Evlib part 2

Battery

For more information, please call +65 6243 0050 or email [email protected]

www.ev-li-ionbatteryforum.com

This is Part 2 of the Presentations from the EV Li-ion Battery Forum 2009

Forum Day 1 & 2 September 2009 Shanghai

Join in the discussionlook for the

group on

Lithium Ion Battery and Electric Cars Shanghai Sept 2009

Dr. Sankar Das Gupta

CEO , Electrovaya

• Climate Change

• Urban pollution

• Rising oil prices

• Energy security

• Healthcare costs

• Government initiatives

900 million vehicles worldwide rely on fossil fuels 50 - 70 million new vehicles on the road each year 85 Million Barrels of oil Burnt every day

“It’s the batteries, Stupid”

Notes: (1) James Woolsey – former CIA Director (2) George Shultz – former US Secretary of State

The Honorable R. James Woolsey The Honorable George P. Shultz Co-Chairmen

Fuel reformer

Oil Lines

Oil Pan

Water Cooling system

Catalytic Converter

Fuel Injection System

Various Auxiliary System

Engine

Transmission

Electric Motor

Onboard Charge & Motor Controller

Battery System

Muffler

Gas Tank

Electric Vehicle Components Unnecessary Internal Combustion Components

Electric drive train

Nanotechnology

A 30 kWh system (e.g. small BEV) requires

240 x Electrovaya 35Ah cells

7120 x 18650 cells (commercial phosphate)

3390 x 26650 cells (commercial phosphate)

Ener

gy D

ensi

ty (W

h/kg

)

• Most of world Lithium Ion Battery production uses organic liquid NMP (N- Methyl Pyrollidone)

• NMP recently suspected of reproductive Toxicity (birth defects) California 2001, EU 2003

• Electrovaya – Unique Production Technology does not use NMP

“Zero Emission Manufacturing for Zero Emission Vehicles”.

DistributedIntelligence

ControlIntelligence

Battery Engineering Team

Thermal Engineering Team

Power Electronics Team

Mechanical Engineering Team

Electrical Engineering Team

Battery System

1. Mississauga, Ontario Canada

2. New York State, U.S.A.

3. Licensee, Miljobil Joint Venture - Norway

Strategic Implications of Unique Manufacturing:

• Zero emission manufacturing process - Thus can manufacture anywhere – urban areas (Toronto), countries (Norway) with minimal environmental footprint

• Capital cost for Manufacturing Plant is lowest for the industry - Thus can expand more cost effectively

Mississauga, Ontario Canada

Cell Mfg. Module Build

Production Flow

verificationsystem build integrationSystem design

Commercial

iterativework

Battery R&D Team (Scientists, Engineers, Technicians)

Thermal Engineering Team (Engineers, Technicians)

Power Electronics Team (Computer Scientists, Engineers, Technicians)

Mechanical Engineering Team (Scientists, Engineers, Technicians)

Electrical Engineering Team (Engineers, Electricians, Technicians)

Systems Engineering (Engineers, Scientists, Technicians)

