high energy novel cathode / alloy automotive cell · milestone: complete the synthesis of advanced...

Jehwon Choi, Kevin Eberman, Leif Christensen, Zhonghua Lu, Bill Lamanna, Ang Xiao, Jagat Singh

3M Electronics Materials Marketing Division

May 14, 2012

Project ID # ES131

This presentation does not contain any proprietary, confidential, or otherwise restricted information

High Energy Novel Cathode / Alloy Automotive Cell

ES131 High Energy Novel Cathode / Alloy Automotive Cell

Overview Timeline

start: 10/01/2011 finish: 1/15/2015 15% complete

Budget

Total project funding DOE share: $4,577,909 Contractor share: $1,961,961 Funding received in FY11: $ 0 Funding for FY12 : $1,700,000

Barriers Cycle Life, Energy, Cost and Thermal Stability

Targets

Increase in energy density > 40% Reduce Cost > 25 % Maintain thermal stability and cycle life

Partners

Argonne National Laboratory Dalhousie University


To develop a high-performance battery cell for electrical vehicle with high energy density and low cost by integrating advanced chemistries

at least 40% (1.4X base Wh/l) increase in energy density compared to baseline cell performance (NMC111 and Graphite)

35% increase in energy for advanced high voltage cathode 70% increase in volumetric capacity for alloy anode at least 25% lower cost per unit energy at cell level for a comparative integrated

advanced materials cell to a baseline materials one

Project Objectives ES131


Milestones Month/Year Milestone or Go/No-Go decision

Apr-12 Milestone : Complete the synthesis of advanced materials in quantities to build cells

July-12 Milestone : Complete the prototype large cell build with baseline material

Sep-12

Go/No-Go Decision : Demonstrate advanced cathode with composite density of 2.57Wh/cc or high and 95% capacity retention after 50 cycles Demonstrate advanced anode composite with > 760 mAh/cc (70% increase over graphite) and 95% capacity retention after 50 cycles Data on one or more > 1.5Ah cell designs capable of supporting baseline and advanced materials testing under test guideline. Data enables down selection cell design for next phase Evaluation data of baseline materials in one or more relevant cell designs having > 1.5Ah capacity and less than 20% capacity fade after 500 cycles with a 60% swing in capacity at room temperature


Approach to Cathode Development Approach 1 : NMC material with high Ni content (Ni ≥ ½) Approach 2 : “Oxygen-release” cathode materials

Explore the compositions in two composition triangles Enable the high voltage cycle by engineering the particle

Based on the above phase diagrams, we explored compositions by the following experiment design (without morphology control) Factor 1: Ni/Mn, Factor 2: Co, Factor 3: Li/M, Factor 4: Temperature Response: Energy between 2.5-4.7V, Cycle life, Crystal density (All at 30oC)


Approach to Anode Development Si

In Region of Interest, Optimizing • Composition • Morphology • Surface

Explored trade-off between low irreversible capacity and low thickness per cycle

Optimizing Composition, Morphology, Surface


Accomplishments - Cathode

Compositional exploratory study shows that low Ni/Mn ratio with low cobalt region is most promising in meeting the project goal

Ni/Mn

Co

2150

2200

2250

2300

2350

2400

2450

2500

2550

2600

2650

2700

2750

2800

2850

2900

2950

Ni/Mn

Co

1450

1550

1650

1750

1850

1950

2050

2150

2250

2350

2450

Ni/Mn

Co

-20

-19

-18

-17

-16

-15

-14

-13

-12

-11

-10

-9-8-7-6-5-4-3-2

Composite Energy at C/16 rate Composite Energy at 1C rate

Capacity Loss



Several potential candidates have been scaled up and meet goal. More sintering process optimization and composition exploring are on

going.

