Transcript
3M Advancements in Electrolyte Additives The Battery Show, November 12-14, 2012
3M™ Battery Materials
Agenda Advances in 3M LIB Electrolyte y Development p How additives can impact battery performance and p lower costs help Next generation 3M additive development direction and data Innovative approaches to identifying useful,
new electrolyte additives How 3M is finding the needle in the hay stack 2
3M™ Battery Materials
3M Battery Materials – Enabling Lighter, Smaller, Safer, Higher Performing Lithium Ion Batteries. Batteries 3M™ NMC Cathode Compositions of layered Ni, Mn, and Co metal oxides for a balance of power, power energy, thermal stability and lower cost.
3M™ Battery Electrolyte HQ-115 Improves battery capacity retention and cycle life life. Reduces swelling and gas generation in thin form factor pouch cells.
3M™ Silicon-Based Anode* Twice the energy density vs. conventional graphite leading to a significant increase in cell energy.
3M Redox Shuttle BE 3M™ BE-3.9V 3.9V Chemical cell balancing that simplifies battery pack electronics and helps reduce cost.
3M™ Next Generation Electrolytes* Longer battery calendar life and improved p pperformance at high g voltage g and high temperatures.
3M™ High Energy Cathode* Breakthrough of 40% higher cell capacity when matched with 3M Si Anode leading to 25% to 40% increase in available cell energy.
*In development
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3M has capability in key lithium ion battery materials and has the unique ability to integrate new materials for customer-specific solutions.
3M™ Battery Materials
3M Battery Materials Technology Roadmap – Automotive LIB
With high performance separator
%Increase vs. vs current Hi or Low loading Si Anode type Cathode type Lower Cut-Off Voltage
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3M materials technology provides a path towards more than a 40% increase in energy
3M™ Battery Materials
3M™ Battery Electrolyte HQ-115 Uses Electrolyte Additive (2-5 wt% in electrolyte) Widely Wid l usedd ffor th the llastt 10 years Principal Electrolyte Salt Lithium Polymer Battery for EV or Telecom back-up applications Certain rechargeable coin cells and primary Li batteries
Benefits Improved capacity retention at high temperatures Reduced gas generation at high temps Reduced swelling/prismatic Reduced venting/round cell
Impedance control for improved cell life and safety Can impact cell design and total cost of the battery pack
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Li + -
N
SO2CF3 SO2CF3
3M™ Battery Materials
3M Battery Electrolyte HQ-115 additive for impedance control
Float Charge Test: 18650 Graphite/LiCoO2 cells
Single layer PE separator (23 micron), Constant 4.2V hold at 60oC Base Electrolyte: 1M LiPF6/EC:DMC:EMC (1:1:1) No additive vs. 4% HQ-115 additive
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• Shorting observed after ~ 20 days with no electrolyte additive present. • No shorting observed with 4% HQ-115 electrolyte additive after > 35 days • Can influence separator and cell design to provide lower total cell cost.
