General Introduction on Lithium Batteries

General Introduction on Lithium Batteries

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Description: Batteries:- devices that transform chemical energy into electricity. Electrochemical Cell: Batteries consist of electrochemical cells that are electrically connected An electrochemical cell comprises 1. a negative electrode to which anions (negatively charged ions) migrate, i.e.

the anode - donates electrons to the external circuit as the cell discharges; 2. a positive electrode to which cations (positively charged ions) migrate, i.e. the cathode.

3. electrolyte solution containing dissociated salts, which enable ion transfer between the two electrodes, providing a mechanism for a charge to flow between positive and negative electrodes; 4. a separator which electrically isolates the positive and negative electrodes.

 
Author: Rodrigo Lassarote Lavall PhD  | Visits: 336 | Page Views: 700
Domain:  Green Tech Category: Battery & Fuel Cell 
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Contents:
Università degli Studi di Pavia
Dipartimento di Chimica Fisica “M. Rolla”

General introduction on lithium
batteries

Dr. Rodrigo Lassarote Lavall
(pos-doc)

Advisor: Prof. Piercarlo Mustarelli
1

General introduction on lithium
batteries

Battery: definition
Some historical aspects
Batteries types
Lithium batteries
Research activity in lithium batteries

2

General introduction on lithium
batteries

Battery: definition
Some historical aspects
Batteries types
Lithium batteries
Research activity in lithium batteries

3

Batteries
Definition: devices that transform chemical energy into electricity
Every battery has two terminals: the
positive cathode (+) and the negative
anode (-)
Functioning
Device switched on
electrons produced

chemical reaction started
electrons travel from (-) to (+)

electrical work is produced
Source:http://chemistry.hull.ac.uk/lectures/mgf/Lithium-Ion%20Batteries.ppt#256,1,Lithium-Ion Batteries

4

Electrochemical Cell
Batteries consist of electrochemical cells that are electrically connected
An electrochemical cell comprises:
1. a negative electrode to which anions (negativelycharged ions) migrate, i.e. the anode - donates
electrons to the external circuit as the cell
discharges;
2. a positive electrode to which cations (positivelycharged ions) migrate, i.e. the cathode.
3. electrolyte solution containing dissociated salts,
which enable ion transfer between the two
electrodes, providing a mechanism for charge to
flow between positive and negative electrodes;
4. a separator which electrically isolates the
positive and negative electrodes.
Source:http://chemistry.hull.ac.uk/lectures/mgf/Lithium-Ion%20Batteries.ppt#256,1,Lithium-Ion Batteries

5

General introduction on lithium
batteries

Battery: definition
Some historical aspects
Batteries types
Lithium batteries
Research activity in lithium batteries

6

Battery History

1800

Jungner

7
Source:www.physics.nus.edu.sg/solidstateionics/LIB%20JULY2008.ppt

Battery History
The modern battery was developed by
Alessandro Volta in 1800.
Ingredients: Zinc, Saltwater paper, and Silver
An electrochemical reaction.
The “Voltaic Pile”

8
Source:http://www.kentlaw.iit.edu/faculty/fbosselman/classes/Spring2008/PowerPoints/BryanLamble.ppt

Battery History
Shortly after Volta Leclanche´ introduced the
zinc–carbon cell;
1859: Gaston Plante´ the lead-acid battery;
1899 by Waldemar Jungner with the nickel–
cadmium battery.

