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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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
High Energy Novel Cathode / Alloy Automotive Cell
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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)
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
Accomplishments - Cathode
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
Accomplishments - Cathode
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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.
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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.
ES131 High Energy Novel Cathode / Alloy Automotive Cell
-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
High Energy Novel Cathode / Alloy Automotive Cell
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
Accomplishments - Cell Integration
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
Accomplishments - Cell Integration
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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
Accomplishments - Cell Integration
> 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
ES131 High Energy Novel Cathode / Alloy Automotive Cell
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
High Energy Novel Cathode / Alloy Automotive Cell
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
High Energy Novel Cathode / Alloy Automotive Cell
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