The Role of Carbon in Lithium Ion Batteries

© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe

Dr. Emma Kendrick

Sharp Laboratories Europe

The Role of Carbon in Lithium Ion

Batteries

© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe

Sharp Laboratories of Europe

Established: February 1990

Location:

Oxford Science Park, U.K.

Patents Filed >500

Work at SLE has two aims:

To carry out research where SLE has special expertise

Displays, Devices, Health, Energy, Solar, Software, Lighting

To help Sharp businesses develop products for Europe

(Displays for mobile phones and automotive, Camera

modules, Solar Systems, Lighting Systems)

Slide 2

London

Oxford


Sharp Laboratories of Europe (SLE)

Slide 3

Software & services:

- e-learning, mobile

services

Display user interface:

- Image processing

- Hardware components

LCD modules:

- Integrated electronics

Mobile phones:

-- Novel functions

Displays

Energy – HEMS, storage,

local fit & standards,

novel technology

Healthcare – Point of care devices,

Soft health

Health and Energy Technology Group

LED lighting:

- Luminaire design

Electronic

components:

LEDs, laser diodes,

Solar cells:

- High efficiency cells

Advanced Optical Devices Group

Information tech. European Design Centre Technical support for EU

business

-- Mobile phones,

cameras, solar


Contents

Energy Storage Markets

3C

Automotive

Stationary

Energy Storage Requirements

Lithium Ion Batteries

Electrode Development

Graphite in Lithium ion Batteries

Slide 4



Slide 5

Automotive

Appliances / DIY Stationary Storage

Starter Batteries

HEV/PHEV

BEV

Power Tools

Mobile Phone

Lap-top

Digital Cameras

UPS

Ancillary Grid Services

Portable (3C markets)

Appliances / DIY Stationary Storage


※ The figures for the scale of the automotive market were estimated in 2011 from the company production plan and from 2012 estimated by Nomura Research Institute.

(March 2010)

※ PC, mobile market scale figures estimated from Nomura report (Dec. 2010)

※ Provisional calculation of storage cell requirements for PV installations as storage cells: 3kWh to PV 1kW.

Global Energy Storage Market Size

Slide 6

£15B

£41.7B


Portable Devices (3C) – CY 2011

Slide 7

Takeshita tutorial 2011 - THE 28th INTERNATIONAL

BATTERY SEMINAR & EXHIBIT


Electric Vehicles

Slide 8

Takeshita tutorial 2011 - THE 28th INTERNATIONAL BATTERY SEMINAR & EXHIBIT

Modified for % EV-type (Takeshita 2009-10)


Stationary Energy Storage

Slide 9

Electricity Generation

Power Stations

Industrial

Commercial

Domestic

Off-Grid

Slide 9

Off- Grid

400kV

400kV

275kV

11 - 33kV

230V

230V 132kV

Renewable Power Generation

Community / District

Home

Industrial


Residential Energy Storage (Europe)

Slide 10

Frost and Sullivan (2011) SLE commissioned market study


European Domestic - Residential

Slide 11

SHARP Europe : Market evaluation: PV-CHP-storage installations in Europe

© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Slide 12

Power and Discharge Time

Energy Storage technologies

Bulk Power

Management

T&D Grid Support Load

Shifting UPS Power Quality

Li-ion Battery

Pumped Hydro

Flow Batteries Zn-Cl, Zn-Air, Zn-Br

VRB PSB New Chemistries

NaS Battery

NaNiCl2 Battery

Advanced Lead Acid

SMES High Power super capacitors

High Power Fly wheels

Nickel Metal Hydride

Nickel Cadmium

Lead Acid Battery

High Energy

Supercapacitors

Compressed Air ES

1kW 10kW 100kW 1MW 10MW 100MW 1GW

System Power Rating and Module Size

Dis

ch

arg

e T

ime

at

Ra

ted

Po

we

r

Se

co

nd

s

M

inu

tes

H

ou

rs

SMES : superconducting magnetic energy storage


Battery Property Requirements

Slide 13


Battery Requirement Considerations

Low cost

High energy density

Safe

Good rate capabilities

Good cyclability

Low toxicity

Recyclable

14

Competitive in battery market

Long time between recharges

No overheating, or explosions

Fast charge and discharge times

Long battery life

Safer, cheaper disposal

Environmentally friendly


Lithium Ion Batteries

Slide 15


Li-ion Cell - Discharging

16

Copper

Current

Collector

Aluminium

Current

Collector

2Li0.5CoO2 + Li+ + e- 2 LiCoO2

C6Li C6 + Li+ + e-

Electrolyte

+

+

+

+

+ -

-

-

-

Graphite

(C6)

-

Discharging

The anode

Electrons flow out of anode

[oxidation – loss of electrons]

The cathode

Electrons flow into cathode

[Reduction – gain of electrons] -

+ Li

e-

Co4+ + e- Co3+ C6- C6 + e-

LiCoO2

Cathode

LiCoO2

Anode

Graphite (C6)


