal maintenance, reducing life cycle costs
of energy production.
• Modular in design, offering flexibility in size
and efficiencies in manufacturing
• Can be utilized for combined heat and power
purposes, further increasing the efficiency of
energy production
3
Construction and working principle of fuel cell
Fuel Cell Design

• It consist of an anode
(negative side), a
cathode (positive side)
and an electrolyte that
allows charges to move
between the two sides
of the fuel cell
• Electrons are drawn
from the anode side to
the cathode through an
external circuit
producing direct
current electricity
4
Working Principle
• A single fuel cell consists of an electrolyte sandwiched
between two thin electrodes (a porous anode and
cathode)
• Hydrogen, or a hydrogen-rich fuel, is fed to the anode
where a catalyst separates hydrogen's negatively
charged electrons from positively charged ions
(protons)
• At the cathode, oxygen combines with electrons and, in
some cases, with species such as protons or water,
resulting in water or hydroxide ions, respectively
• The electrons from the anode side of the cell cannot
pass through the membrane to the positively charged
cathode
5
Cont..
• They must travel around it via an electrical
circuit to reach the other side of the cell
• This movement of electrons is an electrical
current.
• 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
• Still, a single fuel cell produces enough
electricity for only the smallest applications
6
Cont..
• 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
• Fuel cells are classified primarily by the kind of
electrolyte
• 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
• There are several types of fuel cells currently under
development, each with its own advantages,
limitations, and potential applications
7
Difference between battery and

fuel cell
Battery Fuel Cell
• Batteries are closed • Fuel cells and solar cells can
thermodynamic systems be viewed as “open”
that contain a finite and thermodynamic systems
exhaustible internal supply that operate at a
of chemical energy thermodynamic steady
(reactants) state
• Store Energy • Produce Energy
• Dependent • Undependably Scaling (Size
• Low energy density of cell and fuel reservoir)
• Reachable or thrown away • High energy density
• Energy is produced as long
as the fuel is supplied
8
Advantages
• High efficiency than combustion cycle
• No moving parts
• No emission
• Easy independent scaling between power
(determined by the fuel cell size) and capacity
(determined by the fuel reservoir size)
• Fuel cells offer potentially higher energy densities
than batteries and can be quickly recharged by
refuelling, whereas batteries must be thrown away
or plugged in for a time-consuming recharge
9
Disadvantages
• Cost represents a major barrier to fuel cell
implementation
• Fuel availability (Hydrogen)
• low volumetric energy density
• Hydrogen storage
• Operational temperature
10
Fuel Cell Types

• Phosphoric acid fuel cell (PAFC)
• Polymer electrolyte membrane fuel cell
(PEMFC)
• Alkaline fuel cell (AFC)
• Molten carbonate fuel cell (MCFC)
• Solid-oxide fuel cell (SOFC)
11
Comparison of Fuel Cells
12
Polymer Electrolyte Membrane

(PEM) Fuel Cells (PEMFC)
• In polymer electrolyte
membrane (PEM) fuel
cells, protons move
through the electrolyte to
the cathode to combine
with oxygen and
electrons, producing
water and heat
• Polymer electrolyte
membrane (PEM) fuel
cell uses a polymeric
membrane as the
electrolyte, with platinum
electrodes
13
Cont..
• These cells operate at relatively low
temperatures
• Polymer electrolyte membrane (PEM) fuel cells
is also called as proton exchange membrane
fuel cells
• PEM fuel cells use a solid polymer as an
electrolyte and porous carbon electrodes
containing a platinum catalyst
• They are typically fuelled with pure hydrogen
supplied from storage tanks or onboard
reformers
14
Cont..
Anode Reaction: H2 → 2H+ + 2e−
Cathode Reaction: ½ O2 + 2H+ + 2e– → 2H2O
Overall Cell Reaction: 2H2 + O2 → 2H2O
• 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
15
Cont..
• 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
• Developers are currently exploring
platinum/ruthenium catalysts that are more
resistant to CO
16
Direct Methanol Fuel Cell

• Another type of PEM fuel cell is the direct
liquid fuel cell or DLFC where the liquid anode
fuel can be methanol known as direct methanol
fuel cell (DMFC)
• It is similar to PEM fuel cell, where it polymer
membrane as electrolyte
• It also uses noble metal catalyst (typically
platinum) at anode to enable the
electrochemical reaction
• Operating temperatures are in the range of 50
–120 °C
17
Cont..
• The DMFC relies upon the oxidation of
methanol on a catalyst layer to form carbon
dioxide
• Water is consumed at the anode and produced
at the cathode
• Protons (H+) are transported across the proton
exchange membrane (Nafion) to the cathode
where they react with oxygen to produce water
• Electrons are transported through an external
circuit from anode to cathode, providing power
to connected devices
18
19
Cell Reactions
• Anode reaction
CH3OH + H2O ⟶ 6H+ + 6e- + CO2
• Cathode reaction
1½O2 + 6H+ + 6e- ⟶ 3H2O
• Over all reaction
CH3OH + 1½O2 ⟶ 2H2O + CO2
20
Reversible voltage (Vrev)

