Ionic

Battery
They have no memory effect,
which means that you do not have
to completely discharge them
before recharging, as with some
other battery chemistries.

 Lithium-ion battery (LIB)

 Lithium-air battery
 Zinc-air battery
 Magnesium-air battery
 Aluminum-air battery
 Sodium-ion battery
 Current Energy Storage Techniques and Outlook

Significant Terms: Challenges:

 Energy Density (Volume) & Specific power Energy  Increasing demand of high energy density &
 Power density & Specific power high power density power sources
 Cycle life & Calendar life  Li-ion battery is meeting some of them like
 Safety & Cost EVs.
 Energy density of Li-ion battery is limited by the intercalation
Capacitor
Ultracapacitor chemistry of electrodes

Metal Metal Metal

Metal

Surface Storage : Capacitor & Supercapacitor

Bulk Storage: Battery (Stores lot more energy)
E= 0.5 CV2 and C=1/thickness
DMs thickness: >1000nm Electrolytes solution
Double Layer Thickness is less than 1 nm
 Lithium-Ion Battery Load
Discharger
Charger
e-
I e- I

Separator Cathode
Anode Separator Anode
Cathode

Li+ Li+ Li+ Li+

Li+ Li+ Li+ Li+

Li+ Li+ Li+ Li+ Li+

Li+ Li+ Li+ Li+ Li+ Li+
Li+
Li+ Li+ Li+ Li+
Li+ Li+ Li+ Li+

Electrolyte Electrolyte

Example: Lithium Cobalt Oxide cathode

Co is being oxidized from Co3+ to Co4+ during charging. Co is being reduced from Co4+ to Co3+ during discharge.
 Lithium-ion battery (LIB)

Who invented lithium-ion batteries??

Lithium-ion power packs were pioneered at Oxford University

in the 1970s by chemist John Goodenough and his colleagues
Phil Wiseman, Koichi Mizushima, and Phil Jones. Their
research was published in 1980 and turned into a commercial
technology by Sony, who produced the first lithium ion
batteries in the early 1990s. Around 5 billion are manufactured
every year most of them in China.

Professor
University of Texas at Austin
 Why LIB instead of general batteries?
A battery is essentially a chemical experiment happening in a small metal
canister. Connect the two ends of a battery to something like a flashlight and
chemical reactions begin: chemicals inside the battery slowly but systematically
break apart and join themselves together to make other chemicals, producing a
stream of positively charged particles called ions and negatively charged
electrons. The ions move through the battery; the electrons go through the
circuit to which the battery's connected, providing electrical energy that drives
the flashlight. The only trouble is, this chemical reaction can happen only once
and in only one direction: that's why ordinary batteries usually can't be
recharged.

Fig. Ordinary batteries, such as this zinc carbon

one, cannot be recharged because the
chemical reactions that generate the power
are not reversible.
 Lithium-ion battery (LIB)
Components

 A Positive electrode The movement of these lithium ions happens at

 A Negative electrode a fairly high voltage, so each cell produces 3.7
 A separator volts. This is much higher than the 1.5 volts
typical of a normal AA alkaline cell.
Electrolytes: Lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent,
such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate.
 5 types of LIBs based Types of LIBs
on Cathode
materials
1. Lithium-Cobalt Oxide Battery
Used mostly in handheld electronics (Cell phones, Laptops and Cameras).
Risky especially when damaged, Cobalt is scarce and expensive, Low discharge
rates, Highest energy density (110-190) Wh/kg.

LCO

Snapshot of LCO battery

 Types of LIBs
2. Lithium-Manganese Oxide Battery
Lower cost, Longer life and inherently safe, Used in Hybrid Vehicles, Cell phones,
Laptops; High discharge rates, Lower energy density (110-120) Wh/kg.