Mechatronics Team

Type

of L

abou

r Req

uire

d

Pre-commercialization Activities

OEMs Delivery Vans & Buses

PassengerCars

maya-300Urban cars

Plug-in Hybrid Electric Vehicles

Battery Electric Vehicles

Off-Road

Production : USA, Canada, Norway

Delivery Vans PHEV Conversions

•••

CorporateHomepageFeature

••

•••

•

奇瑞新能源目 CNEAT

C - Pure electricity Technology

二00九年九月



提

一、奇瑞公司介

二、奇瑞新能源展

三、主要池品技参数

四、下一步的需求



奇瑞品已出口到全球70多个国家和地区



提









2000.12，完成奇瑞汽目的可行性分析与立，成立汽目

2001.10，申承担了“十五”一期863 划“奇瑞混合力 ” 目

2002.12，第一 3 ISG混合力功能研制完成，于2003.2通 863 划收。

2004.09，第二 5 ISG混合力功能研制完成，并承担了“十五”二期863

划“QR混合力研。



2002.01，A11 公司内立，并申承担了“十五”一期863 划“QR

” 目

2002.12，第一 2 A11 功能研制完成。

2003.02，第二 5 A11 功能研制完成，并通 863 划收。





2004.11，以奇瑞主，国合作研，行A21_ISG中度混合与A21_BSG

度混合等两款混合力工程化与化研：

行了3 化开，了奇瑞两种混合力的化

建立了新能源开平台，如件、硬件平台等

培养了奇瑞新能源开的核心人

列入863 划有4个

技与利奇瑞所有

BSG 度混合力

ISG中度混合力



2007年10月，奇瑞在湖投放10台A21 BSG出租行示范。每台行超 20万公里，共累示范超 200万公里据与反，在湖市出租行，BSG 油在10%左右



奇瑞公司提供58 A21_ISG与A21_BSG两种混合力，在2008年北京奥会期，成功行了示范，体了“ 色奥 ”的宗旨。



2009年1月，奇瑞A21 BSG混合力在湖批量上市，首期上市150 。截至在，已行近8万公里，累行 1200万公里。

2009年底，奇瑞A21 ISG混合力将批量上市



混：BSG

中混：ISG

全混

2008 2009 2010 2011

A5

A5

A3

B22

QQ3 S18b

Q21

S18 A5

Q21

混

合

力

2012



提







1

2

4

6

10

2

4

6

100

2

4

6

1000

(W

h/k

g)

100

101

102

103

104

(W/kg)

Lead -Acid

Capacitors

IC Engine

Ni-MH

Li-ion

Lead -Acid

Capacitors

IC Engine

Ni-MH

Li-ion

EV

HEV

PHEV



ISG

QQ EV M1 PHEV

A5 PHEV

BSG

NiH

AGM





a)

b) 336 V

c) 40Ah

d) 0.2C 98%

e) 80%

f) 1C

g) 13.4 kWh

h) 3C

i) 1C

j) 30 21KW

k) 100%DOD 2000

l) 220 kg





提







我的目

……



安全与主要性能相兼



池本体

一步提高比能量（EV及PHEV）

一步提高比功率（PHEV）

一步提高高温循和低温性能

一步提高均匀一致性和安全性

一步降低成本(重要)



系池包

化、等

循寿命考核，如常循和工况循

安全性能考核，如使用初期和使用中后期

境用性考核，如温度和机械等



控制（管理系）

化SOC和SOH算法，特别是SOH算法

开展磁兼容性能考核

池包系包括管理系在内的力蓄池系性能的合考核，如寿命、境适性等



！

8Ah LMO Hi-Power cell, 89Wh/Kg, 1700W/Kg

Cycling peformance of LMO cell module (100%DOD)

Rate performances of 40Ah LFP cell at 25°C

Power density

Energy density

Life

Safety Cost

Working temp.range

FreedomCAR Energy Storage Goals

J.M. Tarascon, M. Armand, Nature, 414, 2001, 359

Cathode Voltage

vs Graphite

Specific

Capacity

Price Application Safety

LiCoO2 3.7V 140Ah/kg $35/kg Consumer Low

LiNoCoMn 3.6V 155Ah/kg $24/kg Consumer

Powertool

mid

LiNiCoAl 3.55V 170Ah/kg $26/kg Consumer

Industial

Low/mid

LiMn2O

4 3.8V 110Ah/kg $12/kg Powertool

Vehicel

High

LiFePO4 3.2V 150Ah/kg $30/kg Powertool

Vehicel

High

Voltage

vs Graphite

Specific

Capacity

Price

Anode Graphite 0V 330Ah/kg $10/kg

Hard Carbon 0.3V 250Ah/kg $40/kg

Li4Ti

5O

12 1.3V 160Ah/kg $25/kg

Graphite Anode

Hard Carbon Anode Li4Ti5O12 Anode

H. Li, X. J. Huang et al,

Electrochemical and Solid-State Letters, 2 (11) 547-549 (1999)

