Research Progress of Advanced Lithium Ion Polymer Battery Technology
The 34th Florida International Battery Seminar
Peter Cheng
Highpower Research Institute
----------------------------------------------------March 21st,2017
Highpower Company Introduction
Highpower Battery Product & Application Introduction
4.45V High Energy Density Battery Technology
Polymer Power Battery Technology
Acknowledgements
Contact Information
Content
Company Introduction A Nasdaq(HPJ) Listed Company in 2008 Which Founded in 2001,Headquarter Located
in Shenzhen, China
With the employee in Shenzhen, Huizhou, Ganzhou, Suzhou, Hong Kong, Taiwan and San Francisco
Sales & Marketing
ResearchInstitute Finance HRSourcing &
Procurement
Ganzhou Highpower
President & CEO
Huizhou Highpower
Shenzhen Icon
ShenzhenHighpower
Shenzhen Springpower
IT
.NiMH .Polymer .Polymer/Cylindrical/Power Cell
.Total Solution .Recycle (NiMH & Li-ion)
Social ResponsibilityVision-Mission-Core Value
Huizhou Yipeng
Highpower Li-ion Battery Type
Highpower Li-ion Battery Application
High Energy Density Consumer Battery Roadmap Cathode System Improvement Anode System Improvement Electrolyte System Improvement 4.45V battery performance
• Charge/Discharge curve
• High temperature 85±2 ℃ storage performance
• High temperature 60±2 ℃ long time storage performance
• Low temperature performance
• Room 23±2℃ temperature cycle life performance
• High temperature 45±2 ℃ cycle life performance
• Safety performance
4.45V High Energy Density Battery Technology
High Energy Density Consumer Battery Roadmap
Cathode System Improvement
285 300 315 330 345 360 375 39090
100
110
120
130
140
150
160
170
180
2010 2012 2014 2016 2017 2018 2020
130mAh/gLFP 3.6V
156mAh/gLFP 3.6V
95mAh/gLMO 4.2V 150mAh/g
LMP 4.2V
160mAh/g
LMFP 4.2V
LVP 3.0-4.8V 152-163 mAh/g
LNMP 3.5-5.2V130mAh/g
LCoP 3.5-4.9V 130-140 mAh/g
2008
NMC 523
165/175mAh/g4.35/4.40V
142mAh/g
LCO-4.2V
Doping & Coating
LCO-4.55V
205mAh/g
2022
NCM 523155mAh/g
4.2V
NCM 811190/200mAh/g
4.20/4.35VNCM 622
178mAh/g4.35V
LCO-4.35/4.40V
Doping & Coating
165/172mAh/g
Doping & Coating
182mAh/g
LCO-4.45V
Doping & Coating
LCO-4.50V
194mAh/g
L2MO4.6-5.0V
xLi2MnO3•(1-x)LiMO2(M=Mn, Ni, Co)
250mAh/g
LiNi0.5Mn1.5O4 3.5-5.2V 140-148 mAh/g (Spinel)
NMC 424NMC 111 145 mAh/g
4.2V145 mAh/g4.2V
NCA185/195mAh/g
4.20/4.35V
High
Safety
High
Energy
Density
Cathode System Improvement
System update materials structure analysis:
4.20V LCO 4.35V LCO 4.45V LCO
4.45V LCO precursor doping technology
Element Weight Atom
O K 34.59 65.92Al K 0.39 0.44Co K 65.02 33.64Total 100
Cathode System Improvement
Precursor doping improve LCO structural stability; System update high potential materials show excellent stability , phase transition had been
suppressed; High potential material metal ions dissolution contend decreased obviously.
System update materials metal ions dissolution comparison:
Anode System ImprovementC
apac
ity D
ensi
ty (m
Ah/
g)
170
310
310
340
2000
450
20202009 2012 2013 2014 2016 2018 20222008
360
Artificial/Natural Composite Graphite
Modified Artificial Graphite
350 Amorphous CarbonCoating Modified
Graphite
350
Li Metal
Solid Battery
3600Metal/Carbon Composite
800450
Si(SiOx)/GraphiteHigh Energy Density
MCMB
310
LTO
170
Artificial Graphite
340
Hard/Soft Carbon
300HC
SC
Rapid charge
Anode System Improvement Deign thought SEM Anode energy density
First generation: conventional graphite
Third generation:
Second generation:
Easy graphitization; Secondary particle to decrease expansion;
Mix primary and secondary particle increaseefficiency and density;
Binder system:Acrylic acid
Normal SBR
FSN-1
Electrolyte System Improvement System update: optimize solvent and additive:
System Solvent Additive4.20V EC/DEC/EMC/PC VC/PS4.35V EC/DEC/EMC/PC FEC/PS/DTD/SN…4.45V EC/PC/DEC/PP FEC/PS/DTD/DENE/HTC..