LMO

Snapshot of LMO battery

 Types of LIBs

3. Lithium-Nickel Manganese Cobalt Oxide Battery

Longer life and inherent safety, Cobalt is scarce and expensive, Less prone to heating
Used in Power tools, e-bikes and electric power trains, Lower energy density (95-130) Wh/kg

Snapshot of NMC battery

 Types of LIBs
4.Lithium-Iron Phosphate Battery
Dramatically reduces the risks of overheating and fire.
Offers much less volumetric capacity
Used in power tools and medical equipment
Longer-life and inherently safe
Lower Energy Density (95-140) Wh/kg

5.Lithium-Titanate Battery
Can operate at very low temp (-40°C)
Rapid charge and discharge
Used in Mitsubishi i-MiEV
Lower inherent voltage 2.4 V (compared to 3.7 V)
Lower energy density (30-110) Wh/kg
 How LIB works ?

As their name suggests, lithium-ion batteries are all about the movement of lithium
ions. The ions move one way when the battery charges (when it's absorbing power);
they move the opposite way when the battery discharges (when it's supplying power).

It is a soft, silvery-white alkali metal. Under standard conditions, it

is the lightest metal and the lightest solid
element.

Specific Capacity of 3861mAh/g

 How LIB works ?

Lithium-Ion Battery Charge

Electrolyte

Graphite LiMO2

SEI 12
SEI
Lithium-Ion Battery Discharge

Electrolyte

Graphite LiMO2

SEI SEI 13
 How LIB works ?

During charging, lithium ions (yellow circles) flow from the positive electrode
(red) to the negative electrode (blue) through the electrolyte (gray). Electrons
also flow from the positive electrode to the negative electrode, but take the
longer path around the outer circuit. The electrons and ions combine at the
negative electrode and deposit lithium there.

 When no more ions will flow, the battery is fully charged and ready to use.

During discharging, the ions flow back through the electrolyte from the
negative electrode to the positive electrode. Electrons flow from the negative
electrode to the positive electrode through the outer circuit, powering your
laptop. When the ions and electrons combine at the positive electrode, lithium is
deposited there.

 When all the ions have moved back, the battery is fully discharged and needs
charging up again.
 Lithium-ion battery (LIB)

How are the lithium ions (Li+)stored?

Negative Graphite electrode (blue) Positive cobalt-oxide electrode (red)

 Lithium-ion battery (LIB)
The negative graphite electrode (blue) is shown on the left, the
positive cobalt-oxide electrode (red) on the right, and the lithium
ions are represented by yellow circles. When the battery is fully
charged, all the lithium ions are stored between layers of
graphene (sheets of carbon one atom thick) in the graphite
electrode (they have all moved over to the left). In this charged-
up state, the battery is effectively a multi-layer sandwich:
graphene layers alternate with lithium ion layers. As the battery
discharges, the ions migrate from the graphite electrode to the
cobalt-oxide electrode (from left to right). When it's fully
discharged, all the lithium ions have moved over to the cobalt-
oxide electrode on the right. Once again, the lithium ions sit in
layers, in between layers of cobalt ions (red) and oxide ions
(blue). As the battery charges and discharges, the lithium ions
shunt back and forth from one electrode to the other.
 Lithium-ion battery (LIB)

Lithium ion battery advantages

There are many advantages to using a li-ion cell of battery. These li-ion battery
advantages include:

High energy density: The much greater energy density is one of the chief
advantages of a lithium ion battery or cell. With electronic equipment such as
mobile phones needing to operate longer between charges while still consuming
more power, there is always a need to batteries with a much higher energy
density. In addition to this, there are many power applications from power tools to
electric vehicles. The much higher power density offered by lithium ion batteries is
a distinct advantage.

Self-discharge: One issue with batteries and cells is that they lose their charge
over time. This self-discharge can be a major issue. One advantage of lithium ion
cells is that their rate of self-discharge is much lower than that of other
rechargeable cells such as Ni-Cad and NiMH forms.
 Lithium-ion battery (LIB)
No requirement for priming: Some rechargeable cells need to be primed when they
receive their first charge. There is no requirement for this with lithium ion cells and
batteries.

