Fuel Cell Engineering

(CH368)

Hari Prasad Dasari, Ph.D.

Assistant Professor
Chemical Engineering Department
National Institute of Technology Karnataka
INDIA
 03-05
M.Tech 10-11 13- 14
Energy Systems
Visiting Scientist Post-Doc Fellow
99-03 05-10
B.Tech Ph.D. 11-13 14-15
Chem. Eng. Nano-Materials Sci. & Eng. STAR Post-Doc Fellow DST-INSPIRE Faculty

04-05

Publications in peer reviewed journals 27

Korean patents/Conf. Papers 02/02 15-Till date
Assistant Professor
Books/Book chapters 01
Manuscripts In preparation 05
Citations 721
H-index 15
I10-Inex 22
2
Applications of Ceria-based materials

1 Solid-Oxide Fuel/Electrolysis Cells

2 Hydrocarbon Processing

Ceria 3 Three-way converters

4 Thermo-chemical Fuel Production

Cubic fluorite structure

5 Gas sensors

Oxygen storage capacity (Ce3+/Ce4+)

High affinity towards O2
Thermal stability
Image Courtesy: Wikipedia 3
 Anode Material Development Electrolyte Material
θ Novel Ni-CZO as anode cermet for IR-SOFCs
θ Single-step Glycine-Nitrate-Process  Lowering the sintering temperature of Electrolyte
Electrolyte  Controlling nano-particle size
θ Partial Oxidation of Methane
θ Steam Reforming of Methane  Liquid-phase sintering approach
θ Nickel nano-particle sintering effect  Microwave effect
θ Electrochemical behavior of Ni-CZO anode

Anode
Ceria-based H2-
materials Electrode

H2-Electrode Material
 H2-Production from water-splitting reaction
 H2-Electrode Half-cell measurements
Catalyst (Ni-YSZ and Ni-CZO electrodes)
Catalytic Activity
 CO oxidation activity on RE-CZO oxides
 Soot oxidation activity on LSC perovskites
 RWGS activity on SOEC cathodes

4
Class Schedule

Time Table
MON TUE WED THU FRI
APC (M.Tech) 3-5 10-11 11-12
FCE (B.Tech) 10-11 11-12 1-2

Where ??? Faculty Room

Room no.
APC Seminar Hall
FCE Class

5
Syllabus

Overview of Fuel Cells:

What is a fuel cell, brief history, classification, how does it work,
why do we need fuel cells, Fuel cell basic chemistry and thermodynamics,
heat of reaction, theoretical electrical work and potential,
theoretical fuel cell efficiency.

Fuels for Fuel Cells:

Hydrogen, Hydrocarbon fuels, effect of impurities such as CO, S and others.

Fuel cell electrochemistry:

Electrode kinetics, Types of voltage losses, Polarization curve,
fuel cell efficiency, Tafel equation, exchange currents.

6
Syllabus (Cont.)

Fuel cell process design:

Main PEM fuel cell components, materials, properties and processes:
membrane, electrode, gas diffusion layer, bi-polar plates, Fuel cell
operating conditions: pressure, temperature, flow rates, humidity.

Solid-Oxide Fuel Cells:

Main components of solid-oxide fuel cells, Cell stack and designs,
Electrode polarization, testing of electrodes, cells and short stacks, Cell,
stack and system modeling

Fuel processing:
Direct and in-direct internal reforming,
Reformation of hydrocarbons by steam, CO2 and partial oxidation,
Direct electro-catalytic oxidation of hydrocarbons, carbon
decomposition, Sulphur tolerance and removal ,
Using renewable fuels for SOFCs
7
 Text Books…

•Gregor Hoogers
Fuel Cell Technology Hand Book, CRC Press, 2003.

•Karl Kordesch& Gunter Simader,

Fuel Cells and Their Applications, VCH Publishers, NY, 2001.

•F. Barbir,
PEM Fuel Cells: Theory and Practice (2nd Ed.) Elsevier/Academic
Press, 2013.

•Subhash C. Singal and Kevin Kendall,

High Temperature Fuel Cells: Fundamentals, Design and Applications,

8
Method of Evaluation…

Mid-Semester Examination --- 30 Marks

Surprise tests --- 20 Marks
End Semester Examination --- 50 Marks
Total --- 100 Marks

9
Reasons for taking this course
…
 A
 B
 C

CR Contact Information…
 A
 B
 C

10
Interested in Research @NITK…
 DST-INSPIRE Project (2014-2019)
“Future Materials for Solid-Oxide Fuel /Electrolysis Cells”
Project Cost: 35 lakhs
o NITK-KIST Project ( 11.5 Lakhs) Electrolyte Materials (2016-17)
o NITK-KIST Project ( 11.5 Lakhs) Soot oxidation (2017-18)
o Indo-US Project (91.3 Lakhs) Methanol production (Co-PI) (2016-19)
o DST-SERB- Early Career Research Award (51 Lakhs) Electrolytes (2017-
2020

Contact:
[email protected]
9177304950  Sorry this semester no
Facebook (Hari Prasad Dasari) vacancy for research students…
11
Welcome to Fuel Cell world …

12
 What is a Fuel Cell…

A Fuel Cell is a electro-chemical device that

continuously converts chemical energy into
electrical energy (and some heat) for as long as
fuel and oxidant is supplied.

Image Courtesy: NASA.gov Image Courtesy: Adv. Mater. 24 (2012) 3373 13

Fuel Cell Working Principle …
Combustion Reaction
H2 + ½ O2 ↔ H2O
Activation Energy (Ea)- (1889) (k joules/mole)
Minimum energy that must be input to a chemical system
with potential reactants to cause a chemical reaction.

Arrhenius Equation- (k=Ae-Ea/RT)

Relationship between Activation Energy and the rate at
which the reaction proceeds.

14
 Catalyst –
A Substance that modifies the transition state to lower Activation energy
is called a catalyst.

Image Courtesy: Wikipedia 15

 e-
Anode
Electrolyte Load

Cathode e-
Fuel Cell Schematic
In fuel cell, Hydrogen and Oxygen are separated by a
gas-impermeable electrolyte membrane
Transport species(ions) in electrolyte ( H+, O2-, OH-, CO32-)

H+ O2-

Half-Cell reaction (anode) H2 ↔ 2H+ + 2e- H2 + O2- ↔ H2O + 2e-

Half-Cell reaction (cathode) O2 + 4e- + 4H+ ↔ 2H2O O2 + 4e- ↔ 2O2-

Net reaction H2 + ½ O2 ↔ H2O H2 + ½ O2 ↔ H2O

16
 OH- CO32-

Half-Cell reaction (anode) H2 +2OH-↔ H2O + 2e- H2 + CO32- ↔ H2O + CO2 + 2e-

Half-Cell reaction (cathode) O2 + 4e- + 2H2O↔ 4OH- ½ O2 + CO2 +2e- ↔ CO32-

Net reaction H2 + ½ O2 ↔ H2O H2 + ½ O2 ↔ H2O

Why Hydrogen is used as fuel for most of the fuel Cells...

1. It is highly reactive when suitable catalysts are used

2. It can be produced from hydrocarbons
3. It has a very high energy density (32.67 kWh/kg)
4. It can be stored cryogenically for closed environment applications like space

17
 Advantages of Fuel Cells…
Advantages of Fuel Cells…

1. Simple with direct energy conversion

2. Show efficiencies greater than the existing IC Engines
3. Silent without any rotating/moving components
4. Fuel and size flexibility
5. Can be explored for CHP generation (combined heat and power)

Disadvantages of Fuel Cells…

1. Extremely Expensive
2. No Hydrogen infrastructure supply
3. Pure Hydrogen is required for Low-temperature Fuel Cells
and this decreases the efficiency

Image Courtesy: Nature 400 (1999) 619 18

Classification Fuel Cells…

 Based on Electrolyte Type

1. Alkaline Fuel Cell (AFC)-

2.Proton Exchange membrane

(polymer electrolyte membrane) (PEMFC)-
3. Direct Methanol Fuel Cell (DMFC)-

4. Phosphoric Acid Fuel Cell (PAFC)-

5. Molten Carbonate Fuel Cells (MCFC)

6. Solid-Oxide Fuel Cell (SOFC)

19
 Schematic representation of fuel cell…

High-Temperature
Fuel Cells

Low-Temperature
Fuel Cells

Schematic representation of fuel cell

Image Courtesy: University of Cambridge (Web source) 20

Fuel Cell Types and Applications…

Fuel cell type DMFC PEMFC AFC PAFC MCFC SOFC

Electrolyte type Polymeric ion Polymeric ion Immobilized Immobilized Immobilized Ceramic
exchange exchange alkaline salt liquid liquid molten
membrane membrane solution phosphoric carbonate
acid
Operating temper 20 – 90 30 – 100 50 – 200 ~220 ~650 500 – 1000
ature (°C)
Charge carrier H+ H+ OH– H+ CO32– O2–
Power range (W) 1 – 100k 1 – 100k 500 – 10k 10k – 1M 100k – 10M+ 1k – 10M+
Applications and main advantages:
Portable Higher energy density than
electronics batteries and faster recharge.
Cars boats and Zero emissions and higher
spaceships efficiency.
Domestic CHP Efficiency and reliability

Distributed power Efficiency, emissions and less

generation, CHP, noise
buses

Able to internally
reform CH4
× × × × √ √

21
Anode –
A type of electrode where fuel reacts or oxidizes and liberates electrons

Cathode –
A type of electrode where oxygen (usually from air) undergoes reduction

Electrolyte –
A chemical compound/material that conduct ions from one electrode to
other
Direct Fuel Cell –
A type of fuel cell in which a hydrocarbon fuel is fed directly to the fuel cell
without requiring an external reformer to generate hydrogen and carbon
mono-oxide

22
Fuel Cell History…

1776– Henry Cavedish

Discovered that water is the compound
1801– Humphry Davy
formed when hydrogen and oxygen reacts
Demonstrates the principles of
what become fuel cells
1839– William Grove
Invents the ”Gas Battery” the 1st fuel cell.
1889– Charles Langer &
Ludwig Mond
Develop Grove’s invention and name 1950s– General Electric (GE)
the fuel cell Invents the proton exchange membrane
fuel cell.
1959– Francis Bacon
Demonstrates a 5 kW alkaline fuel cell 1960s– General Electric (GE)
NASA 1st uses fuel cells in space missions
1970s–
Oil crisis prompts the development of
Alternative energy technologies
1980s–
US Navy uses fuel cell in submarines
Including PAFCs
23
Brief History of fuel cells
…
William Robert Grove (1811 -1896),
a Welsh lawyer turned scientist, won renown
for his development of an improved wet-cell
battery in 1838

In 1800, British scientists William Nicholson

William Robert Grove and Anthony Carlisle had described the process
Electrolysis Set-up of using electricity to decompose water into
hydrogen and oxygen.
But combining the gases to produce electricity
and water was, according to Grove

24
 Christian Schönbein (1799 -1868) and
Johann Poggendorff (1796 -1877)

were among a number of scientists who debated

the question of exactly how Grove's gas battery
worked
Christian Schönbein
Friedrich Wilhelm Ostwald (1853 -1932),
a founder of the field of physical chemistry,
provided much of the theoretical
understanding of how fuel cells operate.