• The reversible energy which is denoted as (Vrev)
is the minimum voltage that is needed to be
supplied in order to start the electrochemical
reaction
• The reversible voltage can be determined
through change in Gibb’s (∆G) free energy
equation.
∆G = ∆H-T∆S
∆G = n F Vrev
21
Example Reversible Voltage

• ∆H and ∆S are the standard change in enthalpy
(286 kJ/mol) and entropy of electrolysis
process at temperature (T), at standard
condition (25°C and 1 atm), the Gibbs free
energy for splitting of water is calculated to be
237.2 kJ/mol, Faraday’s (F) constant value is
96485 C/ mole and number of electrons (n) is
2.
• Vrev = ∆G/nF
• Vrev =1.229 V
22
Activation voltage (Vact )

• The reversible voltage is not sufficient to keep the
electrochemical reaction active, some extra potential is
supplied known as activation voltage (𝑽𝒂𝒄𝒕 )
• The activation voltage is the function of coefficient of
electrode and temperature. The activation voltage for a
given temperature can be calculated using the equations at
constant temperature.
𝒕
𝑽𝒂𝒄𝒕 = 𝑺 𝐥𝐨𝐠 𝑰+𝟏
𝑨
Where, t and S are overvoltage coefficient at electrode in A-1m2 and V

respectively, A and I are area of electrode and current passed through electrodes
respectively
23
Ohmic voltage (𝑽𝒐𝒉𝒎 )

• The voltage loss is developed due to the resistance of
electrolyte, electrodes and leads etc. is collectively
represented as Ohmic voltage (𝑽𝒐𝒉𝒎 )
• The Ohm voltage is the function of temperature
• The ohm voltage for a given temperature can be calculated

using the equation
𝑟
𝑉𝑜ℎ𝑚 = 𝐼
𝐴
Where ‘r’ is the parameter related to ohm resistance in Ωm2
24
Cell voltage (𝑽𝒄𝒆𝒍𝒍 )

• Cell voltage or cell over-voltage potential is the total
sum of potential applied in the electrolyser and it is
the sum of reversible, activation and Ohmic voltages
• The cell voltage can be calculated for a given
temperature by the equation
𝑉𝑐𝑒𝑙𝑙 = 𝑉𝑟𝑒𝑣 + 𝑉𝑎𝑐𝑡 + 𝑉𝑜ℎ𝑚
𝑡 𝑟
𝑉 = 𝑉𝑟𝑒𝑣 + 𝑆 log 𝐼 +1 + 𝐼
𝐴 𝐴
25
Physical Interpretation of ΔG =
ΔH - TΔS
• ΔH represents the total energy of the system
• TΔS represents the “unavailable” energy (that
which cannot be converted to useful work)
• Therefore G represents the “free” energy or the
energy available to do useful work
26
Thermodynamics of Fuel Cell

• Energy conversion efficiency of a fuel cell is
ratio of the actual voltage at a given current
density to the maximum voltage obtained
under no load (open circuit) conditions
𝑂𝑛 𝐿𝑜𝑎𝑑 𝑉𝑜𝑙𝑡𝑎𝑔𝑒
𝞰=
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑜𝑝𝑒𝑛 𝑐𝑖𝑟𝑐𝑢𝑖𝑡 𝑣𝑜𝑙𝑎𝑡𝑔𝑒
27
Thermodynamic Analysis: 1st

Law
• It states that the change in the internal energy
(ΔH) of a closed system is equal to the amount
of heat supplied (Q) to the system, minus the
amount of work (W) performed by the system
on its surroundings
∆𝐻 = 𝑄 − 𝑊
Electrical work is, in general, described by the
relation
𝑊 = 𝑉rev 𝐼 ∆𝑡
where Vrev is the cell voltage or reversible cell
voltage and I is the current
28
Cont..
• In a fuel cell reaction, electrons are transferred
from the anode to the cathode, generating a
current
• The amount of electricity (IΔt) transferred when
the reaction occurs is given by nF, 𝐼∆𝑡 = 𝒏𝑭
• Where, n = number of electrons transferred, F =
Faraday’s constant = 96,493 coulomb's
• So the electrical work can be calculated as
𝑊 = 𝑛𝐹𝑉rev (Work done on the surrounding)
The First Law then becomes: ∆𝑯 = 𝑸 − 𝒏𝑭𝑽𝒓𝒆𝒗
29
Thermodynamic Analysis: 2nd