Si

Si

Cu foil

nano-Si/C After discharging

Electrochem. agglomeration

Si Composite Anode materials

1

2

3

4

5

6

7

8

LFP/Graphite

*Patent licensing fee is not included

Tianjin Lishen Battery Joint-stock Co.,Ltd

Zhang Na

2-3 Sep, 2009 EV Li-ion Battery Forum, Shanghai, China

Outline

Safety The number one concern for passenger vehicles

Availability Meet a wide temperature range of -30 to 60

Durability Cycle and calendar life must allow for 10~15 years of battery operation

Cost Batteries for EV with large batteries require low cost

Background-Key Materials Challenges

Voltage Range/V

Capacity /(mAh/g) Cycle Life Cost Safety

LiMn2O4 3.0-4.2 100 120 Good Low Better

LiFePO4 2.0-3.6 130 150 Excellent Low Excellent

NCM 2.5-4.2 150 Better High Good

NCA 2.5-4.2 150 Better High Good

•At least four different cathode chemistries are being considered in power battery

•NCA and NCM are the choices for high energy density

•LFP shows the lowest energy density due to low voltage and low material density

Cathode Chemistry in Lishen

KPI of Cathode Materials

•Most cathode materials exhibit a strong exothermal reaction with the electrolyte in the charged state which can lead to a thermal runaway of the battery

•LFP is completely stable and allows the development of an intrinsically safe cell

Safety of Cathode Material

DSC of LiNi1/3Co1/3Mn1/3O2 LiMn2O4LiFePO4 and Electrolyte at 4.3V

Study on LiFePO4 in Lishen—Basic Performance

Energy Type Power Type

Items A B C D E F G H

Surface area (m2/g) 9 11 16 10 14 18 15 14

Tapped density (g/cm3) 0.8 1.0 0.9 1.1 1.0 1.0 1.0 0.6

Particle size (μm) (D10) 2.2 1.5 0.6 1.1 0.8 0.75 0.2 0.2

(D50) 5.4 3.4 2.3 4.2 4.5 5.1 0.8 0.6

(D90) 9.1 5.9 11.2 10.3 12.2 16.6 4.8 5.0

Moisture (ppm) 420 800 300 500 1100 100 410 700

Discharge capacity (mAh/g)

148 150 145 148 145 143 143 152

Processability Hard Hard Hard Hard OK OK Hard Harder

Study on LiFePO4 in Lishen—SEM

A B

C D

Study on LiFePO4 in Lishen—SEM

E F

G H

Study on LiFePO4 in Lishen—Discharge Performance

Discharge Performance:A E B C D F

Study on LiFePO4 in Lishen—Cycle Life

Cycle Life( According to cycle life trend line): B C A E D

Study on LiFePO4 in Lishen—Discharge Performance

Discharge Performance: G E

Study on LiFePO4 in Lishen—Safety performance

All the Materials are Safe!

NoExplosion No Fire

NoExplosion No Fire

Safety & Abuse Testing

Nail Penetration Nail: 3- 8mm,Speed:10-40mm/s

Hot Oven 150 /10min

Over Charge1C/10V

Short Circuit

Over Discharge

NoExplosion No Fire

NoExplosion No Fire

NoExplosion No Fire

NoExplosion No Fire

Crush

Properties of anode materials

SEM

Structure

LTO SC HC MCMB Item

Anode Chemistry in Lishen

KPI of anode materials

Particle size D50/(μm)

Capacity /(mAh/g)

Tap Density/(g/cc) Advantage Disadvantage

Graphite (MCMB) 8.104 300 1.3 Low cost;

High capacity Low temp.;

Rapid charge

Hard Carbon 9.146 430 0.9 High Power;

Longevity

Energy; Initial Efficiency; low

tap density

Soft Carbon 11.216 360 0.8 Low cost; Longevity

Low energy density; low tap

density

Li4Ti5O4 9.7 150 1.2 High Power;

Longevity Low Temp.; Safety

Low energy density

Charge Capacity (mAh)

Ano

de e

lect

rode

Pot

entia

l (V

)

1.5V Vs Li

0.1V Vs Li

LTO

Graphite

Soft Carbon

Charge curves of anode materials

Hard carbon has the excellent specific capacity, and the charge and discharge curve shows good gradient, which is propitious to

estimate the SOC of the battery .