Low maintenance: One major lithium ion battery advantage is that they do not
require and maintenance to ensure their performance. Ni-Cad cells required a
periodic discharge to ensure that they did not exhibit the memory effect. As this
does not affect lithium ion cells, this process or other similar maintenance
procedures are not required.

Variety of types available: There are several types of lithium ion cell available. This
advantage of lithium ion batteries can mean that the right technology can be used
for the particular application needed. Some forms of lithium ion battery provide a
high current density and are ideal for consumer mobile electronic equipment.
Others are able to provide much higher current levels and are ideal for power tools
and electric vehicles.
 Issues of LIBs
Anode

Current collector
Active material Conducting material Binding material

Li cathode

Li cathode
Discharging
Charging

Volume expansion Volume Contraction

lose connection
lose connection

Dead weight

Fig. Issues of lithium-ion battery during charging and discharging

19
 Issues of LIBs
 Inadequate power density. The energy density (150-250 Whkg-1) is not big
enough to run the Evs for long range.

 The usable capacity is lower than theoretical capacity and diminishes with
the rate of cycling.
 Large polarization losses during charging and discharging which leads to low
energy efficient, and the cyclic life is limited due to capacity fading during
cycling

 The societal needs in the present energy scenario require the development of
inexpensive, thermally stable, and safe lithium batteries with high energy
and power densities.

Pb-acid 3000 kg
Ni-MH 1200
kg 20
 Issues of LIBs
The Li-ion battery disadvantages also include:

Protection required: lithium ion cells and batteries are not as robust as some
other rechargeable technologies. They require protection from being over
charged and discharged too far. In addition to this, they need to have the current
maintained within safe limits. Accordingly one lithium ion battery disadvantage is
that they require protection circuitry incorporated to ensure they are kept within
their safe operating limits. Fortunately with modern integrated circuit technology,
this can be relatively easily incorporated into the battery, or within the equipment
if the battery is not interchangeable.

Ageing : One of the major lithium ion battery disadvantages for consumer
electronics is that lithium ion batteries suffer from ageing. Not only is this time or
calendar dependent, but it is also dependent upon the number of charge
discharge cycles that the battery has undergone. When a typical consumer
lithium cobalt oxide, LCO battery or cell needs to be stored it should be partially
charged - around 40% to 50% and kept in a cool storage area. Storage under these
conditions will help increase the life.
 Issues of LIBs

Transportation: Another disadvantage of lithium ion batteries is that there can

be certain restrictions placed on their transportation, especially by air. Although
the batteries that could be taken in aircraft carry-on luggage are unlikely to be
affected, care should be taken not to carry any more lithium ion batteries than
are needed. Any carried separately must be protected against short circuits by
protective covers, etc.

Cost: A major lithium ion battery disadvantage is their cost. Typically they are
around 40% more costly to manufacture than Nickel cadmium cells. This is a
major factor when considering their use in mass produced consumer items
where any additional costs are a major issue.

Immature technology: Lithium ion battery technology is a developing area. This

can be a disadvantage in terms of the fact that the technology does not remain
constant. However as new lithium ion technologies are being developed all the
time, it can also be an advantage as better solutions are coming available.

