Energy Material

Energy Materials
Course instructor: Srijan Sengupta (8420424711)
Teaching assistant: Ankit Dev Singh (9680895770)
Kindly form a WhatsApp group of the same name (Energy Materials-2022)
Class code: qjbibvp

codex777rdo
Meet Link: https://classroom.google.com/c/NDk4MzU2MDcxMjk5?cjc=qjbibvp
Relative grading; 90 and above = A*;

Narrow down approach
Energy materials/ materials Materials for

Battery materials Lithium ion batteries
for energy storage and electrochemical
conversion energy storage
1. Primary batteries Intro
2. Secondary batteries Negative electrode
1. Electrical 1. Battery
• Lead-acid Positive electrode
2. Electrochemical 2. Fuel cell
• Zn-silver oxide Electrolyte
3. photoelectrochemical 3. Supercapacitor
• Ni-cadmium Construction Research
4. Mechanical
• Ni-iron Testing
5. Thermal
• Ni-Zn Failure and
1. Corrosion • Ni-H2 degradation
• Ni-metal hydride
2. Electrodeposition • Lithium ion
Evaluation pattern
Events Objective Marks Wt. Classes/lectures
Lectures 10 (intro + 9)
Class tests 1 (50 marks: T/F, MCQ) 20 1
Presentation Each day 6 ppts (8 + 2 Q/A minutes) [total 6 x 3] 30 3
Assignments 1 (10): numerical problems 10 -
End Semester (20 objective + 20 subjective/numerical) 40 -
Total 100 14
Books/NPTEL Courses:
1. ELECTROCHEMICAL POWER SOURCES: Batteries, Fuel Cells, and Supercapacitors;
VLADIMIR S. BAGOTSKY, ALEXANDER M. SKUNDIN, YURIJ M. VOLFKOVICH
2. Robert A. Huggins; Advanced Batteries: Materials Science Aspects
3. HANDBOOK OF BATTERIES; David Linden, Thomas B. Reddy

Srijan Sengupta
Lecture 1: Introduction M&ME
srijansengupta@iitj.ac.in
• A consized course, merely an overview in a nutshell

• More emphasis on materials rather than the process
Energy materials
Storage as stabilizer
Energy storage
Energy conversion Not using for the

Energy harvesting (Solar cell) time being,
Source is fixed/defined Law of excess, will use later
Immediate use: impractical conversation of Supercapacitor
Harvesting + storage = reliability energy (fuel cell) Battery
Energy conversion/exchange
FROM TO APPLICATION
Heat Heat Exhaust gases to

heat-exchanger
Electrical Electrical Capacitor
Heat Mechanical Steam turbine,

Sterling engine
Chemical Mechanical Combustion

(via Heat) engine
Mechanical Electrical Generator
Heat Electrical Thermoelectric
Chemical Electrical Fuel cells, Primary

& secondary
batteries
Energy harvesting
SOURCE FROM TO APPLICATION
Sun heat heat Heat exchanger
heat mechanical Sterling engine, steam engine
heat electrical thermoelectric
light electrical Solar cells
light chemical Food, Solar fuel, artificial
photosynthesis
How does our home function
Light
Light
(photovoltaics) Heat
(electric heater,
Mechanical geyser, induction
(wind)
Electrical energy
cooker)
Chemical Input in home Mechanical
(fuel cell)
(fan, mixer, drill)
Heat Medium
Chemical Convert and re-convert
(heat engines,
(car battery charge)
steam turbine)
Store before Electrical As it is
conversation Store after conversation
How does our home function
Light
Light
(photovoltaics) Heat
Mechanical (electric heater,
(wind) Electrical energy geyser, induction
Chemical cooker)
(coal-plant, Input in home Mechanical
fuel cell) (fan, mixer, drill)
Heat Medium
Chemical Convert and re-convert
(heat engines,
(car/ phone battery charge)
steam turbine)
Electrical As it is
Store before
conversation Modern method Store after conversation Conventional method
Convert every form of energy to electrical energy
Do not convert. Store as it is (in the same form)
Spend electrical energy by again converting to other forms of energy
Wind – flywheel
After spending store the excess electrical energy
Solar – chemical (solar fuel, hydrogen)
Heat – thermal energy storage
As electrical energy As chemical energy (again convert)
Convert whenever necessary (need based
conversion) capacitor battery
Increase energy exchange than conversion Converting 3 times; Redundant
Conventional method
1. Electrical energy storage: capacitor, supercapacitor

2. Electrochemical energy storage: batteries, pseudo or hybrid capacitors
Modern method
1. Solar energy harvesting (light & heat)
a. Conventional: solar cell - battery combination

Modern: solar fuel/hydrogen storage - fuel cell combination
b. Conventional: solar thermal energy – external combustion engine – generator – battery combination
Modern: solar thermal energy – thermal energy storage – external combustion engine – generator or
- heat pump/thermoelectric combination
2. Wind energy Demand of heat: simply exchange – geyser, immersion heater
Conventional: windmill/any rotating mill powered by mechanical power – generator – battery combination
Modern: windmill /any rotating mill powered by mechanical power – flywheel – generator combination
Demand of mechanical work: simply exchange – motor, fan, drill

Energy Materials (1 Credit; 14 classes)
Lectures Broad Topic Specific Topics
Fundamental: subject briefing, subject outcome, other topics that I teach, introduction-narrow down,
01 Introduction
bifurcation of the lectures, evaluation (student ppt), course materials, Tas, ppt topics
02 Capacitor: Documentary + assignment + distribution of topics
Electrical
03 Capacitor materials: Ceramic, Polymer, Electrolytic
(static)
04 Supercapacitor: concept, materials development: electrode and electrolyte
Fundamental of primary cell: History/background, Voltaic cell, Batteries as a form of corrosion, Voltage:
standard redox table, Voltage in non-standard state, Capacity, Energy /Power density of batteries, curent
05
from a cell, Polarization, rate capability, Different primary batteries: Daniel, Gravity, Pogendroff, Zn air, Zn-C
with alkaline version
Fundamental of secondary batteries: History/background, Attempt for Zn-MnO2 cell rechargeable cell,
06 Lead-acid batteries, Properties of NiOOH electrodes as cathode materials and Cd as anode materials,
Chemical & Nickel- Cadmium batteries, Nickel metal hydride batteries.
Electro-chem
Li-ion battery: fundamentals: half and full cell configuration, cell charge-discharge, degree of freedom and
ical shape of the voltage graph, development of electrolyte materials,, Battery testing (LIB); Development of
07
positive electrode materials-metal oxide, phosphates; Development of negative electrode materials (metal),
intercalation and reconstruction mechanism, graphite, stress busting strategies, binary alloy.
08 Fuel cell – Concept, classification and materials development, Ni-H2 battery, Pseudocapacitors
Electrolytic hydrogen production, Photosynthesis: photo-electrochemical hydrogen production, compressed
09
and liquid hydrogen gas storage, chemical hydrogen storage
Mechanical Flywheels, Pumped hydro storage, Compressing air storage,
10
Thermal Molten salt technology, eutectic mixtures, Phase-change materials
11 Class test 1
12 Student ppt
13 Student ppt
14 Student ppt
Si Topics Group
1 Zero Energy Building/ Net Zero Energy building
2 Challenges/ Competition faced by EV with emphasis to Indian market

3 Stand Alone Electricity Generation Using Animal Power
4 Solar/ Wind power homes with emphasis to India: how to proceed, cost analysis, govt subsidy, examples
5 Agricultural products from which value- added carbon functional materials can be synthesized
6 Supercapacitors as standalone energy sources
7 Trolleybus
8 Solar fuel
9 Aqueous lithium ion batteries
10 Sand batteries
11 Flywheel vehicles
12 Thermoelectric & piezoelectric materials
13 Human powered vehicles
14 Carbon nanomaterials for energy conversion and storage

15 Solar thermal energy storage
Fundamental: subject briefing, subject outcome, other topics that I teach, introduction-narrow down, bifurcation of the
01 Introduction
lectures, evaluation (student ppt), course materials, Tas, ppt topics
Electrical
(static)
Fundamental of primary cell: History/background, Voltaic cell, Batteries as a form of corrosion, Voltage: standard redox
05 table, Voltage in non-standard state, Capacity, Energy /Power density of batteries, current from a cell, Polarization, rate
capability, Different primary batteries: Daniel, Gravity, Pogendroff, Zn air, Zn-C with alkaline version
Fundamental of secondary batteries: History/background, Attempt for Zn-MnO2 cell rechargeable cell, Lead-acid batteries,
06 Properties of NiOOH electrodes as cathode materials and Cd as anode materials, Nickel- Cadmium batteries, Nickel metal
hydride batteries.
Chemical &
Electro-chemic Li-ion battery: fundamentals: half and full cell configuration, cell charge-discharge, degree of freedom and shape of the
al voltage graph, development of electrolyte materials,, Battery testing (LIB); Development of positive electrode
07
materials-metal oxide, phosphates; Development of negative electrode materials (metal), intercalation and reconstruction
mechanism, graphite, stress busting strategies, binary alloy.
Electrolytic hydrogen production, Photosynthesis: photo-electrochemical hydrogen production, compressed and liquid
09
hydrogen gas storage, chemical hydrogen storage
10
11 Class test 1
12 Student ppt
13 Student ppt
14 Student ppt
EM Lecture 2: Mistry of the Leyden Jar: capacitors
Francis
Hauksbee
This effect later became the

basis of the gas-discharge
lamp, which led to neon
lighting and mercury vapor
lamps
Light that is
emitted by
a mercury-fille
d barometer tu
be when the
tube is shaken
Jean Picard
Barometric light
They found material such as silk would not convey electricity. The line for transmission was
suspended by silk threads to prevent contact with the ground
Gray and a friend, Jean Desaguliers, conducted experiments which showed that objects
such as cork, as far as eight or nine hundred feet away, could be electrified by connecting
them to the glass tube with wires
They discovered distant objects could not be electrified if the transmission line made
contact with earth. It was found that metal objects held in the hand and rubbed showed no
signs of electrification. However, when mounted on a non-conductor, they became
electrified
Stephen Grey
1. Electricity could move

2. Certain materials conduct
electricity, certain materials
impede electricity and store it
Able to store electricity
without understanding
mechanism it.
Petrus Van Musschenbroek
Benjamin Franklin
What is my take from the video
Francis Hauksbee Engineer, Technician, used to make Corona effect, ionization of gas,
vacuum and pneumatic pumps Mercury lamp
Stephen Grey Silk dyer, Marchant Conductors and insulators,

proper design of experiment,
concrete conclusion
Petrus Van
Musschenbroek Research scholar all through Accidentally invent the
Leyden Jar; failed to explain too
Benjamin Franklin Businessman Businessman, use knowledge of

accountancy to solve the mistry
Solution/explanation need not come from a person who has dedicated life for research/ all through an academician. It came
from people with rationality having other forms of practical experience: more capable of producing practical solution…
+ -
S
Leyden
Jar
+ -
+ -
Permittivity is a measure of the

electric polarizability of a dielectric
Dielectric constant is the ratio of permittivity Q

of a material and permittivity of vacuum
V
Dielectrics
A dielectric is an electrical insulator that can be polarized by an applied electric field.
Because of dielectric polarization, positive charges are displaced in the direction of the field and negative charges shift in
the direction opposite to the field (for example, if the field is moving in the positive x-axis, the negative charges will shift
in the negative x-axis). This creates an internal electric field that reduces the overall field within the dielectric itself.
If a dielectric is composed of weakly bonded molecules, those molecules not only become polarized, but also reorient so
that their symmetry axes align to the field
Permittivity of air?
Paraelectric Ferroelectric
When most materials are polarized, the polarization induced, P, is almost exactly proportional to the applied external electric
field E; so, the polarization is a linear function. This is called linear dielectric polarization.
Some materials, known as paraelectric materials, show a Ferroelectricity is a characteristic of certain materials that have
more enhanced nonlinear polarization a spontaneous electric polarization that can be reversed by the
application of an external electric field
SrTiO3, LiNbO3, PbTiO3 PbZr/TiO3, BaTiO3, PbTiO3, LiNbO3

