Dr.

Nalini G Sundaram
Materials Science Division
Plan of the Talk
1. Introduction To Battery Basics:Some Definitions

2. History of Battery Innovation

3. Types of Batteries

4. The Lithium Ion Battery

5. Current Research on Cathode, Anode and Electrolyte

Materials

6. Applications : Mobile phones, Laptops, Vehicles

7. Safety

8. Future Directions
 Battery Basics: Some Definitions
➢ Battery: A system which converts
chemical energy into electrical energy
Therefore, we can call a battery is an
electrochemical cell

➢ Electrodes are electrical conductors in the

cell where chemical reactions take place
The anode is the electrode where oxidation
takes place
The cathode is the electrode where reduction
takes place

➢ Electrolyte: the medium through which

ions are transported between the two
electrodes, to allow internal current flow.
Generally either a liquid, paste or gel.

➢ Separator: A porous material to

Positive electrode
physically separate the anode and
Negative electrode
cathode to prevent shorting Electrolyte
Separator
The voltage of the whole cell is the electrical energy that it gives off, measured in
volts (V). It depend on the difference between the potential of the two redox couples
involved
The current is the rate at which electrons pass through the cell, measured in
amperes (A)

Electrochemical Capacity: The electrical charge effectively stored in a primary or

secondary battery and available for transfer during discharge. Usually expressed in
ampere-hours per gram (Ah/g) or milliampere-hours per gram (mAh/g).

Specific Energy (Wh/kg) – The nominal battery energy per unit mass, sometimes
referred to as the gravimetric energy density. Along with the energy consumption of
the vehicle, it determines the battery weight required to achieve a given electric
range.

Energy Density (Wh/L) – The nominal battery energy per unit volume, sometimes
referred to as the volumetric energy density.

Power Density (W/L) – The maximum available power per unit volume. It determines
the battery size required to achieve a given performance target.

Specific Power (W/kg) – The maximum available power per unit mass. It determines
the battery weight required to achieve a given performance target.
 “Baghdad Batteries”
◦ ~1000-2000 years ago.
◦ Terracotta jars containing a copper cylinder
separated from an iron rod by a non-conductive
stopper, and filled with an electrolyte.
◦ Debated uses: electroplating
 The Voltaic Pile
◦ Invented by Alessandro Volta in 1800
◦ Zinc and Copper with a cloth soaked in brine

 The Daniel Cell

◦ Invented in 1836 by John Daniell

 The lead-acid cell

◦ Invented in 1859 by Gaston Planté
◦ First rechargeable battery

 The zinc-carbon cell

◦ Invented in 1887 by Carl Gassner
 The Nickel-Cadmium Battery
◦ Invented in 1899 by Waldmar Jungner.

 The common Alkaline Battery

◦ Invented in 1955 by Lewis Urry

 The Nickel Metal-Hydrid Battery

◦ NiMH batteries for smaller applications started to be on the
market in 1989.

 Lithium and Lithium-ion Batteries

◦ First lithium batteries sold in the 1970s
◦ First lithium-ion batteries sold in 1991
◦ First lithium-ion polymer batteries released in 1996
 Primary Batteries – Disposable
 Secondary Batteries – Rechargeable
 emf – Electromotive force, voltage
 Ampere∙hour (Ah) = 3600 coulombs, a
measure of electric charge
 Watt ∙hour (Wh) = 3600 joules, a measure of
energy
 Ah = (Wh) / emf
Primary batteries are disposable because
their electrochemical reaction cannot be
reversed.
Secondary batteries are rechargeable,
because their electrochemical reaction
can be reversed by applying a certain
voltage to the battery in the opposite
direction of the discharge.
  Can lose 8 – 20% charge every year at room
tempurature.
 Discharge AAAperformance
AA 9V dropsC at low
D

temperatures.
Capacity 1.250
(Ah)
2.890 0.625 8.350 20.500

Voltage 1.5 1.5 9 1.5 1.5

Energy 1.875 4.275 5.625 12.525 30.75
(Wh)

Alkaline: used in common Duracell and

Energizer batteries, the electrodes are zinc
and manganese-oxide, with an alkaline
electrolyte. (disposable)
 Batteries: The Alkaline Battery
Oxidation
Zn(s) + 2 OH- (aq) → Zn(OH)2(s) + 2 e-
Reduction
2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH- (aq)
Net
Zn(s) + 2 MnO2(s) + H2O(l) → Zn(OH)2(s) + Mn2O3(s)

But – the Mn2O3 is

not sticky, and
doesn’t remain
attached to the
electrode. This
battery is not
rechargeable
 Nickel cadmium
 Nickel metal hydride
 Alkaline
 Lithium ion
 Lithium ion polymer
 Lead acid
Nickel-cadmium: (NiCd)
✓rechargeable,
✓“memory effect”

Nickel-metal hydride: (NiMH)

✓rechargeable
✓no “memory effect”

Lithium-Ion: (Li-Ion)
✓rechargeable
✓no “memory effect”
What are Batteries, Fuel Cells, and Supercapacitors, Chem Rev, 2004, 104,
4245, Martin Winter and Ralph J. Brodd
Periodic Table Symbol: Li

Atomic Weight: 3 (light!)