Law
• Consider the fuel cell to be ideal for now,
meaning that it is reversible and thus behaves
as a perfect electrochemical apparatus
• “ If no changes take place in the cell except
during the passage of current, and all changes
which accompany the current can be reversed
by reversing the current, the cell may be called
a perfect electrochemical apparatus.”
30
Cont..
• Heat transferred during a reversible process
was expressed as
𝑄 = 𝑇∆𝑆
• Where, T is absolute temperature and ∆S is
change in entropy
• Combining the First and Second Law analysis,
we get
∆𝐻 = 𝑇∆𝑆 − 𝑛𝐹𝑉rev
n𝐹𝑉rev = −(∆𝐻 − 𝑇∆𝑆)
31
Enthalpy of Reaction
• The difference between the heat of formation of
the reactants and products is known as the heat
of reaction
• Let us consider the reaction of formation of
water which is exothermic
H2 + ½O2 = H2O + heat
32
Cont..
• The heat of reaction is calculated by
subtracting the sum of all the heats of
formation of the reactants from those of the
products
1
∆𝐻 = ℎ𝑓 − ℎ𝑓 − ℎ𝑓
𝐻2 𝑜 𝐻2 2 𝑜2
• Where “hf” represents the heat of formation for
each reactant.
• The heat of formation of any element is zero,
while that of liquid water at 25oC (77oF) is –286
kJ/mol
33
Cont..
• Thus
𝑘𝐽 kJ
∆𝐻 = −286 − 0 − 0 = −286
𝑚𝑜𝑙 mol
• The sign convention states that the heat of
reaction for all exothermic reactions is negative
• The heat of reaction is given assuming the
reactants and products are both at atmospheric
pressure and 25oC (77oF) where the product
water will be in liquid form
34
Gibbs Free Energy

• Similar to the change in enthalpy of a reaction,
as well as the heat of combustion,
• The change in Gibbs free energy of a reaction is
the difference between the sum of Gibbs free
energies of the products and reactants.
• The sign convention is the same as that for
enthalpy, where a negative Gibbs free energy
denotes energy is released from the reaction.
35
Cont..
• Change in Gibbs free energy can be given by
∆𝐺𝑓 = 𝐺𝑓, 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐺𝑓, 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
• If all the Gibbs free energy could be converted
to electrical energy, then the fuel cell reaction is
said to be reversible
• Then change in Gibbs free energy of the
reaction is related to the voltage of the fuel cell
by the equation
∆𝐺𝑓 = −𝑛𝐹𝑉rev
36
Cont..
• Change in Gibb’s (∆G) free energy equation can
be represented in terms of enthalpy and
entropy
∆G=∆H-T∆S
• As there is no change in temperature ΔT = 0
• So the equation becomes ∆G=∆H
37
Nernst Equation
• Nernst Equation describes how Gibbs free
energy of reaction and open circuit voltage and
power generation of a fuel cell depends on
pressure and product streams
• The Nernst equation is often used to calculate
the cell potential of an electrochemical cell at
any given temperature, pressure, and reactant
concentration.
• The equation was introduced by a German
chemist named Walther Hermann Nernst.
38
Derivation of Nernst Equation

• Step 1:
• Consider a metal in contact with its own salt
aqueous solution.
• Reactions of metal losing an electron to become an
ion and the ion gaining electron to return to the
atomic state are equally feasible and are in an
equilibrium state.
Mn+ + ne– → nM
• In the reduction reaction, ‘n’ moles of an electron
is taken up by the ion against a reduction potential
of Ered.
39

• Step 2: The work done in the movement of electron
Wred = nFEred
• Where, F is Faraday = 96487 coulomb (electrical
charge carried by one mole of electrons)
• Change in the Gibbs free energy is an indication of
the spontaneity and it is also equal to the
maximum useful work (other than volume
expansion) done in a process.
• Combining work done and Gibbs free energy
change:
Wred = nFEred = – ∆G or ∆G = – nFEred
40

• Step 3:
• Change in the free energy at standard
conditions of 298K and one molar /one
atmospheric pressure conditions is ∆G°. From
the above relation, it can be written that
∆G° = – nFE °red
• Where, E°red is the reduction potential
measured at standard conditions.
41

• Step 4
• During the reaction, concentration keeps changing
and the potential also will decrease with the rate of
reaction.
• To get the maximum work or maximum free
energy change, the concentrations have to be
maintained the same. This is possible only by
carrying out the reaction under a reversible
equilibrium condition.
• For a reversible equilibrium reaction, vant Hoff
isotherm says:
∆G = ∆G ° + RT lnK
42