In 1893, he experimentally determined the

interconnected roles of the various
components of the fuel cell: electrodes,
electrolyte, oxidizing and reducing agents,
Johann Poggendorff anions, and cations
Friedrich Wilhelm Ostwald
25
Emil Baur

Emil Baur (1873 -1944) of Switzerland

Baur's work included high temperature
devices (using molten silver as an electrolyte)
and
a unit that used a solid electrolyte of clay
and metal oxides

26
Francis Thomas Bacon Francis Thomas Bacon (1904 -1992)
began researching alkali electrolyte fuel
Cells in the late 1930s.

In 1939, he built a cell that used nickel

gauze electrodes and operated under
pressure as high as 3000 psi

In 1958 he demonstrated an alkali cell

using a stack of 10-inch diameter
electrodes for Britain's National Research
Development Corporation

27
Comprehensive History of fuel cells…

The principle of the fuel cell was discovered by German scientist

Christian Friedrich Schönbein in 1838 and published in the January 1839 edition
of the "Philosophical Magazine".
Based on this work, the first fuel cell was developed by Welsh scientist Sir William
Robert Grove in 1843. The fuel cell he made used similar materials to today's
Phosphoric-acid fuel cell.
It wasn't until 1959 that British engineer Francis Thomas Bacon successfully
developed a 5kW stationary fuel cell. In 1959, a team led by Harry Ihrig built a
15kW fuel cell tractor for Allis-Chalmers which was demonstrated across the US
at state fairs. This system used potassium hydroxide as the electrolyte and compr
essed hydrogen and oxygen as the reactants.
Later, in 1959, Bacon and his colleagues demonstrated a practical five-kilowatt
unit capable of powering a welding machine, which led, in the 1960s to Bacon's
patents being licensed by Pratt and Whitney from the U.S. where the concepts
were used in the U.S. space program to supply electricity and drinking water
(hydrogen and oxygen being readily available from the spacecraft tanks).

28
UTX's UTC Power subsidiary was the first company to manufacture and
commercialize a large, stationary fuel cell system for use as a co-generation
power plant in hospitals, universities and large office buildings.
UTC Power continues to market this fuel cell as the PureCell 200, a 200kW
system. UTC Power continues to be the sole supplier of fuel cells to NASA for use
in space vehicles, having supplied the Apollo missions and currently the
Space Shuttle program, and is developing fuel cells for automobiles, buses, and
cell phone towers; the company has demonstrated the first fuel cell capable of st
arting under freezing conditions with its proton exchange membrane automotive
fuel cell.
A so-called water fuel cell (1989) is an unrelated claim of a perpetual motion
device, which in fact was not claimed to function the way a fuel cell does.
In 2006 Staxon introduced an inexpensive PEM fuel cell module for system
integration. In 2006 Angstrom Power, a British Columbia based company, began
commercial sales of portable devices using proprietary hydrogen fuel cell
technology, trademarked as "micro hydrogen."

29
PEM fuel cells being installed in a Gemini 7 spacecraft
(Source: Smithsonian Institution, from the Science Service Historical Images Collection,
courtesy of General Electric)

The alkaline fuel cell system as used on the space shuttles.

Honda fuel cell car

30
Fuel Cell At KIST (Korea)

Hyundai- FCEV

Unmanned air craft

31
Fuel Cell (Japan)

32
 Fuel Cell Basic Chemistry & Thermodynamics
….

Heat of Reaction
Higher and lower heating value of Hydrog
en
Theoretical Electrical Work

Theoretical Fuel Cell Potential

Effect of Temperatur
e
Effect of Pressur
e
Theoretical Fuel Cell Efficien
cy
Carnot Efficiency my
th
33
Basic Reactions

Half-Cell reaction (anode) H2 ↔ 2H+ + 2e-

Half-Cell reaction (cathode) O2 + 4e- + 4H+ ↔ 2H2O

Net reaction H2 + ½ O2 ↔ H2O

Heat of Reaction

H2 + ½ O2 → H2O + heat ∆H=???

The heat (or enthalpy) of a chemical reaction (∆H) is the difference between
the heats of formation of products and reactants

34
 ∆H= (H products) – (H Reactants)

∆H= ((hf )H2O) – ((hf )H2 + ½ (hf )O2)

(hf )H2O = –286 kJ/mol (at 25°C) (liquid water)

(hf )H2 = 0
(hf )O2 = 0
∆H= (-286) – (0 + 0) = -286 kJ/mol
∆H >0 (endothermic reaction)
∆H< 0 (exothermic reaction)
∆H =0 (No heat is lost or gained)
H2 + ½ O2 → H2O (l) + heat ∆H=-286kJ/mol
H2 + ½ O2 → H2O (l) + 286kJ/mol

Hydrogen’s Heating Value –

It is the amount of heat that may be generated by a complete combustion
of 1 mole of hydrogen (286 kJ/mol)
35
Hydrogen’s Higher Heating Value (HHV)–
The measurement should show that 286 kJ of heat is
released . This is known as Hydrogen’s higher heating
value.

Hydrogen’s Lower Heating Value (LHV) –

The measurement should show that 241 kJ of heat is
released . This is known as Hydrogen’s higher heating
value.

Heat of evaporation of water (at 25°C)–

The difference between the HHV and LHV.
286-241 = 45kJ/mol

36
Theoretical Electrical Work…

Enthalpy (H) –
A thermodynamic function of a system, equivalent to the sum of the
internal energy plus the product of its volume multiplied by the
pressure exerted on it by the surroundings (H = U + PV ).
Chemical Terms ….∆H= HProducts –Hreactants

Entropy (S) –
For a closed thermodynamic system, a quantitative measure of thermal
energy that is not available to do work (mechanical/chemical/electrical).
Chemical Terms…∆S = SProducts – SReactants

37
Theoretical Electrical Work…

Gibbs free energy (∆G) – ∆H ∆G

The portion of reaction enthalpy
(∆H)(or hydrogen’s higher
heating value) that can be
converted in to electricity
T∆S
Energy Input and outputs for a fuel cell as an energy
∆G= ∆H – T ∆S conversion device

∆S= SProducts – SReactants Enthalpies and Entropies of formation for fuel cell
Reactants and Products at 25°C and 1 atm
∆S= (sf )H2O – ((sf )H2 + ½ (sf )O2)
hf (kJ/mol sf (kJ/mol.K
) )
Hydrogen (H2) 0 0.13066
Oxygen (O2) 0 0.20517
Water (liquid), H2O (l) -286.02 0.06996
Water (vapor), H2O (g) -241.98 0.18884

38
At 25°C, calculate the electrical energy (∆G) and heat produced
if the water (liquid), H2O (l) is the product???

∆G= ∆H – T ∆S

∆G= (-286.02) – ((273+25)*(0.06996 – ((0.13066) + ½ (0.20517))

∆S= (sf )H2O – ((sf )H2 + ½ (sf )O2)

∆G= -237.34 kJ/ mol Theoretical electrical work
-∆G = 237kJ/mol
Heat produced = (∆H - ∆G) = 286.02-237.34= 48.68 kJ/ mol

At 25°C, calculate the electrical energy (∆G) and heat generated

if the water (vapor), H2O (g) is the product???

-∆G= 228.61 kJ/ mol

39
Theoretical Fuel Cell Potential…

In general, electrical work is the product of charge and potential

H2 ↔ 2H+ + 2e-
W el= q.E W el= electrical work ( J/mol)
q = charge (Coulombs/mol)
E = potential (Volts) O2 + 4e- + 4H+ ↔ 2H2O

H2 + ½ O2 ↔ H2O
q= n.Navg. qel
n = no. of electrons per molecule of H2 = 2 electrons
Navg = No. molecules per mole (Avagadro’s No.)
= 6.022 * 1023 molecules/mol
qel = charge of 1 electron= 1.602 * 10-19 coulombs/electron

Product of Navg. qel is Faraday’s constant (F)=96,485 coulombs/ electron

W el= q.E = nFE W el= -∆G

-∆G=nFE E=(-∆G/nF) E=237,340/2*96,485 (J/coulombs) = 1.23 (V)

At 25C, the theoretical fuel cell potential is 1.23V

40
 Theoretical Fuel Cell Efficiency

Fuel Cell Efficiency can be expressed as a ratio of electrical

energy and enthalpy of chemical reaction
∆H ∆G
ɳ = ∆G/ ∆ H

At Hydrogen’s HHV,

ɳ = 237 kJ/ 286 kJ

T∆S
= 82.86~ 83%
Energy Input and outputs for a fuel cell as an energy
At Hydrogen’s LHV, conversion device

ɳ = 228 kJ/ 241 kJ

= 94.60~ 95%
Fuel Cell Efficiency can also be expressed as a ratio of two potentials:

ɳ = (∆G/nF)/ (∆H/nF) ɳ = (237000/2* 96,485 )/(286000/2*96,485)

= 1.23/1.482 = 83%
Where,
∆G/nF = 1.23 V is the theoretical fuel cell potential,
∆H/nF = 1.482 V is the potential corresponding to Hydrogen’s HHV or thermo-neutral potential
41
 Carnot Efficiency Myt
h

Carnot Theorem: Qin

No engine operating between two heat TH
reservoirs can be more efficient than a
Carnot engine operating between the same Wout
reservoirs.
Carnot efficiency : TC
Is the maximum efficiency that a heat engine Qdeg ɳ = Wout /Qin
may have operating between two temperatures = 1-(Tc/TH)

ɳ = Wout /Qin Carnot Process Efficiency

= 1-(Tc/TH)
Efficiency at Maximum Power

ɳ = 1- √(Tc/TH)

Efficiency vs. Power curve for Carnot Engine

Image Courtesy: F. Barbir “PEM Fuel Cells: Theory and Practice” 42
 The Carnot efficiency does not apply to fuel cells because a fuel cell is not a
heat engine; rather, it is an electrochemical converter.

Fuel Cell at Low Temp.

Significantly higher than any heat
engine operating between the same
two temperatures

In Fuel Cells
The theoretical efficiency is determined
by Gibb’s free energy and enthalpy of
Hydrogen/Oxygen reaction Theoretical Efficiencies of a Carnot
engine and a Fuel Cell as a function of
temperature

Image Courtesy: F. Barbir “PEM Fuel Cells: Theory and Practice” 43

Theoretical Fuel Cell Potential…(Effect of Temperatur
e)

Theoretical Fuel cell potential changes with cell temperature

∆G= ∆H – T ∆S

E=∆G/nF

E= (∆H-T∆S)/nF E= (∆H/nF) –(T∆S/nF)

An increase in cell temperature results in a lower theoretical cell potential.

T T

∆HT = H298.15 + ∫c p dT ∆ST = S298.15 + ∫ (1/T) c p dT

298.15 298.15

Specific heat (cp) of any gas is also the function of T.