A function of
Material Geometric
property property
How far can you increase the voltage?
Electrical breakdown or dielectric breakdown is a process that occurs when an electrical

insulating material, subjected to a high enough voltage, suddenly becomes an electrical
conductor and electric current flows through it. All insulating materials undergo breakdown when
the electric field caused by an applied voltage exceeds the material's dielectric strength
Electrical breakdown may be a momentary event (as in an electrostatic discharge) or may lead to a
continuous electric arc if protective devices fail to interrupt the current in a power circuit. In this
case electrical breakdown can cause catastrophic failure of electrical equipment, and fire hazards
In a solid, it usually occurs when the electric field becomes strong enough to pull outer valence
electrons away from their atoms, so they become mobile, and the heat created by their collisions
releases additional electrons. In a gas, the electric field accelerates the small number of free
electrons naturally present (due to processes like photoionization) to a high enough speed that
when they collide with gas molecules they knock additional electrons out of them, called ionization,
which go on to ionize more molecules creating more free electrons and ions in a chain reaction
Fundamental: subject briefing, subject outcome, other topics that I teach, introduction-narrow down, bifurcation of the
01 Introduction
lectures, evaluation (student ppt), course materials, Tas, ppt topics
Electrical
(static)
Fundamental of primary cell: History/background, Voltaic cell, Batteries as a form of corrosion, Voltage: standard redox
05 table, Voltage in non-standard state, Capacity, Energy /Power density of batteries, current from a cell, Polarization, rate
capability, Different primary batteries: Daniel, Gravity, Pogendroff, Zn air, Zn-C with alkaline version
Fundamental of secondary batteries: History/background, Attempt for Zn-MnO2 cell rechargeable cell, Lead-acid batteries,
06 Properties of NiOOH electrodes as cathode materials and Cd as anode materials, Nickel- Cadmium batteries, Nickel metal
hydride batteries.
Chemical &
Electro-chemic Li-ion battery: fundamentals: half and full cell configuration, cell charge-discharge, degree of freedom and shape of the
al voltage graph, development of electrolyte materials,, Battery testing (LIB); Development of positive electrode
07
materials-metal oxide, phosphates; Development of negative electrode materials (metal), intercalation and reconstruction
mechanism, graphite, stress busting strategies, binary alloy.
Electrolytic hydrogen production, Photosynthesis: photo-electrochemical hydrogen production, compressed and liquid
09
hydrogen gas storage, chemical hydrogen storage
10
11 Class test 1
12 Student ppt
13 Student ppt
14 Student ppt
+ -
S
Leyden
Jar
+ -
+ -
Permittivity is a measure of the

electric polarizability of a dielectric
Dielectric constant is the ratio of permittivity Q

of a material and permittivity of vacuum
V
A function of
Material Geometric
property property
How far can you increase the voltage?
Electrical breakdown or dielectric breakdown is a process that occurs when an electrical

insulating material, subjected to a high enough voltage, suddenly becomes an electrical
conductor and electric current flows through it. All insulating materials undergo breakdown when
the electric field caused by an applied voltage exceeds the material's dielectric strength
Electrical breakdown may be a momentary event (as in an electrostatic discharge) or may lead to a
continuous electric arc if protective devices fail to interrupt the current in a power circuit. In this
case electrical breakdown can cause catastrophic failure of electrical equipment, and fire hazards
In a solid, it usually occurs when the electric field becomes strong enough to pull outer valence
electrons away from their atoms, so they become mobile, and the heat created by their collisions
releases additional electrons. In a gas, the electric field accelerates the small number of free
electrons naturally present (due to processes like photoionization) to a high enough speed that
when they collide with gas molecules they knock additional electrons out of them, called ionization,
which go on to ionize more molecules creating more free electrons and ions in a chain reaction
Dielectrics
A dielectric is an electrical insulator that can be polarized by an applied electric field.
Because of dielectric polarization, positive charges are displaced in the direction of the field and negative charges shift in
the direction opposite to the field (for example, if the field is moving in the positive x-axis, the negative charges will shift
in the negative x-axis). This creates an internal electric field that reduces the overall field within the dielectric itself.
If a dielectric is composed of weakly bonded molecules, those molecules not only become polarized, but also reorient so
that their symmetry axes align to the field
Permittivity of air?
Paraelectric Ferroelectric
When most materials are polarized, the polarization induced, P, is almost exactly proportional to the applied external electric
field E; so, the polarization is a linear function. This is called linear dielectric polarization.
Some materials, known as paraelectric materials, show a Ferroelectricity is a characteristic of certain materials that have
more enhanced nonlinear polarization a spontaneous electric polarization that can be reversed by the
application of an external electric field
SrTiO3, LiNbO3, PbTiO3 PbZr/TiO3, BaTiO3, PbTiO3, LiNbO3

Materials Development w.r.t. Capacitors
d
olarize
p Insulator
Restricted by Dielectric
dielectric
breakdown
Materials property Increase capacitance Geometry
Choose materials with high Decrease the gap

Increase electrode-dielectric interface area
dielectric constant between the plates
S↑
↑ d↓
Ceramic capacitor
Then how come all the commercial ceramic
capacitors use dielectrics with low K values?
• Begin to develop erratic deviations in capacitance versus
temperature as the value of K goes up
Paraelectric
Ferroelectric
• Ferroelectric to
Paraelectric
transformation
Why the commercial ceramic capacitors use
dielectrics with low K values?
• Variations in voltage
Capacitance measured or applied with higher voltage can
drop to values of -80% of the value measured with the
standardized measuring voltage of 0.5 or 1.0 V
• Capacitance change with time is known as

“aging”
Aging is caused by a gradual re-alignment of the crystalline structure of
the ceramic and produces as exponential loss in capacitance. Most
general-purpose state-of-the-art dielectrics found in industry have
aging rates varying from 1.5 percent to 4 percent
• piezoelectric reactions
High K dielectric ceramic capacitors piezoelectric reactions under
mechanical stress.
Class 1:
The basic materials of class 1 ceramic capacitors are composed of a mixture of finely ground granules of paraelectric materials such as
Titanium dioxide (TiO2), modified by additives of Zinc, Zirconium, Niobium, Magnesium, Tantalum, Cobalt and Strontium
Class 2: High capacitance values available in very small size. made of ferroelectric materials such as barium titanate (BaTiO3) and suitable
additives such as aluminium silicate, magnesium silicate and aluminium oxide. "ferro-electric" and vary in capacitance value under the
influence of the environmental and electrical operating conditions.
• The dielectric is made from finely powered materials.

• Disc elements are pressed in dies
• Fired at high temperature to produce a very dense structure (sintering). Single-plate elements are usually cut from
larger sheets of fired ceramic material.
• Electrodes are formed from a compound containing powered silver, powered low-melting glass, and an organic binder.
• This material is screen printed onto the discs or onto the sheets from which the single plates will be cut.
• Another firing step removes the binder and melts the glass, binding the silver glass matrix to the ceramic surfaces
A much more sophisticated design is called the " monolithic"
ceramic capacitor. It offers much higher capacitance per unit
volume. The ceramic material acts both as dielectric and as
encapsulant of the basic element. Electrodes are buried
within the ceramic and exit only on the ends. The ends are
surrounded with a type of powdered silver-glass compound
Polymer capacitors
Thickness – 1 mm - Tc
Area – projected area (2 cm sq.) Ac
Price = 1.18 INR/0.0022 µF

= 536.36 INR/µF
• The original film capacitors did not use plastic film at all, but paper. The pores in the paper, and also various
chemical and physical contaminants, all mitigated against very compact or reliable capacitors. Compound
dielectric constant (paper + air). Not intimate contact: Contact resistance.
• The next step was to impregnate the paper with some dielectric fluid such as an oil. This really produced a
mixed dielectric with the characteristics, such as the value of K, the breakdown voltage, and temperature
stability, being comprised of contributions from both paper and the impregnant
DC Voltage
It is not difficult to move from the parallel-plate model to

the design of what is called the "film-foil" capacitor.
The dielectric material is sandwiched between two pieces

of metal foil which become the electrodes. The thickness
of the plastic film determines the separation between
electrodes, and the operating area of the capacitor is the
area of the electrodes opposing each other
Metal foil thickness – 25 micron

Dielectric layer thickness – 25 micron
As the various synthetic plastic materials particularly the

thermoplastic materials-were developed, their superiority over Tensile load, hole, short circuit, melting,
paper for most applications became apparent permanently joined
Another major class of plastic film capacitors is known as "metallized
film“. Instead of using free-standing metal foil, the electrodes are
vacuum-deposited (sputtered) on the dielectric film, and their
thickness might be 1/100 of that of foil electrodes (25 µm)
Another advantage resulting from the metallizing technique. The

metallized capacitors have a self-healing characteristic called
"clearing". The metallic film imposed on the plastic is very thin and if
a breakdown by either a hole or contaminant occurs, a tiny area of
the thin film surrounding the breakdown point burns away. This
leaves the capacitor operable, but with a slightly reduced capacitance Tensile load, hole, short circuit, melting,
permanently joined
Thickness – 25/100 = 0.25 µm

Advances in technology have now Area – projected area (1mm/25 µm
allowed depositing plastic onto metal 40 cm sq.)
instead of depositing metal onto
Price = 84 INR /20 µF
plastic. With this process, both sides = 4.2 INR/µF
of the foil are coated resulting in two
layers of dielectric to guard against
pinholes in the formed jelly roll.
Electrolytic capacitors
Use of dielectric materials having higher dielectric constants (K) will also increase the capacitance of the device,
with a decrease in unit size. The search for better materials will continue
Obviously, increasing the area (A) of the capacitor plates will increase the capacitance of the device. This would
tend to increase size, but since only the area, not the thickness, of the plates is significant (in most applications)
the plates could be made thinner to offset the increase. Ways were developed to produce ever thinner metal
foils, and to deposit thin metallic films directly on both sides of a paper or plastic ribbon which then can be
rolled up
To further improve capacitance we need a thin ceramic layer which can be coated on top a metal foil electrode
such that the net assembly is flexible and can be rolled up. So, we shall get the benefit of high dielectric constant
as well as high surface/ contact area
But how is it possible?

Anodizing is an electrolytic passivation process used to increase the thickness of the natural
Anodizing process oxide layer on the surface of metal parts
Aluminium alloys are anodized to increase corrosion resistance and to allow dyeing (colouring), improved lubrication, or
improved adhesion. The anodic layer is insulative. This barrier oxide layer has a thickness which is a function of the applied
voltage: about 14 angstroms per volt at room temperature. The processes also exist
for titanium, zinc, magnesium, niobium, zirconium, hafnium, and tantalum
Charles Pollak found out that the oxide layer on an aluminum anode remained stable in a neutral or mild alkaline
electrolyte, even when the power was switched off
Oxide layer thickness 30 – 800 nm
Electrolysis
Replace
Aluminium density: 2.7 g/cm³
Pt with Al
Pt Aluminium oxide density: 3.98 g/cm³
Only Al
Anodized
more mass is added

volume increases
more molar mass
volume decreases
The first industrially realized electrolytic capacitors consisted of a metallic
box used as the cathode. It was filled with a borax electrolyte dissolved in
water, in which a folded aluminum anode plate was inserted. Applying a DC
voltage from outside, an oxide layer was formed on the surface of the
anode. Once the oxide is formed, the arrangement was used as it is as the
capacitor with Al as anode, Al2O3 as the dielectric and Borax electrolyte
as the other electrode. The metallic box was used as the current
collector/container to hold the liquid.
The advantage of these capacitors was that they were significantly smaller
and cheaper than all other capacitors at this time relative to the realized
capacitance value.
Why borax electrolyte is used?
Electrolytic capacitors are polarized components due to their asymmetrical

construction and must be operated with a higher voltage (ie, more positive) on
the anode than on the cathode at all times. For this reason the anode terminal is
marked with a plus sign and the cathode with a minus sign. Applying a reverse
polarity voltage, or a voltage exceeding the maximum rated working voltage of as
little as 1 or 1.5 volts, can destroy the dielectric and thus the capacitor. The
failure of electrolytic capacitors can be hazardous, resulting in an explosion or
fire
Film-foil Al-electrolyte
capacitor
One of the major breakthroughs in this field occurred in the early 1900’s. It
consisted of
• an aluminum foil ribbon, on the surface of which a thin film of