Like sodium and potassium, an alkali metal.

(Group 1 – #s 1 through 7)

Highly reactive, with a high energy density.

High electrochemical potential

➔➔
❖ Pioneering work for the lithium battery began in 1912 by G.
N. Lewis
❖ early 1970’s when the first non-rechargeable lithium batteries
became commercially available with lithium metal

❖ Li-metal unstable rendered it unsafe and impractical

❖ The Lithium-Ion battery has a slightly lower energy density

than Lithium metal, but is much safer.

 Dr. John Goodenough invented lithium cobalt oxide cathode

materials while at Oxford University. His technology was
used in the first commercial Li-ion battery, launched by
SONY in 1991
 Based on Intercalation Chemistry using
transition elements
Graphite (-), cobalt or manganese (+)
Nonaqueous electrolyte
 Features
+40% more capacity than NiCd
+Flat discharge (like NiCd)
+Self-discharge 50% less than NiCd
◦ Expensive
POWER – High energy density means greater
power in a smaller package.
160% greater than NiMH
220% greater than NiCd
HIGHER VOLTAGE – a strong current allows it to
power complex mechanical devices.
LONG SHELF-LIFE – only 5% discharge loss per
month.
✓10% for NiMH, 20% for NiCd
 Intercalation
In chemistry, intercalation is the reversible inclusion of a molecule
between two other molecules. Ex: graphite intercalation
compounds.
These electrodes have two key
properties:

➢open crystal structure, which

allow the insertion or extraction of
lithium ions

➢the second is the ability to

accept compensating electrons at
the same time.

Intercalation Hosts
 ❑ Layers of Lithium that
lie between slabs of
octahedra formed by Co
and O2 atoms

❑ Oxygen in CCP
arrangement. The space
group is R-3m

❑Lithium extraction from

the structure is favoured

Above 4.5 V level ie On

about removal of 0.5
First Generation Li-ion Batteries?? lithium, the oxygen layers
rearrange themselves to
give HCP of oxygen
forming CoO2
Cathode: LiCoO2
Anode: Graphite
Electrolyte:LiPF6 dissolved in a mixture of propylene
carbonate and diethyl carbonate
Separator: micro porous polyethylene or polypropylene film
 ❑ Li-ion battery system
•Electrochemical chain Electrochemical Reactions
characterized by continued
• Cathode
transport of lithium ions from a c
higher potential ( anode) to a LiCoO 2 Li1-xCoO2 + xLi+ + x e-
d
lower potential (cathode). • Anode
c
Cn + xLi+ + x e- CnLix
•Electrical energy liberated d
while discharging is equal to
• Overall
the change in lithium free
c
energy due to the transfer. LiCoO2 + Cn Li1-xCoO2 + CnLix
d

23
 Lithium-Ion Battery Discharge

Electrolyte

Charging
Discharging
Co3+ Co4
Co4+ Co3+
Cu AL
Current Current

Collector Collector

Graphite LiMO2

SEI SEI
Lithium-Ion Battery Charge

Electrolyte

Cu AL
Current Current
Collector Collector

Graphite LiMO2

SEI SEI
• During discharge Li ions are dissociated from the
anode and migrate across the electrolyte and are
inserted into the crystal structure of the host
compound of cathode.
• At the same time the compensating electrons
travel in the external circuit and are accepted by the
host to balance the reaction.
•During charging, lithium in positive electrode material
is ionized and moves from layer to layer and
inserted into the negative electrode.
• The process is completely reversible. Thus the
lithium ions pass back and forth between the
electrodes during charging and discharging.

PH 0101 Unit-5 Lecture-7 26

Disadvantanges of the LiCoO2-Graphite anode
battery: Need for Research and Development

➢Only 50% of the Li content can be taken out before

the structure collapses Lower capacity

➢ Less thermally stable because of oxygen loss at

elevated temperatures

➢Unsafe: Flammable Electrolytes

➢Expensive and toxic

➢Not affordable and not environmentally friendly

➢Low voltage for PHEV application

Requirements of a good Cathode material
❑ The material contain a readily reducible/ oxidizable ion, for
example a transition metal

❑Reacts with lithium in a reversible manner.