An empirical relationship can be used

cp= a +bT +cT2 a, b & c = empirical coefficients, different for each gas

44
 T

∆HT = H298.15 + ∫c p dT
298.15
∫ (u+v)dx = ∫ u dx+ ∫ vdx
T
∫ c dx = cx
∆HT = H298.15 + ∫ (a +bT +cT ) dT 2

∫ x dx = (x )/2
298.15
2

∆HT = H298.15 +∆a(T-298.15)

+∆b(T2-298.152)/2 ∫ x dx = (x )/3
2 3

+∆c(T3-298.153)/3
T

∆ST = S298.15 + ∫ (1/T) c p dT

298.15

∆ST = S298.15 + ∫ (1/T) (a +bT +cT ) dT 2

298.15

45
 T

∆ST = S298.15 + ∫ (1/T) (a +bT +cT ) dT

2

298.15

∆ST = S298.15 + ∫ ((a/T) +b + cT) dT

298.15

∆ST = S298.15 + ∆a ln (T/298.15)

+ ∆b(T-298.15)
+ ∆c(T2-298.152)/2

Where ∆a, ∆b & ∆c are the difference between the coefficients a, b & c, respectively, for
products and reactants

∆a = aH2O – (aH2 + ½ aO2) ∆b = bH2O – (bH2 + ½ bO2) ∆c = cH2O – (cH2 + ½ cO2)

46
The coefficients for the temperature dependencies of Cp (J/mol/K)

a b c

Hydrogen (H2) 28.91404 -0.00084 2.01 * 10-6

Oxygen (O2) 25.84512 0.012987 -3.90 * 10-6
Water (liquid), H2O (g) 30.62644 0.009621 1.18 * 10-6

Change of Enthalpy, Gibbs Free Energy, and Entropy of Hydrogen/Oxygen

Fuel Cell Reaction with Temperature and Resulting Theoretical Cell Potential

T(K) ∆H (kJ/mol) ∆G (kJ/mol) ∆S (kJ/mol/ Eth (V)

K)
298.15 -286.02 -237.34 -0.16328 1.230
333.15 -284.85 -231.63 -0.15975 1.200
353.15 -284.18 -228.42 -0.15791 1.184
373.15 -283.52 -225.24 -0.15617 1.167

47
Theoretical Fuel Cell Potential…(Effect of Pressure)

For an isothermal process, the change in the Gibb’s free energy may be shown to be:

dG= Vm dP Vm= molar Volume ( m3/mol)

P = Pressure (Pa)

For an ideal gas:

PVm= RT

Therefore:

dG= RT(dP/P)

After Integration:
Go= Gibb’s free energy at std. temperature and
∆G= Go + RT ln (P/Po) Pressure (25C and 1 atm.)
Po= standard pressure (1 atm.)

48
 For any chemical reaction:

jA + kB → mC +nD

The change in the Gibb’s free energy is the change between the products and reactants

∆G= (mGc +nGD) – (jA+ kB)

(Pc/Po)m (PD/Po)n
∆G= Go + RT ln (P/Po) → Go + RT ln
∆G=
(PA/Po)j (PB/Po)k

P= partial pressure of the reactant or product species

This is known as Nernst Equation Po= standard pressure (1 atm)

For any Hydrogen/Oxygen Fuel Cell reaction the Nernst equation becomes:

PH2O
∆G= Go + RT ln
PH2 PO2 0.5

49
 PH2O
E=∆G/nF ∆G= Go + RT ln
PH2 PO2 0.5 PH2 PO2 0.5

E= Eo + (RT/nF) ln
PH2O

When liquid water is produced in the Fuel Cell, PH2O = 1

E= Eo + (RT/nF) ln (PH2 PO20.5)

Cell potential is a function of temperature and pressure

temperature pressure
E= ((∆H/nF) –(T∆S/nF))+ ((RT/nF) ln (PH2 PO20.5))

E= (1.482 –(0.000845(T)))+ ((0.0000431(T) ln (PH2 PO20.5))

50
What is the cell potential (E) of a hydrogen/air fuel cell at 90°C with reactant gases
at atmospheric pressure and with liquid water as a product?
And also calculate the efficiency of the cell?

E= (1.482 –(0.000845(T)))+ ((0.0000431(T) ln (PH2 PO20.5))

51
Fuels for Fuel Cells

Hydrogen

Hydrocarbon fuels

Effect of impurities CO, S and others

52
Hydrogen is an ideal fuel and versatile energy carrier,
and its advantages include the following

1. Available
2. Easy to Produce
3. Renewable
4. Convenient fuel for transportation
5. Versatile, converts easily to other energy forms at the use end
6. High utilization efficiency
7. Environmentally compatible (Zero or low Emission)

53
 Global Energy Systems transitions. 1850-215
0
Image Courtesy: “Fuel Cells: Principles and Applications” ;B. Viswanathan & M. A. Scibioh 54
 Hydrogen-Carbon Ratio, world
energy mix

The atomic hydrogen-carbon ratio

Image Courtesy: “Fuel Cells: Principles and Applications” ;B. Viswanathan & M. A. Scibioh 55
Hydrogen Production Ways (Methods)…

Steam Reforming Currently most effective

Fossil Fuels
Partial Oxidation Needs some improvements

Electrolysis
Water
Thermo-chemical Requires High Temperatures

Gasification Needs some improvements

Bio-Mass
Microbial Slow Kinetics

95% of hydrogen is currently produced by steam reforming

56
Thermo-chemical Fuel Production

Water
When water is heated to above 2500oC,
it separates into oxygen and hydrogen in
a process known as thermolysis.

However, at such high temperatures, it is

difficult to prevent the oxygen and
hydrogen from recombining to form water.

Thermo-chemical
H2
Separation,
Chemical Catalysts → At less than 2500°C
O2

57
Thermo-chemical
(1) Sulfur-Iodine (S-I) Cycle
The S–I cycle is a three-step thermo-chemical cycle
used to produce hydrogen.

The S–I cycle consists of three chemical reactions whose

net reactant is water and whose net products are
hydrogen and oxygen.

All other chemicals (S-I) are recycled

58
STEP 1
I2 + SO2 + 2 H2O → 2 HI + H2SO4 (120 °C)
Bunsen Reaction

HI is separated by distillation or
liquid/liquid gravitic separation.
STEP 2
2 H2SO4 → 2 SO2 + 2 H2O + O2 (830 °C)
The water, SO2 and residual H2SO4 must be separated from
the oxygen byproduct by condensation.
STEP 3
Net reaction
2 HI → I2 + H2 (450 °C)
2H2O→ O2 + H2
59
 Advantages and disadvantages of S-I Cycle

1. All fluid (liquids, gases) process, therefore well suited for continuous operation;
2. High utilization of heat predicted (about 50%), but very high temperatures required
(at least 850 °C);
3. Completely closed system without byproducts or effluents (besides hydrogen and
oxygen);
4. Corrosive reagents used as intermediaries (iodine, sulfur dioxide, sulfuric acid);
therefore, advanced materials needed for construction of process apparatus;
5. Suitable for application with solar, nuclear, and hybrid (e.g., solar-fossil) sources of
heat;
6. More developed than competitive thermo-chemical processes (but still requiring
significant development to be feasible on large scale).

60
What will be the energy source to SOLAR ENERGY
provide H2 for a hydrogen economy
(left)?

Image Courtesy: Chem. Commun. (2005) 4635-46 61

1 Hr of Sun’s Energy is enough
for 1 year of world’s energy
consumption
How to harvest such a huge
ENERGY from SUN ???

62
 Thermo-chemical
(2) Solar-thermal H2 Production

Image Courtesy: S. Abanades, Solar Energy 80 (2006) 1163

Image Courtesy: S. M. Haile et al. Science 240(2003) 721

63
 Thermo-chemical
(2) Solar-thermal H2 Production

STEP 1
High-Temperature Solar Disassociation
(Metal reduction)

2CeO2 (s) → Ce2O3 (s)+ ½ O2 (g) (~1500 °C)

Endothermic reaction

STEP 2

Water reduction (Metal oxidation)

Ce2O3 (s) + H2O→ 2CeO2 (s) + H2(g) (400-600 °C)

Exothermic reaction
64
 Advantages and disadvantages Solar-Thermal
H2 Production

1. Energy source (SUN), Reactive media (water) are readily available and renewable.
2. The resultant fuel (H2) and its product water are environmentally friendly.
3. Can be used for large scale power generations
4. Solar concentration can generate high temperature and diminish the requisite of
surface area of efficient electrical energy conversion components.

1. Environmental concerns- Although electricity generated at a solar thermal plant is

emissions-free, the manufacturing process still has a significant impact on the
environment both on land and in the air.
2. Storage Issues - electricity is obtained only when the sun is shining,
making cloudy and night time hours a hindrance to the steady flow of electricity.
3. Cost – Large scale projects- Advantage becomes a disadvantage when it comes to
finance these firms.

65
Fossil Fuels
Steam Reforming
Steam reforming, sometimes called Fossil fuel reforming is a method
for producing hydrogen or other useful products from hydrocarbon fuels such
as natural gas.

This is achieved in a processing device called a reformer which reacts steam

at high temperature with the fossil fuel.
Steam Reforming of Methane (SRM) is widely used in industry to make hydrogen.

CH4+ H2O → CO + H2 (600-800oC) (Endothermic reaction)

(Nickel as a catalyst)

CO+ H2O → CO2 + H2 (300-400oC) (Exothermic reaction) (water-gas shift reaction)

66
Schematic of SRM/ POM

67
Reforming for fuel cells
Advantages of reforming for supplying fuel cells

-Vehicle- On board reforming for transportation sector

-Production of fuels (H2) and (CO) using fossile fuels

Disadvantages of reforming for supplying fuel cells

-Produces CO2 gas-harmful for environment

-high cost (for fuel cells)
-Utilization of fossil fuels

68
Partial Oxidation
Partial oxidation is a process in which natural gas or a heavy
hydrocarbon fuel (heating oil) is mixed with a limited amount
of oxygen in an exothermic process.

Possible reaction equation (heating oil):

C12H24 + 6O2→ 12CO +12H2

Possible reaction equation (coal):

C24H12 + 12O2→ 24CO +6H2

69
Partial Oxidation of methane

CH4+ ½ O2→ CO +2H2 (exothermic reaction) 500-700°C

70
Bio-Mass
Biomass is biological material derived from living,
or recently living organisms.

It most often refers to plants or plant-based

materials which are specifically called lignocellulosic
biomass.

Sugarcane plantation in Brazil

71
As an energy source, biomass can either be used directly via
combustion to produce heat, or indirectly after converting it to
various forms of bio-fuel.

A co-generation of power plant: waste food 72

Conversion of biomass to bio-fuel can be achieved
by different methods which are broadly classified into
: thermal, chemical, and biochemical methods.

Thermal conversion

Thermal conversion processes use heat as the dominant mechanism to

convert biomass into another chemical form. The basic alternatives of
combustion (pyrolysis, and gasification) are separated principally by the
extent to which the chemical reactions involved are allowed to proceed
(mainly controlled by the availability of oxygen and conversion temperature).