aluminum oxide has been formed electro-chemically
• a water-based (borax electrolyte) electrolyte fluid which acts as the
opposing plate. Paper soaked with borax is kept in between
• a second strip of aluminum foil, and a porous strip of paper
interposed between them were rolled up together and suspended in
the liquid electrolyte
Salient features
• the oxide dielectric has a thickness on the order of 0.03 micron (30 nm)
• because of very thin layer of the ceramic dielectric, it can be coiled. the dielectric
constant (K) of this oxide is approximately 8, compared to 5 for paper, or 3 for
polycarbonate film
• Actual surface area is much higher than the projected area.
Drawback
The oxide dielectric has rectifier properties, blocking current flow in one direction but
offering low resistance in the opposite direction; it is therefore limited to DC applications,
and a voltage reversal of more than a volt or two will cause breakdown of the film and
destruction on the capacitor
Further improvements
• increasing the area of the surface even more
• Uniform layer-by-layer growth of the dielectric coating
by immersion in an acid
Further improvements bath such as hydrochloric
acid, or electro-chemically
• etching the anode plate. The etching action exposes the by immersion in a
grain structure, enormously increasing the area of the conductive, corrosive bath
surface such as a solution of
sodium chloride
RESEARCH
• Etching techniques to enhance the surface
area of high-purity aluminium foil
Failure
The presence of impurities (principally copper, silicon,

magnesium, iron, and zinc), in the anode foil, can result in
early failure of an electrolytic capacitor:
• Particles of other metals do not form an oxide barrier

layer as aluminum does, hence constitute leakage paths
• form galvanic couples with aluminum and will produce

hydrogen gas in the presence of an electrolyte
• reduce the efficiency of the oxide-layer barrier and

causing generation of excessive heat
RESEARCH
• Practical manufacturing techniques for the
production of high-purity aluminium foil
Tantalum electrolytic capacitor
Tantalum capacitors are much smaller in size than aluminum electrolytic
capacitors of the same capacitance
They have an equivalent series resistance (ESR) ten times smaller than the ESR of
aluminum electrolytic capacitors, which allows for larger currents to pass through
the capacitor with less heat generated
• Tantalum is a conflict mineral. Tantalum electrolytic capacitors are considerably more expensive than
comparable aluminum electrolytic capacitors
• After tantalum is mined, it goes through complex extraction processing which, at elevated temperatures,
reduce the oxide to tantalum powder. Powder metallurgy techniques are used to make plates, sheets, and wire
Now it is possible
Price =
536.36 INR/µF mm to even go down
to 1 - 0.5 mm
mm Cc
CP=1/50Cc
SP=20SC SSS
dp= 1/20dc
Cp = (1/50)*20*20
Price =
= 8 Cc
4.2 INR/µF
Ce=4Cp
Se=10Sp
Price = de=1/100dp
1.2 INR/µF SSL
Ce = 4*10*100 =
4000 Cp
Now it is possible
Price =
536.36 INR/µF mm to even go down
to 1 - 0.5 mm
mm Cc
CP=1/50Cc
SP=20SC SSS
dp= 1/20dc
Cp = (1/50)*20*20
Price =
= 8 Cc
4.2 INR/µF
Ce=4Cp
Se=10Sp
Price = de=1/100dp
1.2 INR/µF SSL
Ce = 4*10*100 =
4000 Cp
Lecture 4: Supercapacitors
What if the
voltage < 1.23 V
3-8 Å
In-situ dielectric formation Intimate contact between solid and liquid

Research
1. Materials with high porosity
2. Electrolyte with high electrochemical potential window
Electrodes
Supercapacitor electrodes are generally thin coatings (~ 25 µm) applied and electrically
connected to a conductive, metallic current collector
• high surface areas per unit volume and mass

• good conductivity
• long-term chemical stability
• high corrosion resistance
• high temperature stability
Generally, the smaller the electrode's pores, the greater the capacitance and specific energy.
However, smaller pores increase equivalent series resistance (ESR) and decrease specific
power.
Applications with high peak currents require larger pores and low internal losses, while
applications requiring high specific energy need small pores. Tunable.
Carbon materials are prospective electrode materials for industrialization. In the fabrication
of supercapacitors, various forms of carbon are the most employed electrode materials due
to:
• high surface area (porous, spongy)

• pore-size distribution
• pore shape and structure,
• electrical conductivity
• surface functionality
• low cost
• availability
• well-established electrode production technologies
The most commonly used electrode material for supercapacitors is carbon in various
manifestations such as activated carbon (AC), activated carbon fibre (ACF),
carbide-derived carbon (CDC), carbon aerogel.
Assignment: Agricultural products from which value-
Activated carbon added carbon functional materials can be synthesized
• Sun dried for 2–3 days and crushed

• The dried coconut shell was then kept in muffle furnace at 300 °C for 5 h
• Soak this charcoal in chemical solution CaCl2 (25 wt.%) for 18–20 h to become activated
charcoal
• Wash this activated charcoal with double distilled water
• Keep the samples in oven at 110 °C (overnight) for drying
• Chemical activation has been widely used to obtain porous activated carbons with very high
surface areas
KOH as an activating agent is one of the most effective agents employed for organic
materials. KOH is mostly preferred over other activating agents because it causes more
localized reactions with the carbon precursor and is more effective for highly ordered
materials. The chemical reaction between KOH and carbon during activation proceeds as:
6KOH + 2C → 2K + 3H2 + 2K2CO3
The reaction is then further continued by decomposition of K2CO3
K2CO3 melts at 891 °C

K2CO3 = K2O + CO2 (t > 1200° C)
Extremely porous (hierarchical) form of carbon with a high specific surface area - a common
approximation is that 1 gram (a pencil-eraser-sized amount) has a surface area of roughly
1,000 to 3,000 square metres (about the size of 4 to 12 tennis courts). The bulk form used in
electrodes is low-density with many pores, giving high double-layer capacitance.
Low conductivity
Carbon aerogel Resorcinol
Formaldehyde
Carbon aerogel
as formed
Micro-porosity
Fragile
Carbon aerogel
activated
nano-porosity
Made via pyrolysis of resorcinol-formaldehyde aerogels and

are more conductive than most activated carbons
Highly porous (400–1200 m2/g ), synthetic, ultralight material

Activated carbon fibres produced from activated carbon and have a
typical diameter of 10 µm. a very narrow
pore-size distribution that can be readily
controlled.
Advantages of ACF electrodes include low

electrical resistance along the fibre axis and
good contact to the collector
The surface area of ACF woven

into a textile is ~ 2500 m2/g.
Carbide-derived carbon
derived from carbide precursors by high-temperature extraction of metals from carbides as

precursors, such as binary silicon carbide and titanium carbide
• High temperature chlorination

• Vacuum decomposition
• Hydrothermal decomposition
• Allow fine-tuning of porous networks: tunable pore diameters (from micropores to

mesopores) to maximize ion confinement,
• Better control over surface functional groups than activated carbons
• Increasing pseudocapacitance by faradaic H2 adsorption treatment. CDC electrodes with
tailored pore design offer as much as 75% greater specific energy than conventional
activated carbons.
The production of SiCl4 by high temperature reaction of Chlorine gas with Silicon Carbide
was first patented in 1918 by Otis Hutchins, with the process further optimized for higher
yields in 1956. 2
The surface area ~ 3000 m /g
MC (solid) + 2 Cl2 (gas) → MCl4 (gas) + C (solid) storage capacities for hydrogen up to 3.86 wt. %
Temperatures above 1000 °C result in predominantly

graphitic carbon and an observed shrinkage of the
material due to graphitization
Halogen treatment at temperatures between 200 and

1000 °C has been shown to yield mostly disordered
porous carbons with a porosity between 50 and ~80
vol% depending on the precursor
The term "chlorine treatment" is to be preferred over chlorination as the chlorinated product, metal
chloride, is the discarded byproduct and the carbon itself remains largely unreacted.
Aqueous
Non- aqueous
Price =
536.36 INR/µF
Price =
4.2 INR/µF
Price =
1.2 INR/µF
22000uF
560 INR
0.026
INR/uF
Lecture 6
The shock from
the electric fish
did not produce
a spark
People received electric shock

same as the Leyden jar
The amount of electricity Charge

Intensity Potential difference/ Voltage
Attracted by use of
electricity in medical
treatment
Animal electricity Generated by Hauksbee’s
with Hauksbee’s Machine; not the frog
machine
Volta
tasted
electricity
Dissimilar metals in contact

with the electrolyte produce
voltage
Animal electricity
Without Hauksbee’s
machine
L
L L
Battery
Corrosion
Energy generation
Electrochemical cells generate electrical energy due to electrochemical reactions. The

electrical energy available is
Electrical energy = volts × current × time For 1 mole of M n moles of electrons are exchanged
= volts × coulombs 1 mole electron carry 1 Farad charge
1 mole = 6.23 x 10-23; charge of e = 1.6 x 10-19 coulomb
= ∆E x Q 1 Farad = 6.23 x 10-23 x 1.6 x 10-19 = ~96500 coloumb
= ∆E x nF n mole electron carry n Farad (nF) charge
where,
E is electromotive force (emf) of the cell (volts).
Q = net charge exchanged between the electrodes; Q = nF
n is the number of electrons involved in the chemical reaction

F is Faraday’s constant = 96 500 C (g equiv.)−1 The gram equivalent is the molecular mass
divided by the number of electrons involved (change in oxidation number) in the reaction
Battery parameters:
1. Voltage [V]
2. Capacity (Amount of charge stored) [Q]
3. Specific capacity (Amount of charge stored/ mass or volume)
4. Energy density / specific energy [QV]
5. Power density / specific Power [QI]
6. Discharge efficiency : Qexternal/Qtheoretical
7. Cell configuration
8. Material selection; effect of structures on propery
∆G = -nF∆E Nernst’s equation
2nd law of thermodynamics: ∆G = negative: spontaneous reaction
∆E = positive: spontaneous reaction
How to get the values of ∆E?
Absolute free energy is not possible to obtain. We only get the difference in free energy
for a certain reaction.
Since most of the metals replace hydrogen, So
hydrogen evolution equation is made a reference and
del G is calculated and then del E or potential difference
is calculated. Del E can also be measured
electrochemically…
This potential of hydrogen half cell (at
platinum electrode) at the standard state
(unit activity of H+) reaction is assumed as 0
Common
cathodic
Anodic reactions reaction
Reference
electrode
Assumes ∆G change for to be zero

Standard state: Unit activity
Standard state: Unit activity If ∆E = positive, Open circuit
∆E = Ecathode – Eanode reaction possible potential VOLTAGE
Galvanic cell
Q: with time,
voltage will
electrode increase/decrease
/remains constant
electrolyte and why so?
Cathode
Anode
Cathode potential:
0V
= 0 – (-0.76)
= 0.76 V
Voltage in non-standard state
To determine the potential in non-standard
state, Nernst’s eq can be used
K = a2Al3+.a3H2/a2Al.a6H+
Nernst’s eq:
∆GP,T = -nF∆E; ∆Go = -nF∆Eo

