low cost components: screening of advanced battery materials · low cost components: screening of...

Low Cost Components:Screening of AdvancedBattery Materials Andy Jansen (new PI), Jun Liu Chemical Sciences and Engineering Division

Tuesday, February 26th, 2008

DOE Vehicle Technologies ProgramAnnual Merit Review, FY2008Hybrid Electric SystemsEnergy Storage / Applied Battery ResearchBethesda, Maryland

This presentation does not contain any proprietary or confidential information.

Vehicle Technologies Program

Outline � Purpose of Work

� Address Previous Review Comments

� Barriers

� Approach

� Performance Measures and Accomplishments

– Coated graphites and soft carbons from Hitachi Chemical – ConocoPhillips graphites (discussed in low temperature work) – Mitsubishi Power Graphite – LiMnPO4 from HPL

� Technology Transfer� Publications

� Plans for Next Fiscal Year� Summary


Purpose of Work

� Identify and evaluate battery materials made by vendors from around the world that have the potential to offer low cost, long calendar life and better abuse tolerance. This past year’s effort was focused on lower cost graphites.

Reviewer Comments from Aug. ’06 Merit Review� “Evaluate lower cost graphite”

– Received and tested new graphite materials from Hitachi Chemical, Mitsubishi Chemical, and ConocoPhillips


Barriers

� Identify lithium-ion battery materials, with enhanced stability, that lower cell-level costs while simultaneously extending life and enhancing inherent abuse tolerance. – An overwhelming number of materials are being marketed by

vendors. How to select and screen these materials within the effort allocated to this project?


Approach � Consider materials that are commercially viable

– Avoid materials based on rare elements, expensive precursors, or elaborate processing

� Many commercial materials were developed for high energy applications, not high power – Evaluate these materials for HEV use by testing their rate

capability, HPPC impedance, and cycle life

– Use laboratory scale cells • Coin cell (1.6 cm2) • SS planar test fixture (32 cm2) • Pouch cells (25 to 50 cm2)

� Evaluate materials for use in the higher energy PHEV � Recommend promising materials for further thermal abuse evaluation

and consider for use in longer-term aging studies.


Advantages of New Carbon Anode Materials SMG: surface modified graphite

¾ Hitachi Chemical is developing a surface modified Natural Graphite (NG) using a “fusing technology” to develop several new carbon anodes with high capacity, long life, and low cost

¾ Surface modifications are very homogeneous and have a thickness as low as 10 nm

¾ Material is tolerant to 30% PC and doesn’t require the use of EC based electrolyte

SC: soft carbon¾ Hitachi Chemical is developing a soft carbon as a replacement to the hard

carbon used at the moment in HEV battery development, which is desired for cathodes that have flat voltage plateaus

MPG: Mitsubishi Power Graphite

¾ Mitsubishi Chemical developed a surface modified graphite for high power Li-ion battery application (HEV)


Particle Shape Not Affected by Hitachi ModificationNatural graphite with round-edge shape

Surface modification decreased specific surface area from 5 m2/g to 2 m2/g


Untreated: SMG (Blank)-20 D50:19.8 μm S.A.: 5.0 m2/g Tap Density: 0.80 g/cm3

Treated: SMG-NAL1-20C D50:23.4 μm S.A.: 2.0 m2/g Tap Density: 0.87 g/cm3

Volt

age,

V

Vo

lta

ge

, V

Modification has Small Effect on Graphite’s Power

SMG (Blank)-20 SMG-NAL1-20C 1.8 1.8 Vs. Lithium in 1.2M LiPF6, EC/EMC(3:7)1.6 1.6