73
 pyrolysis gasification

Char-
partially burn (an object) so as to blacken
its surface

Tar-
dark, thick, flammable liquid distilled from
wood or coal, consisting of a mixture of
hydrocarbons, resins, alcohols, and other
compounds. It is used in road making and
for coating and preserving timber.

74
Disadvantages of Bio-Gas fuels

A major challenge for waste gasification technologies is to reach an acceptable

(positive) gross electric efficiency.

The high efficiency of converting syngas to electric power is counteracted by

significant power consumption in the waste preprocessing, the consumption of
large amounts of pure oxygen (which is often used as gasification agent), and gas
cleaning.

Another challenge becoming apparent when implementing the processes in real life
is to obtain long service intervals in the plants, so that it is not necessary to close
down the plant every few months for cleaning the reactor.

75
 Range of Fuels for SOFCs

Oxygenates Butanol Formic Acid

Range of potential practical fuels for
SOFCs

Image Courtesy: “High-Temperature SOFCs”; S. Singhal & K. Kendall 76

 SOFC device powered by Butane (C4H10
)

SOFC Stack Heat

Butane Integrated
(C4H10) Internal
H2 + CO Anode
and air Reformer
H2O+ CO2
+ Power
+ Heat
Schematic of a small-scale SOFC device powered
by butane.
In remote, small-scale, stand-alone applications where there is no existing
natural gas supply, bottled gas (consisting of propane/butane) offers significant
practical advantages over natural gas.

Image Courtesy: “High-Temperature SOFCs”; S. Singhal & K. Kendall 77

In remote, small-scale, stand-alone applications where there is no
existing natural gas supply, bottled gas (consisting of propane/butane)
offers significant practical advantages over natural gas.

However, the problems of carbon deposition and coking are

considerably more severe with higher hydrocarbons than with
methane.

Thus SOFCs operating on bottled gas are more susceptible to

deactivation and poor durability due to carbon deposition, and thus
the challenge to avoid carbon deposition is considerably greater.

78
SOFC device powered by waste bio-gas

SOFC Stack
Integrated
Internal
Reformer

H2 + CO
Bio-Gas
+air Desulphurization Anode
Unit H2O+ CO2
+ Power
+ Heat
Schematic of a small-scale SOFC device powered
by waste bio-gas.

At present the difficulty in utilizing these gases, because of their

variable composition and often low level of methane
79
Direct and Indirect Internal Reforming SO
FCs

Internal Reforming

A separate fuel processor, external reforming decreases the major

efficiency advantage and cost benefits of SOFC systems over
low-temperature fuel cells.

Internal reforming -increases the system efficiency- recuperating

waste heat - cost of the system by elimination of the external
reformer

Internal Reforming of SOFCs

Direct Internal Reforming
In-Direct Internal Reforming

80
Internal Reforming of SOFCs
(1) Direct Internal Reforming

Direct reforming of the fuel on the anode offers the simplest and
most cost effective design for an SOFC system, and in principle
provides the greatest system efficiency with least loss of energy
Hydrogen reacts with oxygen ions =
Electricity + Heat + Steam and Carbon dioxide exhaust
Internal Reforming of methane = Hydrogen + CO

Anode
Electricity
Electrolyte O-- ions Load
output
Cathode

Air Input Oxygen = Oxygen ions Air Exhaust

81
Role of anode for Direct Internal Reforming

Firstly, as a hydrocarbon reforming catalyst, catalyzing the

conversion of hydrocarbons to hydrogen and carbon monoxide

Secondly, as an electro-catalyst responsible for the

electrochemical oxidation of H2 and CO to H2O and CO2,
respectively

Finally, as an electrically conducting electrode

82
Advantages of Direct Internal Reforming
High-efficiency results from utilizing the heat from the exothermic
electrochemical oxidation reaction to reform the hydrocarbon fuel,
which is a strongly endothermic reaction.
Consuming the hydrogen to form steam, which can then reform
more of the hydrocarbon fuel, the electrochemical reactions help
drive the reforming reaction to completion.

Major Problems
Sharp endothermic cooling effect at the cell inlet-inhomogeneous
temperature distributions - can result in cracking of the anode
and electrolyte materials
Carbon formation on the anode by cracking of hydrocarbons
(CH4)
83
 H2O+ CO2

SOFC Stack Heat

Integrated
Internal
H2 + CO Anode
Hydrocarbon Reformer
H2O+ CO2
fuel
+ Power
+ Heat

Schematic of a in-direct internal reforming SOFC

with recirculation of the anode exist gas

84
 Anode +O2-
Hydrocarbon H2 + CO H2O + CO2 + Power
fuel + Steam
Anode +O2-
H2 + C H2O + Power
(Carbon build-up)

Possible reaction pathways in a directly reforming SOFC

85
 Internal Reformer Anode +O2-
Hydrocarbon H2 + CO H2O + CO2 + Power
fuel +
Excess H2O
Steam
Anode +O2-
H2 + CO2 H2O + CO2 + Power

Schematic of reaction process in an SOFC with indirect

internal reforming

86
Methods of Hydrogen Storage

(1) Storing hydrogen as gas

(2) High-Pressure Gas Cylinders
(3) Liquid Hydrogen Storage 1 Kg of H2– 11m3 volume

(4) Storage via Chemical Methods

(5) Hydrogen in Metal hydrates

Challenge –Pack Hydrogen as close as possible i.e., high volumetric

density – Ease of reversibility of uptake and release

87
Hydrogen storage methods and phenome
na
Storage Mass Vol. densit T P Phenomena and Rema
Method (mass%) y (Kg/m3) (oC) (bar) rks

High 13 <40 RT 800 Compressed gas in light

Pressure weight cylinders (tensile
gas strength of material is
Cylinders 2000 MPa)

Liquid-Hydrogen Size 70.8 -252 1 Liquid H2 continuous

in cryogenic dependent lossof few % per day of
tanks hydrogen at RT

Adsorbed ~2 20 -80 100 Physisorption

Hydrogen (molecular H2) on
materials example
carbon and fully
reversible

88
Hydrogen storage methods and phenome
na
Storage Mass Vol. densit T P Phenomena and
Method Density y (Kg/m3) (oC) (bar) Remarks
(mass%)
Adsorbed on the ~2 150 RT 1 H2 (Atomic H2) inter-
interstitial calation in host sites in a
host metal, metals,
metallic hydrates workin
g at RT and are fully
reversible
Complex <18 150 100 1 Complex compounds ([Al
Compounds H4-] or [BH4-], desorption
at elevated temperature
and adsorption at high
temperatures
Metals and <40 >50 RT 1 Chemical oxidation of m
Complexes etals with water and rele
together with ase of H2, not directly
water reversible
89
(1) Storing hydrogen as gas

Three isotopes of hydrogen are known –

Hydrogen or protium (H), Deuterium (D) and the unstable Tritium (T)

Because of single electron in the atom–

These isotopes from covalent molecules H2, D2 and T2, respectively

Hydrogen has ambivalent behavior towards other elements–

Occurring as an anion (OH-) or cation (H+) in the ionic compounds

90
 H2 Temperatur Vol. Density
e (Kg/m3)
(C)
Solid -262 70.6
Liquid -253 70.8
Gas 0 0.089886

At ambient temperature (25C), Hydrogen gas is described by the

van der waals equation

Where,
P= gas pressure, V= volume, T= Absolute Temp., R= Gas Constant
a= dipole interaction or repulsion constant, b=volume occupied by
hydrogen molecule, n= no. of moles 91
(2) High-Pressure Gas Cylinders

The most common storage system is high pressure gas cylinders–

Operated at maximum pressure of 20 Mpa.

The wall thickness of a cylinder capped with two hemispheres is given

by–
(dw/do) = ∆p/(2 σv + ∆p)

dw = wall thickness, do= outer dia. of the cylinder

∆p= over-pressure, σv = tensile strength of material

The ideal material for a high-pressure cylinder should have a very

High tensile strength, low density and does not react with hydrogen

92
The safety of pressurized cylinders is a concern, especially in highly
populated regions.

The pressure vessels should consist of the following layers-

(1) An inner polymer layer over-wrapped with carbon-fiber composite
(which is a stress-bearing component)
(2) Outer layer of an aramid (heat-resistant) material capable of
withstanding mechanical and corrosion damage.

Industry set target,

110Kg H2 in a 70 MPa cylinder with gravimetric density = 6mass% and
vol. density = 30Kg/m3
Drawbacks-
Low hydrogen density, very high gas pressures in the system

93
 Industry set target,
110Kg H2 in a 70 MPa cylinder
with gravimetric density = 6mass%
and vol. density = 30Kg/m3

Drawbacks-
Low hydrogen density, very high
gas pressures in the system

Image Courtesy: web source 94

 (3) Liquid Hydrogen Storage

Triple Point-
A point in the phase
diagram at which
solid, liquid and vapor
phases co-exists
Critical Point-
A point in the phase
diagram at which both the
liquid and gases have
same density and therefore
indistinguishable

Liquid hydrogen – line from the

triple point 21.2 K (-252°C) and critical point 32K (-241°C)
95
Liquid hydrogen is stored in cryogenic tanks at -252°C

The pressure in a closed storage system at RT could increase to 104 bar

Liquefaction cycle Joule-Thompson cycle (Linde Cycle)-

The gas is first compressed and then cooled in a heat exchanger

and then it passes through a throttle valve where it undergoes an
isoenthalpic Joule-Thomson expansion, producing some liquid.

The cooled gas is separated from the liquid and returned to the
compressor via the heat-exchanger

Drawbacks-
Large amount of energy is necessary for liquefaction and the
continuous boil-off of hydrogen- (limited to space applications)
96
Linde Cycle

97
 Drawbacks-

Large amount of energy is

necessary for liquefaction

continuous boil-off of hydrogen-

(limited to space applications) and

where cost is not an issue
Image Courtesy: web source 98
(4) Storage Via Chemical Methods

Hydrogen can be generated by reacting metals and chemical

compounds with water

Sodium (Na) , Lithium (Li)

2Na + 2H2O → 2NaOH + H2

Gravimetric Hydrogen Density of Sodium (Na) = 3 mass%,

Gravimetric Hydrogen Density of Lithium (Li) = 6 mass%

Major Challenge- Reversibility and control of thermal reduction

process in order to produce pure metal in a solar furnace

99
 The process has been successfully demonstrated by Zinc

ZnO→ Zn + ½ O2

Zn + H2O → Zn + H2

H 2 O → H2 + ½ O 2

Image Courtesy: web source (Aldo Steinfeld research outputs) 100

(5) Hydrogen in Metal-hydrides

Hydrogen reacts at elevated temperature with many transition

metals and their alloys to form hydrides

The electropositive elements are most effective.