K= (equilibrium constant)
Can also be written
for partial reactions -nF∆E = -nF∆Eo + RTlnK
(Without electron)
∆E = ∆Eo - (RT/nF)lnK
At equilibrium ∆E = ∆Eo - (2.303 x 8.314 x 298/n x 96500)logK
o
∆E = ∆E - (0.059/n)
Standard reduction
logK
Concentration of the
potential species (deviation from
unit activity)
Q1: Find the reduction potential of Zn in 0.01 molar Zn solution
Zn2+ + 2e = Zn Q1: Find the reduction potential of Zn in 0.01 molar
Activity of the Zn solution
K = aZn/aZn2+ condensed
phase is one
K = 1/aZn2+ For Zn, the tendency to corrode increases in 0.01
molar Zn solution than standard state
∆E = ∆Eo - (0.059/n)logK (a) T (b) F
∆E = ∆Eo - (0.059/n)log(1/aZn2+)
∆E = -0.76 – 0.0295log(1/0.01) Zn = Zn2+ + 2e
∆E = -0.76 – 0.0295log(100)
∆E = -0.76 – 0.059log(10) If Zn2+ goes down, then reaction will shift towards
∆E = -0.76 – 0.118 high
∆E = – 0.878 V
For Zn, the tendency to corrode decreases by 0.118
V in 0.01 molar Zn solution than standard state
(a) T (b) F
Q2: Find how the potential of hydrogen reference electrode changes with pH?
K = aH2/a2H+ aH2 = pH2 = 1 … [open atmosphere]
K = 1/a2H+ pH 14
0
∆E = ∆Eo - (0.059/n)logK ∆E (V)
o 2
∆E = ∆E - (0.059/n)log(1/a H+)
∆E = ∆Eo - (0.059/2) x 2log(1/aH+) -0.827
∆E = 0 – 0.059log(1/aH+)
∆E = 0 – 0.059log(1/[H+])
∆E = – 0.059pH
When [H+] = 1, pH = 0; highly acidic; ∆E = 0 V
When [H+] = 10-14, pH = 14; highly basic; ∆E = -0.059x14 = -0.827 V
Q3: Find the voltage of voltaic cell at a Zn ion concentration of 0.01 molar Zn at pH = 4
Battery parameters:
1. Voltage [V]
• Reduction potential table (standard state)
• Nernst equation (non-standard state)
4. Power density / specific Power [VI]
7. Material selection; effect of structures on property
Zn + 2 H+ = Zn2+ + H2 (gas) CAPACITY & ENERGY
TARGET: specific energy of gasoline
CAPACITY = -47.5 MJ = -(47.5/3.6) = -13.2 kWh/Kg
Charge delivered by the cell
Specific energy gasoline -13.2
SPECIFIC CAPACITY = = 20.3
Specific energy Voltaic cell - 0.65
Charge delivered by the cell (/mole) ENERGY
or per gm/Kg ΔG = -nFΔE
ΔG = -nF x ΔE kWh = 103 * W * 3600 s
Charge delivered by the reactant (balanced re.) = 103 * 3600 Ws
= nF = 2*96500 ENERGY = NET CHARGE X VOLTAGE = 3.6 * 106 Ws
mAh = 10 -3 * A * 3600 s = CAPACITY X VOLTAGE
= 193000 coulomb = 10 -3 * 3600 As = 3.6 * 106 J
= (193000/3.6) mAh = 3.6 coulomb SPECIFIC ENERGY = 3.6 * MJ
= 53611.11 mAh 1 Coulomb = (1/3.6) mAh Energy delivered by the cell
1 MJ = (1/3.6) kWh
(/mole) or per gm/Kg
Weight of mole of reactant (balanced re.)
= weight of (Zinc + 2*weight of hydrogen ion)
SPECIFIC ENERGY This is theoretical
= weight of (Zinc + 2*weight of hydrogen atom)
= SPECIFIC CAPACITY X VOLTAGE
= 65.3 + 2 Specific capacity/energy
= 67.3 gm
Energy density (of a voltaic cell) In practical, weight of the
Specific capacity (capacity/mass) = -796.6 * 0.76 [mAh * V] electrolyte/solvent, copper
= 53611.11/67.3 mAh/gm = -605.42 mWh/g (Wh/Kg) disc, separator, connections,
packaging need to be
= 796.6 mAh/gm (Ah/Kg) = -0.65 kWh/Kg considered
Battery parameters:
1. Voltage [V] 12 V
• Reduction potential table (standard state) 54 Ah
1. Capacity (Amount of charge stored) [Q]: For full battery pack
2. Specific capacity (Amount of charge stored/ mass or volume): when compare with
another sources of energy (harvest/storage) such as gasoline, supercapacitor
Polarization
What if current is
drawn from battery?
Depends on material
Depends on surface properties
Depends on substrate position
Depends on hydrogen partial pressure
Voltage and
capacity in Depends on bath
Transient state concentration
When Bath viscosity

current is
flowing
Graphical representation
Voltage
calculated
Voltage after
IR and polarization losses
Change in
electrolyte Latent heat Specific heat
composition
T = V; H = Q
Energy
Slow H+ diffusion
Q (charge) = A (current) * s (time)
If A is fixed, then it is V vs. t curve
P (power) = V (voltage) * A (current) OCP: V full V exp

Corrosion of Zn in de-aerated acid coupled with another metal: Precious metal (Cu, Au, Pt)
Corrosion of Zn in de-aerated acid coupled with another metal: batteries
Ic (Pt)
Ic (Zn)
Corrosion
Negligible icouple
Ic = Ic (Zn) + Ic (Pt)
Ia = Ia (Zn)
L
Discharge efficiency : Qexternal/Qtheoretical

I = V/(R + r)
OCP INTERNAL
RESISTANCE
Corrosion of Fe in de-aerated acid (a better battery?)
According to the emf series, zinc has a more
active potential than iron, E ◦(Zn) = −0.76 V, E ◦
(Fe) = − 0.44 V, hence zinc should corrode
more easily than iron, but, surprisingly, iron
corrodes faster than zinc
Better to couple Fe with Cu
rather than Zn with Cu
Baghdad battery
(150 BC – 223 AD)
Corrosion of Zn in de-aerated acid coupled with another metal: Active metal (Fe)
L
iH2(Fe)
Negligible
iH2(Zn)
Ic = Ic (Zn) + Ic (Fe) Zn
Fe H2
Ia = Ia (Zn) + Ia (Fe) Fe 2+ H +
Negligible
A cheap and better

battery with Zn & Fe couple
iFe iZn
Zn serves as –ve electrode
Fe provides surface for +ve
reaction
Standard state: Unit activity If ∆E = positive, Open circuit
∆E = Ecathode – Eanode reaction possible potential VOLTAGE
Galvanic cell
Q: with time,
voltage will
electrode increase/decrease
/remains constant
electrolyte and why so?
Cathode
Anode
Cathode potential:
0V
= 0 – (-0.76)
= 0.76 V
Voltage in non-standard state
To determine the potential in non-standard
state, Nernst’s eq can be used
K = a2Al3+.a3H2/a2Al.a6H+
Nernst’s eq:
∆GP,T = -nF∆E; ∆Go = -nF∆Eo

K= (equilibrium constant)
Can also be written
for partial reactions -nF∆E = -nF∆Eo + RTlnK
(Without electron)
∆E = ∆Eo - (RT/nF)lnK
At equilibrium ∆E = ∆Eo - (2.303 x 8.314 x 298/n x 96500)logK
o
∆E = ∆E - (0.059/n)
Standard reduction
logK
Concentration of the
potential species (deviation from
unit activity)
Q1: Find the reduction potential of Zn in 0.01 molar Zn solution
Zn2+ + 2e = Zn Q1: Find the reduction potential of Zn in 0.01 molar
Activity of the Zn solution
K = aZn/aZn2+ condensed
phase is one
K = 1/aZn2+ For Zn, the tendency to corrode increases in 0.01
molar Zn solution than standard state
∆E = ∆Eo - (0.059/n)logK (a) T (b) F
∆E = ∆Eo - (0.059/n)log(1/aZn2+)
∆E = -0.76 – 0.0295log(1/0.01) Zn = Zn2+ + 2e
∆E = -0.76 – 0.0295log(100)
∆E = -0.76 – 0.059log(10) If Zn2+ goes down, then reaction will shift towards
∆E = -0.76 – 0.118 high
∆E = – 0.878 V
For Zn, the tendency to corrode decreases by 0.118
V in 0.01 molar Zn solution than standard state
(a) T (b) F
Q2: Find how the potential of hydrogen reference electrode changes with pH?
K = aH2/a2H+ aH2 = pH2 = 1 … [open atmosphere]
K = 1/a2H+ pH 14
0
∆E = ∆Eo - (0.059/n)logK ∆E (V)
o 2
∆E = ∆E - (0.059/n)log(1/a H+)
∆E = ∆Eo - (0.059/2) x 2log(1/aH+) -0.827
∆E = 0 – 0.059log(1/aH+)
∆E = 0 – 0.059log(1/[H+])
∆E = – 0.059pH
When [H+] = 1, pH = 0; highly acidic; ∆E = 0 V
When [H+] = 10-14, pH = 14; highly basic; ∆E = -0.059x14 = -0.827 V
Q3: Find the voltage of voltaic cell at a Zn ion concentration of 0.01 molar Zn at pH = 4
Battery parameters:
1. Voltage [V]
• Reduction potential table (standard state)
Zn + 2 H+ = Zn2+ + H2 (gas) CAPACITY & ENERGY
TARGET: specific energy of gasoline
CAPACITY = -47.5 MJ = -(47.5/3.6) = -13.2 kWh/Kg
Charge delivered by the cell
SPECIFIC CAPACITY = = 20.3
Specific energy Voltaic cell - 0.65
Charge delivered by the cell (/mole) ENERGY
or per gm/Kg ΔG = -nFΔE
ΔG = -nF x ΔE kWh = 103 * W * 3600 s
Charge delivered by the reactant (balanced re.) = 103 * 3600 Ws
= nF = 2*96500 ENERGY = NET CHARGE X VOLTAGE = 3.6 * 106 Ws
mAh = 10 -3 * A * 3600 s = CAPACITY X VOLTAGE
= 193000 coulomb = 10 -3 * 3600 As = 3.6 * 106 J
= (193000/3.6) mAh = 3.6 coulomb SPECIFIC ENERGY = 3.6 * MJ
= 53611.11 mAh 1 Coulomb = (1/3.6) mAh Energy delivered by the cell
1 MJ = (1/3.6) kWh
(/mole) or per gm/Kg
Weight of mole of reactant (balanced re.)
= weight of (Zinc + 2*weight of hydrogen ion)
SPECIFIC ENERGY This is theoretical
= weight of (Zinc + 2*weight of hydrogen atom)
= SPECIFIC CAPACITY X VOLTAGE
= 65.3 + 2 Specific capacity/energy
= 67.3 gm
Energy density (of a voltaic cell) In practical, weight of the
Specific capacity (capacity/mass) = -796.6 * 0.76 [mAh * V] electrolyte/solvent, copper
= 53611.11/67.3 mAh/gm = -605.42 mWh/g (Wh/Kg) disc, separator, connections,
packaging need to be
= 796.6 mAh/gm (Ah/Kg) = -0.65 kWh/Kg considered
Battery parameters:
1. Voltage [V] 12 V
Polarization
What if current is
drawn from battery?
Depends on material
Depends on surface properties
Depends on substrate position
Depends on hydrogen partial pressure
Voltage and
capacity in Depends on bath
Transient state concentration
When Bath viscosity

current is
flowing
Battery parameters:
1. Voltage [V] 12 V
Voltaic Cell
Hydrogen gas bubbles attaches to the copper surface: hydrogen gas is

insulator, reduces surface area : current drawn is very weak
Daniell Cell: John Frederic Daniell
earthen
pot
MW 65.3 MW 63.5
Voltage Standard state: Unit activity
earthen
pot
MW 65.3 MW 63.5
Cathode
Voltage in standard state
∆E = Ecathode – Eanode = 0.34 – (- 0.76) = 1.1 V
Anode
Zn + Cu2+ = Zn2+ + Cu K = Zn2+ / Cu2+
ΔE = ΔE0 - (RT/nF) lnk

= 1.1 – (8.314*298*2.303)/(2*96500)*log (aZn2+) / (aCu2+)
= 1.1 – 0.029*log (aZn2+ / aCu2+)
Specific Capacity & Energy (at standard state)
Zn + Cu2+ = Zn2+ + Cu
Specific capacity
= (charge transferred for 1 mole of reactants/

mass of 1 mole of reactants)
= (2*96500)/(63.5+65.3) coulomb/gm
= (1/3.6)*(2*96500)/(63.5+65.3) mAh/gm
= 416 mAh/gm
Specific energy
= - Specific capacity * voltage

