New protocols for safe and long

lived LIB fast charging

Oumkeltoum Lazraq, Asela Bandara,
Audy B. M. Abduh, Rachid Yazami

4/4/2019 1
 KVI Group Organisation

KVI
Holding Company

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Outline
• A brief introduction to entropymetry
• Applications of entropymetry
• Fast charging methods
• “Natural charging”, Non-linear
Volammetry (NLV)
• “Cascade Pulse Charging” (CPC)
• Summary

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A brief introduction to entropymetry

• Basic equations:

(x)
(x)=OCV at any SOC ‘x’

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Entropymetry in 3 steps
10% SOC

3.72 25°C 25°C 26

Open Circuit Potential, OCP (V)

DS
24

DH
3.71 22

Temperature (°C)
20°C
20
3.70
18
C/6 15°C
3.69 16

3.68
OCP vs. T is
measured at #
14
12
OCP
SOC
10°C 10
3.67 OCP, entropy and
0 20 40 60 80 100 120 140 160 enthalpy are plotted
Time (min) vs. SOC

3.708
Open Circuit Potential, OCP (V)

3.706

3.704 Entropy and

3.702
enthalpy show more
variations than OCP
3.700
OCP vs. T
3.698 slope is
determined
3.696
10 12 14 16 18 20 22 24 26
Temperature (°C)

Confidential
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 Applications of entropymetry

Confidential
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Applications of entropymetry
1. Chemistry recognition

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2. SOC assessment

The Universal Battery SOC Law

• This law applies to all tested chemistries, including

 LIB, NiCd, NiMH,

 Li-MnO2, Li-FeS2
 Alkaline Zn/MnO2 and Zn/C cells

• the cell’ chemistry and on SOH

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 1. Alkaline Zn/MnO2 cells

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 SOC-DS-DH 3D plots

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 SOC vs. P.SOC
(P.SOC=predicted SOC from Equation 1)

a = -621.76
b = 0.3708
 = -4.510
R2=0.973

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 2. ZINC /CARBON DRY CELL

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 SOC vs. P.SOC

a = -383.19
b = 1.595
 = -3.414
R2 = 0.987

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 3. Lithium (primary) cells

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 a. Li/MnO2 cells

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 Cell1: 3D plots

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 SOC=f(∆S, ∆H)
• SOC= -1800+1,611 (∆S)-6,627(∆H)
• R²=0,9982

SOC (%)

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 Cell 2 3D plots

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 SOC vs. S, H
• ∆H=-286,89936+0,17536 ∆S
• R²=0,99213

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 b. Li/FeS2 cells

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 Li-FeS2 cells

SOC ∆ ∆

167.3 0.8 0.2 0.98

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2. SECONDARY (RECHARGEABLE) CELLS

a. Lithium Ion Cells

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 SOC-DS-DH 3D plots

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 SOC vs. (DS, DH)
SOC= a +bDS +DH

a = -471.6797
b = 0.4299
 = -1.4449

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Linear relationship applies to all LIB chemistries

#1 #2 #3

#4 #5

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 SOC vs. (DS, DH) linear relationship
Battery # a b  R2

1 -471.6797 0.4299 -1.4449 0.989

2 -422.2317 0.7183 -1.3116 0.996

3 -438.1669 0.3607 -1.3688 0.991

4 -445.4292 0.6906 -1.3734 0.994

5 -423.5349 0.4894 -1.3335 0.994

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 SECONDARY (RECHARGEABLE) CELLS

b. Ni-MH

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 SOC-DS-DH 3D plots Ni-MH

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 SOC linear relationship

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3. SOH assessment

on SOH
Cycle # SOH (%) a b  R2
(55 ºC, 1C-rate)
0 100 -523.56 0.31312 -1.6159

50 97.7 -453.82 0.08161 -1.4162

100 92.9 -438.82 0.15153 -1.3736

150 91.5 -417.76 0.024905 -1.3119

200 89.5 -414.18 0.081835 -1.3004 0.99+

50 88.5 -432.2 0.15816 -1.3561

300 86.6 -390.2 0.095205 -1.2439

350 84.7 -434.42 0.18258 -1.3638

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 4. SOS assessment

Internal short-circuit model for

thermal runaway

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4. SOS assessment
Internal Short-Circuit Detection