Examples: Scandium, Lanthanides and actinide members of
Titanium and vanadium groups
Many of these compounds (MHn) show large deviation from ideal
stoichiometry (n= 1,2,3,4…) and can exists as multi-phase systems

Metallic hydrides of inter-metallic compounds (ABxHn) are of great

interest

101
Element A – rare earth or an alkaline earth metal and tends to form
stable hydrate

Element B – trantional metal and form unstable hydrates

The reaction of the hydrogen gas with metal undergoes an absorption

process

The hydrogen atom contribute its electron to the band structure of

the metal
At small hydrogen to metal ratio (H/M < 0.1), the hydrogen is
exothermically dissolved in the metal (solid-solution, alpha-phase)
The metal lattice expands its volume proportional to its hydrogen
concentration by approximately 2~3 Å3

102
The most important families of hydride-forming inter-metallic compounds

Inter-metalli Prototype Structure

c
compound
AB5 LaNi5 Hexagonal Phase
AB2 ZrV2,ZrMn2, TiMn2 Hexagonal or cubic
AB3 CeNi3, YFe3 Hexagonal, PuNi3 type
A2B7 Y2Ni7, Th2Fe7 Hexagonal, Ce2Ni7 type
A6B23 Y6Fe23 Cubic, Th6Mn23 type
AB TiFe, ZrNi Cubic, CrB type
A2B Mg2Ni, Ti2Ni Cubic, Ti2Ni type

Image Courtesy: Fuel Cells (B. Vishwanathan & M. Aulice Scibioh) 103
 Image Courtesy: Web source

Image Courtesy: Matinez-Franco E et.al., Ing. Invest. Y technol. 11(2010) 352 104
Hydrogen in complex-hydrides

Light metals of group 1,2, and 3 (Ex: Li, Mg and Al) give large
variety of metal-hydrogen complexes
Interesting because of their light weight and the number of
hydrogen atoms per metal atom

The hydrogen in the complex hydrates is often located in the

corners of tetrahedron with B or Al [BH4]- or [AlH4]-

The negative charge of the anion [BH4]- or [AlH4]- is compensated

with a cation, like, Li or Na.

105
The hydrates of borane, the tetrahydroborates M(BH4) and
tetrahydroaluminates M(AlH4) are interesting storage materials.

They are stable and decompose at elevated temperature.

Decomposition of NaAlH4.

NaAlH4 ↔ 1/3 Na3AlH6 + 2/3 Al + H2 (3.7 wt%)

1/3 Na3AlH6 ↔ 3NaH + Al + 3/2H2 (3.0 wt%)

106
Essential requirements that should be satisfied by metal-hydrates
proposed for hydrogen storage at commercial level.
(1) High hydrogen content.
(2) Facile reversibility of formations and decomposition reactions.
(decompose at moderate temperatures (use solar, automobile
exhaust and waste heat sources)

(3) Resistant to deactivation some contaminants like O2,H2O, CO2,

CO and others.
(4) Total cost of hydrate (raw materials, processing and production)
should be affordable.

107
Hydrogen Production By CO2 Reforming of Methan
e

With increasing population and rapid technology development, it is

possible that we have begun to encounter alteration of the climate.
(Global Warming Issue!!!)
Green House Gases (CO2, CH4, O3, N2O) to a significant extent come
from the combustion of fossil fuel (Coal, Oil etc)
A potential useful reaction for reducing the impact of CO2 is
needed and was found to be CO2 (or dry) reforming of methane

CH4 + CO2 → 2CO + 2H2 ∆H= +247 kJ/mol

H2/CO = 1, which is a desirable for GTL (Gas-to-Liquid) applications

108
 Hydrogen Production from CO2 Reforming of Metha
ne

Technology is needed to control CO2

Image Courtesy: Web source 109

Image Courtesy: Devendra Pakhare Chem. Soc. Rev. (2014) Image Courtesy: Int. J. Hyd. Energy 32(2007)1782

Major drawback with CO2 reforming of Methane is carbon deposition.

CH4 → C + 2H2 ∆H= +75 kJ/mol

2CO → 2C + CO2 ∆H= -171kJ/mol
(Boudouard reaction)
110
Direct Electro-catalytic oxidation of methane

There have been a number of reports of the use of

ceramic membrane reactors and solid oxide fuel cells (SOFCs) for
methane partial oxidation (POx).

Both these approaches seek to combine the POx catalytic reaction

with electrochemically produced pure oxygen
(i.e. electrochemical partial oxidation, or EPOx), thereby yielding
Syngas + electricity

Elimination of explosive methane–oxygen mixtures.

Note that steam reforming can be used to convert methane to

syngas internally to SOFCs.
The syngas is then oxidized to H2O and CO2 by the SOFC as it
produces electricity.
111
EPOx is distinct from this in that electricity is produced during the
reforming process, rather than after reforming, such that syngas
can be output as a useful chemical product.
In SOFC reactor approach, the desired overall reaction in
partial oxidation

CH4 + O2- → CO + 2H2 + 2e- ∆H= 22 kJ/mol (750°C)

Total SOFC currents and methane flow rates are adjusted to yield
an O2−/CH4 ratio ≈ 1

This is quite different than direct-methane SOFCs, where the aim is

to produce electricity by completely oxidizing methane:

¼ CH4 + O2- → ¼ CO2 + ½ H2O+ 2e- ∆H= -200 kJ/mol (750°C)

112
 Comparison of reactions shows that for a given sized
SOFC (i.e. that transports a given amount of O2−),
the same amount of electricity (2e−) is produced, while the
methane feed rate and the products are different.

This SOFC EPOx approach has two potential advantages over

other syngas production methods.
First, two useful products, syngas and electricity, are produced;
in contrast, conventional SOFCs produce only electricity and
ceramic membranes produce only syngas.

Second advantage is that EPOx can potentially build on an

increasingly well-developed SOFC technology

113
 Schematic SOFC- EPOx set-up

Image Courtesy: J Power Source 161(2006)460 114

Carbon Deposition

Carbon deposition on reforming catalysts

Nickel catalysts after reforming of dodecane (C12H26).

115
 Carbon deposition on SOFC anodes

SEM images of a conventional anode (a), and

an improved anode (b) after direct butane power generation.

116
Sulfur tolerance and Removal
Dimethyl Sulfide ((CH3)2S)
Odorants, 5ppm Sulphur

Natural Gas Diethyl Sulfide ((C2H5)2S)

Frequently present, Ethyl Mercaptan ((C2H5)HS)

@low levels

Hydrogen Sulfide (H2S)

HT Fuel Cells, Internal reforming
catalysts show some tolerance to Sulfur
Carbonyl Sulfide(COS)

Desulfurization units prior to the natural gas entering fuel cells

should be established

117
At low concentrations of sulfur-containing compounds, the
adsorption of sulphur on nickel is reversible, and thus
low concentrations of sulfur in the feed gas can be tolerated,
especially at higher operating temperatures

Any adsorbed sulfur can be removed,

and the activity restored to the original activity, by switching to
a sulfur-free fuel feed or by a short exposure to steam

However, at higher sulfur concentrations,

irreversible sulfidation of the catalyst or anode can occur

118
Sulfur can be removed by various methods

(High-Temperature Desulfurization) (350 to 400°C)

(C2H5)2S + 2H2 → 2C2H6 + H2S

(molybdenum or cobalt active metals supported on Alumina

H2S + ZnO → ZnS + H2O

(Adsorption on Carbon!!!)

119
Using renewable fuels for FCs

Generating renewable electricity is an important way to reduce

carbon dioxide (CO2) emissions and many countries are installing
wind and solar power plants to help meet targets for cutting CO2

Drawbacks ----
Wind (Tends to blow intermittently)
Solar (Available during daytime, issue with Clouds)

Storage Issue----
Ideally, excess renewable energy generated during times of
plenty can be stored for use during periods when
sufficient electricity is not available.

120
Storing this energy is a difficult task:
Batteries and similar technologies perform well over short
timescales, but over periods of weeks or months a different
approach is necessary.

Energy storage in the form of hydrogen is one such possibility!!!!

Excess electricity is fed into an electrolyser to split water into its

constituent parts, oxygen and hydrogen.

The hydrogen is then used in fuel cells to produce electricity

when needed, releasing the stored energy back to the grid.

121
 Using renewable fuels for FCs

Fuel cells in renewable energy systems

Image Courtesy: Fuel Cells Today 122
Key Benefits!!!!
This process allows excess energy produced in wind farms and
solar power plants to be stored and used, instead of wasted.

Increasing the utilization of renewable power plants helps

to maximize the return on investment and lower the cost of
electricity.

The most efficient way to convert hydrogen back to electricity is

via fuel cells.

123
Microbial Fuel Cells

A microbial fuel cell (MFC) or biological fuel cell is a

bio-electrochemical system that drives a current by using bacteria
and mimicking bacterial interactions found in nature.

TWO Categories

Mediator MFCs : A Chemical that transfers electrons from the bacteria

in the cell to the anode

Mediator-Less MFCs : The bacteria itself have a electrochemically

active redox proteins such as cytochromes on their outer membrane
that can transfer electrons directly to the anode

124
Material requirements of MFCs

Bio-catalysts:
To convert chemical energy to electrical energy
bacteria, enzymes or cell organisms….)
Substrates (for Oxidation @ Anode):
Methanol, Organic acids or Glucose( abundant source of energy)

Substrates (for Reduction @ Cathode):

Oxygen or hydrogen peroxide (H2O2)

125
Schematic of a MFC
126
 Mr. Clean The Iron-Breather
(aka Shewanella) (aka Geobacter)

1um KEY Players!!!

1um

Electron transfer mechanisms:

Direct transfer

Electron transfer (through mediator)

Nano-wires

127
MFCs using electron relays for coupling of intracellular electron transfer
processes with electrochemical reactions at anodes

Microorganism Nutritional Mediator

Subtrate

E. coli Glucose Methylene blue

Proteus vulgaris Glucose Thionine

Bacillus subtilis

Proteus vulgaris Sucrose Thionine

Lactobacillus plantarum Glucose Fe(III)EDTA

Escherichia coli Acetate Neutral Red

128
Bacteria used in biofuel cells when membrane-penetrating
Electron Transfer Mediators (dyes) are applied

Alcaligenes eutrophus E. Coli (image width 9.5 m) Anacystis nidulans 200 nm

Proteus
vulgaris Pseudomonas putida
Bacillus subtilis

Streptococcus
lactis
Pseudomonas
aeruginosa
129
When micro-organisms consume a substance such as sugar in
aerobic conditions, they produce carbon dioxide and water.

However, when oxygen is not present, they produce carbon di

oxide, protons, and electrons, as described below

C12H22O11 +13 H2O → 12CO2 + 48H+ + 48e-

130
Advantages of MFCs…

Generation of energy from bio-waste/organic matter

Direct conversion of substrate energy to electricity

No harmful effluents

131
 Fuel Cell Electro-Chemistry

Electrode Kinetics
Voltage Loses
Polarization Curve
Fuel Cell Efficiency, Tafal Equation and
Exchange Currents

132
Electro-Chemistr
y
A branch of chemistry that deals with the relations
between electrical and chemical phenomena.
Involves Redox (Reduction and Oxidation) Reaction
s
(Electron transfer reactions)

e-
Anode
Electrolyte Load

Cathode e-
Fuel Cell Schematic
133
Electrode Kinetics
(Reaction Rate, Reaction constants,
Current-Potentional Relationship,
Exchange Current Density )

At Anode: At Cathode:

H2 → 2H+ + 2e- ½ O2 +2H+ + 2e- → H2O

These reactions occur at the interface between electrolyte

and electrode.