No SEI forming, which can improve the low temp. electron

conductivity. the voltage Vs. Li is 1.5V, which can effectively avoid

the creating of the lithium dendrites.

The properties of soft carbon is between hard carbon and

artificial graphite.

Hard Carbon

Electrochemical performances—rated discharge

Because of the intrinsic properties, hard carbon is benefit to be discharged at large current. The hard carbon displays the higher voltage than soft carbon and MCMB at high rate discharge.

Electrochemical performances—rated charge

Time of charging to 90%SOC (10C)

Anode Time/min MCMB 12.8

HC 7.3

SC 5.4

LTO 5.6

LTO shows excellent high rate charging property, which is better than HC and SC, and the high rate charging capacity of the MCMB is the least.

Electrochemical performances—cycle life

Low temperature performance

Batteries are the primary barrier in making electric-drive vehicles possible. Li-ion batteries can best meet the electric-drive challenge;

LiFePO4 is an intrinsically safe system with good cycle life. At present LiFePO4 platform is one of the best choice for EV/HEV application in Lishen;

MCMB and hard carbon are used in Lishen present EV/ HEV cell products; Li4Ti5O12 has higher rate charge ability (at low Temp. vs. AG) , so it seems that Li4Ti5O12 is the best choice for next generation HEV application;

Raw material is one of the key premise for good battery, but the electrode process is a big challenge for battery maker due to the property of LiFePO4. Lishen has sound base and enough manufacture experience to penetrate the EV market.

Conclusions

Thank You!

Solar Wind

°

°

°

1

1

2

2 3

3 4

4 5

5

μ

(1st cycle rate: C/20, other cycles: C/5)

http://www.hnei.hawaii.edu/

  Carbon-based economy (pollutions) will be gone eventually

  Clean electricity-based economy will take over   Electrified transportation will prevail

  How can we insure a safe and optimal operation of a power source or energy storage (PS/ES) system?   Field testing?   Laboratory testing?   Modeling & simulation?   All of the above?

  What tools do we need to reach that objective?   Model/simulation? Diagnosis? Prognosis?   Are they easy to handle?   Can they be used in real time ?   Can they be used to forecast the available capacity ?

Data collection

  How to understand field data?   Analyze the duty/generation cycle

  Link usage (duty cycle) to size & performance of the PS/ES system

  Allow accurate sizing of the battery pack for geographically-dependent duty cycle

Pattern Recognition

Duty cycle analysis

Data collection Event D, high wind speed, low gusts distribution

Pattern Recognition

Duty cycle analysis

Event cycle analysis

Event forecasting

  How to understand battery degradation ?   Battery electrochemical behavior is:

  Rate dependent   Temperature dependent   Age dependent

  Need to test the cells under appropriate protocols   Derived from representative usage

schedule (rate, temperature)   Matrix of different parameters

  Rate   Pulses   Temperature   …

Small scale tests Specific protocols

Performance under load

Rate, T, … effects

  Degradation is often complex   Need a reference point (SOC tracing)   Need in situ characterization

  Incremental capacity analysis   Close-to-equil. OCV analysis Small scale tests

Specific protocols

Life & degradation mechanisms

  Single cell model   Derived from performance tests

  ECM approach: accurate & not computation intensive



Cell performance model

Rate, T effects

  Single cell to pack modeling   Accommodate cell-to-cell variations   Adapt to topology



Cell to cell variations


Pack model

Rate, T effects

  Diagnostic and prognostic tools   Developed from knowledge in

single cell testing and analysis   Nominal vs. anomalies   ID & Quantification




Prognostic model


Diagnostic model

Pack model

Life & degradation mechanisms

Rate, T effects

  Diagnostic and prognostic tools

Real time data V,SOC

Analysis and

prognostic module

V,SOC

I,T,SOC,SOH




Prognostic model


Diagnostic model

Pack model

Data collection

Pattern Recognition

Duty cycle analysis

Event cycle analysis

Event forecasting Life & degradation mechanisms

Rate, T effects

Representative usage schedule

  More details ―   Roadmap

  M. Dubarry, V. Svoboda, R. Hwu and B.Y. Liaw, “A roadmap to understand battery performance in electric and hybrid vehicle operation,” J. Power Sources 174 (2007) 366.

