Lithium Ion Batteries: Going the Distance (Feb 2011)

Lithium Ion Batteries : Going the DistanceGoing the Distance

Axeon Technologies Ltd, Dr Allan Paterson 17th Feb 2011

Plan

Introduction to Axeon

Products - Automotive

Lithium Ion Cell Chemistry

Currently Available Technology

3

Future Developments?

Role of Nano-technology

R&D Projects / Collaborations

Case Study

Axeon : The CompanyAxeon : The Company

About Axeon

Axeon designs and manufactures advanced

lithium-ion battery systems for a variety of end

market applications:

Automotive (electric and hybrid vehicles)

Energy storage

Cordless power tools

5Axeon Confidential

Cordless power tools

Mobile products

Europe’s largest privately-owned independent

lithium-ion battery systems supplier,

processing over 70 million cells a year

150 professional and 300 production staff

Axeon Locations

6Axeon Confidential

Current locations:

UK, Dundee – HQ, Engineering, automotive production

UK, Birmingham – Sales and engineering office

Poland – volume production, planned automotive production

Germany – European business development, strategic purchasing

Switzerland – Small pack engineering

Italy – Sales office

US, Detroit – Sales Office

Asia - strategic purchasing

Axeon’s automotive experience

Over a million vehicle miles driven since 2007 =

Electric urban delivery vehicle: producing in volume for British manufacturer

Axeon is developing smaller lighter batteries using innovative battery technology

Designing and developing PHEV packs for JLR

7Axeon Confidential

miles driven since 2007 = 20MW of batteries shipped

Volume production; conversion

of Peugeot vehicles for the leading British vehicle converter. Range includes cars, people carriers and vans

HEV sports car: developing leading-edge technology for premium European manufacturer

Product Areas

Energy Storage

Micro-generation (~10-15KWh)

Community energy storage (25-100KWh)

Utility level (MW)

Niche solutions (e.g. hybrid ferries)

Power Tool

8Axeon Confidential

Power Tool

High volume, low cost manufacture

A-rated supplier to Bosch

Mobile Power

Solutions for applications that require advanced

electronics

Bespoke solutions

Complete solution

9Axeon Confidential

Cell sub component production and test

Cell Electroactive “Ingredients” e.g. Coatings

Cell Raw Materials/process e.g. Lithium Carbonate

Cell Assembly and test

Battery Assembly and test

Battery pre conditioning

Battery Supply Value Chain

Inform

Responsible

Support

Axeon Value Proposition

Partnership Strategy

Technology

Academic research

Cell suppliers (see next

10Axeon Confidential

slide)

Governments

Participation with

relevant industry

bodies

Our cell partnerships are key

Axeon, which is cell-agnostic, has

relationships with all major suppliers of high

capacity Lithium cells

Local staff & agents assigned to cell audit

All suppliers subject to on-site quality audits

All cells subject to in-house qualification


All cells subject to in-house qualification

Verification of supplier specifications

Environmental testing

Cycle testing

Abuse testing

Lithium Ion Cell ChemistryLithium Ion Cell Chemistry

“Rocking chair” Lithium Ion Battery


Negative Electrode Electrolyte Positive ElectrodeGraphite Li+ ions

& SeparatorLiCoO2

Issues : Expensive, Toxicity, Cycle life, Power

Research concentrated on replacing LiCoO2

LiFePO4 [LFP] / LiNi1/3Mn1/3Co1/3O2 [NCM] / Other?

LiMn2O4

Cell Chemistry - The Challenges

Future Development Requires…..

Reduce cost – materials (raw and synthesis)

Improve safety – short circuits, thermal runaway.

Cycle life – 1000s for EV, cycle life 10,000s for HEVs

Calendar life - 10 years (transport)


Calendar life - 10 years (transport)

Power Density – HEV, PHEV

Energy Density – PHEV, EV, load leveling

� Materials Chemistry Challenges

Main contender cell chemistries

Cell level

Energy

density /

Wh/kg

Cell level

Energy

density /

Wh/l

Durability

Cycle life

(100 %

DoD)

Price

$/Wh

(Estimate)

Power

C-rate

Safety

Thermal

Runaway onset

LiCoO2 170-185 450-490 500 0.31-0.46 1C 170oC

LiFePO4

EV/PHEV

90-125 130-300 2000 0.3-0.6 5C cont.