Electrode should be porous in nature!!!

134
Reaction Rate
Electro-chemical reactions involve both a transfer of elect
rical
charge and a change in Gibbs energy.
The rate of a electro-chemical reaction is determined by an
activation energy barrier that the charge must overcome in
moving from electrolyte to electrode or vice versa.
The speed at which an electro-chemical reaction proceeds o
n the electrode surface is the rate at which the electrons are
released or consumed (Electrical current)

Current Density is the current (of electrons or ions) per unit

surface area
135
 From Faraday’s law,
the current density is proportional to charge transferred and
the consumption of the reactant per unit area
i = nFj
nF is the charge transferred (Coulombs/mol)
j is the flux of reactant per unit area (mol/ cm2 s)

∴ The reaction rate can be easily measured by a current

measuring device (net current).

net current is the difference b/w forward and reverse current

on the electrode.

136
 In general, an electro-chemical reaction involves either
oxidation or reduction of the species.

Red → Ox + ne- Ox + ne- → Red

On an electrode, at equilibrium conditions, i.e., when no

external current is being generated, both the processes,
oxidation and reduction occur at equal rates
Ox + ne- ↔ Red

The consumption of the reactant species is proportional to

their surface concentration.

137
 For Forward reaction, the flux (j), takes the form,

jf = kf.Cox
kf=Rate coefficient of forward reaction (reduction), (s-1)
Cox= surface concentration of the reactant species (mol/cm2)

Similarly, for Backward reaction, the flux (j), takes the for
m,
jb = kb.CRed

kf=Rate coefficient of backward reaction (oxidation), (s-1)

CRed= surface concentration of the reactant species (mol/cm2)

138
 Each of these two reactions either releases or consumes
electrons
The net current generated is the difference between the
electrons released and consumed
i = nFj
i = nF (jf-jb)
i = nF (kf.Cox -kb.CRed)

At equilibrium, the net current = 0, although the reactions

proceeds in both directions simultaneously.

The rate at which these reactions proceed at equilibrium is

called the exchange current density
139
Reaction Constants; Transfer Coefficient
From Transition State Theory, for electrochemical reaction,
the relationship b/w reaction rate constant (k) and Gibbs Free
Energy (∆G) :

k = (kBT/h) exp (-∆G/RT)

Where:
kB= Boltzman’s constant, 1.38 * 10-23 JK-1
h = Plank’s constant, 6.626 * 10-34 J s

Gibbs free energy for the electro-chemical reactions may be

considered to constitute both chemical and electrical terms:

140
In case of reduction,
∆G = ∆Gch + αRdFE

In case of oxidation,

∆G = ∆Gch - αOxFE
Where:
Ch = Chemical component of Gibbs free energy
α = transfer coefficient
F = Faraday’s constant
E =Potential

In general, both the electrochemical reactions (O2 reduction

and H2 oxidation) involve more than one step and more than
one electron.

141
At steady state condition, the rate of all steps must be equal
and it is determined by the slowest step in the sequence
which is referred as rate-determining step.

In the fuel cell electrochemical reactions, (αRd + αOx)need not

necessarily be 1.

In general, (αRd + αOx) = n/v.

Where
n= no. of electrons,
v=stoichiometric number defined as the number of times the
rate determining step must occur for the overall reaction to
occur once.

142
The forward (reduction) and backward reaction (oxidation)
reaction rate coefficient are:
kf = ko,f exp (- αRdFE/RT) kb = ko,b exp (αOxFE/RT)

i = nF (kf.Cox - kb.CRed)

i = nF (ko,f Coxexp (- αRdFE/RT) - ko,b CRedexp (αOxFE/RT)) Eq.1

At equilibrium, the potential is Er and the net current =0,

although the reactions proceeds on both directions
simultaneously.

The rate at which these reactions proceed at equilibrium is

called the exchange current density(io).
143
At equilibrium, Forward reaction = backward reaction :

i 0= nF ko,f Coxexp (- αRdFE/RT) = nFko,b CRedexp (αOxFE/RT)) Eq.2

By combining Eq.1 and Eq.2, we obtain the relationship b/w

current density and potential:

i = io (exp (- αRdF(E-Er)/RT) – exp (αOxF(E-Er)/RT))

This is known as Butler-Volmer Equation…

Er = reversible or equilibrium potential
( anode = 0, cathode = 1.23V)

144
(E-Er), difference b/w the electrode potential and the reversible
potential is called Over-potential. It is the potential difference
required to generate current

Butler-Volmer equation is also valid for anode and cathode

reaction also:
At anode:

ia= io,a (exp (- αRd, a F(Ea-Er,a)/RT) – exp (αOx, aF(Ea-Er,a)/RT))

At cathode:

ic= io,c (exp (- αRd, c F(Ec-Er,c)/RT) – exp (αOx, cF(Ec-Er,c)/RT))

145
At anode:

ia= io,a (exp (- αRd, a F(Ea-Er,a)/RT) – exp (αOx, aF(Ea-Er,a)/RT))

The over-potential on the anode is positive (+) (Ea>Er,a)

0
ia= io,a (exp (- αRd, a F(Ea-Er,a)/RT) – exp (αOx, aF(Ea-Er,a)/RT))

ia= - io,a exp (αOx, aF(Ea-Er,a)/RT))

The negative (-) sign, indicates that the electrons are leaving
the electrode.

146
At cathode:

ic= io,c (exp (- αRd, c F(Ec-Er,c)/RT) – exp (αOx, cF(Ec-Er,c)/RT))

The over-potential on the cathode is negative (-) (Ea< Er,a)

Negligible value
ic= io,c (exp (- αRd, c F(Ec-Er,c)/RT) – exp (αOx, cF(Ec-Er,c)/RT))

ic= io,c (exp (- αRd, c F(Ec-Er,c)/RT)

147
Voltage Losses

Fuel cell with a load: (a) in Open Circuit (b) Closed Circuit

It will not generate any current & Potential is expected to drop even
cell potential would at least or further as a function of current
close to theoretical cell potential being generated
(unavoidable losses) 148
Types of voltage losses…

Activation Polarization
Internal Currents and Crossover Losses
Ohmic (Resistive) Losses
Concentration Polarization
Factors effecting the voltage losses
Kinetics of the electrochemical reactions
Internal electrical and ionic resistance
Difficulties in getting the reactants to reaction sites
Internal (stray) currents
Crossover of reactants
149
Activation Polarization

Always some voltage difference from equilibrium is needed

to get the electrochemical reaction going (Activation Polarization)

The activation polarization is associated with sluggish electrode

kinetics
Higher the exchange current density, lower the Activation
Polarization losses
These losses can occur at both anode and cathode.
Oxygen reduction requires much higher potentials, i.e., it is a
much slower reaction than hydrogen electrode.

150
At relatively high negative overpotentials (cathode), the first term
in the Butler-Volmer equation becomes predominant, which allows
for expression of potential as a function of current density

∆Vact,c= Er,c –Ec = (RT/ αcF) ln (i/io,c)

Similarly, Positive overpotentials (anode), the second term

in the Butler-Volmer equation becomes predominant, which allows
for expression of potential as a function of current density

∆Vact,a = Ea –Er,a = (RT/ αaF) ln (i/io,a)

151
Activation polarization of hydrogen oxidation reaction is much
smaller than the activation polarization of oxygen reduction
reaction. ∆Vact,a <<∆Vact,c

Tafel equation is a simplified way to express the activation losses

∆Vact = a+ b log (i)

a = -2.3 (RT/αF) log (io) b = 2.3 (RT/αF)

b is called the Tafel Slope

152
If the voltage-current (V-I) relationship is plotted in logarithmic
scale, the main parameters a, b, io are detectable.

Potential loss due to activation polarization in log scale 153

If activation polarization is the only loss in a fuel cell, the cell
potential would be:

Ecell = Ec-Ea= Er- ∆Vact ,c-∆Vact ,a

Ecell = Er- (RT/ αcF) ln (i/io,c) - (RT/ αaF) ln (i/io,a)

Neglected
Ecell = Er- (RT/ αcF) ln (i/io,c) - (RT/ αaF) ln (i/io,a)

Ecell = Er- (RT/ αF) ln (i/io,)

This equation has the same form as the Tafel Equation

154
Internal Currents and Crossover Losses

Although the electrolyte is not electrically conductive, some small

amount of H2 will diffuse from anode to cathode , and some
electrons may also find a “shortcut” through membranes.

Each H2 molecule that diffuses through the electrolyte membrane

and reacts with O2 molecule on the cathode side of fuel cell
results in two fewer electrons in the generated current of
electrons that travels through an external circuit.

These losses are insignificant (at closed circuit).

(rate of H2 permeation << H2 consumption)

155
The total electrical current is the sum of the external (useful)
current and current losses due to fuel crossover and internal
currents:
I= I ext + I loss

Current divided by the electrode area, A, is current density.

i = I/A ⇒ i= i ext + i loss

Ecell = Er- (RT/ αF) ln (i/io,) ⇒

Ecell = Er- (RT/ αF) ln ((iext +iloss)/io,)
156
Ohmic (Resistive) Losses

Ohmic losses occurs –

Resistance to the flow of ions in the electrolyte &
Resistance to flow of electrons through the electrically conductive
Fuel cell components

These losses can be expressed by Ohm’s law :

∆Vohm= i Ri
Where:
i = current density (A/cm2)
Ri = total cell resistance
(ionic, electronic & contact resistance, Ω /cm2)
Ri = Ri,i + Ri,e +Ri,c
157
 Voltage-Current (V-I) Plots:

Activation polarization

Potential losses due to ohmic resistance and activation

polarization on normal scale
158
Concentration Polarization

Concentration polarization occurs –

When a reactant is rapidly consumed at the electrode by the
electrochemical reaction so that the concentration gradients are
established

∆Vconc. = (RT/nF) ln (CB/CS)

Where:
CB = bulk concentration of the reactant (mol/cm3)
CS = concentration of the reactant at the surface of the Catalyst/
Anode/ Cathode (mol/cm3)

159
According to Fick’s law of one dimensional diffusion,

The flux of a reactant is directly proportional to its

concentration gradient
N = D (CB-CS). A / δ
Where:
N = Flux of reactants (mol/s)
D =diffusion coefficient of the reacting species (cm2/s)
A = electrode active area (cm2)
δ = diffusion distance (cm)

In the study state, the rate at which the reactant is consumed in

the electrochemical reaction is equal to the diffusion flux
N = I/(nF)
160
N = D (CB-CS). A / δ ⇒ I/nF = D (CB-CS). A / δ

I/A = nFD (CB-CS)/ δ ⇒ i = nFD (CB-CS)/ δ

Lower the surface concentration, higher the current density

0 (when the rate of consumption becomes
equal to the diffusion rate)
i = nFD (CB-CS)/ δ

iL = nFD CB/ δ Limiting current density

161
By combining the following equations, a relationship for voltage
loss due to concentration polarization is obtained

∆Vconc. = (RT/nF) ln (CB/CS) i = nFD (CB-CS)/ δ

iL = nFD CB/ δ

∆Vconc. = (RT/nF) ln (iL/(iL-i))