9

General introduction on lithium
batteries

Battery: definition
Some historical aspects
Batteries types
Lithium batteries
Research activity in lithium batteries

10

Primary vs. Secondary Batteries
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.
11
Source:http://www.kentlaw.iit.edu/faculty/fbosselman/classes/Spring2008/PowerPoints/BryanLamble.ppt

Standard Modern Batteries
Zinc-Carbon: used in all inexpensive AA, C and D dryCarbon
cell batteries. The electrodes are zinc and carbon, with an
acidic paste between them that serves as the electrolyte.
(disposable);
Alkaline: used in common Duracell and Energizer
Alkaline
batteries, the electrodes are zinc and manganese-oxide,
with an alkaline electrolyte. (disposable);
Lead-Acid: used in cars, the electrodes are lead and leadAcid
oxide, with an acidic electrolyte. (rechargeable).
12

Battery types (cont’d)
Nickel-cadmium: (NiCd)
cadmium
rechargeable,
“memory effect”
Nickel-metal hydride: (NiMH)
hydride
rechargeable
“memory effect” (less susceptible than NiCd)
Lithium-Ion: (Li-Ion)
Ion
rechargeable
no “memory effect”

13

General introduction on lithium
batteries

Battery: definition
Some historical aspects
Batteries types
Lithium batteries
Research activity in lithium batteries

14

Lithium Battery Development

Pioneering work for the lithium battery began in
1912 by G. N. Lewis but it was not until the early
1970’s when the first non-rechargeable lithium
batteries became commercially available.
In the 1970’s, Lithium metal was used but its
instability rendered it unsafe.

15

Schematic diagram of Li-metal battery

Lithium Battery Development
Attempts to develop rechargeable lithium batteries
followed in the eighties, but failed due to safety
problems.
The Lithium-Ion battery has a slightly lower
energy density than Lithium metal, but is much
safer. Introduced by Sony in 1991.

16
Schematic diagram of Li-ion battery

Lithium secondary battery
1972 Define the concept of chemical intercalation

Schematic diagram of Li-metal battery

Schematic diagram of Li-ion battery
17
Source:http://diamond.kist.re.kr/DLC/R&D_DB/images/battery/6.ppt#266,1,History of Lithium secondary battery;
J.-M. Tarascon and M. Armand , Nature, 414, 359, 2001.

Lithium secondary battery
1972 Define the concept of chemical intercalation

In chemistry, intercalation is the reversible inclusion of a
molecule between two other molecules. Ex: graphite intercalation
compounds.

18

Lithium secondary battery
1972 Define the concept of chemical intercalation

In chemistry, intercalation is the reversible inclusion of a
molecule (or group) between two other molecules (or groups).
Examples include DNA intercalation, graphite intercalation
compounds, etc.
Graphite intercalation compounds are complex materials where an
atom, ion, or molecule is inserted (intercalated) between the
graphite layers. In this type of compound the graphite layers
remain largely intact and the guest species are located in between
19
Figure:Space-filling model of potassium graphite KC8 (side view) from: http://en.wikipedia.org/wiki/Graphite_intercalation_compound

A Li-ion battery is a electrochemical device which
converts stored chemical energy directly into
electricity.
To a large extent, the cathode material limits the
performance of current Li-ion batteries



V
Separator

+

-

Cathode
Li Li Li Li Li Li
Active material

Anode
Li Li Li Li Li Li
Graphite

Non-aqueous electrolyte



During charging an external voltage
source pulls electrons from the
cathode through an external circuit to
the anode and causes Li-ions to move
from the cathode to the anode by
transport through an liquid
electrolyte.
During discharge the processes are
reversed. Li-ions move from the
anode to the cathode through the
electrolyte while electrons flow
through the external circuit from the
anode to the cathode and produce
power.
20

Source:http://www.math.wpi.edu/MPI2008/TIAX/MPI-web.ppt#256,1,Modeling battery electrode properties

Principle of Operation

Discharging

Charging
Co3+

Co4+

Co4+

Co3+

LiCoO2
21
Source: www.physics.nus.edu.sg/solidstateionics/LIB%20JULY2008.ppt

Cathode Current Collector

More details on the transport of Li-ions.

