3M Advancements in Electrolyte AdditivesThe Battery Show, November 12-14, 2012

3M™ Battery Materials

AgendaAgenda

Advances in 3M LIB Electrolyte Developmenty pHow additives can impact battery performance and help lower costspNext generation 3M additive development direction and data

Innovative approaches to identifying useful, new electrolyte additivesnew electrolyte additivesHow 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 Higher Performing Lithium Ion Batteries.

3M™ NMC Cathode Compositions of layered Ni, Mn, and Co metal oxides for a balance of power

3M™ Battery Electrolyte HQ-115Improves battery capacity retention and cycle life Reduces swelling and

3M™ Silicon-Based Anode*

metal oxides for a balance of power, energy, thermal stability and lower cost.

and cycle life. Reduces swelling and gas generation in thin form factor pouch cells.3M™ Redox Shuttle BE-3.9V

Twice the energy density vs. conventional graphite leading to a significant increase in cell energy.

3M Redox Shuttle BE 3.9VChemical cell balancing that simplifies battery pack electronics and helps reduce cost.

3M™ Next Generation Electrolytes*Longer battery calendar life and improved performance at high voltage

3M™ High Energy Cathode*Breakthrough of 40% higher cell capacity when matched with 3M Si p p g g

and high temperatures.capacity when matched with 3M Si Anode leading to 25% to 40% increase in available cell energy.*In development

3

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

%Increase vs current

performance separator

%Increase vs. currentHi or Low loading Si Anode type

Cathode typeLower Cut-Off Voltage

4

3M materials technology provides a path towards more than a 40% increase in energy

3M™ Battery Materials

3M™ Battery Electrolyte HQ-115N

SO2CF3Li + -

UsesElectrolyte Additive (2-5 wt% in electrolyte)

Wid l d f th l t 10

NSO2CF3

Li

Widely used for the last 10 yearsPrincipal Electrolyte SaltLithium Polymer Battery for EV or Telecom back-up applicationsCertain rechargeable coin cells and primary Li batteries

BenefitsImproved capacity retention at high temperaturesImproved capacity retention at high temperaturesReduced gas generation at high tempsReduced swelling/prismaticReduced venting/round cellReduced venting/round cell

Impedance control for improved cell life and safetyCan impact cell design and total cost of the battery pack

5

3M™ Battery Materials

3M Battery Electrolyte HQ-115 additive for impedance control

Float Charge Test: 18650 Graphite/LiCoO2 cellsSingle layer PE separator (23 micron), Constant 4.2V hold at 60oC

Base Electrolyte: 1M LiPF6/EC:DMC:EMC (1:1:1)Base Electrolyte: 1M LiPF6/EC:DMC:EMC (1:1:1)No additive vs. 4% HQ-115 additive

• Shorting observed after ~ 20 days with no electrolyte additive present.

6

• 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 DevelopmentGoals:Identify next generation electrolyte additivesPrimary objective is Improved High Temperature and HighVoltage performance

Strategy:Develop additives that are capable of forming a kinetically stabilizing film or layer on the electrode surface (anode or cathode) 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

7

3M™ Battery Materials

Voltage Drop after Storage

0.11

0.12

0 08

0.09

0.10

Drop

 (V)

0.06

0.07

0.08

Volta

ge 

0.05

Developmental additives significantly reduce cell

8

Developmental additives significantly reduce cell voltage drop after storage

3M™ Battery Materials

Reversible Capacity Loss on Storage

11%

12%

s (%)

8%

9%

10%

Capacity Loss

5%

6%

7%

Reversible C

5%

Developmental additives reduce reversible

9

capacity loss after storage

3M™ Battery Materials

Irreversible Capacity Loss after Storage

6%

7%

(%)

3%

4%

5%

Capacity Loss 

1%

2%

3%

Irreversible C

0%

I

Developmental additives reduce irreversible

10

Developmental additives reduce irreversible capacity loss after storage

3M™ Battery Materials

Long-term Cycling after Storage

1

1.05

Power shut down

g y g g

Capacity Retention at 200th Cycle

0.95

1

acity

 (cycle 1)

85%

90%

95%

eten

tion %

0.85

0.9

ormalized

 Cap

a

Control1%L 20602A 75%

80%

85%

Capa

city Re

0.75

0.8

0 50 100 150 200 250

No 1%L‐20602A

1%L‐218861%L‐218331%L‐19920

75%

0 50 100 150 200 250Cycle 4.2-3.0V, C/2 rate, and 45oC

Developmental additives increased capacity

11

Developmental additives increased capacity retention after cycling

3M™ Battery Materials

Long-term Cycling after Storage0.35

s (V)