Sample_description Voltage C1 (mAh/g) D(mAh/g) D_Energy (mWh/g)

Electrode density (g/cc)

Energy density (Wh/cc)

Capacity Retention

OL_based Cathode A 4.8V 272 211 807 3.35 2.70 0.98 3M BC-723K (Coating B) 4.7V 237 205 810 3.45 2.8 0.96 4.8V 246 215 848 3.45 2.9 Engineered Cathode 126M 4.8V 287 230 871 3.40 3.0 0.98

0 100 200 300Capacity (mAh/g)

2.5

3

3.5

4

4.5

52.5

3

3.5

4

4.5

5

Volta

ge (V

)

2.5

3

3.5

4

4.5

5

OL Based Cathode A (2nd cycle)

Coated BC-723K (Coating B)

126M

0 40 80 120 160 200Cycle No.

80

120

160

200

24080

120

160

200

240

Cap

acity

(mA

h/g)

80

120

160

200

240

OL Based Cathode A

BC-723K (Coating B)

126M

Cycle Life Charge Discharge Profile



The surface treatment has a clear benefits for the capacity retention at high voltage and high temperature

Floating Test Profile Capacity Loss Comparison

Sample Reversible Capacity (mAh/g)

Capacity Loss (%) Before Floating After Floating

3M BC-723K (No Coating) 198 0.08 99.9

3M BC-723K (Coating A) 206 69.7 66.2

3M BC-723K (Coating B) 199 116.8 41.3


Accomplishments - Anode

Material Type

Specific Capacity

1st Cycle Efficiency Density Composite

Vol-Cap PSD D50 SSA

(mAh/g) (%) (g/cc) (mAh/cc) (um) (m2/g) A 840 85% 4.1 1230 3 5 B 840 85% 4.1 1230 7 3 C 860 90% 4.1 1260 8 3 D 850 88% 4.0 1230 8 4 E 1250 76% 2.7 1290 8 9 F 1000 84% 3.4 1270 10 4 G 1100 85% 3.3 1340 14 5

2011

20

12

In previous DOE program developed A and B In current DOE program improved efficiency and

developed range of lower expansion materials All meet performance goals

Composite Vol-Cap calculated for 63:30:2:5 wt%, Alloy:Graphite:SuperP:LiPAA, with 25% porosity at full expansion/lithiation.


Accomplishments - Anode

Identified new type of Si material (Type D) with improved cycle life Carbon coating improves the cycling performance of Si material

(Type E)

Increased capacity retention with Type D material compared to Type C material in symmetrical cells at high temperature.

Carbon coating improves the performance of Type E materials in composite electrodes with high rate cycling.


-0.25

-0.20

-0.15

-0.10

-0.05

0.000.01 0.10 1.00 10.00 100.00 1,000.00

R (im

age

/ oh

m)

Frequency (Hz)

EIS at 0C after storage at 4.3V and 60C for 20 days

Control0.3%DS32%VC2%VC+0.3%DS3

• 3M new DS3 electrolyte additives improved storage performance of NMC 18650 cells at HT and HV. • Synergy observed - combination of DS3 and VC works best.

4.05

4.1

4.15

4.2

4.25

4.3

0 100 200 300 400 500

Volta

ge (V

)

Time (hrs)

OCV of NMC 442/GR 18650 cells on Storage at 4.3V (100% SOC) and 60C for 20 days

Control0.3%DS32%VC2%VC+0.3%DS3

60%

65%

70%

75%

80%

Control 0.3%DS3 2%VC 2%VC+0.3%DS3

Capa

city

Ret

entio

n %

Capacity Retention of NMC 442/GR 18650 cells after Storage at 4.3V (100% SOC) and 60C for 20 days

DS3 Reduced Impedance on Storage

DS3 Improved Capacity on Storage

DS3 Reduced Voltage Drop

Accomplishments - Electrolyte ES131


Accomplishments - Cell Integration

Test Protocol established and preliminary testing initiated

Testing Protocol, Data Acquisition & Reporting will be performed in conformance to USABC’s ‘Electric Vehicle Battery Test Procedures Manual’; Rev 2; Published January 1996.