Main Property Considerations

Energy and Power Density

Cost

Safety

Slide 17

© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Slide 18

Energy Density

Cathode

Anode

141 mAh/g

3.8 V

3.7 V 141 Ah/kg = 512 Wh/kg


Cost

19

Metal prices

• Co unstable price

• Co/Ni most expensive

• Fe and Mn significantly lower cost


Cost

Material cost analysis : 18650 (Standard cylindrical cell)

LiCoO2 vs Graphite

20

LCO $30/Kg - 2006 LCO $70/Kg - 2008

Current Price - $30/Kg Takeshita Tutorial 2009 – Market Update on NiMH, Li Ion & Polymer Batteries


Safety

Safety Tests

Over charge

Short circuit

Hot box - 130°C

Nail penetration

Crush

Over charge test

LiCoO2 vs Graphite

18650.


Cathode Safety

22

LiMn2O4 LiCoO2 LiNiO2 LiFePO4

• MO2 high heat evolution – Nickel oxides highest risk

– LiMn2O4, framework

– LiFePO4 – polyanion system

SEI Layer

LiMO2

Electrolyte (flammable)

Separator (Shutdown) Overcharge: LiCoO2Li0.5CoO2Co2O3+Li2O+O2+heat

SEI breakdown ~150 C: LiC6+LiPF6+SolventCO2+heat

Ni>Co>Mn

Anode - Graphite


Li-ion Cell Manufacture

Electrode Construction

Cell Construction

Active Materials

Conducting Additives

Slide 23


Li-ion Cell Construction

Slide 24

Cathode:

– Aluminium current collector

– Double-sided composite:

LiCoO2/carbon/PVDF

Anode

– Copper current collector

– Double-sided composite:

Graphite/carbon/PVDF

Separator (porous PE)

Electrolyte

– Salt (LiPF6) + solvent

Separator

Aluminium Tag (cathode)

Nickel Tag (anode)

Laminated Pouch


Electrode Manufacture

Slide 25

Composite Mix Coating Drying

Active Material

Binder Solution

Conductive Additive

Pump / Hopper


Composite Cathodes

Slide 26

Timcal SuperP

http://www.azonano.com/article.aspx?Articl

eID=2315

Carbon Black

Carbon Fibres

Composite Cathode

Active Cathode Material


Effect of Formulation

Composition ratio 1 2 3 4 5

NCA [wt. %] 84 84 84 84 84

Super P [wt. %] 0 2 4 6 8

SFG6 [wt. %] 8 6 4 2 0

PVdF [wt. %] 8 8 8 8 8

Slide 27

Table 3. Composite slurries with different content of conductive agents.

Improve Electronic conductivity of electrode

Increase porosity

Optimise Performance

Capacity and Rate

Improve Life time

Influence of Electrode Preparation on the Electrochemical Performance of

LiNi0.8Co0.15Al0.05O2 Composite Electrodes for Lithium-Ion Batteries l

Journal of Power Sources, In Press, Available online 21 March 2012, H.Tran, G.

Greco, C. Täubert, M. Wohlfahrt-Mehrens, W. Haselrieder, A. Kwade

http://www.sciencedirect.com/science/article/pii/S0378775312006167?v=s5














Summary of Electrode Properties

3-D electronic conductivity

3-D ionic conductivity

Porosity

Gravimetric and Volumetric Energy Densities

Adhesion to Current Collector

Slide 28

Considerations during Formulation Optimisation


Graphite Anode in Batteries

Slide 29


Graphite

Slide 30

Edge

Plane

Basal

Plane

Current collector

Schematic of Graphite and lithiated graphite, (b) graphite article schematic showing basal planes and edge planes

Li+

Li+


Graphite Types

Slide 31

[i] W.-H. Zhang et al. / Journal of Power Sources 174 (2007) 766–769 [ii] http://www.timcal.com/scopi/group/timcal/timcal.nsf/pagesref/MCOA-7S6K2K/$File/Brochure_Carbon_Powders_for_Lithium_Battery_Systems.pdf [iii] Fig. 2. FE-SEM images of the carbon samples: (a) MCMB Hyun D. Yoo, Yuwon Park, Ji Heon Ryu, Seung M. Oh, Electrochemical activation behaviors studied with graphitic carbon electrodes of

different interlayer distance, Electrochimica Acta, Volume 56, Issue 27, 30 November 2011, Pages 9931-9936, ISSN 0013-4686, 10.1016/j.electacta.2011.08.117. [iv] Y. Chang, H. Sohn, C. Ku, Y. Wang, Y. Korai, I. Mochida, Anodic performances of mesocarbon microbeads (MCMB) prepared from synthetic naphthalene isotropic pitch, Carbon, 37, Issue 8, 1

January 1999, Pages 1285-1297, ISSN 0008-6223, 10.1016/S0008-6223(98)00325-X.