0.08

0.1

resis

0.3

ge Hysteresis

0.06

oltage

 Hyster

0.25

verage

 Voltag

Control

1%L‐20602A

1%L‐21886 0.02

0.04

ormalize

d Vo

Control

1%L‐20602A

1%L‐21886

0.20 50 100 150 200 250

Av

Cycle

1%L‐21833

1%L‐19920

00 50 100 150 200 250

NCycle

1%L‐21833

1%L‐19920

Cycle Cycle

Developmental additives reduced cell impedance

12

Developmental additives reduced cell impedance rise during long term cycling

3M™ Battery Materials

Summaryy Developmental additives have demonstrated significant benefits

at low concentrations in electrolyte formulations Reduced voltage drop Reduced capacity loss Reduced cell impedance rise after storage at elevated temperature.p g 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 temperatureimpedance at high temperature

13

3M™ Battery Materials

Acceleration of additive evaluation using high throughput g g g pscreening methods

Project Goal: Identify Project Goal: Identify electrolytes that will improve cycling of 3M Si alloy Anode and HE NMC Cathode MaterialsHE NMC Cathode Materials 192 cells made in a single day 64 different electrolyte

formulations Project completion in 2.5

months

14

Excerpt Presented with Permission from Wildcat Discovery Technologies Inc.

3M™ Battery Materials

Acceleration of additive evaluations using high precision coulometry3M has supported ($$) the construction of this high precision system at Dalhousie University

• Traditional battery cyclers do not measure coulombic efficiency (CE) with great accuracy.g y

• 100’s of cycles are necessary to identify effects of electrolyte additives on battery performance

24

1BC723

Control1% VC2% VC

0 998

0.999

CE High precision coulometry

distinguishes changes in

0.997

0.998 coulombic efficiency in only 20 cycles, which greatly accelerates cell evaluation

15

0 4 8 12 16 20Cycle

Excerpt Presented with Permission of Prof. Jeff Dahn

3M™ Battery Materials

3M Battery Materials Laboratory CapabilityMaterials, Electrochemical and Abuse Characterization Powder x-ray diffraction BET surface area analysis Horiba Particle size analysis

S f 3 C State of Art 3M Central 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 Anode – Metal alloys and metals - >30 kg per batch Cathode - Novel cathode materials - >30 kg per batch Perfluorinated products and intermediates 10Kg /wk 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 Pouch Cell CapabilityStac ed ouc Ce Capab ty

16

3M™ Battery Materials

3M Battery Materials – R&D integration

Product Commercialization

3M Division Labs 3M Corporate LabsNext-Term R&D 2-5 yrs Out• Fundamental Materials Research• Materials Synthesis and Scale-up

• Global Customer Support• Supporting Fundamental and Applied

Materials Research

• Fundamental Materials Research• materials discovery• synthesis techniques

• Disruptive Technology Selection

3M Country LabsLong-Term R&D 5-10 yrs Out

University / Dalhousie

Customer Commercialization• Applications Development• Specific Customer Materials

Development and Scale-up

Long Term R&D 5 10 yrs Out• Fundamental Materials Research

• materials discovery• synthesis techniques

• Fundamentals of cell performance• Researcher Development

17

Thank You!Thank You!

Electronics Markets Materials Division3M Electronics3M Center, Building 225-3S-06St. Paul, MN 55144-1000

Warranty and Limited Remedy: 3M warrants that each 3M product meets the applicable 3M product specification at the time 3M ships the product. 3M MAKES NO OTHER EXPRESS OR IMPLIED WARRANTIES OR CONDITIONS, INCLUDING ANY IMPLIED WARRANTY OR CONDITION OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. If the 3M product does not conform to this warranty, the sole and exclusive remedy is, at 3M’s option, replacement of the 3M product or refund of the purchase price. Limitation of Liability: Except where prohibited by law, 3M will not be liable for any loss or damage arising from the 3M product, whether direct, indirect, special, incidental or St. Paul, MN 55144 1000

www.3M.com/electronics consequential, regardless of the legal theory asserted.

© 3M 2013. All rights reserved. 3M is a trademark of 3M Company.