© 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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Contents
Energy Storage Markets
3C
Automotive
Stationary
Energy Storage Requirements
Lithium Ion Batteries
Electrode Development
Graphite in Lithium ion Batteries
Slide 4
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Energy Storage Markets
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
※ 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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Portable Devices (3C) – CY 2011
Slide 7
Takeshita tutorial 2011 - THE 28th INTERNATIONAL
BATTERY SEMINAR & EXHIBIT
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Electric Vehicles
Slide 8
Takeshita tutorial 2011 - THE 28th INTERNATIONAL BATTERY SEMINAR & EXHIBIT
Modified for % EV-type (Takeshita 2009-10)
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Residential Energy Storage (Europe)
Slide 10
Frost and Sullivan (2011) SLE commissioned market study
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe
Battery Property Requirements
Slide 13
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe
Lithium Ion Batteries
Slide 15
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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)
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Cost
19
Metal prices
• Co unstable price
• Co/Ni most expensive
• Fe and Mn significantly lower cost
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Safety
Safety Tests
Over charge
Short circuit
Hot box - 130°C
Nail penetration
Crush
Page 21
Over charge test
LiCoO2 vs Graphite
18650.
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Li-ion Cell Manufacture
Electrode Construction
Cell Construction
Active Materials
Conducting Additives
Slide 23
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Electrode Manufacture
Slide 25
Composite Mix Coating Drying
Active Material
Binder Solution
Conductive Additive
Pump / Hopper
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Composite Cathodes
Slide 26
Timcal SuperP
http://www.azonano.com/article.aspx?Articl
eID=2315
Carbon Black
Carbon Fibres
Composite Cathode
Active Cathode Material
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe
Graphite Anode in Batteries
Slide 29
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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+
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Summary
Energy Storage Markets
Lithium ion battery manufacture
Electrode Properties
Graphite in Lithium ion batteries
Slide 32
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe
SPARE SLIDES
Slide 33
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Cylindrical Cell
Slide 34
18650 cell construction
Cylindrical Cell
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe
Li-ion Cathodes and Anodes
Slide 37
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Anode
Slide 39
Timcal SuperP Timcal Graphite (natural)
Zaghib et al, http://dx.doi.org/10.1016/j.jpowsour.2005.03.141,
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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,
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
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)
© 2011 | Health and Energy Technology Group | Sharp Laboratories of Europe Health and Energy Technology Group | Sharp Laboratories of Europe
Hard Carbon Anodes
Higher Capacities
Synthesis Routes
Structure Optimisation
Slide 42
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.
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