= - 416* 1.1 mAh/gm*V
= - 457.6
mWh/gm
[605.42 mWh/g voltaic cell]
Specific Capacity & Energy (at standard state)
H+ must diffuse to
earthen Usual the porous pot:
pot design solid state diffusion:
slow process
MW 65.3 MW 63.5
Zn Cu Modified Ionic diffusion

Frenchman design through liquid:
ZnSO4 solution
by the name fast process
of Callaud
CuSO4 Gravity
solution cell Once built
can not be moved
Zinc-air batteries
In 1878 a battery was designed in which the Q: energy density of a Zinc-air cell?
copper electrode of the Voltaic cell was replaced
by a porous carbon electrode and the KOH was Total charge Specific energy
chosen as the electrolyte (more conductivity, low = 2*96500 = -1.6*659.42
IR loss). At such a high pH, 2H+ + 2e = H2 reaction = 193000 coulomb = -1055.07 Wh/Kg
does not take place. Rather, O2 get reduced. = 53611.11 mAh
= -1.6*821
Zinc-air batteries use oxygen from ambient Specific capacity = -1313.6 Wh/Kg
atmosphere to produce electrochemical energy. = 53611.11/81.3
Upon opening the battery to air, oxygen diffuses = 659.42 Ah/Kg Practical
into the cell and is used as the cathode reactant. -470 Wh/Kg
Zn(OH)2 Specific capacity
= 53611.11/65.3
= 821 Ah/Kg
0.4 V
Since one active material lies outside of the cell,
-1.2 V the majority of the cell’s volume contains the other
active component (zinc), thus on a unit volume
basis, zinc-air (oxygen) batteries have a very high
energy density.
• Cathode material must not oxidize
• Cathode material must not corrode (in presence of water and oxygen)
• Cathode material must be porous to make passage for oxygen gas to enter and react effectively throughout the
surface
• Water should not stick to the surface of the cathode material
Limitations in technology prevented the commercialization of zinc-air (O2) batteries until the 1930s. In 1932,
Heise and Schumacher constructed alkaline electrolyte zinc-air (O2) batteries which had porous carbon air
cathodes impregnated with wax to prevent flooding. These batteries are noted for their very high energy
densities but low power output capability
The thin, efficient air cathode used in today’s zinc-air (O2)

button batteries was made possible through the emergence of
fluorocarbons as a polymer class. The unique surface
properties of these materials, hydrophobicity combined
with gas porosity, made possible the development of thin,
high-performance gas electrodes using a Teflon bonded
catalyst structure and a hydrophobic cathode composite
Fluorocarbons
sometimes referred to as perfluorocarbons or PFCs, are, strictly speaking, organofluorine compounds with the
formula CxFy, wherein all C-H bonds have been replaced by C-F bonds
Hydrophobic in spite of porosity (capillary action)

MnO2 Electrodes in Aqueous Systems
2-
C H2 C
+
H o Conversion o
p 2H+ + 2e = H p
2
H+ p H2 p
e e
4+ H+ r r
H+ M M
n Intercalation n
O O
H+ Mn4+ + e = Mn3+
2 O
H+ H+ H
Manganese dioxide
Crystal structure
Drawback of voltaic cell
Hydrogen gas is insulator, reduces effective area of the C H2 C

cathode. Current is very low. Power (V x I) is low H +
o Conversion o
p 2H+ + 2e = H p
2
H+ p H2 p
e e
H+ r r
MnO2
H+ M M
n Intercalation n
O O
H+ Mn4+ + e = Mn3+
2 O
H+ H+ H
+ 2+
Zn + 2 H = Zn + H2 (gas) Zn + Cu2+ = Zn2+ + Cu (solid) Zn + Mn4+ = Zn2+ + Mn3+ (ion)
Zn = Zn2+ + 2e
2Mn4+ + 2e = 2Mn3+
Zinc-Carbon
(Leclanche´) and
Zinc-Chloride batteries
Alkaline-manganese dioxide batteries More conductivity
On discharge, the manganese dioxide cathode undergoes

at first a one-electron reduction to the oxyhydroxide,
At a lower voltage, MnOOH can then be discharged further
Anode discharge reaction in highly caustic electrolyte

produces the soluble zincate ion
electrolyte becomes saturated with zincate, causing the

product of the reaction to change to Zn(OH)2
TARGET: specific
energy of gasoline
= -47.5 MJ/Kg =
-(47.5/3.6) = -13.2
kWh/Kg
442 Wh/Kg
85–190
Wh/Kg
Battery as an energy conversion device

Primary Secondary Cost of electricity: 8 INR/unit (kWh) in India
Cost of refiling 2.4 Wh = 8*2.4/1000
•an AA rechargeable cell has 275 = 0.0192 INR
•A primary AA cell has 15
2500 mAh @ 1.5V = 3.75 Wh 2000 mAh @ 1.2V = 2.4 Wh INR
INR
Cost of electricity: 28 INR/unit (kWh) in GER
•A primary AAA cell has •an AAA rechargeable cell has 235
10 Cost of refiling 2.4 Wh = 28*2.4/1000
1000 mAh @ 1.5V = 1.5 Wh 800 mAh @ 1.2V = 0.96 Wh INR
INR = 0.0672 INR
Let us assume after x cycles costs are equal
15*(2.4/3.75) * x = 275 + 0.0192 * x

x = 28.7 cycles
15*(2.4/3.75) * x = 275 + 0.0672 * x

x = 28.7 cycles
If a secondary battery can run for 100 cycles, then net cost is = 275 + 0.0672*100 = 281.72 INR
Cost of replacing 100 AA cells = 100*15*(2.4/3.75) = 960 INR

TARGET: specific
energy of gasoline
= -47.5 MJ/Kg =
-(47.5/3.6) = -13.2
kWh/Kg
442 Wh/Kg
85–190
Wh/Kg
Battery as an energy conversion device

Primary Secondary Cost of electricity: 8 INR/unit (kWh) in India
Cost of refiling 2.4 Wh = 8*2.4/1000
•an AA rechargeable cell 275 = 0.0192 INR
•A primary AA cell has 15
2500 mAh @ 1.5V = 3.75 INR has INR
2000 mAh @ 1.2V = 2.4 Cost of electricity: 28 INR/unit (kWh) in GER
Wh 235
10 Wh Cost of refiling 2.4 Wh = 28*2.4/1000
•A primary AAA cell has INR INR = 0.0672 INR
1000 mAh @ 1.5V = 1.5 •an AAA rechargeable cell
Wh has Let us assume after x cycles costs are equal
800 mAh @ 1.2V = 0.96
Wh 15*(2.4/3.75) * x = 275 + 0.0192 * x
x = 28.7 cycles
15*(2.4/3.75) * x = 275 + 0.0672 * x

x = 28.7 cycles
If a secondary battery can run for 100 cycles, then net cost is = 275 + 0.0672*100 = 281.72 INR
Cost of replacing 100 AA cells = 100*15*(2.4/3.75) = 960 INR

Lecture 6: Secondary batteries
Alessandro Volta's discovery, that electricity could be produced by placing two dissimilar metals on opposite
sides of a moistened paper
In 1800, Nicholson and Carlisle carried out an exact opposite experiment. They thought if the chemical energy
can be converted to the electrical energy, then the later can also be applied to carry out a chemical reaction,
Therefore, using Volta's primitive battery as a source, they applied electric current and could decompose water
into oxygen and hydrogen.
Established the connection

between chemistry and
electricity
Humphrey Davey prepared the first elemental sodium by
electrolysis of a sodium hydroxide (NaOH) melt.
Following his footsteps, Andreas Marggraf electrodeposited

Zn from acidic ZnSO4 solution.
Deposition of metals is a reduction process. However, in an

electrolytic cell, both reduction and oxidation reaction takes
place simultaneously. Therefore, it is also possible carry out a
chemical reaction by oxidation.
Ruetschi reported
formation of MnO2
from a solution of If some of the Mn4+ ions are missing
MnSO4, in which, (cation vacancies), their missing positive
Mn2+ ion oxidizes to charge is compensated by H+ in the
Mn4+ ions. crystal structure.
Electrochemically more active
The idea of a reversible cell:
Electrodeposition of Zn and electrolytic formation of MnO2 opened up an entirely new window for the battery researchers.
Scientists thought that if from a single bath both electrodeposition of Zn (reduction) and electrolytic formation of MnO 2
(oxidation) can be performed simultaneously, then the Zn/MnO2 cell can be made reversible by application of current.
This means that the battery need not to be recycled once Zn has oxidized and dissolute to Zn 2+ and Mn4+ have reduced to
Mn2+, but can simply be brought back to pristine Zn and MnO2 by applying current
Attempt to make a Zn/MnO2 reversible cell:
• Cells would lose their ability to be recharged due to the expansion of the
cathode. Depending on the load
and age of the battery and the capacity was reduced because of this higher
end voltage.
• Due to volume expansion, stress is generated leading to fracture. Mechanical
integrity is lost
• Neither MnO2 or MnOOH is conductive
• Dendritic growth of zinc during charge which can lead to internal short circuits
• Oxygen evolving at cathode tends to oxidize carbon (for Zinc-air)
Though the chemistry is reversible, mechanical integrity is lost with cycles

Pb-acid reversible cell:
Pb does not react with 34 % H2SO4
PbO2 is conductive (resistivity 10−4 Ω·cm)

-0.39 V
PbO2 is insoluble in water
PbSO4 is virtually insoluble in water
0.00443 g/100 mL (20 °C)
+1.69 V
Assignment: Pb-acid battery: possible reasons of failures
Q: Find energy density
Total mass:
= 207.2 + 239.19 + 2*98
= 642.39 gm
Total charge:
= 2*96500
= 193000 coulomb
Charge/mass (th.)
= 193000/642.39
= 300.44 coulomb/gm
= 83.45 mAh/gm
-0.39 V
Energy/mass (th.)
+1.69 V = 83.46*2.08 mAh/gm
= 173.58 Wh/Kg
Nickel Electrodes in Aqueous Systems
Actually, this electrode is not metallic nickel at all, but a two-phase mixture of nickel hydroxide and nickel
oxy-hydroxide
cycling reaction containing this electrode involves back and forth conversion between the β Ni(OH) 2 structure
and the β NiOOH structure. It has been well established that these are separate phases
Ionic Ionic + electronic

Although the electrode potential when this
two-phase structure is present is appreciably
above the potential at which water is oxidized to
form oxygen gas. But gaseous oxygen evolution
cannot happen if the solid electrolyte Ni(OH)2
separates the water from the electronic
conductor NiOOH. Oxygen evolution can only
occur when the electronically conducting NiOOH
phase is present on the surface in contact with
the aqueous electrolyte.
Cadmium electrodes in Aqueous Systems
ZnO dissolves in KOH electrolytes, producing an appreciable
concentration of zincate ions, Zn(OH)42−, in which the Zn2+
cations are tetrahedrally surrounded by four OH− groups.
Nonuniform zincate composition gradients during
recharging, as well as the ZnO on the surface, lead to the
formation of protrusions, filaments, and dendrites during
the redeposition of zinc from the electrolyte at appreciable
currents.
It is seen that Cd(OH)2 is stable when

Cd is in contact with water. The
potential of the cadmium electrode is
determined by the potential of the
sub-triangle that has water, Cd(OH)2,
and cadmium at its corners.
Nickel - cadmium batteries
Only problem is Cd toxicity