  M. Dubarry, N. Vuillaume, B.Y. Liaw, and T. Quinn, “Vehicle evaluation, battery modeling, and fleet-testing experiences in Hawaii: A roadmap to understanding evaluation data and simulation” J. Asian Electric Vehicles 5 (2007) 1033.

  Event pattern recognition   B.Y. Liaw, M. Dubarry, “From driving cycle analysis to understanding battery

performance in real-life electric hybrid vehicle operation” (invited) to the Special Issue on Hybrid Electric Vehicles, J. Power Sources 174 (2007) 76.

  Battery Analysis   M. Dubarry, V. Svoboda, R. Hwu and B.Y. Liaw, “Capacity and power fading

mechanism identification from a commercial cell evaluation,” J. Power Sources 165 (2007) 566.

  M. Dubarry, V. Svoboda, R. Hwu and B.Y. Liaw, “Capacity loss in rechargeable lithium cells during cycle life testing: The importance of determining state-of-charge” J. Power Sources 174 (2007) 1121.

  Modeling   M. Dubarry and B.Y. Liaw, “Development of a universal modeling tool for

rechargeable lithium batteries,” J. Power Sources 174 (2007) 856.

TRK7335.000 61CN 0809 EV09TRK7335.000 61CN 0109 FLA1

Troy A. Hayes, Ph.D., P.E.

General Manager

Exponent China

+1 (650) 688-7127 (US)

+86 (571) 2802 1727 (China)

[email protected]

September 3, 2009

TRK7335.000 61CN 0809 EV09

Who We Are

• Professional services firm

• Engineering & scientific consulting

• 650+ consulting and technical staff

• Best known for analyzing accidents

& failures

• Design and manufacturing

consulting based on FA experience

TRK7335.000 61CN 0809 EV09

Outline

• Technologies used for identifying defective cells

– X-Ray

– CT Scanning

– Hi-Pot testing

– OCV

– Sorting

– Imaging laser tab welds

– Tab-to-cell impedance (soft pouch)

• Maintaining your brand’s trust

– Recalls – when and why?

– Managing a recall

TRK7335.000 61CN 0809 EV09

TRK7335.000 61CN 0809 EV09

X-Ray

• X-Ray is useful as a 100% inspection procedure to verify proper anode/cathode alignment

– Note: this is not 100% accurate

• X-Ray is also useful when used on a sampling basis (using both is most desirable)

TRK7335.000 61CN 0809 EV09

X-Ray

Ni tab kink

TRK7335.000 61CN 0809 EV09

X-Ray

TRK7335.000 61CN 0809 EV09

CT Scanning

• CT Scanning can be used on a sampling basis to evaluate: – Metallic contamination

– Holes in active material

– High-density spots in active material

– Wrinkles in electrodes/current collectors

– Delamination of electrodes

– Detailed alignment

– Deformation of windings associated with tabs, bends etc.

• Disadvantages: – Slow for a complete scan (7 hours for an 18650)

– Expensive ($250K USD for a good machine)

TRK7335.000 61CN 0809 EV09

CT Scanning

100 x 100 x t=50 μm Fe 50 x 50 x t=20 μm Ni

TRK7335.000 61CN 0809 EV09

CT Scanning

• Cu dissolution due to repeated over-discharge

• Cathode delamination

TRK7335.000 61CN 0809 EV09

Hi-Pot Testing

• How were the Hi-Pot values chosen?

– Need a properly-designed DOE

• Metallic particle size/type

• Voltage level and application time

– Will vary with capacity/size

• Hi-Pot failures

– Data analysis

– Failure analysis

– Closed-loop corrective action

TRK7335.000 61CN 0809 EV09

OCV Testing

• How are the limits chosen?