RPT (Reference Performance Test) - Constant Current Capacity ( C/3); DST (Dynamic Stress Test) discharge Capacity; Peak Power Capability

Establish Test Protocol Preliminary Cycle Life Testing

2.7

2.9

3.1

3.3

3.5

3.7

3.9

4.1

4.3

0 5 10 15 20 25 30

Volta

ge (V

)Time (hrs)

RPT at BOL Cycle Life Test



Single Rectangular Planetary Blade Single Disperser Blade

Old Mixer New Mixer

Double Helical Planetary Blade Double Disperser Blade (with bottom scraper) Side wall scrapper Sanitary fitting in discharge port for easy Filtering

New mixer provides better mixing for superior performance



Preliminary data tends to indicate more robust stacked pouch cell design

Method I Method II Method III

pouch w/ tape pouch w/o tape tab w/ tape tab w/o tape

140C 871.60 427.24 530.13 288.83180C 2146.05 1786.53 2581.83 2018.10

0.00

500.00

1000.00

1500.00

2000.00

2500.00

3000.00

Aver

age f

orce

Pouch Sealing Study Tab welding to Electrode MFZ

Key to pouch cell seal Sealing Temperature Thermo polymer tape

Method III gives max yield Method I gives tears in MFZ Method II gives drop in cell OCV during

formation



> 30% energy improvement from baseline chemistry by integrating 3M HE cathode and alloy anode

Reference cell Advanced cell A

Cell Design

Cathode NMC 723 C-S 126M

Anode Graphite 65%Alloy/35% graphite

Composite density (C) 3.3g/cc 3.3g/cc

Separator 25 25

Cycling range 2.8V to 4.25V 2V to 4.45V

Capacity 1.97Ah 2.90Ah

Test Results

Energy 7.30Wh 9.89Wh (+35%)

Wh/L 445 600 Wh/kg 184 225

Capacity fade @30 0% Slight increase

Capacity fade @200 2% -

0

0.5

1

1.5

2

2.5

3

3.5

0 5 10 15 20 25 30Cycle #

Cel

l cap

acity

(Ah)

0.96

0.98

1

1.02

1.04

1.06

1.08

1.1

CE

NMC/graphite Baseline, 7.3Wh

Advanced Cathode/alloy anode, 9.9Wh

36% more energy

Charge : C/6-rate 4.45V C/20-cutoff Discharge : C/6-rate 2.0V-cutoff

Cell Design 18650 cell capacity and cycling data


Dalhousie University (Jeff Dahn and Mark Obrovac) Technical discussion for most of lithium ion battery related areas.

Argonne National Lab (Ira Bloom and David Robertson)

Testing procedure (EV protocol) discussion.

Collaborations ES131


Demonstrated multiple cathode concepts which can meet the project goal.

Identified several new Si anode materials with improved efficiency and reduced expansion, which can meet the project goal.

Identified new electrolyte additive which improved the performance of baseline materials at high voltage and high temperature test condition.

Optimization of stack pouch cell is still on-going : critical issues of sealing and table welding studied.

Test protocol (EV) was established and preliminary data were generated using large cell test vehicles.

Achieved > 30% increase in energy compared with that of baseline chemistry by integrating new high energy cathode and Si alloy materials in 18650 formats

Summary ES131


Continue to optimize the composition and planning to initiate the morphology control. Initiate the experiments to find new electrolytes based upon fluorochemical chemistry enabling high voltage cycling. The exploration of composition spaces for new Si alloys will be continued in tandem with optimization of coating methods and coating chemistries in next quarter. Continue to focus on stack cell process validation and build 18650 & pouch cells using baseline material and generate complete set of data package using established EV test protocol. Continue to build and monitor the cycling performance of high capacity large cells using advanced cathode and anode materials

Proposed Future Work ES131


high energy novel cathode / alloy automotive cell · milestone: complete the synthesis of advanced...

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