• Both the anode and cathode are made from a collection of
powder particles which are bonded together into a
3-D
porous body (electrode).
• During discharge, ion transport in the electrode occurs as
follows (green line)
1. Li-ion starts in the bulk of a anode particle.
2. It undergoes solid state diffusion in the particle.
3. At the surface it disassociates from the e- and enters the
electrolyte which occupies the pores of the electrode.
4. The ion is transported through the electrolyte (liquid phase
diffusion) to the cathode.
5. In enters the cathode.
6. It undergoes solid state diffusion in the cathode.
• At the same time, the electron must pass through the collection
of solid particles to a metal current collector where it can be
extracted from the cell and used to power a device (red line). It
can not travel in the electrolyte.

6
5
4
4

Electrolyte

4
3
1
2

22

Anode Current Collector
Source:http://www.math.wpi.edu/MPI2008/TIAX/MPI-web.ppt#256,1,Modeling battery electrode properties

Key Battery Attributes

Energy Density: Total amount of energy that can be stored per unit mass or
volume. How long will your laptop run before it must be recharged?
Power Density: Maximum rate of energy discharge per unit mass or volume. Low
power: laptop, i-pod. High power: power tools.
Safety: At high temperatures, certain battery components will breakdown and can
undergo exothermic reactions.
Life: Stability of energy density and power density with repeated cycling is needed
for the long life required in many applications.
Cost: Must compete with other energy storage technologies.
23
Source: http://www.math.wpi.edu/MPI2008/TIAX/MPI-web.ppt#256,1,Modeling battery electrode properties

Advantages of Using
Li-Ion Batteries
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 SELF-LIFE – only 5% discharge loss per
month.
10% for NiMH, 20% for NiCd
Source: http://www.kentlaw.iit.edu/faculty/fbosselman/classes/Spring2008/PowerPoints/BryanLamble.ppt

24

Comparison of the different battery technologies in
terms of volumetric and gravimetric energy density.

25
Source: J.-M. Tarascon and M. Armand , Nature, 414, 359, 2001.

Lithium Battery Evolution

26
Source: Scrosati, B. Journal of Power Sources 116 (2003) 4–7

Cathode Materials Challenges:
The most desirable cathode materials are strong
oxidizing agents that can react with and
decompose organic electrolytes;
In extreme cases, problems with internal shorts or
improper voltages can trigger exothermic
reactions, leading to thermal runaway and
catastrophic failure.

27

Source:http://ecow.engr.wisc.edu/cgi-bin/getbig/interegr/160/johnmurphy/3lectureno/archivedle/lecture15_walz.ppt#299,1,Energy Storage, Lithium
Ion Batteries, and Electric Vehicles

Electrolyte Challenges:

Liquid electrolyte
Problems : leakage, sealing, non-flexibility of the
cells, side reactions with charged electrodes;

Explosions
28
Source: www.physics.nus.edu.sg/solidstateionics/LIB%20JULY2008.ppt

Outcome Of Catastrophic Battery
Failure

29
Source: http://www.ostp.gov/galleries/PCAST/zinc_matrix.ppt#295,1,Advanced Battery Technology

May 29, 2006
8:28 am US/central
By David Schechter

30

Source:http://ecow.engr.wisc.edu/cgi-bin/getbig/interegr/160/johnmurphy/3lectureno/archivedle/lecture15_walz.ppt#299,1,Energy Storage, Lithium
Ion Batteries, and Electric Vehicles

None of the existing electrode materials alone can
deliver all the required performance characteristics
including high capacity, higher operating voltage, long
cycle life and safety.

RESEARCH AND DEVELOPMENT
31
Source: modified from http://www.kentlaw.iit.edu/faculty/fbosselman/classes/Spring2008/PowerPoints/BryanLamble.ppt

General introduction on lithium
batteries

Battery: definition
Some historical aspects
Batteries types
Lithium batteries
Research activity in lithium batteries

32

Active materials for
rechargeable Li-based cells

33
Source: J.-M. Tarascon and M. Armand , Nature, 414, 359, 2001.

LiFePO4 active material
for lithium batteries
Potentially low cost and plentiful elements;
Environmentally benign;
Theoretical capacity = 170 mAh/g
Different synthetic methods: sol-gel, solid state, hydrothermal...