162
 If the voltage-current (V-I) relationship is plotted

Potential loss due to concentration polarization

163
 Polarization Curve

Voltage losses in the fuel cell

164
Activation losses-larger losses that can occur at any
current density for a fuel cell
Activation losses >> Ohmic losses> Concentration losses

∆Vcell = Er – (∆Vact) – (∆Vconc) –∆Vohm

Activation & concentration polarization can occur at both

anode & cathode

Vcell = Er – (∆Vact + ∆Vconc) a– (∆Vact + ∆Vconc)c –∆Vohm

165
By combining the following equations, a relationship between fuel
cell potential and current density (fuel cell polarization curve) can
be obtained…

∆Vact,c= Er,c –Ec = (RT/ αcF) ln (i/io,c) (Activation Polarization)

∆Vact,a = Ea –Er,a = (RT/ αaF) ln (i/io,a)

∆Vohm= i Ri (Ohmic loss)

∆Vconc. = (RT/nF) ln (iL/iL-i) (Concentration polarization)

Vcell = Er – (∆Vact + ∆Vconc) a– (∆Vact + ∆Vconc)c –∆Vohm

166
 Vcell = Er – (∆Vact + ∆Vconc) a– (∆Vact + ∆Vconc)c –∆Vohm

Vcell = Er,T,P – (RT/ αcF) ln (i/io,c) - (RT/ αaF) ln (i/io,a) -

(RT/nF) ln (iL,c/iL,c- i) – (RT/nF) ln (iL,a/iL,a- i) - iRi

(If hydrogen cross over and internal current losses are also
taken in account ) ( i = i ext + i loss)

167
 Fuel Cell Efficiency

Fuel cell efficiency-

Ratio b/w electricity produced and the hydrogen consumed.
The two must have same units (watts or kilowatts)
ɳ= Wel/WH2

Electricity produced is the product of voltage and current.

Wel = V.I
Where:
I = current in amperes
V= cell potential in volts

According to Faraday’s law, Hydrogen consumed is

directly proportional to the current

168
 According to Faraday’s law, Hydrogen consumed is
directly proportional to the current

WH2 = ∆H(I/nF)

Where:
WH2 = energy value of hydrogen consumed in joules / s (watts)
∆H = Hydrogen Higher Heating value (286k J/mol)

ɳ= V / (∆H/nF) ∆H/nF = 1.482 or 1.254 @ HHV or LHV

Is fuel utilization
ɳ= V / (∆H/nF) * ɳ fu
169
Calculate the nominal power output?

In a H2/air fuel cell,

α=1, i0 = 0.001mA/cm2 , Ri = 0.2Ω cm2, T=60°C,
atmospheric pressure, Electrode active area = 100cm2,
i = 970 mA/cm2

170
Wel = V.i A

Vcell = Er,T,P – (RT/ αcF) ln (i/io,c) - (RT/ αaF) ln (i/io,a) -

(RT/nF) ln (iL,c/iL,c- i) – (RT/nF) ln (iL,a/iL,a- i) - iRi

E r,T,P = 1.482 – 0.000845T + 0.0000431T ln (PH2PO2 0.5)

E r,T,P = 1.189V
Vcell = 0.6V
Wel = 58.2 W

171
 PEM Fuel Cells

PEM Cell components:

Materials, Properties and processes
Membranes
Electrodes

Gas Diffusion Layer Bi-Polar Plates

Fuel Cell operating conditions:
Temperature, Pressure, Flow rates, Humid
ity

172
Microscopic view of PEMFC

173
Overall View of PEMFC

The multilayer assembly of the membrane sandwiched between the two

electrodes is commonly called the membrane electrode assemble, or MEA.

The MEA is then sandwiched between the collector/separator plates- Bipolar Plates

174
PEM Cell components:

Main PEM Cell components and processes

175
The following processes take place inside the fuel cell (the numbers corre
spond to those in the Figure given):
1. Gas flow through the channels; some convective flows may be induced
in the porous layers.
2. Gas diffusion through porous media.
3. Electrochemical reactions, including all the intermediate steps
4. Proton transport through proton conductive polymer membrane
5. Electron conduction through electrically conductive cell components
6. Water transport through polymer membrane including both electro-chemical
drag and back diffusion
7. Water transport (both vapor and liquid) through porous catalyst layer and
gas diffusion layers

8. Two phase flow of unused gas carrying water droplets

9. Heat transfer, including both conduction through solid components of
the cell and convection to reactant gases and cooling medium

176
 Membrane

Membrane:
-Exhibit relatively high proton conductivity
-adequate barrier to the mixing of fuel and reactant gases
-Chemical and mechanically stable in FC environments

PEM FC Membranes are made of perflorocarbonsulfonic acid (PSA) ionomer

PSA is a co-polymer of tetrafluorethylene (TFE) & perfluorosulfonate monomers

Nafion-is best known PEM FC Membrane (Dupont Company)

Structure of PSA polymer (Nafion)

177
How does this Membrane effect

(1) Water uptake

(2) Physical properties
(3) Protonic conductivit
y
(4) Water transport
(5) Gas permeation

178
 (1) Water uptake
The protonic conductivity of a polymer membrane is strongly dependent on
membrane structure and its water content

The water content in a membrane is usually expressed as grams of water per gram of
polymer dry weight
(or)
as number of water molecules per sulfonic acid groups present in the polymer

λ = N(H2O)/N(SO3H)

The maximum amount of water in the membrane strongly depends on the state of
water used to equilibrate the membrane.

Boiled water - 22 molecules of water/ sulfonic acid group

Vapour phase - 14 molecules of water/ sulfonic acid group

179
 Water uptake in proton conductive
membranes at 30 C

1. At the low vapor activity region, aH2O (0.15–0.75), water uptake

increases to about 5,

2. At the high vapor activity region, aH2O (0.75–1.0), water uptake

increases sharply to about 14.4.

180
 (2) Physical Properties
Water uptake results in the membrane swelling and changes its dimensions,
which is a very significant factor for fuel cell design and assembly.

Nafion membrane properties at various water contents.

181
Dimensional changes are in the order of magnitude of 10%, which must be
taken into account in cell design.

A new microreinforced expanded polytetrafluorethylene (ePTFE) polymer

electrolyte membrane targeted specifically toward PEMFC applications.
(WL Gore & Associates, 1995)
These membranes exhibit much
higher strength, better dimensional stability, lower gas permeability, &
higher conductivity than comparable nonreinforced Nafion membranes

182
 (3) Proton conductivity
Proton conductivity is the most important function of the polymer membranes
used in fuel cells.

The protonic conductivity of fully hydrated membrane is about 0.1 S/cm at

room temperature.
The conductivity of PFSA membranes is a strong function of water content and
temperature

183
Proton conductivity dramatically increases with temperature & at 80°C reaches
0.18 S/cm for a membrane immersed in water.

Ionic conductivity (in S/cm) to water content and temperature with the
following expression:

Possible ways of ionic conductivity of Nafion-like materials:

(1) At very low water contents (λ=2-4) hydronium ions (H3O+) move vehicle
mechanism.

(2) As the water content increases(λ=5-14) easier movement of hydronium

ions (H3O+) is facilitated

184
(3) At fully hydrated membranes {λ> 14), water in interfacial regions
screens weakly bound water from ion-dipole interactions, and both
water and ions move freely.

Mechanisms of water and hydronium ions

movement through PFSA
ionomer at various hydration levels

185
 (4) Water Transport

There are several mechanisms of water transport across a polymer membrane

Water is produced on the cathode side as the result of the electrochemical

reaction
The rate of water generation (in mol s-1cm-1) is:

i= current density (A/cm2), F=Faraday’s constant

186
Water is dragged from the anode to the cathode by protons moving
through the electrolyte. This is called electroosmotic drag.

The flux of water due to electroosmotic drag (in mol s-1cm-2) is :

ξ= electroosmotic drag coefficient defined as number of water

molecules per proton & is a function of membrane hydration (λ)

Water generation & electroosmotic drag would create a large concentration

gradient across the membrane.

Due to this gradient, water diffuses back from the cathode to the anode.

187
The rate of water diffusion (in mol s-1cm-2) is:

D = water diffusion coefficient in ionomer of water content (λ)

∆C/ ∆z = water concentration gradient along with z-direction

In addition to diffusion due to concentration gradient, water may be

hydraulically pushed from one side of the membrane to the other if there
is a pressure difference between the cathode and the anode.
The rate of hydraulic permeation (in mol s-1cm-2) is:
k = hydraulic permeablity coefficient in
ionomer of water content (λ)
∆P/ ∆z = pressure gradient along with
z-direction 188
 (5) Gas permeation

In principle, the membrane should be impermeable to reactant species.

However, because of the membrane's

essentially porous structure, its water content and solubility of hydrogen
and oxygen in water, some gas does permeate through the membrane.

Permeability is a product of diffusivity & solubility:

D = diffusivity ( cm2s-1)
S = solubility ( mol cm3 Pa-1 )
Pm = permeability( mol cm s-1 cm-2 Pa-1)

1 Barrer = 10-10 cm3 cm s -1 cm -1 cm-2 Hg

189
Electrode

A fuel cell electrode is essentially a thin catalyst layer pressed between

the membrane and it is a porous, electrically conductive substrate.
It is the layer where the electrochemical reactions take place.

There are three kinds of species that participate in the electrochemical

reactions, namely gases, electrons and protons.

These reactions can take place on a portion of the catalyst surface where
all three species have access.

Electrons travel through electrically conductive solids, including the

catalyst itself.

Protons travel through membrane,- therefore the catalyst must be in

intimate contact with the membrane.

190
Finally, the reactant gases travel only through voids,- therefore the
electrode must be porous to allow gases to travel to the reaction sites.
At the same time, product water must be effectively removed; otherwise
the electrode would flood and prevent oxygen access.

As shown graphically in Fig(a),

the reactions take place at the
three-phase boundary, namely
membrane, solid, and void phases.

However, this boundary has an

infinitesimally small area

191
In practice, because some gas may permeate through the polymer, the
reaction zone is larger than a single three-phase boundary line.

The reaction zone may be enlarged by either "roughening'' the surface of

the membrane or by incorporating ionomer in the catalyst layer (Fig. b)

In an extreme case, the entire catalyst surface may be covered by a thin

ionomer layer (Fig. c)

192
The most common catalyst in PEM fuel cells for both oxygen reduction
and hydrogen oxidation reactions is platinum.

In the early days of PEMFC development large amounts of Pt catalyst were

used (up to 28mg cm-2)
In the late 1990s, with the use of supported catalyst structure, this was
reduced to 0.3-0.4 mg cm -2.
Catalyst surface area that matters, not the weight, so it is
important to have small platinum particles (4nm or smaller) with large
surface area finely dispersed on the surface of catalyst support, typically
carbon powders (>75 m2/g)

To minimize the cell potential losses (rate of proton transport &reactant

gas permeation) this catalyst layer should be made reasonably thin.