1.4 1.4 Charge 1

1.2 Charge 1

1.0 Discharge 1

Charge 2

0.8 Discharge 2

Charge 3

Volt

age, V

1.2 Discharge 1 Charge 2

1.0 Discharge 2

0.8 Charge 3 Discharge 3

0.6 Discharge 3 0.6

0.4 0.4

0.2 0.2

0.0 0.0

0 50 100 150 200 250 300 350 400 0 100 200 300 400

Capacity, mAh/g Capacity, mAh/g 4.5

4.5 Vs. Gen 3d (+) in 1.2M LiPF6, EC/EMC(3:7)+ 2%LiBF2C2O4

4.0 4.0

3.5 Voltag

e, V

3.5

3.0 3.0

10C 5C 2C C/2 10C 5C 2C 1C

C/2 1C

2.5 2.5

0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5

Capacity, mAh Capacity, mAh


40

50

Low ASI of Hitachi SMG Anodes Enables Use In HEV

Gen.3 (+) vs. SMG (blank)-20 Anode

D50:19.8 μm ASI-Disc ASI-Chrg

� HPPC ASI decreases as

AS

I, o

hm

*cm

2

30 particle size decreases 20

� Abuse tolerance is next criteria10

0

0 10 20 30 40 50 60 70 80 90 100

DOD, % Electrolyte: 1.2M LiPF6, EC/EMC(3:7)+ 2%LiBF2C2O4

0

10

20

30

40

50

AS

I, o

hm

*cm

2

ASI-Disc ASI-Chrg D50:7.8 μm

Gen.3 (+) vs. SMG-NAL1-7C Anode

0

10

20

30

40

50

AS

I, o

hm

*cm

2

ASI-Disc ASI-Chrg

D50:11.9 μm

Gen.3 (+) vs. SMG-NAL1-10C Anode

0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

DOD, % DOD, %


Particle Shape Not Affected by Hitachi ModificationSoft Carbon (using specified coke as raw material)

After treatment, specific surface area decreased from 11.3 m2/g to 2.4 m2/g


Untreated: SC-(Blank)-10 D50:10.3 μm S.A.: 11.3 m2/g Tap Density: 0.43 g/cm3

Treated: SC-CAL1-10B D50:12.1 μm S.A.: 2.4 m2/g Tap Density: 0.54 g/cm3

Volt

age,

V

Voltag

e, V

Modification Improves Soft Carbon’s Rate Capability

Soft Carbon-(blank)-10 Soft Carbon-CAL1-10B 3.0 3.0

Charge 1 Vs. Lithium in 1.2M LiPF6, EC/EMC(3:7)2.5

Discharge 1 2.5

Charge 2Charge 1 Discharge 2

2.0 Charge 3 2.0 Discharge 1

1.5

1.0

Discharge 3

Volt

age, V

Charge 2 Discharge 2

1.5 Charge 3 Discharge 3

1.0

0.5 0.5

0.0 0.0

0 50 100 150 200 250 300 0 50 100 150 200 250 300 Capacity, mAh/g Capacity, mAh/g

4.5 4.5 Vs. Gen 3d (+) in 1.2M LiPF6, EC/EMC(3:7)+ 2%LiBF2C2O4

4.0 4.0

3.5 Voltag

e, V

3.5

3.0 3.0 10C 5C 2C C/2 10C 5C 2C C/2

1C 1C

2.5 2.5 0 0.5 1 1.5 2 0 0.5 1 1.5 2

Capacity, mAh Capacity, mAh


Good Cycle Performance of Hitachi Anodes atC/1 Rate

Soft Carbon SMG Graphite Vs. Gen 3d (+) in 1.2M LiPF6, EC/EMC(3:7)+ 2%LiBF2C2O4

1.8 3.0 1.6

2.5 1.4

D50:10 μm Charge Discharge

D50:20 μm Charge Discharge

Cap

acit

y, m

Ah

1.2

1.0

0.8

0.6

Cap

acit

y, m

Ah

2.0

1.5

1.00.4

0.2

0.0

0.5

0.0 0 20 40 60 80 100 0 20 40 60 80 100

Cycle Number Cycle Number


Mitsubishi Chemical’s Graphite has Good Capacity

Capacity close to 350 mAh/g vs. Li

2.5 MPG: Mitsubishi Power Graphite

2.0 Sample MPG 113

(synthetic) 1.5

Mean Particle Size 13.4 μm 1.0

Specific Surface Area 3.6 m2/g 0.5

Tapping Density 1.07 g/cc 0.0

0 100 200 300 400 Capacity, mAh/g

Vo

ltag

e, V


Mitsubishi Electrodes are Designed for High Power Mitsubishi also made a cathode electrode, NMC-05-F, from Li[Lix(Ni1/3Co1/3Mn1/3)1-x]O2

ASI,

Ohm

.cm

2

40

35

30

25

20 0 5 10 15 20 25 30 35

Discharge Rate

Mitsubishi vs. MCMB Mitsubishi vs. MPG113

NMC-05-F vs. MPG113

1.2M LiPF6, EC/EMC (3:7)+3 wt% LiBF2C2O4 Pouch cell (25 cm²), Room Temperature

NMC05-F vs. MCMB 10-28 (Gen3d)


Olivine LiMnPO4 as Cathode for Lithium Batteries

• LiMnPO4 has a flat 4.2 V plateau, which is 600 mV higher than LiFePO4, Olivine structure and a theoretical capacity of almost 178 mAh/g (possibility of reducing the

(orthorhombic)

number of cells and cost by taking advantage of high cell voltage)

[PO4]

• Mn2+ and Mn3+ are very stable and less oxidizing than Ni4+ in conventional 4 V [LiO6] LiNi0.8Co0.2O2 oxide (potential for long calendar life and safety) [MnO6]

But!!!