Flake graphite

Spherical Graphite

Surface modified Spherical Graphite

Spherical or Potato shaped Graphite

Artificial Graphite

MCMB

Natural Graphite

http://www.timcal.com/scopi/group/timcal/timcal.nsf/pagesref/MCOA-7S6K2K/$File/Brochure_Carbon_Powders_for_Lithium_Battery_Systems.pdf





Summary


Lithium ion battery manufacture

Electrode Properties

Graphite in Lithium ion batteries

Slide 32


SPARE SLIDES

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Cylindrical Cell

Slide 34

18650 cell construction

Cylindrical Cell


Supercapacitors

http://electronicdesign.com/article/components/carbon-foam-whips-up-greater-power-density-for-sup

Slide 35

Activated Carbon – High Surface areas

Carbon Aero gels – no binder required (high power)

Carbon Nano-tubes – high surface area, accessable pores


Activated Carbon Electrodes

Slide 36

O. Barbieri et al. / Carbon 43 (2005) 1303–1310

Electronn Microscopy Society: 11. “MICROGRAPH OF

ACTIVATED CARBON FROM COCONUT HUSK FIBRE "

(CATEGORY : SCANNING ELECTRON MICROSCOPY) -

3RD PRIZE WINNER: JEFRI SAMIN

Activated carbon from coconut-

shell-based for supercapacitors

Journal of Power Sources, Volume

141, Issue 1, 16 February 2005,

Pages 198-203

Mukta S. Dandekar, Girish Arabale,

K. Vijayamohanan

Vulcan XC72

MM192

http://www.sciencedirect.com/science/article/pii/S0378775304009759






Li-ion Cathodes and Anodes

Slide 37


Lithium Iron Phosphate LiFePO4

Electronic conductivity lower

than those of mixed metal

oxides

Modification

Reduction in particle size

Pyrolytic carbon deposit

Improved performance

Cost

38

http://www.phostechlithium.com/prf_lifepower_e.php

Space group Pnma

a=10.329 Å, b=6.007 Å, c=4.692 Å

Yamada, A.;Yashima, M. (2009) Nippon Kessho

Gakkai-Shi 51, 175-181

PO4

F

e

Li

http://www.phostechlithium.com/index.php


Anode

Slide 39

Timcal SuperP Timcal Graphite (natural)

Zaghib et al, http://dx.doi.org/10.1016/j.jpowsour.2005.03.141,

http://dx.doi.org/10.1016/j.jpowsour.2005.03.141


Other Anodes

Materials Li C Li4Ti5O12 Si Sn

Density (g cm−3) 0.53 2.25 3.5 2.33 7.29

Lithiated phase Li LiC6 Li7Ti5O12 Li4.4Si Li4.4Sn

Theoretical specific capacity (mAh g−1) 3862 372 175 4200 994

Theoretical charge density (mAh cm−3) 2047 837 613 9786 7246

Volume change (%) 100 12 1 320 260

Potential vs. Li (∼V) 0 0.05 1.6 0.4 0.6

Volume Expansion

Composites to absorb

volume expansion

Morphology optimisation

Slide 40

Table 1. Comparison of the theoretical specific capacity, charge density, volume

change and onset potential of various anode materials.

http://dx.doi.org/10.1016/j.jpowsour.2010.07.020,

http://dx.doi.org/10.1016/j.jpowsour.2010.07.020


Commercial Composite Anodes

Sony Sn Alloy Anode

composite consisting of a graphite

phase and an amorphous alloy

alloy phase consists of mainly tin and

cobalt, with a tin:cobalt ratio of about

1:1, and small amount of titanium

where the particle size of the alloy phase

is less than 1 μm.

Slide 41

Element Weight % (ICP or C wt. loss)

C 36 : Sn 27 : Co 16 :Ti 2.42

Carbon: Alloy 36 wt. % : 46 wt. %

Carbon: Alloy 45 wt. % : 45 wt. %

1 (Sony Patent)

Chemistry and Structure of Sony’s Nexelion Li-ion Electrode Materials Jeff Wolfenstine,

Don Foster, Jeff Read and Jan Allen Army Research Laboratory Adelphi, Maryland, USA

Panasonic Silicon Alloy (2012)

4 Ah cell (previously 3.1 Ah)

Large format:

12.2 Wh (carbon anode) 13.6

Wh (silicon anode)


Hard Carbon Anodes

Higher Capacities

Synthesis Routes

Structure Optimisation

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Voltage profiles of hard carbon prepared by pyrolysis of sucrose in argon gas. Heat treatment

temperatures are indicated

Fig. 1. Plot of reversible capacity for lithium vs heat treatment temperature for a

variety of carbon samples (open symbols, hardcarbons; solid symbols, soft

carbons). These data are for the second charge–discharge cycle of lithium–carbon

test cells. The three regions of commercial relevance are shown. This graph has

been taken from the work of Dahn et al.

The Role of Carbon in Lithium Ion Batteries

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