Compared to lead–acid batteries, Ni–Cd batteries have 50 % higher specific
energy. A Ni–Cd battery is smaller and lighter than a comparable lead–acid
battery
Ni–Cd batteries typically last longer, in terms of number of charge/discharge
cycles, than other rechargeable batteries such as lead/acid batteries
The battery performs very well under rough conditions, perfect for use in the
portable tools. The batteries are more difficult to damage than other
batteries, tolerating deep discharge for long periods. In fact, Ni–Cd batteries
in long-term storage are typically stored fully discharged
-0.68 V 0.52 V
Cd(OH)2 Ni(OH)2
Specific cap.
Total weight Total charge = 53611.12/295.8
= weight of Cd + 2*weight of NiO(OH) = 2*96500 columb = 181.24 mAh/gm
= 112.4 + 2*91.7 = 2*96500/3.6 mAh
= 72.08 + 91.7 = 53611.12 mAh Specific energy
= 295.8 gm = 1.2*181.24
= 217.48 mAh/gm
Pb Zn/Cd ? Metallic hydrides
PbO2 – PbSO4 MnO2 – MnOOH MnO2 – MnOOH
H2SO4 KOH KOH NiO2 - NiOOH
NiO2 - NiOOH
H+ OH- H+
Pb2+
Shifting from
metals to metal alloys
Hydrides of this type form according to either one of two main mechanisms:
• The first mechanism involves the adsorption of dihydrogen, succeeded by the cleaving of the H-H bond, the delocalization
of the hydrogen's electrons, and finally the diffusion of the protons into the metal lattice.
• The other main mechanism involves the electrolytic reduction of ionized hydrogen on the surface of the metal lattice, also
followed by the diffusion of the protons into the lattice. The second mechanism is responsible for the observed temporary
volume expansion of certain electrodes used in electrolytic experiments
There are two major families of hydrides currently being produced that can be roughly identified as AB 5 and AB2
alloys.
The AB5 alloys are based upon the pioneering work in The other major group of materials that are now being
the Philips laboratory that started with the used as battery electrodes are the AB2 alloys. There are
serendipitous discovery of the reaction of gaseous two general types of AB2 structures, sometimes called
hydrogen with LaNi5. The basic crystal structure is of Friauf-Laves phases: the C14, or MgZn2, type in which the
the layered hexagonal CaCu5 type. Alternate layers B atoms are in a close-packed hexagonal array, and the
contain both lanthanum and nickel, and only nickel. C15, or MgCu2, type in which the B atoms are arranged in
a close-packed cubic array. Many materials can be
prepared with these, or closely related, structures. The A
atoms are generally either Ti or Zr. The B elements can be
V, Ni, Cr, Mn, Fe, Co, Mo, Cu, and Zn.
Nickel–metal hydride battery (H+ battery) Favourable kinetic properties
for high-rate performance
-0.83 V 0.52 V
Specific cap.
Total weight = 26805.56/163.78
= weight of LaNi5 + weight of NiO(OH) = 163.67 mAh/gm
= 432.5/6 + 91.7 = 163.67 mAh/gm (Wh/Kg)
= 72.08 + 91.7 Total charge
= 163.78 gm = 96500 columb Specific energy
= 96500/3.6 mAh = 1.35*163.78
= 26805.56 mAh = 221 mWh/gm (Wh/Kg)
Nickel–metal hydride battery (H+ battery) We have reached the saturation point w.r.t.
ionic diffusion (current)
I have been maximized

-0.68 V 0.52 V
Q is also maximized (not only due to material
choice; but also, due to compact design)
OH-
Discharge
What to do next?
OH-
charge
E = VQ; P = VI
Cd(OH)2 Ni(OH)2 Now target V
-0.83 V 0.52 V
Replace hydrogen reaction with a more
negative reaction.
H+
Discharge Select a strong electropositive element
Lithium
H+
• potential (-3 V SHE)
charge
• Mass (AW 6.94)
Cd
NiO2 - NiOOH
KOH
0.52 V
OH-
1.2 V wrt hydrogen
-0.68 V
-3 V wrt hydrogen
MH
NiO2 - NiOOH
KOH Voltage = 1.2 – (-3) = 4.2 V
0.52 V
+ Total weight
H
= weight of LiCoO2 + weight of Li
= 91 + 6.94 = 97.94 gm
-0.83 V
Total charge = 96500 columb
? = 96500/3.6 mAh
?
Voltage > 3 volt; Can we use aqueous electrolyte? = 26805.56 mAh
NiO2 - NiOOLi
? Specific cap. = 26805.56/97.94
?V
We need a Li+ conducting non-aqueous electrolyte = 273.7 mAh/gm
Li+
We need a positive electrode which can host Li+ Specific energy = 4.2*273.7
-3.00 V = 1149.54 Wh/Kg
We need a negative electrode which can host Li Energypr = 225 Wh/Kg

Working principle of a lithium ion battery
Working principle
1.2 V wrt -3 V wrt

hydrogen hydrogen
Copper Aluminium
Electrolytes in lithium systems
Water Molten salt Molten salt eutectic Non-aqueous Ionic liquids

solvent High temp. req. Solvent
LiCl–KCl: 380 °C significantly lower
LiCl: 605 °C LiF–LiBr–KBr: 280 °C organic cations melting points
Out of
Li2O: 1483 °C LiCl–KCl–AlCl3: 86 °C and carbonate
question LiCl–NaCl–KCl–AlCl3: 61 °C larger the
anions
One ternary salt found structural groups, and
to be promising Problem regarding Li the lower their electrical
LiClO4, LiAsF6, charges, the easier it
replacing K and Al at high LiBF4, LiPF6 salts
LiAlCl4: 145 °C discharge rates is for thermal energy to
break them apart
between 1.68 and LiF–LiCl–LiI: 334 °C
4.36V vs. lithium at LiF–LiCl–LiBr–LiI: 325 °C NaBr melts at 747◦C.
25◦C tetrabutylammonium
Not possible to use solid Li bromide melts at 104◦C
Assignment: aqueous lithium ion batteries

Non-aqueous Solvent
Ethylene carbonate is very attractive. However, its melting point is relatively high
Propylene carbonate was an early choice as a cosolvent, but it was recognized that this combination caused
defoliation of graphitic negative electrodes
solutions of ethylene carbonate with either dimethyl carbonate or diethyl carbonate are stable up to 4.8 V
(from 1.7 to 4.8 V)
Salts Used in Electrolytes for Li-ion Cells
Most Li-ion electrolytes in current use utilize LiPF6 as the salt as its solutions offer high ionic conductivity, 10-3 S/cm, high
lithium ion transference number (0.35)
However, the salt is costly, hygroscopic, and LiPF6 yields hydrofluoric acid (HF) upon reaction with water
Formation of solid electrolyte interface (SEI)
LIPF6 in EC/DMC/DEC
Li-metal oxide
Graphite
Li-ion cell is a
multi-electrolyte
system
They generally have much lower vapor pressures than the organic cation carbonates in which
Ionic Liquids the organic species are relatively small, flammable, and sometimes toxic
The primary difference between the ionic liquids discussed here and the inorganic molten salts is that they have
significantly lower melting points
The melting point is related to the energy necessary to break the bonds holding the component species together. This is
sometimes called their lattice energy. In general, the larger the structural groups that act as ions, and the lower their
electrical charges, the easier it is for thermal energy to break them apart from each other.
Thus organic cations with quaternary ammonium groups, designated as (R4N+), have low lattice energies, and have much
lower melting points than their alkali metal cation analogs. As an example, NaBr melts at 747◦C, whereas
tetrabutylammonium bromide melts at 104◦C.
ionic liquid electrolyte that has been used is a ternarymixture:

PYR14TFSI+x LiTFSI+y PEGDME (or TEGDME).
LiTFSI is Libis(trifluoromethane sulfonyl)imide

PYR14TFSI is N-methyl-N-butylpyrrolidinium bis(trifluoromethane sulfonyl)imide,
TEGDMEis tetra(ethylene glycol)dimethyl ether, and
PEGDMEis poly(ethylene glycol)dimethyl ether
Solid
electrolytes
• Lithium solid electrolytes might be useful in cells that operate at elevated temperatures, where the common
liquid electrolytes are no longer stable
• Do not need a separator, enhanced energy density
• Battery can be placed in any orientation
• Can bear rough handling
• No problem of electrolyte leaking, flammability and thermal runaway
There are two major reasons why lithium-conducting solid electrolytes are not being used in common batteries at
the present time:
• One is that they have conductivities that are far less than the organic liquid solvent materials that are currently
used. Low power rating
• The other is that the solid electrode materials that are now used in lithium systems undergo volume changes as
lithium is added or deleted. Because the electrodes breathe as they are cycled, there are significant mechanical
stresses placed upon the electrolyte. This causes problems with thin solid electrolyte layers
Lecture 8: Li-ion cell cathodes
Requirements for positive electrode materials
Air stable
Introduction of the concept that one can reversibly insert
lithium into solids to produce electrodes with useful potentials
and capacities.
Air stable
This was first demonstrated by Whittingham in 1976, who
investigated the addition of lithium to the layer-structured TiS2
to form LiTiS2, where x went from 0 to 1. F=C-P+2
Air stable
Subsequently, the insertion of lithium into a

significant number of other materials, including F=C-P+2
V2O5 and V6O13 was investigated
Air stable
C=3
P = 1, 2
Independent
variable = 1
F = 0, 1
These positive electrode materials were typically stable in air. As the insertion of lithium causes the
potential to decrease, and those positive electrodes necessarily operated at potentials lower than
that of air, the voltage of such cells was limited to about 3V.
On the other hand, if a positive electrode material initially contains lithium, and some or all of the
lithium is deleted, the potential goes up, rather than down, as it does upon the insertion of lithium.
Therefore, if the cathode material already

contain lithium, and this lithium can be
electrochemically extracted, it is possible to
have positive electrode materials that react
with lithium at potentials above about 3V
First demonstrated in Prof. Goodenough’s laboratory in
Oxford. The first examples of materials initially Not air stable
containing lithium, and electrochemically deleting
lithium from them, were the work on Li1−xCoO2 and
Li1−xNiO2 in 1980. They showed that it is possible in this
way to obtain high reaction potentials, up to over 4V.
The shift in concept to the use of air-stable positive Air stable at

electrode materials that already contained lithium, and lithiated form
their operation by the deletion of lithium, led to the
possibility of batteries with significantly higher voltages.
1+ 3+ 0 4+
LiCoO2 = Lix+Li1−xCoO2
1D diffusion in certain channels
2D diffusion along basal plane
3D very open structure, diffusion in all direction
possible
Nasicon
Lecture 9
Negative Electrodes in Lithium Cells
Elemental Lithium Electrodes Lithium has the lowest potential, Lowest weight per unit charge
Specific problems with the use of elemental lithium in recharging

Dendrites
If the current density is such that solute depletion in the electrolyte near the electrode surface causes the local gradient of the
element’s chemical potential in the electrolyte immediately adjacent to the solid surface to be positive. Under such a condition
there will be a tendency for any protuberance upon the surface to grow at a faster rate than the rest of the interface. This
leads to exaggerated surface roughness, and eventually to the formation of either dendrites or filaments.
Filamentary Growth
Interfacial layers often have defects in their structure that can lead to local
variations in their properties. Regions of reduced impedance can cause the
formation of deleterious filamentary growths upon recharge of the
electrode. This is an endemic problem with the use of organic solvent
electrolytes in contact with lithium electrodes at ambient temperatures.
This phenomenon can result in the metal deposit having a hairy or spongy
character. During a subsequent discharge step, the protrusions often get
disconnected from the underlying metal, so that they cannot participate in
the electrochemical reaction, and the rechargeable capacity of the
electrode is reduced.
Thermal Runaway
The organic solvent electrolytes react with lithium and form either
crystalline or amorphous product layers upon the surface of the electrode
structure. These reactions are exothermic and cause local heating.
Experiments using an accelerating rate calorimeter have shown that this
problem increases dramatically as cells are cycled, presumably due to an
increase in the surface area of the lithium due to morphological instability
during repetitive recharging
Lithium carbon alloy electrodes
Graphite
Any effect on cell voltage?