193
194
In general, higher Pt loading results in voltage gain, assuming equal
utilization and reasonable thickness of the catalyst layer.
However, when current density is calculated per area of Pt surface then
there is almost no difference in performance.
The key to improving the PEM fuel cell performance is not in increasing
the Pt loading, but rather in increasing Pt utilization in the catalyst
layer.
195
196
Gas Diffusion Layer (GDL)

A layer between the catalyst layer and bipolar plates is called a

gas diffusion layer, electrode substrate, or diffuser/current collector.

Although it does not directly participate in the electrochemical reactions, a

GDL in PEM fuel cells has several important functions:

• It provides a pathway for reactant gases from the flow field

channels to the catalyst layer, allowing them access to the entire active
area (not just to those adjacent to the channels).

• It provides a pathway for product water from the catalyst layer to

the flow field channels.

• It electrically connects the catalyst layer to the bipolar plate, allowing

the electrons to complete the electrical circuit.

197
• It also serves to conduct heat generated in the electrochemical
reactions in the catalyst layer to the bipolar plate, which has
means for heat removal

• It provides mechanical support to the MEA, preventing it from

sagging into the flow field channels.

Required Properties of GDL:

• It must be sufficiently porous to allow flow of both reactant gases
& product water
• It must be both electrically and thermally conductive, again in both
through-plane and in-plane.
• The pores of the GDL facing the catalyst layer must not be too big
(Because the catalyst layer is made of discrete small particles)

• It must be sufficiently rigid to support the ''flimsy'' MEA.

198
cm)

Typical GDLs made of carbon paper & carbon cloth

Thickness – (0.017~0.04cm)
Density- (0.21~0.73 g/cm3)
Porosity – (70 ~ 80%)
199
 (1) Treatments and coatings

Diffusion media are generally made hydrophobic to avoid flooding in their

bulk.

Typically, both cathode and anode gas diffusion media are PTFE treated.

A wide range of PTFE loadings have been used in PEMFC diffusion

media (5% to 30%), _ dipping the diffusion media into a PTFE solution
followed by drying and sintering.

In addition, the interface with the adjacent catalyst layer may also be
fitted with a coating or a micro-porous layer to ensure better electrical
as well as efficient water transport in and out of the diffusion layer.
This layer (or layers) consists of carbon or graphite particles mixed with
PTFE binder. (Resulting in a pore size b/w 0.1~0.5μm)
(Carbon paper 20~50 μm)

200
Fuel cell performance with treated and untreated carbon fiber paper

201
 Micro-
porous Layer

GDL

GDL with a micro-porous layer

202
Image Courtesy: Benziger Group, Princeton University

203
 (2) Porosity

GDL- generally Porous in nature (70-80%)

Porosity of a GDL may be easily calculated from its areal weight, thickness,
and the density of the solid phase

Where:
WA= Areal weight (g/cm2)
ρ real = solid phase density
d= Thickness

Porosity may be measured by mercury porosimetry.

204
 (3) Electrical Conductivity

GDL functions – to connect electrically the catalyst layer to bi-polar plate.

Only a portion of the bipolar plate makes the contact (the other portion is
open for access of reactant gases), the GDL bridges the channels and
redistributes electrical current.

Because of this, both through-plane &

in-plane resistivity's of GDL are important.

Image Courtesy: Web source

205
 (4) Compressibility

GDL - compressed to minimize the contact resistance losses.

Both carbon papers and carbon cloths are relatively soft and easily
deformable materials.
Cloth is more compressible than paper.
Under cyclic compression test
they both exhibit a weakening
of the material.

The first compression stress-strain

curve is different than the one
resulting from subsequent cycles.

Stress-strain curves for carbon paper & carbon cloth 206

 (5) Permeability

Effective diffusion coefficients in typical PEMFC diffusion media include

the effects of material porosity and tortuosity.

In most cases they reflect bulk as opposed to Knudsen diffusion

(because the pore diameters are several orders of magnitude higher than the
mean free path of gas molecules.)

However, Knudsen diffusion may be prevalent in micro-porous layers

where the pore size can approach the gas molecule mean free path.

Convective flow resistance of the diffusion media is given as either a

Gurley number or a Darcy coefficient.

207
Where:
Q=Volumetric flow rate (m3/s)
KD= Darcy coefficient (m2)
A = Cross-sectional area perpendicular to flow area(m2)
μ = Gas viscosity (Kg/m/s)
l = length of the path (thickness of diffusion media) (m)
∆P= Pressure drop (Pa)

208
Bi-Polar Plates

The two plates on each side of the

MEA may be considered as two halves
of a bipolar plate.
The bipolar collector/separator plates
have several functions in a fuel cell stack.
Required properties follow from their
functions, namely:
• Connect cells electrically in series—
electrically conductive.
• Separate the gases in adjacent cells—
impermeable to gases.
• Provide structural support for the stack—
Adequate strength yet (they must be lightweight).
• Conduct heat from active cells— thermally conductive.
• Typically house the flow field channels—conformable.
209
210
 (1) Materials

(1) Metallic Plates

The bipolar plates are exposed to a very corrosive environment inside a fuel
cell (pH 2 ~3 & temp.60°C~80°C).

Typical metals such as aluminum, steel, titanium, or nickel would corrode in a

fuel cell environment, & dissolved metal ions would diffuse into the
membrane
Lowers ionic conductivity & reduce the fuel cell life.
In addition, a corrosion layer on the surface of a bipolar plate would increase
electrical resistance.

Metallic plates - coated with a non-corrosive - electrically conductive layer.

(graphite, diamond-like carbon, conductive polymer & noble metals).

211
The effectiveness of the coating in protecting the bipolar plate from the
corrosive PEM fuel cell environment depends on:

(i) corrosion resistance of coating

(ii) micro-pores and micro-cracks in the coating layer

(iii) difference b/w the TEC of the base material and coating.

Advantage of metallic plates:

Metallic plates : mass manufacturing & made very thin (<1 mm),
(compact and light-weight stacks)

Drawback of metallic plates:

Need for protective coating & the problems associated with those in
fuel cell operation

212
 Graphite composite plates

Carbon composite bipolar plates have been made using

Thermoplastics (poly-propylene, poly-ethylene, or poly-vinylidene-fluoride) or
Thermoset resins (phenolic, epoxies, and vinyl esters) with
fillers (carbon/graphite powder, carbon black, or coke-graphite) &
with or without fiber reinforcements.

These materials are typically chemically stable in fuel cell environment,

although some thermosets may leach and consequently deteriorate.
Depending on the rheological properties of these materials they are suitable
for compression molding, transfer molding, or injection molding.

Composite Graphite/ Metallic Plates

A sandwich of two embossed graphite foils with a thin metallic sheet (Ballard)
Graphite (corrosion resistance), Metal (impermeable, structural rigidity, light wt)
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Fuel Cell operating conditions:
Temperature, Pressure, Flow rates, Humidity
Operating Pressure

A fuel cell may be operated at ambient pressure or it may be pressurized.

The issue of pressurization related- water management.

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When a fuel cell is fed the reactant gases from a pressurized tank,
its pressure is controlled by a backpressure regulator placed at the outlet

This pressure regulator keeps the desired,

preset pressure at the fuel cell outlet.

The inlet pressure is always higher because

of inevitable pressure drop in tiny channels in
side the fuel cell.

Very often, in laboratory settings, the inlet

pressure is not even recorded.

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when the reactant gas (for example, air) is fed to a fuel cell by a mechanical
device, a blower or a compressor, which is the case in any practical system, it
is the inlet pressure that matters

The compressor or the blower

must be capable of delivering the
required flow rate at desired pressure.

The backpressure regulator may still

be used to pressurize the cell, or if no
backpressure regulator is used, the
gas leaves the cell at atmospheric
pressure.

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Operating Temperature

The cell temperature is another operating parameter that may be selected

and preset.

In general, a higher operating temperature results in higher cell potential.

For each fuel cell design there is

an optimal temperature

The operating temperature-must

be selected from the system
perspective

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A fuel cell generates heat as a by-product of the electrochemical reaction.

To maintain the desired temperature, heat must be taken away from a fuel cell.
Some heat dissipates from the outer surface of the fuel cell and some heat mus
be taken away with a cooling system.

Medium that takes away the heat may be air, water, or a special coolant.

H generated + H brought (reactant gases)

= H dissipated from outer surface + H from the reactant gases + H Coolant

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The temperature inside a fuel cell may not be uniform; it may vary
from inlet to outlet, from inside out, or from cathode to anode.

The cell temperature may be approximated by the following temperatures,

which are much easier to measure than the cell temperature:

• surface temperature
• temperature of air leaving the cell
• temperature of coolant leaving the cell

None of the above is exactly the cell operating temperature.

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Reactants Flow rate

The reactants flow rate at the inlet of a fuel cell must be equal to or higher
than the rate at which those reactants are being consumed in the cell.
Consumption rate (mols/s) of H2, O2 and H2O (generated) can be determined
by Faraday’s law:

where:
N = consumption rate (mols/s)
I = current (A)
F = Faraday's constant (C mols/s)

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The mass flow rates of reactants consumption (in g /s) are then:

flow rates of gases are expressed in standard liters per minute (slpm).
In Fluid mechanics the std. temperature is 15°C
For any ideal gas, mols and volumes are directly related by the equation
of state:
PV = NRT
Molar volume is:
Vm = (8.314*288.15)/101300
= 0.02365 m3 mol-1
Vm = (RT)/P = 23.65 l mol-1
= 23650 cm3 mol-1
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The volumetric flow rates of reactants consumption
(in standard liters per minute or slpm) are:

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The ratio between the actual flow rate of a reactant at the cell inlet and the
consumption rate of that reactant is called the stoichiometric ratio, S.

Fuel utilization is reverse of stoichiometric ratio:

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 Hydrogen Hydrogen Oxygen

Even in a dead-end mode, hydrogen has to be periodically purged, because

of accumulation of inert (N2) or water.
Fuel utilization formula changes with gas supply mode !!!!

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The frequency & duration of purge depends on purity of hydrogen,
rate of nitrogen permeation & water transport through membrane.

In calculating the fuel cell efficiency, the loss of hydrogen due to purging must
be taken into account.

where:
Nloss = rate of hydrogen loss (mol/s)
Nprg = rate of hydrogen purge (mol/s)
Ʈ prg = duration of hydrogen purge (s)
fprg = frequency of purges ( per sec )

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 Fuel utilization in various modes of operation is summarized below.

Dead-End & Recirculation mode:

Dead-End with purging Mode:

Flow-Through Mode:

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 Air

Two reasons for improvement fuel cell performance (with excess air):

1. Higher flow rate helps remove product water from the cell.
2. Higher flow rates keep oxygen concentration high.

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A fuel cell with 300 cm2 active area operates at 0.6 A/cm2 and 0.65 V.
Air is supplied at stoichiometric ratio of 2 and at a atmospheric pressure,
Operating temperature of 60C,

Calculate the Actual Flow rate, Hydrogen Flow rate , Water (liquid)
generated in grams/sec, fuel cell efficiency, Heat generated from the cell.

NAir = NO2/0.21

ή= V/1.48 ( Use only this equation)

Heat generated (Q) = (Wel / ή ) - Wel

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