10C pulse

270oC

LiFePO4

HEV

80-108 200-240 >1000 0.8-1.2 30C cont.

50C pulse

270oC


NCM HEV 150 270-290 1500 0.5-0.58 20C cont

40C pulse

215oC

NCM EV/PHEV 155-190 330-365 1500 0.5-0.58 1C cont

5C pulse

215oC

Titanate vs

NCM / LMO

65-100 118-200 12000 1-1.7 10C cont.

20C pulse

Not susceptible

NCA 95-120→190 280 >1000 0.45-0.6 4C cont

10C pulse

200oC

Manganese

Spinel EV/PHEV

90-110→160 280 >1000 0.45-0.55 3-5C cont 255oC

Example - Lithium Iron Phosphate

LiFePO4 remains attractive for Automotive

Electrochemical Performance

Cycle Life / Power capability

Enabled by new Nano-materials

Nano-particulate agglomerates – Fast diffusion

Doped / Carbon coated to make better conductor


Safety

No oxygen release

Avoid thermal runaway

Issues

Cost / cycle life for Ultrahigh Power application

Materials Chemistry Challenge → New Advanced Battery Materials

High Power Density HEV – Future? → “Nano-Materials”

High surface area – Internal = Meso-porous materials

External = Nano-tubes/wires

Cell Chemistry - Future Developments

Nano-

rods/wires

TiO (B) C-Coated

Mesoporous LiMn2O4


Next generation nano-phosphates – Li-[Transition Metal]-Phosphates {Mn/Co/V}

Hurdles– cost, energy density

Advanced Surface coatings SiO2 , RuO2, etc

20nm

TiO2(B) C-Coated

LiMnPO4

Alternative Battery Chemistries

High Energy Density EV – Future ? →

Lithium Transition Metal Oxide CathodesE.g. Layered xLi2MnO3• (1-x)LiMO2

An electrochemically inactive (Li2M'O3) component is integrated with an

electrochemically active (LiMO2)component to provide improved structural and

electrochemical stability.

High energy density, High cell voltage, Long cycle life.

Alloys of Li with Silicon (Si) or Tin (Sn)

Nexilion, Sony Corporation (C/Sn/Co))


Nexilion, Sony Corporation (C/Sn/Co))Amorphous Alloy - Very high energy density / capacity

However very large volume expansions that need to be accommodated

Limited size/capacity cells produced commercially so far

New Improved Electrolyte - Higher operating voltages

The use of high V cathodes limited by the solvent oxidation >4.4 V vs. Li/Li+.

Requires new electrolytes → Ionic liquids show most promise.

Poor conductivity limits rate capability.

Lithium-Air Batteries – High Energy Density?

Potentially 10 x Energy Density compared to current Li-ion tech

Use of porous cathode, small % catalyst allows rechargeability

Hurdles – cycle life, rate capability.

“Battery 500” project : IBM, UC Berkeley and five US National Labs

Electric vehicle battery that gives up to 500 miles per charge

IBM believes its nano-scale semiconductor fabrication techniques can


IBM believes its nano-scale semiconductor fabrication techniques can

increase the surface area of

the lithium-air battery's

electrodes by 100 times.

⇒ achieve range goal

2 year feasibility study

Lithium-Air Schematic

Dispense with intercalation cathode use O2 from air!

Li2O2

Dis-charge

20Li anode Electrolyte Composite porous cathode

O2

charge

Li+Li+

Lithium-Air Schematic

Dispense with intercalation cathode use O2 from air!

Li2O2

Charge

21

Li+Li+

O2

Charge

Li anode Electrolyte Composite porous cathode

Li-Air – The Challenges...