• Where,
• K is the equilibrium constant
• K = Product/Reactant = [M]n/[M]n+
• R is the Gas constant =8 .314 J/K mole
• T is the temperature in Kelvin scale.
43

• Step 5:
• Substituting for free energy changes in ant
Hoff equation,
⸰ 𝑀
−𝑛𝐹𝐸𝑟𝑒𝑑 = −𝑛𝐹𝐸𝑟𝑒𝑑 + 𝑅𝑇 ln 𝑛+
𝑀
° 𝑀𝑛
= −𝑛𝐹𝐸𝑟𝑒𝑑 + 2.303 𝑅𝑇 log
𝑀𝑛+
• Dividing both sides by – nF,
𝑛
° 2.303 𝑅𝑇 𝑀
𝐸𝑟𝑒𝑑 = 𝐸𝑟𝑒𝑑 − log 𝑛+
𝑛𝐹1 𝑀
44
Determining Equilibrium
Constant with Nernst Equation
• When the reactants and the products of the
electrochemical cell reach equilibrium, the value of
ΔG becomes Zero
• At this point, the reaction quotient and the
equilibrium constant (Kc) are the same
• Since ΔG = -nFE, the cell potential at equilibrium
is also 0
• Substituting the values of Q and E into the Nernst
equation, the following equation is obtained
° 𝑅𝑇
0 = 𝐸𝐶𝑒𝑙𝑙 − ln 𝐾
𝑛𝐹
45
Fuel Cell Efficiency

• The fuel cell efficiency is described as the ratio
of the electrical energy produced to the heat
that is produced by burning the fuel
• Efficiency
𝑊
𝞰=
𝑄𝑖𝑛
46
Carnot Efficiency
• Efficiency is a measure of usable energy output,
compared to the total energy input of a given
system.
• The theoretical Carnot efficiency of a heat
engine (ηeff) is given by:
𝑇1 − 𝑇2
η𝑒𝑓𝑓 =
𝑇1
47
Theoretical Fuel Cell Efficiency

• The energy input is equivalent to the enthalpy of
reaction (combustion), and the useful energy
output is electrical energy produced.
• If all the Gibbs free energy produced is converted
to electricity, then the thermodynamic fuel cell
efficiency at 25oC (77oF) temperature and 1
atmosphere pressure is given by ratio of the change
in Gibbs free energy (ΔG) to the change in enthalpy
(ΔH) of the fuel cell reaction (using the HHV of
hydrogen)
∆𝐺
𝞰𝑇 =
∆𝐻
48
Losses in an Actual Fuel Cell

• Activation Losses: These losses are caused by
the slowness of the reaction taking place on the
surface of the electrodes.
• A proportion of the voltage generated is lost in
driving the chemical reaction that transfers the
electrons.
• Ohmic Losses: The voltage drop due to the
resistance to the flow of electrons through the
material of the electrodes.
• This loss varies linearly with current density.
49
Cont..
• Concentration Losses: Losses that result from
the change in concentration of the reactants at
the surface of the electrodes as the fuel is used.
• Fuel Crossover Losses: Losses that result from
the waste of fuel passing through the electrolyte
and electron conduction through the
electrolyte.
• This loss is typically small, but can be more
important in low temperature cells.
50
Thank You
51

Unit 1 - 2

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Unit 1 - 2

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SRM Institute of Science and Technology

Fuel Cell Design

Difference between battery and

Fuel Cell Types

Comparison of Fuel Cells

Polymer Electrolyte Membrane

Direct Methanol Fuel Cell

Reversible voltage (Vrev)

Example Reversible Voltage

Activation voltage (Vact )

Where, t and S are overvoltage coefficient at electrode in A-1m2 and V

Ohmic voltage (𝑽𝒐𝒉𝒎 )

• The Ohm voltage is the function of temperature

• The ohm voltage for a given temperature can be calculated

Where ‘r’ is the parameter related to ohm resistance in Ωm2

Cell voltage (𝑽𝒄𝒆𝒍𝒍 )

Thermodynamics of Fuel Cell

Thermodynamic Analysis: 1st

Thermodynamic Analysis: 2nd

Gibbs Free Energy

Derivation of Nernst Equation

Derivation of Nernst Equation

Derivation of Nernst Equation

Derivation of Nernst Equation

Derivation of Nernst Equation

Derivation of Nernst Equation

Fuel Cell Efficiency

Theoretical Fuel Cell Efficiency

Losses in an Actual Fuel Cell

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