Graphite is amphoteric, and either cations or anions can be inserted
into it between the graphene layers. When cations are inserted, the
host graphite structure takes on a negative charge. Cation examples
are Li+, K+, Rb+, and Cs+. When anions are inserted, the host graphite
structure takes on a positive charge, and anion examples are Br-,
SO42- , or SbF6-
Calculate specific capacity of pure Li and LiC6
Theoretical specific capacities of Li and LiC6 are 3862.5 and 372 mAhg-1,
respectively. Capacities typically range from 300 to 350 mAhg -1
Amorphous Hydrogen-Containing Carbons
Graphite
Any advantage?
The electrochemical behavior is quite different

when the carbon has not been heated so high,
and the structure is not so well ordered. There is
a wide range of possible sites in which the lithium The large capacity is due to the formation of C2H2Li2. This s
can reside, with different local structures, and consistent with the amount of hydrogen resent. This
therefore different energies. The result is that the changes the local bonding of the host Carbon atoms form
potential varies gradually, rather than showing sp2 to sp3.
the steps characteristic of more ordered
structures.
GRAPHITE
INTERCALATION
SINGLE PHASE
FAST IONIC MOVEMENT
METALS
CONVERSION/
INTERMETALLIC FORMATION
PHASE CHANGE/DUAL PHASE
SLOW IONIC MOVEMENT
Lithium metal intermetallics

Metallic Lithium Alloys
Material
vol. expansion
Pristine voltage (with gr. capacity Density vol. capacity
[%]
& ref to Li) [V] [mAh/gm] [gm/cc] [mAh/cc]
Fully lithiated
Gr. (LiC6) 0.2-0.02 300-350 2.23 780 12
Zn (Li9Zn4) 0.21-0.02 410 7.14 2927 100
Bi (Li3Bi) 0.85-0.65 560 9.78 5477 110
Pb (Li22Pb5) 0.78-0.45 569 11.34 6452 230
Sb (Li3Sb) 1-0.9 660 6.7 4420 130
Sn (Li22Sn5) 0.66-0.38 993 7.27 7214 260
Al (LiAl) 0.2-0.02 2476 2.7 6685 350
Si (Li22Si5) 0.2-0.02 4200 2.33 9786 400
safety weight Volume: Why important?

Room Temperature Electrolyte:
organic cations and carbonate anions Line compound
LiClO4, LiAsF6, LiBF4, LiPF6 salts
X in sp.
Phases
LixSn Capacity
Li2Sn5 0.4 90
LiSn 1 226
Li7Sn3 2.33 527
Li5Sn2 2.5 565
Li7Sn2 3.5 790
Li22Sn5 4.4 993
A Real Example, The Lithium: Antimony System
as vertical lines in the phase diagram. Thus, if an electrode is initially pure Sb and lithium is added, it
successively goes through two different reactions. The first involves the formation of phase Li2Sb, and can be
written as: 2Li + Sb = Li2Sb
On further addition of lithium, a second reaction occurs resulting in the formation of the second intermediate
phase from the first. This can be written as: Li + Li2Sb = Li3Sb
Potentials of the two plateaus are calculated from thermodynamic data on the standard Gibbs free energies of
formation of the two phases, Li2Sb and Li3Sb.
These values at that temperature are −176.0 kJ/mol and −260.1 kJ/mol, respectively.
The standard Gibbs free energy change, ΔGr◦, related to reaction 1 is simply that of the formation of phase
Li2Sb, ΔGf◦(Li2Sb). From this the potential of the first plateau can be calculated from
E −E◦ = −ΔGr◦/2F = 912 mV
where E◦ is the potential of pure Li.
The potential of the second plateau is related to reaction 2, where ΔGr◦ = ΔGf◦(Li3Sb)−ΔGf◦(Li2Sb),
E −E◦ = −ΔGr◦/F = 871 mV
These energy values can be converted into specific energy, i.e., energy per unit weight. In the case of the first plateau the
maximum theoretical specific energy, MTSE, is simply the standard Gibbs free energy of the reaction divided by the sum of
the atomic weights in the product. This was found to be 1,298 kJ/kg. This can also be expressed as 360 Wh/kg, since 3.6 kJ is
equal to 1Wh
The maximum theoretical specific energy can also be calculated if the composition were to only vary between compositions
Li2Sb and Li3Sb. In this case the voltage is 871 mV and the capacity is only one mole of lithium per mole of original Li 2Sb.
When calculating the MTSE, the weight of the product is that of Li 3Sb, 142.57 g/mol. The result is 589 kJ/kg and 164Wh/kg for
a cell operated in this composition range.
How to tackle large volume expansion
No strategy Active-active strategy Active-inactive strategy
Sn Sn Sn-Cu
Li M Li
Li
Cu
Sn
Li22Sn5 Li-M
Li22Sn5
Reduce particle size

Li-M
Li22Sn5
pulverization
Lithiation study (mix)
Lithiation
Delithiation
Battery type Voltage Capacity Specific Energy Specific Cyclability Charge- Self
Energy density Power discharge discharge
[W·h/kg] [W·h/L] [W/kg] eff. [%]
Pb-acid 2.1 35-40/ 84 35-40/ 174 80-90 180 350 50-95 3-20
Ni-Cd 1.2 40-60/ 180 40-60/ 217 50-150 1200 2000 70-90 10
Ni-MH 1.35 45-89/ 163 60-120/ 220 140-300 250 - 1000 180-2000 66-92 14-70
Li-ion 3.7 27-72/ 273 100–265/ 1150 250–693 250 – 340 250-350 95-99 0.35 - 2.5
Which battery ideally should give the highest energy density? How much?
Li-ion :
LiCoO2
Li-ion :
LiFePO4
Lead-acid
Ni-Cd
Ni-MH
Zn-MnO2
Scope of improvements/ research
Increase the gravimetric/ volumetric
capacity. More Li in the host structure.
mAh/g mAh/cc
Constraint - mass Constraint - volume
Nanostructured material with high

grain boundary area, more diffusion
More effective stress buffering

capability
Increase the gravimetric/ volumetric
capacity. More Li in the host structure. Can pure Li be used?
Enhance solid state diffusion,
search for more open structure
Increase cathode potential Expanded potential window

Search for newer electrolyte
Ecell = Ecathode - Eanode compatible with cathode.
TARGET: specific energy of gasoline Horsepower of an alto car is 40.36 bhp = 40.36*0.7457 = 30.1 kW
= -47.5 MJ/Kg = -(47.5/3.6) = -13.2 kWh/Kg
Battery runtime (full charge) = 153.8 kWh/ 30.1 kW = 5.11 h
= = 11.48 Electricity cost = 153.8 kWh * 8 Rs/kWh = 1230.4 INR
Specific energy Li-ion cell - 01.15
Gasoline cost = 35*106 = 3710 INR were above $1,200 per
Practical kilowatt-hour in 2010
Specific energy gasoline -13.20*0.45 Li-ion battery cost = US$132/kWh
= =26.4 Total battery cost = 132*153.8*70 = 1514905.4 INR
Specific energy Li-ion cell - 00.225
alto car petrol tank capacity = 35 L For alto: let say after x times of filings cost will be equal
35 L gasoline weighs = 0.74*35 = 25.9 Kg 450000 + 3710x = (1514905.4 + 200000) + 1230.4x
Battery weight required for same specific energy X = 510 times filling (1 filing 7 days)
= 25.9*26.4 = 683.76 Kg
510 filings = 510*7/365 = 9.78 years
Weight of an alto car – 757 Kg
Battery weight = 683.76/(683.76+757)= 47.4% Need better battery; must last for more cycles
State-of-the-art battery lasts for 250-300 cycles
Battery energy = 0.225*683.76 = 153.8 kWh
Lecture 10: Fuel cell
Zinc-air batteries
In 1878 a battery was designed in which the manganese dioxide of the alkalline battery was replaced by a
porous platinized carbon/ air electrode.
Zinc/ air batteries use oxygen from ambient atmosphere to produce electrochemical energy. Upon opening the
battery to air, oxygen diffuses into the cell and is used as the cathode reactant.
Since one active material lies outside of the cell, the majority of the cell’s volume contains the other active
component (zinc), thus on a unit volume basis, zinc / air batteries have a very high energy density.
• Cathode material must not oxidize
• Cathode material must not corrode (in presence of water and oxygen)
• Cathode material must be porous to make passage for oxygen gas to enter and react effectively
throughout the surface
• Water should not stick to the surface of the cathode material
Manganese dioxide of the famous Leclanche´ battery was replaced by a porous platinized carbon/
air electrode. Limitations in technology prevented the commercialization of zinc / air batteries until
the 1930s. In 1932, Heise and Schumacher constructed alkaline electrolyte zinc/ air batteries which
had porous carbon air cathodes impregnated with wax to prevent flooding. These batteries are
noted for their very high energy densities but low power output capabilit
The thin, efficient air cathode used in today’s zinc / air button batteries was made possible through
the emergence of fluorocarbons as a polymer class. The unique surface properties of these
materials, hydrophobicity combined with gas porosity, made possible the development of thin,
high-performance gas electrodes using a Teflon bonded catalyst structure and a hydrophobic
cathode composite
Fluorocarbons
sometimes referred to as perfluorocarbons or PFCs, are, strictly speaking, organofluorine compounds with the
formula CxFy, wherein all C-H bonds have been replaced by C-F bonds
Hydrophobic in spite of porosity (capillary action)

Ni-hydrogen batteries
Ni-hydrogen battery is a modified version of Ni-metal hydride battery in which hydrogen is not stored in
hydrides; but, in the form of elemental hydrogen in compressed form.
NiH2 cells using 26% potassium hydroxide (KOH) as an electrolyte have shown a service life of 15 years or more at
80% depth of discharge (DOD) The energy density is 75 Wh/kg, 60 Wh/dm3 specific power 220 W/kg. The
open-circuit voltage is 1.55 V, the average voltage during discharge is 1.25 V.
While the energy density is only around one third as that of a lithium battery, the distinctive virtue of the
nickel–hydrogen battery is its long life: the cells handle more than 20,000 charge cycles with 85% energy efficiency
and 100% faradaic efficiency.
The hydrogen electrodes consist of a Teflon-bonded platinum black catalyst
supported on a photo-etched nickel substrate with Teflon bonding. For Ni-H 2
cells, a hydrophobic Teflon backing was added to these platinum electrodes
to stop water or electrolyte loss from the back side of the negative platinum
electrode during charge and overcharge while readily allowing diffusion of
hydrogen and oxygen gas
The pressure vessel (dome and cylinder), terminal bosses and weld rings are
all fabricated from Inconel alloy 718. The Inconel 718 pressure vessel shells
are manufactured to a near uniform thickness using either a hydroforming or
drawn process and then cut to length. The thickness is determined by the
operating pressure and cycle requirements for the particular use. The
pressure shells are ‘‘age hardened’’ using a standard heat treatment process.
Inconel is a registered trademark of Special Metals Corporation for a family

of austenitic nickel-chromium-based superalloys. They are
oxidation-corrosion-resistant materials well suited for service in extreme
environments subjected to pressure and heat. When heated, Inconel forms a
thick, stable, passivating oxide layer protecting the surface from further
attack. Inconel retains strength over a wide temperature range, attractive for
high temperature applications where aluminum and steel would succumb
to creep as a result of thermally induced crystal vacancies. Inconel's high
temperature strength is developed by solid solution
strengthening or precipitation hardening, depending on the alloy
Fuel cell
If the hydrogen electrode of the Ni-hydrogen battery is combined Fuel cells are different from
with the oxygen electrode of the zinc-air battery, then one ends up most batteries in requiring a
with a fuel cell which is electrolysis in reverse. continuous source of fuel and
oxygen (usually from air) to sustain
the chemical reaction
Individual fuel cells produce

relatively small electrical potentials,
about 0.7 volts, so cells are
"stacked", or placed in series, to
create sufficient voltage to meet an
application's requirements
In addition to electricity, fuel cells

produce water, heat and, depending
on the fuel source, very small
amounts of nitrogen dioxide and
other emissions
Alkaline fuel cell The alkaline fuel cell (AFC), also known as the Bacon fuel
cell after its British inventor, Francis Thomas Bacon, is
one of the most developed fuel cell technologies.
Alkaline fuel cells consume hydrogen and pure oxygen,
to produce potable water, heat, and electricity. They are
among the most efficient fuel cells, having the potential
to reach 70%.
NASA has used alkaline fuel cells since the mid-1960s, in

the Apollo-series missions and on the Space Shuttle
The two electrodes are separated by a porous matrix