Many Issues Remain :

Cyclability

Oxygen Selective Membrane , Suitable Electrolyte,

Recharge Potential / Hysteresis

Rate Capability


Electrolyte stability

How long to commercialisation....10years?

Cell Chemistry – Commercial Availability?

LiMnPO4 and LiFexMnyPO4 Na/Li3[M](PO4)2F3(M=Co,V etc)

Li4Ti5O12 Anode + Mn based Nano-titanate anode + Adv 5V Mn based

Li - Nano-silicon / Tin Alloy + high V TMO

Aerogel Li Vanadates

Li / Sulphur

LiFe-Sulphides/Silicates

Secondary Zn-Air

Secondary Li-Air

Ionic liquid Electrolyte

Conversion rxn, e.g Li/Fe3F3

Rela

tive C

ap

ab

ilit

y

23

2015-2020+?

Q42013

Q12011

Q12012

Q22012

Q32012

Q42012

Q12013

Q22013

Q32013

Q22011

Q32011

Q42011

LiFePO4

LiCoO2

LiMn2O4

LiMn1/2Ni1/2O2

LiFePO4(Doped or Coated with RuO2/TiO2. etc)

LiNi1/3Mn1/3Co1/3O2 LiwMnxNiyCozO2

LiNixCoyAlZO2

Li2MnO3•LiMn1/2Ni1/2O2 Doped Co,Al,Ti etc

Mn Based Nano+Mesoporous

Li2MnO3•LiMn1/2Ni1/2O2

Axeon 2010 Confidential

Possible current/future cell options

Short Term Medium Term Long Term

City / EV LFP / LiMn2O4

Pouch

NCM / TMO

Pouch/Can Silicon/Tin-alloy

Rechargeable

metal air

systems

Urban Delivery EV

LFP/NCM NCM / TMO

Pouch/Can

PHEV LFP/NCM

Pouch

NCM / TMO

Pouch/Can

24

Pouch Pouch/Can

PerformanceHEV

Small Format

LFP

Small Format

LFP

Advanced Nano-

Material

electrodes


R&D ProgramsR&D Programs

Relative theoretical energy densities


Dynamite = 1375 Wh/kgWood = 4000 Wh/kgPetrol = 12000 Wh/kg – highly energy inefficient

Example Axeon Development Projects

OROR


TSB Project (A)

Development roadmap programmes Consortia Status

TSB (A) - Pouch cell NCM/BMS Axeon, Allied & Ricardo Awarded

TSB (B) - TMO/Si Alloy Axeon, St Andrews University, Nexeon, Ricardo Awarded

Future project (C) - Li-Sulphur battery Oxis Energy, Axeon & others TBD Planned

Cells (D) Testing sample cells now Envia Systems Ongoing

TSB Project (B)

Future Project (C)Cells (D)

+ +

Technology Strategy Board R&D Project (A)

“Advanced High Energy Density Battery and Next Generation BMS”

+

For a 30kWh EV battery, cells alone :

Next Generation, Increased Next Generation, Increased Functionality, Smaller, Lighter, Functionality, Smaller, Lighter,

Cheaper, BMSCheaper, BMS

NCMNCMChemistry Chemistry

Pouch CellsPouch Cells+Small City CarSmall City Car


For a 30kWh EV battery, cells alone :

⇒⇒⇒⇒ Weight reduced by ~28%compared to LiFePO4

⇒⇒⇒⇒ Volume reduced by ~ 47%

cells alone

Weight / Volume reduction

NCM pouch cells, up to 340Wh/l and 170Wh/kg. Combined with a smaller/lighter Ricardo BMS should

prove to be a highly efficient technical solution.

Increased performanceHigh efficiency, via adaptive BMS capable of dynamic active and passive balancing.

Project Plan

Work Package Q4 Q5 Q6 Q7 Q8

Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun

Bench Top

Software

“A” Design

“A” Vehicle

“A” Build / Test

NOW


“B” Design

“B” Vehicle

“B” Build / Test

“B” Vehicle Test

“A” Certification

TSB (B): Li-M-Si-O / Si Alloy battery for PHEV

Si based alloy based next generation of negative electrodes

High volumetric and specific energy

Problem – particle fracture due to large volume expansion

Fix – Accommodate stress strain of volume expansion via nanostructure

Coupled with Li-TM-Silicate positive electrode

The University of St Andrews


Coupled with Li-TM-Silicate positive electrode

Overall = High energy density 250 to 300 Wh/kg, low cost.