– IEEE 1725 5.5.7

• Data analysis

• Failure analysis

• Closed-loop corrective action

TRK7335.000 61CN 0809 EV09

Sorting

• Why sort?

• Do you really know what causes the variation between cells of various classes?

– Loading versus other properties

– Self discharge rate

• Is it possible for two independent causes to create a cell of a particular class?

– If so, cells of one class may age differently

2,000 – 2,150 mAh

2,151 – 2,300 mAh

V 3.82V Grade B Grade A

3.82 > V 3.77 Grade D Grade C

Cap Voltage

TRK7335.000 61CN 0809 EV09

Laser Weld Visual Inspection

• Entirely dependent on operator skill

• Is the visual inspection reliable?

TRK7335.000 61CN 0809 EV09

Impedance Measurement Between Tab and Cell (Soft Pouch)

• When the inner polymer layer on the Al pouch is compromised, a current leakage path can occur – Corrosion

– Gas generation

– Cell swelling

– Electrolyte leakage

• Compromised pouches can be identified during production by measuring the impedance between the negative tab and the Al pouch after cell formation and aging

TRK7335.000 61CN 0809 EV09

Part 2: Maintaining Your Brand’s Trust

TRK7335.000 61CN 0809 EV09

Maintaining Your Brand’s Trust

• Recalls are for the consumer’s protection

• Recalls must be properly managed

• Recall as soon as possible – don’t wait

• Recall everywhere, not just where you are required (e.g., by the CPSC)

• Consumers will have more confidence in your brand if they know you are acting in their best interest

• Communicate to the customer

TRK7335.000 61CN 0809 EV09

Limiting a Recall – TRACEABILITY

• Tracing all material lots and equipment is extremely important!

– Cap assemblies

– Electrode batches

– Current collectors

– Slitting blade number

– Winding machine

– The more detail, the better

• Remember, most date codes disappear during a thermal runaway event

– Can you differentiate dates and machines by something internal to the cell?

TRK7335.000 61CN 0809 EV09

Data Analysis

• Need to consider

– End of life

– Time in service at time of incident

– Geography and power type/stability where incidents occur

– Differences in population versus failure rate (e.g., type of charger, etc.)

– Changes on manufacturing line

– Material changes

– Design changes

– Failure rates (Hi-Pot, OCV, etc.)

– Other factors

TRK7335.000 61CN 0809 EV09

Data Analysis

Ex

pe

cte

d N

um

be

r o

f F

ail

ure

s

pe

r M

illi

on

Ce

lls

TRK7335.000 61CN 0809 EV09

Timeline for Possible Contributing Factors

Factor A

Factor B

Cu Foil B

Can vendor B

Winder #2 in use

12 1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 11

2007 2008 2009

Anode material B

Winder #16 in use

TRK7335.000 61CN 0809 EV09

Summary

• Technologies used for identifying defective cells

– X-Ray

– CT Scanning

– Hi-Pot testing

– OCV

– Sorting

– Imaging laser tab welds

– Tab-to-cell impedance (soft pouch)

• Maintaining your brand’s trust

– Recall if necessary

– Manage the recall and communicate to the customer

Make your product as traceable as possible

TRK7335.000 61CN 0809 EV09

Questions?

TRK7335.000 61CN 0809 EV09TRK7335.000 61CN 0109 FLA1

Cell and Battery Pack Analysis, Including:

Auditing, Failure Analysis, Design Review, Testing, CTIA Certification and Regulatory Consulting

24 Offices Worldwide

Boston, Los Angeles, Phoenix, San Francisco and China

+1-888-656-EXPO (US)

www.exponent.com/batteries

[email protected]

+86 571 2802 1788 (China)

www.exponentchina.com

[email protected]

Evlib part 2

Technology

battery rd team scientists

kwh system

shanghai battery join

10a21 bsg

theev liion battery

electric cars shanghai

ah lfp cell

power cell