3M™ Battery Materials
Next Generation Electrolyte Additive Development Goals: Identify next generation electrolyte additives Primary objective is Improved High Temperature and High Voltage performance Strategy: Develop additives that are capable of forming a kinetically stabilizing film or layer on the electrode surface (anode or cathode) at low concentrations in electrolyte. Leverage 3M fluorochemical core competency > 25 fluorinated materials screened from 3M fluochemical library
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3M™ Battery Materials
Voltage Drop after Storage 0.12
Voltage Drop (V)
0.11 0.10 0.09 0 08 0.08 0.07 0.06 0.05
Developmental additives significantly reduce cell voltage drop after storage 8
3M™ Battery Materials
Reversible Capacity Loss on Storage Reversible C Capacity Losss (%)
12% 11% 10% 9% 8% 7% 6% 5%
Developmental additives reduce reversible capacity loss after storage 9
3M™ Battery Materials
Irreversible Capacity Loss after Storage I Irreversible C Capacity Loss (%)
7% 6% 5% 4% 3% 2% 1% 0%
Developmental additives reduce irreversible capacity loss after storage 10
3M™ Battery Materials
Long-term g Cycling y g after Storage g 1.05
1
95%
Capacity Re etention %
No ormalized Capaacity (cycle 1)
Capacity Retention at 200th Cycle
Power shut down
0.95
0.9
0.85
Control 1%L 20602A 1%L‐20602A 1%L‐21886 1%L‐21833 1%L‐19920
0.8
0.75 0
50
90% 85% 80% 75%
100
150
200
250
4.2-3.0V, C/2 rate, and 45oC Cycle
Developmental additives increased capacity retention after cycling 11
3M™ Battery Materials
Long-term Cycling after Storage 0.1
0.3
Control
0.25
1%L‐20602A 1%L‐21886 1%L‐21833
Normalized Vo oltage Hysterresis
Avverage Voltagge Hysteresiss (V)
0.35
0.08 0.06 0.04 Control 1%L‐20602A
0.02
1%L‐21886 1%L‐21833
1%L‐19920
0.2
1%L‐19920
0 0
50
100 150 Cycle
200
250
0
50
100 150 Cycle
200
Developmental additives reduced cell impedance rise during long term cycling 12
250
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Summaryy Developmental additives have demonstrated significant benefits
at low concentrations in electrolyte formulations Reduced voltage drop Reduced capacity loss Reduced cell impedance p rise after storage g at elevated temperature. p
Synergy has been observed between new additives and VC Combination of VC additives is most effective Cycle life improvement correlates with reduced cell impedance.
Developmental additives improve cycle life and reduce
impedance at high temperature
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3M™ Battery Materials
Acceleration of additive evaluation usingg high g throughput g p screening methods Project Goal: Identify electrolytes that will improve cycling of 3M Si alloy Anode and HE NMC Cathode Materials
Excerpt Presented with Permission from Wildcat Discovery Technologies Inc. 14
192 cells made in a single day
64 different electrolyte formulations
Project completion in 2.5 months
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Acceleration of additive evaluations using high precision coulometry 3M has supported ($$) the construction of this high precision system at Dalhousie University
• Traditional battery cyclers do not measure coulombic efficiency (CE) with g great accuracy. y • 100’s of cycles are necessary to identify effects of electrolyte additives on battery performance 1 BC723 Control 1% VC 2% VC
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CE
0.999
High precision coulometry distinguishes changes in coulombic efficiency in only 20 cycles, which greatly accelerates cell evaluation
0 998 0.998
0.997
0
4
8
12
16
Cycle 15
Excerpt Presented with Permission of Prof. Jeff Dahn
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3M™ Battery Materials
3M Battery Materials Laboratory Capability Materials, Electrochemical and Abuse Characterization
Powder x-ray diffraction BET surface area analysis Horiba Particle size analysis S State off Art 3M 3 Central C Analytical 250 m2 Dry room facility for cell assembly and electrolyte Cell Cycling Equipment >1,200 test channels Abuse testing (DSC, ARC, Hot Block, Thermal Ramp, Nail)
Pilot Scale Production and Evaluation
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Anode – Metal alloys and metals - >30 kg per batch Cathode - Novel cathode materials - >30 kg per batch Perfluorinated products and intermediates - 10Kg /wk Hirano Coater (High Precision Automated Electrode Coating 50 Ton calendar mills for electrode finishing 18650 cell winding, fill, and close - >100 cells per week. Stacked Stac ed Pouch ouc Ce Cell Capability Capab ty
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3M Battery Materials – R&D integration 3M Division Labs Product Commercialization • Materials Synthesis and Scale-up • Global Customer Support • Supporting Fundamental and Applied Materials Research
3M Country Labs Customer Commercialization • Applications Development • Specific Customer Materials Development and Scale-up
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3M Corporate Labs Next-Term R&D 2-5 yrs Out • Fundamental Materials Research • materials discovery • synthesis techniques • Disruptive Technology Selection
University / Dalhousie Long Term R&D 5-10 Long-Term 5 10 yrs Out • Fundamental Materials Research • materials discovery • synthesis techniques • Fundamentals of cell performance • Researcher Development
Thank You!
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