• LiMnPO4 has much lower electronic conductivity than LiFePO4


HPL’s LiMnPO4 Cathode Shows Some Promise

Vs. Lithium in 1.2M LiPF6, EC/EMC(3:7) 5.0

Measurement Data sheet 4.5

BET SSA 30 m2/g

Average pore 13.6 nm diameter

Tap density 1.0 g/cm3

Vo

ltag

e, V

4.0

3.5

3.0

2.5 50C 20C 10C 5C 2C 1C

C/2

0 20 40 60 80 100 120

Capacity, mAh/g

LiMnPO4 cathode has a 1st discharge capacity of 126 mAh/g vs. Li and coulombic efficiency of 83 %. More work is needed to increase the capacity.


Technology Transfer � The nature of this work does not lend itself easily to publications

or patents � Results are made available to the DOE, USABC, and battery

developers and suppliers at regular review meetings (depending on vendor agreement)

Publications (Technical Report) � “Advanced Cathode Materials for High Power Applications”, K. Amine, J.

Liu, I. Belharouak, S. –H. Kang, I. Bloom, D. Vissers, and G. Henriksen, J. of Power Sources, Vol.146 Issues 1-2, (2005)111-115

� “Screening Report on Cell Materials for High-Power on Cell Materials for High-Power Li-Ion HEV Batteries”, Technical Report No. ANL-03/16, by J. Liu, A. Kahaian, I. Belharouak, S. Kang, S. Oliver, G. Henriksen, and K. Amine (2003). Available on-line at http://www.ipd.anl.gov/anlpubs/2003/04/46424.pdf


http://www.ipd.anl.gov/anlpubs/2003/04/46424.pdf

Future Work � Investigate materials from different suppliers for high power

(HEV) and high energy (PHEV) application – Hitachi Chemical’s latest batch of anode materials – Li4Ti5O12 from Kyorix, Ishihara, and others – Nano-sized particles LiFePO4 from Mitsui Eng. and others

� New protocol will be implemented for advanced materials evaluation that is beneficial to one or both high power HEVs or higher energy plug-in HEVs

� Continue to evaluate advanced cathode, anode, binder, and electrolyte systems as they become available from various sources


Summary � Hitachi’s surface modified natural graphite has good capacity and

power capability. Full cell ASI at 10C pulse rate is less than 35 Ohm-cm2, which meets the power requirement for HEV application

� The capacity of Hitachi’s soft carbons is lower than graphite, but it has very good power capability. Full cell ASI at 10C pulse rate is less than 35 Ohm-cm2, which meets the power requirement for HEV application

� MPG graphite from Mitsubishi Chemical has very good power capability and higher tap density. Their cathode material also has good power capability

� Manganese-based olivine from HPL is not yet ready for HEV use but advances in this area will be monitored

� ConocoPhillips’ graphite materials also meet HEV power criteria

� The next step is to evaluate the thermal abuse response of these graphite and soft carbon materials


Contributors and Acknowledgments

� Jun Liu (Argonne) � Hitachi Chemical Co., Ltd – Now at SoBright Tech. Co. (China) � Mitsubishi Chemical Corp.

� Khalil Amine (Argonne) � ConocoPhillips Co.

� David Abram (Argonne) � HPL (High Power Lithium)

� Mike Katz (Argonne) � Jack Vaughey (Argonne) � Dennis Dees (Argonne) � Gary Henriksen (Argonne) � Prof. Jai Prakash (IIT) � Shabab Amiruddin (IIT) � Humberto Joachin (IIT)

Support from Tien Duong and David Howell of the U.S. Department of Energy’s Office of Vehicle Technologies Program is gratefully acknowledged.


low cost components: screening of advanced battery materials · low cost components: screening of...

Documents