More detailed in next slide

 THE COST ISSUE
Battery type Cost (US$/W)

AVERAGE PRICE PER CELL IN

2015 Lead- acid 0.15
Ni-Cd 0.95
Li-ion average
$2,45
Li-ion (C- 1.35
price LiCoO2)
Li-ion (C- 1.10
NiMH average
LiMn2O4)
$1,00
price
Ni-MH 2.00

NiCd* average
$0,75
price

0 0,5 1 1,5
2 2,5

$ per cell
Cost of lithium batteries in comparison with other
rechargeable systems

Source : The rechargeable battery market, 2005- Source :TIAX, based on MEDI data
2015, June 2006
 Applications of LIBs

Mars Exploration rover” spirit”

Koizumi taking a 10 minute spin
www.nasa.gov Eliica, Japan Speed – 90km/hr
 Fabrication of LIBs

Mechanical Hydraulic
press
grinder

Tubular
Furnace
Preparation of Composite Electrodes ( Cathode or Anode).
1. Fine powders of the active materials (LiCoO2, CaSnO3, etc) mixed
with conducting carbon (Super PMMM) and PVDF in N-methyl
pyrolidinone (NMP) solvent.
2. PVDF acts as binder that helps the thick film coating to adhere well
to the metal foil.
3. This mixture of active material : conducting carbon :PVDF in fixed
proportion ( say 70:15:15) is stirred to get the homogenous paste like
slurry.
4. The Slurry was coated on to a clean Al or Cu foil. Thick film
was
dried at 100oC in an air.

Thick film coater Furnace

 5. Electrode was then pressed between spherical twin roller at
about 1500 KPa pressure. This ensures that the film of the composite
electrode adheres to the Al/Cu foil.
6.Electrode was cut into circular discs (16-20 mm). Thickness ~
0.05 – 0.12mm
7. Electrode- discs were dried in vacuum oven at 800C for ~ 24
hrs.
8. Electrode disc then transferred to the Glove Box.

O2 and H2O
content < 1ppm

Glove Box
 Assembly of Lithium - Ion Cell
Diameter of coin cell ( 2016) ~ 16mm and height 2.0 mm ……

Parts of Coin cell –

Cup > 16mm diameter and plastic ring, separators
( polypropylene separators; Electronically
nonconducting but solution/ion permeable) Steel
spring for close packing. Finally cell was sealed using
a press and transferred out the glove box

Micropipette Punching
Li ion - coin Cell
Machine
 Electrochemical Characterization

Galvanostatic Cycling and Potentiostatic Cycling:

Galvanostatic Mode: The output voltage of the cell is monitored at constant current.
Potentiostatic Mode: The current is monitored at a particular voltage

Multi cell analyzer

Specific Capacity of the cell :
The capacity of the electrode material in the battery depends on the
amount of Li that can be intercalated / deintercalated into the host structure.

Capacity: Number of Coulombs (Charge) in

(amperes-hours) delivered by a battery.

Specific capacity: Amount of charge delivered per unit weight of electrode active
material (Ah/g or mAh/g ).

Theoretical specific capacity of a Li – containing oxide is calculated by assuming that all the Li
per formula unit of the oxide participate in the electrochemical reaction and is given by
Specific Theoretical capacity (mAh/g) = [F × nLi) / ( M×3600)] × 1000

Where, F = Faraday’s constant( 96,500 coulombs per gm equivalent)

nLi = Number of Li per formula unit of the electrode material
M = Molecular mass of the electrode material.
Theoretical capacity calculation of LIBs

Figure: The inside of a lead-acid battery

 Electron, Ion, and Coulombic Energy

The Motion of an ion in the electrolyte or of an electron in a wire

is a transfer of definite amount of electricity.

The actual amount of electricity transported by a single electron

or a monovalent ion is very small..

1.60186 x 10-19 Coulombs

According to Faraday’s law, 1 gram equivalent of any substance is

equal to 96500 Coulombs, I.e., if the ion is monovalent the total
charge is 96500 Coulombs and if bivalent the charge is twice of this
amount.
 ELECTRON, ION AND COULOMBIC ENERGY

1 Amp : 1 Coulomb / Sec

1 Amp-Sec. : 1 Coulomb
1 Amp. Hr. : 3600 Coulomb
1 Faraday : 96490 Coulombs
96490/3600 = 26.8
Ah
i.e. for 1 electron transfer the coulombic energy is 26.8 Ah
 ELECTRON, ION AND COULOMBIC ENERGY

