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Lithium Ion Battery MaterialsSilicon Alloy Anode Introduction

March 2016

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Solutions for Lithium Ion batteries

Silicon alloy anode powders

Nano-carbon coated Al current

collector

NMC cathode technology

Electrolyte salts and additives

Non-flammable liquid coolant

Acrylate and Fluoropolymer

binders

Thermally conductive tapes, adhesives and elastomers


• Nano-Si in inactive matrix

• Active/inactive domains < 15nm

• High first cycle efficiency

• Remains amorphous on cycling

• Minimizes surface area

• Dilutes volume expansion

• Scalable alloying process

3M Si Anode Design

active

inactive

Si-based alloy provides high energy and long cycle-life


Coin half cells• 91/9 alloy/LiPAA binder wt%

• Cycle 1• Lithiation: C/10 to 5 mV, C/40 trickle

• Delithiation: C/10 to 0.9 V

• Cycle 2+• Lithiation: C/4 to 5 mV, C/20 trickle

• Delithiation: C/4 to 0.9 V

High reversibility

Smooth voltage curve

Stable dQ/dV

Constant capacity

JECS, 161, A783

3M Alloys – Reversibility and Stability


original

improved

Improvements in design and synthesis result in more stable microstructure

dQ/dV peaks at 45 ºC after full lithiation are much more stable

Cycling Stability – dQ/dV

Cycles 10-20


100 150 200 250 300 350Temperature (°C)

0.1

1

10

dT/dt

(°C/

min)

0.1

1

10 LiC6

3M anode

Accelerating Rate Calorimeter (ARC)

Fully charged MCMB or 3M Si alloy reacting with

• EC/DEC

• 1M LiPF6 EC/DEC electrolyte

• 1M LiPF6 EC/DEC/FEC

Safety Testing – 3M high onset temperature


0

2

4

6

8

10

12

14

16

0

40

80

120

160

200

0:00 0:14 0:28 0:43 0:57

Volta

ge

Tem

pera

ture

(°C

)

Time ( Hr:min)

Block (°C)

18650 - pt 1(°C)

18651 -pt 2(°C)

18650 (V)

160ºC Hot Block Test

18650 with NMC and 3M Si alloy/graphite composite

• Formation cycle

• 1 week storage at 60ºC

• Fully charged

Max 10 ºC increase

No thermal run away

Safety Testing – 160ºC Hot Block Test


0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

100 1000

1.20 V

0.90 V

Cap

acity

/ Cap

acity

@C/

8

Specific Rate (mA/g)

C/8C/2

C2C

3C

Electrode Capacity :2.74 mAh/cm2 (C/8)

5C

Coin half cells• 91/9 alloy/LiPAA

Cell lithiated at C/8

Cell delithiated at various currents

Rate capability enables most major applications

3M Si Alloy Rate Capability

UCV


3M 18650 cycling 3M Si alloy/graphite

Expect >75% at 1000 cycles

83% at 500 cycles

On-going without sudden fade

65% at 1000 cycles

1700 cycles w/o sudden fade

18650 with 15%C7 / NCAHigh FEC electrolyte (30%FEC); C/2 charge, 1C discharge

18650 with 15%C7 / NMC622 Low FEC electrolyte (5%FEC); 1C charge, 1C discharge

Electrode: 3 mAh/cm2


• The contribution from the graphite and the alloy are strongly separated

• Higher rates somewhat smear the separation

• Automotive applications typically have limited depth of discharge scenarios

• The full cell can be designed such that the Si alloy is only used occasionally

Capacity Contribution from Graphite and Si Alloy

0 0.2 0.4 0.6 0.8 1Depth of Discharge

0

0.2

0.4

0.6

0.8

1

Cap

acity

Con

tribu

tion

Si AlloyGraphite

0 0.2 0.4 0.6 0.8 1Depth of Discharge

0

0.2

0.4

0.6

0.8

1

Cap

acity

Con

tribu

tion

Si AlloyGraphite

C/20 C/2


Impact on Driving Range

Addition of 15wt% 3M Si alloy to anode for a fixed volume battery.

graphite Si alloy

graphite

+10% energy

0 50 100 150 200 250Miles

Si alloy only cycled during extended driving


Impact on Driving Range

graphite Si alloy

0 50 100 150 200 250Miles

only ~3% probability once every 30 cycles

0 50 100 150 200 250Miles

Probability of Daily Miles Drivenstatistics from real drivers (voltstats.net)


Conceptual Diagram Comparing 3M Alloy to GraphiteCells always completely charged, but what if not always completely discharged?

If always full discharge, then 3M Alloy improves energy only 1st half of cell life.

If usually partially discharge, then 3M Alloy always improves energy.Note: graphite expected to perform worse if partially discharge (its more reductive potential burns electrolyte)

For the end-user, who usually only partially discharges, the 3M Alloy cell expected to consistently delivers higher energy.


In standard testing with full-discharges every cycle:• ~400 cycles to 80% capacity

For partial discharge to 75% (and full-discharge every 10th cycle):• >1000 cycles

For partial discharge to 50% (and full-discharge every 10th cycle):• >1200 cycles

Impact of Limited Depth of Discharge on Cycle Life (Pouch)

75%

50%


3M Silicon Alloy has the best combination of high energy density, low cost and good cycle life

3M Silicon Alloys have excellent long term potential for further energy increases with higher alloy loading

Why Silicon Alloy?Automotive Application Value Comparison

Note: Based on comprehensive cell model and mfg. cost assumptions. Dependence on material validated by prototype cell builds. Baseline from recent commercially available cells.

Cathode Type Si Type Loading Stack Wh/L Stack Wh/kg 18650 $/Wh Swelling Cycle Life Stack Wh/LNMC622 Graphite 0 763 286 0.155 Best BestNMC622 3M C7 Alloy 15% 838 302 0.149 Acceptable Acceptable 9.8%NMC622 Si-C 15% 835 305 0.149 Poor Poor 9.4%NMC622 SiO 15% 780 280 0.165 Good Good 2.2%


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Technical Information: The technical information, recommendations and other statements contained in this document are based upon tests or experience that 3M believes are reliable, but the accuracy or completeness of such information is not guaranteed.

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