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September 4 & 5, 2019 Nonstoichiometric Materials

This document provides an overview of lithium-ion battery technology and materials. It discusses the development of lithium-ion batteries starting from 1976 with the work of Whittingham on titanium disulphide cathode materials. It then summarizes the contributions of Goodenough regarding lithium cobalt oxide and principles of charging/discharging processes. The document outlines various cathode materials developed including lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate and their properties. It also discusses electrolytes, separators, polymer electrolytes and manufacturing processes involved in lithium-ion batteries. Finally, it briefly mentions applications of secondary batteries in areas like aircrafts, missiles and torpedoes.

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Sibasish Mishra
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32 views26 pages

September 4 & 5, 2019 Nonstoichiometric Materials

This document provides an overview of lithium-ion battery technology and materials. It discusses the development of lithium-ion batteries starting from 1976 with the work of Whittingham on titanium disulphide cathode materials. It then summarizes the contributions of Goodenough regarding lithium cobalt oxide and principles of charging/discharging processes. The document outlines various cathode materials developed including lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate and their properties. It also discusses electrolytes, separators, polymer electrolytes and manufacturing processes involved in lithium-ion batteries. Finally, it briefly mentions applications of secondary batteries in areas like aircrafts, missiles and torpedoes.

Uploaded by

Sibasish Mishra
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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CML102

September 4 & 5, 2019

Nonstoichiometric materials
Oxygen sensors

Oxygen separating membranes


Chemistry of Li-Ion Battery
Technology
Supercapacitors Unlike batteries no
chemical reaction takes place when
energy is being stored or discharged
and so supercapacitors can go through
hundreds of thousands of charging
cycles with no degradation.
Graphite Fluoride

Li+
Graphite Fluoride (CFn) structure

Li + (CF)n → Lix(CF)n → C + LiF


Watanabe, N.; Fukuba, M. U.S. Patent
3,536,532, 1970 (Matsuchita, Japan)

CFn
Electrolyte Lithium Metal
Titanium disulphide (TiS2 )

Birth of Reversible Li-ion


Batteries - M.S. Whittingham
(1976)
Titanium disulphide (TiS2 ) structure

E.m.f =2.5 V

Intercalation of Li into TiS2 cathode. The process involves swelling of one crystal axis and charge
transfer from Li to Ti.
Principles of
charging/discharging
processes in a Li-ion
cell
John B. Goodenough

Go thru the article. https://eic.rsc.org/feature/battery-power/2020096.article


Lithium cobalt(III) oxide

Structure of Lithium cobalt oxide (LiCoO2)


J. B. Goodenough (1980,
Oxford)
https://www.revolvy.c
om/main/index.php?s
=John+B.+Goodenoug
E.m.f = 4.0 V
h&stype=videos
Half-reactions
The positive electrode:
Charging

Discharging

The negative electrode :

JBG et al. 1985


Materials system contrast in commercial cells

Items LiFePO4 LiMn2O4 LiMnNiO2 LiCoO2

Gram Capacity(mAh/g) 130-140 90-110 135-145 140

Nominal Voltage(V) 3.2 3.7 3.7 3.7

Cycle Performance ≥2000 ≥500 ≥500 500- 750

Temperature -20°C - 75°C -40°C - 40°C -40°C - 45°C

Discharge Rate Good Ordinary Excellent Ordinary

Raw Material Cost Normal Low Normal Expensive

Environment Effect Friendly Friendly Friendly Toxic

Safety Performance Excellent Good Good Explosion hazard


JBG – Systematic chemical tuning of LiMO2
JBG’s Energy Level Diagrams

LiFexPO4
Large scale synthesis of active materials

• Single phase formation


• High purity
• Particle size (preferably nanoscale)
Electrolyte
Operating temperature : -30ºc to 55ºc
Voltage range : 2.5 V to 5 V
Specific conductivity : >10-2 S cm-2
Liquid Electrolytes
Solvents : Propylene Carbonate (PC),Ethylene Carbonate (EC),
Dimethyl Carbonate (DMC), ‫ץ‬-Butyrolactone
(GBL)
Salts : Li salts containing anions such as ClO4-, BF4-, PF6-,
AsF6- and (SO2CF3)3-, SO2 CF3- and N (SO2 CF3)2-
New salts : Lithium Bisoxalatoborate (LiBOB)

Separators
 Polyolefin materials (PE/ PP)
Polymer Electrolytes
 PEO –low ionic conductivity
 Polymer membrane/ Halogenated copolymers like Polyvinylene
difluoride, Hexafluoro propylene (PVDF, HFP) absorb the
electrolyte making them immobilized gel (Gel Polymer)
 New approaches: Adding nanoparticles into polymer
(Nanocomposite) etc.
Cylindrical cell Ellipso Prismatic cell Prismatic cell Pouch cell
Expanded view of internal construction of cells
Li- ion cell electrode manufacturing facility
SECONDARY SILVER ZINC BATTERIES

FIGHTER AIRCRAFT
Ag- Zn primary batteries (1/2 the turn over of the company)

TORPEDO

 Shelf life improved from 3.5 years to 7 years


MISSILES
Ni/ Cd BATTERIES FOR FIGHTER AIRCRAFTS

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