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4. SOS assessment
Internal Short-Circuit Detection

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4. SOS assessment
Internal Short-Circuit Detection

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 Internal Short-Circuit Detection

~3.70 V
~3.92 V ~3.80 V
~3.96 V

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The Imbedded Chip for online SOC, SOH and SOS
online assessment

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5. Fast charging: beyond CCCV
a. Non-linear voltammetry (NLV)

Solving a differential equation:

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Typical current, voltage, capacity
profiles during NLV charging

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 Charge-discharge profiles
NLV Only Charge & Discharge Profile
36 Mins (Avg)
5 4000

4.5
3000
4

3.5 2000

Current (mA)
1000
Voltage (V)

2.5
0
2

1.5 -1000
1
-2000
0.5

0 -3000
0 50 100 150 200 250 300 350 400
Time (mins)

Series2 Series1

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 Charge profile may be different at each cycle

6 3500

3000
5
2500

2000
4
1500

Current (mA)
Voltage (V)

3 1000

500
2
0

-500
1
-1000

0 -1500
0 50 100 150 200 250 300 350
Tmie (Mins)

Voltage Current

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 Intermittent NLV charge profile
5 10% 20% 30% 40% 50% 60% 70% 80% 90% 4.5
SOC
4.5 4

4
3.5

3.5
3
3
2.5
Voltage (V)

Current (A)
2.5
2
2
1.5
1.5

1
1

0.5 0.5

0 0
0 10 20 30 40 50 60
Time (mins)

Voltage(V) Current(A)

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 Temperature Profile
31
34.5
30.5
33.5
30
32.5
Cell 1 (Temperature) oC

Cell 1 (Temperature) oC
29.5
31.5
29
30.5
28.5

28 29.5

27.5 28.5

27 27.5

26.5 26.5
1:12:00 PM 2:24:00 PM 3:36:00 PM 4:48:00 PM 6:00:00 PM
Time (sec)

Series1 Series2

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Cycle capacity (charge time~36 min)

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5. Fast charging
b. Cascade Pulse Charge (CPC)

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CPC in 10 min: voltage profile

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CPC in 10 min
Current and voltage profile

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Cycle capacity (10 min CPC/-1C)

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 6-step CPC charging
CHARGE PROFILE
4.6

4.5

• C/5 - 2.5min
4.4

• C/2 – 1min
4.3

• C – 0.5min
4.2

4.1

• 2C – 15 sec
VOLTAGE(V)

• 4C – 7.5sec
3.9

• 6C – 5sec
3.8

3.7

3.6

step(SOC)=0.833%
3.5

3.4
0 10000 20000 30000 40000 50000 60000 70000 80000 90000 100000 110000 120000 130000 140000
TIME(S)

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 CPC Summary Table

Charging Highest
C1 C2 C3
Time (min) Voltage (V)
10 12 9 7 4.69

10 14 10 8 4.86
10 9 9 9 4.63
15 1 3 6 4.23
15 6 6 6 4.56
15 6 9 12 4.95
15 12 9 6 4.65
20 1 3 6 4.60
30 1.5 3.5 6.5 4.58
36 6 3 1 4.54
45 1 3 6 4.55

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Summary
• Entropymetry addresses major battery issues
including
• Chemistry, SOC, SOH and SOS
• Two ultra-fast charging methods have been
developed:
• NLV (natural charging in < 20 min)
• CPC (possibly in <10 min)
• These new methods are safe and allow for long
cycle life (>1300#)
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 Thank you
Rachid@kvi-battery.com

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