saturated with an aqueous alkaline solution, such as
potassium hydroxide (KOH). Aqueous alkaline solutions
do not reject carbon dioxide (CO2) so the fuel cell can
become "poisoned" through the conversion of KOH to
potassium carbonate (K2CO3). Because of this, alkaline
fuel cells typically operate on pure oxygen, or at least
purified air and would incorporate a 'scrubber' into the
design to clean out as much of the carbon dioxide as is
1: Hydrogen 2:Electron flow 3:Charge 4:Oxygen
possible.
5:Cathode 6:Electrolyte 7:Anode 8:Water 9:Hydroxyl Ions
Lecture 10: other types of fuel cells
Classification
Design features in a fuel cell include:
• The electrolyte substance, which usually defines the type of fuel cell, and can be made from a number of
substances like potassium hydroxide, salt carbonates, and phosphoric acid
• The fuel that is used. The most common fuel is hydrogen
• The anode catalyst, usually fine platinum powder, breaks down the fuel into electrons and ions
• The cathode catalyst, often nickel, converts ions into waste chemicals, with water being the most common
type of waste
• Gas diffusion layers that are designed to resist oxidization
Proton-exchange membrane fuel cell (PEMFC) A proton-conducting polymer membrane (typically
nafion) contains the electrolyte solution that separates
the anode and cathode sides
On the anode side, hydrogen diffuses to the anode

catalyst where it later dissociates into protons and
electrons. These protons often react with oxidants
causing them to become what are commonly referred to
as multi-facilitated proton membranes. The protons are
conducted through the membrane to the cathode, but
the electrons are forced to travel in an external circuit
(supplying power) because the membrane is electrically
insulating. On the cathode catalyst, oxygen molecules
react with the electrons (which have traveled through
the external circuit) and protons to form water
In addition to this pure hydrogen type, there are

hydrocarbon fuels for fuel cells, including diesel,
methanol (see: direct-methanol fuel cells and indirect
methanol fuel cells) and chemical hydrides. The waste
products with these types of fuel are carbon dioxide and
water.
Direct-methanol fuel cell (DMFC)
Direct-methanol fuel cells or DMFCs are a subcategory of proton-exchange fuel cells in which methanol is used as the fuel.
Their main advantage is the ease of transport of methanol, an energy-dense yet reasonably stable liquid at all
environmental conditions
• Because of the methanol cross-over, a phenomenon by which methanol diffuses through the membrane without
reacting, methanol is fed as a weak solution: this decreases efficiency significantly, since crossed-over methanol, after
reaching the air side (the cathode), immediately reacts with air; though the exact kinetics are debated, the end result is
a reduction of the cell voltage. Cross-over remains a major factor in inefficiencies, and often half of the methanol is lost
to cross-over. Methanol cross-over and/or its effects can be alleviated by
(a) developing alternative membranes
(b) improving the electro-oxidation process in the catalyst layer and improving the structure of the catalyst and
gas diffusion layers
(c) optimizing the design of the flow field and the membrane electrode assembly (MEA) which can be achieved
by studying the current density distributions
• Other issues include the management of carbon dioxide created at the anode, the sluggish dynamic behavior, and the
ability to maintain the solution water.
Reformed methanol fuel cell or indirect methanol fuel cell
Reformed Methanol Fuel Cell
(RMFC) or Indirect Methanol Fuel
Cell (IMFC) systems are a
subcategory of proton-exchange
fuel cells where, the fuel,
methanol (CH3OH), is reformed,
before being fed into the fuel cell.
RMFC systems offer advantages
over direct methanol fuel cell
(DMFC) systems including higher
efficiency, smaller cell stacks, no
water management, better
operation at low temperatures,
and storage at sub-zero
temperatures because methanol is
a liquid from -97.0 °C to 64.7 °C
(-142.6 °F to 148.5 °F). The
tradeoff is that RMFC systems
operate at hotter temperatures
and therefore need more
advanced heat management and
insulation
Phosphoric acid fuel cell Solid acid fuel cell
uses liquid phosphoric acid as an electrolyte. Electrolyte is Solid acid fuel cells (SAFCs) are a class of fuel cells
highly concentrated or pure liquid phosphoric acid (mp characterized by the use of a solid acid material as the
40–42.4 °C). Operating range is about 150 to 210 °C. The electrolyte. They operate at mid-range temperatures, from
electrodes are made of carbon paper coated with a finely 200 to 300 °C
dispersed platinum catalyst. have improved significantly in
stability, performance, and cost At low temperatures, solid acids have an ordered molecular
structure like most salts. At warmer temperatures (between
At an operating range of 150 to 200 °C, the expelled water 140 and 150 degrees Celsius for CsHSO4), some solid acids
can be converted to steam for air and water heating. This undergo a phase transition to become highly disordered
potentially allows efficiency increases of up to 70%. PAFCs "super-protonic" structures, which increases conductivity by
are CO2-tolerant and even can tolerate a CO concentration several orders of magnitude
of about 1.5%, which broadens the choice of fuels they can
use. Because of their moderate temperature requirements and
compatibility with several types of fuel, SAFCs can be
Disadvantages include rather low power density and utilized in remote locations where other types of fuel cells
aggressive electrolyte would be impractical.
Alkaline anion exchange membrane fuel cell
is a type of alkaline fuel cell that uses an anion exchange membrane to separate the anode and cathode compartments
Alkaline fuel cells (AFCs) are based on the transport of alkaline

anions, usually hydroxide OH−, between the electrodes.
Original AFCs used aqueous potassium hydroxide (KOH) as an
electrolyte. The AAEMFCs use instead a polymer membrane
that transports hydroxide anions.
At cathode, oxygen reduction produces hydroxides ions (OH−) that

migrate through the electrolyte towards the anode. At anode,
hydroxide ions react with the fuel to produce water and electrons.
Electrons go through the circuit producing current
The biggest challenge in developing AAEMFCs is the anion exchange membrane (AEM). A typical AEM is composed of a
polymer backbone with tethered cationic ion-exchange groups to facilitate the movement of free OH− ions. This is the
inverse of Nafion used for PEMFCs
Another challenge is achieving OH− ion conductivity comparable to H+ conductivity observed in PEMFCs. Since the diffusion
coefficient of OH− ions is half that of H+ (in bulk water), a higher concentration of OH− ions is needed to achieve similar
results, which in turn needs higher ion exchange capacity of the polymer. However, high ion exchange capacity leads to
excessive swelling of polymer on hydration
Solid oxide fuel cell A solid oxide fuel cell is made up of four layers, three of which are ceramics (hence the
name). A single cell consisting of these four layers stacked together is typically only a
few millimeters thick. Hundreds of these cells are then connected in series to form
what most people refer to as an "SOFC stack". The ceramics used in SOFCs do not
become electrically and ionically active until they reach very high temperature and as
a consequence, the stacks have to run at temperatures ranging from 500 to 1,000 °C.
Reduction of oxygen into oxygen ions occurs at the cathode. These ions can then
diffuse through the solid oxide electrolyte to the anode where they can
electrochemically oxidize the fuel. In this reaction, a water byproduct is given off as
well as two electrons. These electrons then flow through an external circuit where
they can do work. The cycle then repeats as those electrons enter the cathode
material again.
Advantages of this class of fuel cells include high combined heat and power efficiency,
long-term stability, fuel flexibility, low emissions, and relatively low cost.
The largest disadvantage is the high operating temperature which results in longer
start-up times and mechanical and chemical compatibility issues
Molten carbonate fuel cell
Molten carbonate fuel cells use lithium potassium carbonate salt as an electrolyte, and this salt liquefies at high temperatures,
allowing for the movement of charge within the cell – in this case, negative carbonate ions
Like SOFCs, MCFCs are capable of converting fossil fuel to a hydrogen-rich gas in the
anode, eliminating the need to produce hydrogen externally. The reforming process
creates CO 2 emissions. MCFC-compatible fuels include natural gas, biogas and gas
produced from coal. The hydrogen in the gas reacts with carbonate ions from the
electrolyte to produce water, carbon dioxide, electrons and small amounts of other
chemicals. The electrons travel through an external circuit creating electricity and return to
the cathode. There, oxygen from the air and carbon dioxide recycled from the anode react
with the electrons to form carbonate ions that replenish the electrolyte, completing the
circuit
MCFCs hold several advantages over other fuel cell technologies, including their resistance to impurities. They are not prone
to "carbon coking", which refers to carbon build-up on the anode that results in reduced performance by slowing down the
internal fuel reforming process. Therefore, carbon-rich fuels like gases made from coal are compatible with the system. MCFCs
also have relatively high efficiencies. They can reach a fuel-to-electricity efficiency of 50%, considerably higher than the
37–42% efficiency of a phosphoric acid fuel cell plant. Efficiencies can be as high as 65% when the fuel cell is paired with a
turbine, and 85% if heat is captured and used in a combined heat and power (CHP) system
As with SOFCs, MCFC disadvantages include slow start-up times because of their high operating temperature. This makes
MCFC systems not suitable for mobile applications, and this technology will most likely be used for stationary fuel cell
purposes. The main challenge of MCFC technology is the cells' short life span. The high-temperature and carbonate electrolyte
lead to corrosion of the anode and cathode

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Course instructor: Srijan Sengupta (8420424711)

Teaching assistant: Ankit Dev Singh (9680895770)

Kindly form a WhatsApp group of the same name (Energy Materials-2022)

Class code: qjbibvp

Relative grading; 90 and above = A*;

Energy materials/ materials Materials for

3. HANDBOOK OF BATTERIES; David Linden, Thomas B. Reddy

• A consized course, merely an overview in a nutshell

Energy conversion Not using for the

Heat Heat Exhaust gases to

Heat Mechanical Steam turbine,

Chemical Mechanical Combustion

Mechanical Electrical Generator

Heat Electrical Thermoelectric

Chemical Electrical Fuel cells, Primary

1. Electrical energy storage: capacitor, supercapacitor

1. Solar energy harvesting (light & heat)

a. Conventional: solar cell - battery combination

2. Wind energy Demand of heat: simply exchange – geyser, immersion heater

Demand of mechanical work: simply exchange – motor, fan, drill

2 Challenges/ Competition faced by EV with emphasis to Indian market

6 Supercapacitors as standalone energy sources

9 Aqueous lithium ion batteries

12 Thermoelectric & piezoelectric materials

13 Human powered vehicles

14 Carbon nanomaterials for energy conversion and storage

This effect later became the

1. Electricity could move

Stephen Grey Silk dyer, Marchant Conductors and insulators,

Benjamin Franklin Businessman Businessman, use knowledge of

Permittivity is a measure of the

Dielectric constant is the ratio of permittivity Q

SrTiO3, LiNbO3, PbTiO3 PbZr/TiO3, BaTiO3, PbTiO3, LiNbO3

Electrical breakdown or dielectric breakdown is a process that occurs when an electrical

Permittivity is a measure of the

Dielectric constant is the ratio of permittivity Q

Electrical breakdown or dielectric breakdown is a process that occurs when an electrical

SrTiO3, LiNbO3, PbTiO3 PbZr/TiO3, BaTiO3, PbTiO3, LiNbO3

Materials property Increase capacitance Geometry

Choose materials with high Decrease the gap

• Capacitance change with time is known as

• The dielectric is made from finely powered materials.

Price = 1.18 INR/0.0022 µF

It is not difficult to move from the parallel-plate model to

The dielectric material is sandwiched between two pieces

Metal foil thickness – 25 micron

As the various synthetic plastic materials particularly the

Another advantage resulting from the metallizing technique. The

Thickness – 25/100 = 0.25 µm

But how is it possible?

more mass is added

Why borax electrolyte is used?

Electrolytic capacitors are polarized components due to their asymmetrical

• an aluminum foil ribbon, on the surface of which a thin film of

The presence of impurities (principally copper, silicon,

• Particles of other metals do not form an oxide barrier

• form galvanic couples with aluminum and will produce

• reduce the efficiency of the oxide-layer barrier and

15(2.4/3.75) x = 275 + 0.0192 * x

15(2.4/3.75) x = 275 + 0.0672 * x

Cost of replacing 100 AA cells = 10015(2.4/3.75) = 960 INR

15(2.4/3.75) x = 275 + 0.0672 * x

Cost of replacing 100 AA cells = 10015(2.4/3.75) = 960 INR