PHEV Battery Pack construction

Cell Chemistry characterisation

BMS calibration

Pack Engineering and Construction

Further Battery Management System Development

Smaller, Lighter, Cheaper BMS

Q210

Q3 10 Q41 10 Q1 11 Q2 11 Q3 11 Q4 11 Q1 12 Q2 12 Q2 12

Cathode Development

AnodeDevelopment

Scale Up

Cell Fabrication

Project Plan


BMSDevelopment

Initial BMS Testing

Pack Engineering

ChemistryCharacterisation

Testing / Validation Where We Are Now.

= = = =

St Andrews - Technology

Positive electrodes based on Fe highly attractive (cost and safety).

LiFePO4 operates at 3.4V vs. lithium now used in commercial cells.

Electrochemical activity in Li2FeSiO4 reported. (3V vs Li)

Cheaper raw raw materials.

Difficult to prepare single phase, and structural change on cycling

Poor e- conductivity (analogous to phosphates) and room temp performance

Mn highly attractive: higher potential than Fe-Silicate (~ 4V)


possibility of removing more than 1 Li (Mn4+ more stable than Fe4+) => High Capacity => High Energy

Remains Inexpensive and safe

Structures related to LISICON

(LIthium SuperIonic CONductor)

materials with all cations tetrahedrally

coordinated by oxygen.

St Andrews - Technology

Alternative synthetic routes give single phase: (e.g. hydrothermal)

Best reported electrochemistry (50oC and low rate)

All require small particles and carbon coating to achieve satisfactory electrochemical performance

This structure type adopted by numerous other transition metals including Mn, Co

Mn highly attractive: higher potential than Li2FeSiO4 (~ 4V)

Remains Inexpensive and safe

possibility of removing more than 1 Li (Mn4+ more stable than Fe4+)

33

20 30 40 50 60 70 80 900

50

100

150

200

250

300

350

Inte

nsi

ty

2θ / degrees (FeKα1

)

0 2 4 6 8 10 12 14 16 18 200

20

40

60

80

100

120

140

Cap

acit

y /

mA

hg

-1

Cycle number

possibility of removing more than 1 Li (Mn more stable than Fe )

LISICON framework is very flexible – contains interstitial cation sites

Offers a wide range of possible substitutions e.g. Li2+2xM1-xSiO4

Axeon Holdings plc 2009 Confidential

Up to 9x Gravimetric, 3 x Volumetric Energy Density

Silicon Fibres robust to volume change

Nexeon - Technology


Form pillars on particles without harvesting

Pillared Particles ⇒⇒⇒⇒ Hedgehog particles

Lower cost than graphite

Performance

Tune Capacity (mAh/g) by varying pillar : core ratio


Optimised Electrochemical Performance

Step change energy storage → 300Wh/kg

ConclusionsConclusions

Summay

Axeon has extensive real world experience of EV and HEV

batteries including a range of cell chemistries and Battery

Management Systems.

Axeon is “Cell Agnostic” but well connected to cell vendors and

participating in joint research and development programs.

Main chemistries and improved derivatives will be around for

37

some time, but new advanced cell chemistries are rapidly

emerging making a step change in energy storage a possibility.

Nano-Technology - Enabler and playing increasing role.

Axeon has a future view of these rapidly developing

technologies backed up by real research and development

programs and real end customer development projects.


Nobel Court, Tel: +44 (0)1382 400040

Wester Gourdie, Fax: +44 (0)1382 400044

Axeon

Wester Gourdie, Fax: +44 (0)1382 400044

Dundee, DD2 4UH,

Scotland, UK www.axeon.com

Business

Lithium Ion Batteries: Going the Distance (Feb 2011)