(a) Results in an intercalation-type reaction in which the host
structure essentially does not change as lithium is added.

❑ The material react with lithium with a high free energy of

reaction.
(a) High capacity, preferably at least one lithium per transition
metal.
(b) High voltage, preferably around 4 V (as limited by stability
of electrolyte) leading to a high-energy storage.
➢ Rapid reaction with lithium both on insertion and removal
leading to leads to high power density,

➢Must be a good electronic conductor, preferably a metal.

➢ Allows for easy addition or removal of electrons
➢(b)Allows for reaction at all contact points between the
cathode active material and the electrolyte
➢(c) Minimizes the need for inactive conductive diluents, which
take away from the overall energy density.

➢ The material be stable, i.e., not change structure or otherwise

degrade, to overdischarge and overcharge.

➢ The material be low cost.

➢ The material be environmentally benign.

1. Olivine based phosphates systems (LiMPO4 where M = Mn,
Ni) that can deliver more Li

2. Only very few groups have synthesized LiMnPO4 successfully

3. LiFePO4 Has a potential around 4.3 V; LiNiPO4: 5.5V

4. High Lithium Diffusion in LiNiPO4

5. high thermal stability because the oxygen is covalently bound

in the structure

6. Novel approaches for synthesis of nanostructured Olivines are

required to enhance both ionic and electronic conductivity.
8/5/2020 32
 FeO6 Octahedra, PO4
Tetrahdra; Li ions in the
octahedral channels in a zigzag
structures

Hydrothermal Method has been succesfully commercialized

 Influence of Crystal Structure on the Li-ion diffusivity
❖Fast diffusion of Li ions in the
1D channels of the olivine
structure:

❖LiFePO4 synthesized at low

temperature(120°C)
demonstrated almost 7% iron
occupancy on the lithium sites.

❖small electrochemical capacity

due to channels blocked by
defects, even at low current
densities

Time-resolved, synchrotron X- ❖real-time measurement confirmed

ray diffraction is a powerful tool that a significant amounts of defects
for understanding the defect present at room temperature, can be
formation or elimination process completely eliminated above 500 °C
1. Increasing Energy Density
Investigate new high voltage cathodes that can deliver all the
Li in the structure Li2MSiO4 (M= Fe,Co,Mn,Ni)

2. Thin nano-plate materials seem to offer more energy at higher

rate: 30 nm LiFePO4 nano-plates performed better than thick
material

3. Coating of cathodes with either ionically or electronically

conductive material

4. Composite electrodes improved battery performance

8/5/2020 35
 New Materials:

Crystal structures of Li2MnSiO4 showing the lowest energy paths for

lithium ion migration: (a) monoclinic structure; (b) orthorhombic
structure.

Islam M S Phil. Trans. R. Soc. A 2010;368:3255-3267

©2010 by The Royal Society

 discharge
capacity of
165 mA h/g

▪highly ordered LiFePO4/C/graphene nanocomposite has been

developed by a rapid, facile microwavehydrothermal route

▪Ensures high electronic conductivity due to the graphene

▪Intimate contact between electrolyte and electrodes due to the nano-

architecture 8/5/2020 37
Anodes
 Carbon anodes
Capacity~372 mAh/g
 Graphite – layered, low capacity, high
reversibility
 Disordered Carbon- Non-layered, high
capacity. Irreversible capacity loss
Metal coating (Ag,Zn or Sn) of anodes tried
1.Sony successfully used metal composite anode,
showed higher capacity
Inter-metallic compounds may hold the key for a safe
anode

2. Transition metal sulfides (CoS, NiS and FeS) using

conversion reaction for use as anode materials.

➢ These metal sulfides upon incorporation of Li are

expected to form metal and Li2S nano-composites
(this is a reversible reaction).

➢ show very high capacity on the order of 600 mAhr/g

8/5/2020 41
Sony developed a tin-based amorphous
anode material lithium ion storage
capacity per volume ratio increased by 50%,
which increases the overall battery capacity
by 30%.

http://www.sony.net/SonyInfo/News/Press/
200502/05-006E/index.html
 Other options
 Lithium metal nitrides
➢Pros: High capacity(~900 mAh/g), low average voltage
➢Cons: High moisture sensitivity, lack of economic
manufacturing processes

 Inter-metallics
➢Cu6Sn5 – Capacity fading
➢InSb – In (high cost), Sb (toxic)