34
Source: M. Stanley Whittingham. Chemical Reviews, 104 (2004) 4271-4301; R. Dominko,et al. Journal of The Electrochemical Society, 152
(2005) A607-A610; Bo Jin et al. J Solid State Electrochem (2008) 12:1549–1554.

Influence of the synthesis temperature and purity

35
Source: Modified from F. Gao et al. / Electrochimica Acta 53 (2007) 1939–1944

36
Source:Zhihui Xu et al. Materials Chemistry and Physics 105 (2007) 80–85

Influence of the carbon coating

37
Source: S.J. Kwon et al. / Journal of Power Sources 137 (2004) 93–99

38
Source: F. Gao et al. / Electrochimica Acta 53 (2007) 1939–1944

Influence of the amount of carbon

39
Source: M. M. Doeff et al. Journal of Power Sources 163 (2006) 180–184

40
Source: F. Gao et al. / Electrochimica Acta 53 (2007) 1939–1944

Influence of the type of carbon

Source: modified from F. Sauvage et al. Solid
State Ionics 176 (2005) 1869 – 1876

Micro-Raman spectra of a carbon-coated LiFePO4 powder.

Source:M. M. Doeff et al. Electrochemical and
Solid-State Letters, 6 (2003)A207-A209.

41

Influence of the cathode thickness

Cathode Composition (weight%)
70-80% LiFePO4
10-20% Carbon (carbon black or graphite)
5-10% PVDF
42
Source: Journal of The Electrochemical Society, 153 (2006) A835-A839.

Electrolytes
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

43
Source: www.physics.nus.edu.sg/solidstateionics/LIB%20JULY2008.ppt

Electrolytes
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
Source: Scrosati, B. Journal of Power Sources 116 (2003) 4–7

4 types of non-aqueous electrolytes in use:
organic liquid, gel, polymer and ceramic-solid
electrolytes.
44
Source: www.physics.nus.edu.sg/solidstateionics/LIB%20JULY2008.ppt

Polymer Electrolytes

A salt (LiPF6, LiClO4, etc.) dissolved in a high-molecular-weight
polymer matrix (should contain a heteroatom): Poly(ethylene
oxide) PEO
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
45
polymer chains -> ionic conductivity of the electrolyte.
Source: www.physics.nus.edu.sg/solidstateionics/LIB%20JULY2008.ppt

Solid polymer electrolytes: advantages to liquid
electrolytes
High reversibility of the processes (high electrochemical
stability);
Solid => no risk of leakage of electrolyte;
Can be used in a wider range of temperature;
Lightweight
High Flexibility
Possibility of miniaturization.

46

.

Problems: low conductivities at or below room
temperature (10-8 a 10-5 S/cm)

1) Preparation of crosslinked polymer networks,
random, block or comb-like copolymers, withshort
chains of ethylene oxide, in order to minimize
crystallization;
47
Source:E. Quartarone et al. / Solid State Ionics 110 (1998) 1 –14

2)

Utilization of doping salts which form low
temperature eutectics with pristine PEO phase
(plasticizing salts): ex: LiN(CF3SO2)n(n = 2–5);

3) Utilization of organic plasticizers to increase the
flexibility of the host polymer chains;
4) The addition of inorganic and/or organic additives,
with the aim of reducing the crystallizing ability of
the polyether host without reducing the mechanical
properties of the system.
48
Source:E. Quartarone et al. / Solid State Ionics 110 (1998) 1 –14

More recently: gel electrolytes: polymer
matrix are solvated by a large amount of
the trapped solvent;
Polymer acts like a support;
high value of conductivity at room temperature (10–2–10–4
S/cm),
ionic liquid
research activity.

49
Source:T. Yamamoto et al. / Journal of Power Sources 174 (2007) 1036–1040

LIB Technology

Different configurations : a) cylindrical b) coin c) prismatic d) thin and
flat (pLiON).
50
Source: J.-M. Tarascon and M. Armand , Nature, 414, 359, 2001.

51