• Lead acid • Li-ion

For Lead Acid Battery System For Li-ion Battery System
No. of electrons transfer :2 No. of electrons transfer :1
Pos. PbO2 Molecular Wt : 239 g For a 1e- transfer, Coulombic energy
is
Neg. Pb Molecular Wt. :207
g 26.8 Ah
For a 2e- transfer, Coulombic
energy is
2 x 26.8 :
53.6
Ah
 ELECTRON, ION AND COULOMBIC ENERGY

Pb acid: Li-ion:
Pos. active material (PbO2) Pos. active material ( LiFePO4)
required to deliver 1 ampere hour required to deliver 1 ampere hour
(239/53.6) : 4.46g (157.75/26.8) :5.886g/Ah

Neg. active material (Pb) required Neg. active material (C6) required
to deliver 1 ampere hour (207/53.6) to
deliver 1 ampere hour
:3.862 g (72.060/26.8)
Electrolyte (H2SO4): 3.68 g/Ah :2.689 g
Li:6.941,Fe:55.845,P:30.974,O:63.
998
• The theoretical capacity of a material can easily be calculated
from Faraday’s 1st law of electrochemistry
• which states that 1 gram equivalent weight of a material will
deliver96487 coulombs (or 26.8 Ah).
• For LiMn2O4 the equivalent weight (M) is 180.8 g/mol, giving
a theoretical capacity of: 26.8/180.8 = 148 mAh/g

• Inthe same way, the theoretical capacity of Li2Mn2O4 can be

determined to 285 mAh/g, ifthe whole charge/discharge
range is exploited
• The thermodynamic quantity describing the change in energy as a function of changes in Li concentration in the
host matrix is the chemical potential ( µ ), defined as
µ= ƏG
Əx
where G is the Gibbs free energy and x is the number of inserted Li atoms. The change in free energy can also be
expressed as

• where n is the number of electrons in both electrode-reactions δ in the cell-reaction above), F is Faraday’s
constant, and E is the potential difference between the electrodes. By combining (1) and (2), we get the relation
between electrical and chemical energy in the system:

ΔG = -nFE = -δFE
-δFE=µc --µa

• where µc c and µa are the chemical potentials of the lithium ions in the cathode and anode, respectively.
Ampere-hour (Ah)
capacity is the total charge that can be discharged from a fully charged battery under
specified conditions.

People also use Wh (or kWh) capacity to represent a battery capacity. The rated Wh
capacity is defined as

Rated Wh Capacity = Rated Ah Capacity × Rated Battery Voltage:

Power : energy by second ,watt

W=A×V=Current × Voltage
Energy :power multiplied by time
WH=Ah × V=Capacity × Voltage
Capacity : Current × time Ah
Cathode material Discharge Theoretical True density (g Diffusivity
Voltage V vs .Li0 capacity cm-3) (cm2s-1)
(mAhg-1)

LiMnPO4 4.1 171 3.43 10-7

LiFePO4 3.4 170 3.60 10-8

LiCoPO4 4.8 167 3.70 10-9

LiNiPO4 5.1 167 3.89 10-5

Li1.07Mn1.93O4 3.9 117 4.15 ~10-10

LiAl0.05Co0.15Ni0.8O2 3.6 265 4.73 ~10-8

LiCoO2 3.6 274 5.05 ~10-8

Source Theoretical evaluation of high-energy lithium metal phosphate cathode materials in

Li-ion batteries –JPS -165(2007)887-891
 Other Cathode Materials

1. Ohzuku, T.; Brodd, R. J., J.Power Sources 2007, 174, (2), 449-456; 2. Amatucci, G. G.; Pereira, N., J. Fluorine
Chemistry 2007, 128, (4), 243-262; 3. Howard, W. F.; Spotnitz, R. M., J. Power Sources 2007, 165, (2), 887-891.

37