 Oxides
➢Spinel-type oxides- Li4Ti5O12, Li4Mn5O12 and Li2Mn4O12
➢Low voltage spinels + high-voltage cathodes= intermediate
voltage Li-ion cells.
➢Do not produce metallic Li which is a safety concern in LiC6 or
metallic lithium anodes.
 Li salt dissolved in a solvent.
 LIB Operation range : 3.0-4.2 V,
Decomposition potential of H2O = 1.23 V
Aqueous electrolyte not used
 4 types of non-aqueous electrolytes in use:
liquid, gel, polymer and ceramic-solid
electrolytes.
 Liquid electrolytes
➢ Highly ionizable Li-salts - LiPF6, LiAsF6 etc
dissolved in organic carbonates - ethylene
carbonate (EC), dimethyl carbonate (DMC)
etc

➢ Organic carbonates - aprotic, polar, high K,

solvate Li salts at high concentration (>1M),
good ionic conduction.

➢ Problems : leakage, sealing, non-flexibility

of the cells, side reactions with charged
electrodes
 Solid electrolytes
➢ Crystalline or glassy matrix - Li ions move
through vacant/interstitial sites - high σionic
(~10-3 - 10-4 S/cm at 25°C)
➢ Crystalline : Nasicon framework phosphates
– LiM2(PO4)3 and perovskite-based oxides,
(Li,La)MO3 (M = Ge, Zr, Hf)
➢ Glasses : oxides or sulfides
➢ Advantages : (i) No leakage, (ii) Wide
operating temperature range (iii) Better
charge-discharge cycling profile (iv) Long
life – little self discharge.
 Polymer electrolyte

➢ A salt dissolved in a high-molecular-weight polar polymer matrix

E.g. PEO (Poly-ethylene oxide)
➢ Chemically stable – contains only C-O, C-C and C-H bonds.

➢ Cation mobility - cation-ether-oxygen co-ordination bonds,

regulation - local relaxation and segmental motion of the PEO
polymer chains -> high σionic of the electrolyte.
➢ Pros : ease of fabrication, flexibility, lightweight, leak proof
➢ Cons: low conductivities at or below room temperature
Addressed by plasticized or gel electrolytes - polymer electrolytes
with a component (solid or liquid): to enhance the ionic
conductivity.
Lithium Batteries: Applications
Lithium batteries: high
energy density (3 times
lead-acid).
Power sources of choice
for the consumer
electronics market

The application of
lithium batteries spans
beyond the electronics
market
 Panasonic CR2032 coin-type lithium-
magnesium dioxide primary battery
◦ Application: CMOS memory backup
◦ Constant discharge, ~0.1 mA
◦ Weight: 3.1g
◦ 220 mA-h capacity
Applications
 Vehicles Already on the Road
HEV PHEV FCHV

EV Their diffusion is expected

to drammatically increase in
the next few years
35000
US$ Million/CY BEV
30000 PHEV
HEV
25000
Others
20000 BT
Game
15000
MP3
10000 CAM
DSC
5000
PT
0 NBPC

03CY
04CY
05CY
06CY
07CY
08CY
09CY
10CY
11CY
12CY
13CY
14CY
15CY
16CY
17CY
18CY
Courtesy of Dr. Ahiara, Samsung Research,
52
Reference: Institute of Information Technology, Japan Yokohama, Japan
Rechargeable batteries are often
recyclable.
Oxidized Lithium is non-toxic, and can
be extracted from the battery,
neutralized, and used as feedstock for
new Li-Ion batteries.
 Lithium Batteries

Although lithium batteries are established

commercial products

further R&D is still required to

improve their performance to meet
the REP andHEV-EV requirement

Enhancement in safety, energy

density and cost are needed!
THE SAFETY ISSUE
Future Directions
R& D a long way to go before Li-ion Battery match with Gasoline

Trade-off between Power and Energy

 THE ENERGY ISSUE
Energy Density (Wh/kg) → driving range (km)

Comparison of the driving ranges for a vehicle powered by

various battery systems or a gasoline-powered
combustion engine

Middle size car (about 1,100 kg) → using presently available

lithium batteries (150 Wh/kg) → driving 250 km with a single
charge →  200 kg batteries
Enhancement of about 2-3 times in energy
density is needed!
High-Energy Battery Technologies

X 6

5
Where should we go?
Potential vs. Li/Li+

4
"4V"
Oxide
Cathodes
High capacity
3 cathodes
Li-ion
2 Intercalation Super- Battery <200kg/500km
materials Li/O2 , Li/S
1
Carbon
anodes "0V"
High capacity
0
0 250 500 750 1000 1250 1500 1750

Capacity / Ah kg-1

Courtesy of Dr. Stefano Passerini, Munster University