Lithium Ion Battery MaterialsSilicon Alloy Anode Introduction
March 2016
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Solutions for Lithium Ion batteries
Silicon alloy anode powders
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• 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
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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
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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
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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
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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
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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
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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
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• 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
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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
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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)
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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.
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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%
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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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