Mechanism analysis:SN:
DENE:
OO N
N
DTD:
Charge/Discharge Curve Charge & discharge curve: Discharge plateau:
Ratecurrent
Voltage plateau
0.2C 3.876V
0.5C 3.776V
1.0C 3.664V
1.5C 3.592V
2.0C 3.574V
High Temp. Storage Performance(85℃) HT 85℃4hrs test data:
MARK Hot swelling
IMP increase
ratio
Residual capacity
ratio
Recovery capacity
ratio
4.45V-1# 3.93% 10.74% 94.53% 98.40%
4.45V-2# 3.91% 9.68% 92.47% 96.07%
4.45V-3# 2.45% 10.70% 92.63% 95.80%
Aver. 3.43% 10.37% 93.21% 96.75%
Min. 2.45% 9.68% 92.47% 95.80%
Max. 3.93% 10.74% 94.53% 98.40%
Performance chart:
High Temp. Long Time Storage Performance(60℃) 60℃21days test data: Performance chart:
NO Hot swelling Voltage retention
4# 7.21% 4.248
5# 7.39% 4.246
6# 7.12% 4.243
Aver. 7.24% 4.246
Min. 7.12% 4.243
Max. 7.39% 4.248
Low Temperature Performance
MARK ﹣20℃0.2C
﹣10℃0.2C
0℃0.2C
﹣15℃0.5C
﹣10℃0.5C
0℃0.5C
4.45V-7# 46.8% 83.4% 94.2% 30.0% 56.7% 76.5%
4.45V-8# 47.8% 83.3% 93.7% 37.1% 58.9% 78.3%
4.45V-9# 48.3% 82.5% 94.5% 37.9% 59.1% 81.7%
Aver. 47.6% 83.1% 94.2% 35.0% 58.2% 78.8%
Min. 46.8% 82.5% 93.7% 30.0% 56.7% 76.5%
Max. 48.3% 83.4% 94.5% 37.9% 59.1% 81.7%
Low temperature discharge data & performance chart:
Cell low temperature charge disassemble:0℃0.2C 0℃0.3C
Room Temperature Cycle Life Performance
Pass criteria:RT, 0.7/0.5C, 500 cyclescapacity retention≥80%, swelling ratio≤10%;
High Temperature Cycle Life Performance
Pass criteria:RT, 0.7/0.5C, 300 cyclescapacity retention≥80%,swelling ratio≤10%;
Safety Performance
Hot oven test (130℃/30min.) Passed
Short-circuit test (55℃) Passed
Overcharge test (3C/5V) Passed
Crush test Passed
Test Items Test Result
Power Battery Roadmap
High Energy Density Power Battery Performance
High Power Density Power Battery Performance
Highpower Polymer Power Battery Technology
Polymer Power Battery Roadmap
Cell model: HPD76130218AC Dimension: Max7.6*130*218
Chemical system: NCM with special coating technology (152mAh/g)/Graphite
Operation voltage: 2.8~4.2V, nominal voltage 3.7V@1C
Capacity: 20.0Ah(1C,min.),21.0Ah(1C,aver.),2.8V cut down
Cell energy density: 190Wh/Kg
Cell power density: 1200W/Kg
Standard charge/discharge rate: 0.5C/0.5C & 1CA/1CA
Charge & discharge parameter: 4.2V to 0.05C cut off, 2.8V cut down
Cell cycle Life: 1C charge/1C discharge
•Room temp. 2000 cycles 80% residual capacity 10% swelling rate (25℃)
•High temp. 1000 cycles 80% residual capacity 10% swelling rate (45℃)
Safety: QC/T 743
High temperature storage: 60℃/30 days, swelling rate less than 10%
High Energy Density Power Battery Performance
SOC(%)
OCV(V)
SOC(%)
OCV(V)
100 4.184 45 3.66195 4.113 40 3.64390 4.053 35 3.62985 3.999 30 3.61580 3.947 25 3.59875 3.895 20 3.57970 3.843 15 3.55265 3.794 10 3.52160 3.752 5 3.48755 3.715 0 3.44850 3.683
OCV Table & CurveTest Condition : •Charge by 1CA CC-CV to 4.2V while the charging current is taping to 0.05CA. And discharged 5% of the 1C capacity at constant current of 1CA. The discharge repeats 20 times. Cells rest 60 minutes after every discharge. OCV shall be recorded after every pause.
3
3.2
3.4
3.6
3.8
4
4.2
0 20 40 60 80 100O
CV
(V)
SOC(%)
OCV-SOC Profile
Rate Discharge Performance Test Condition : •Cells charged by 1CA to 4.2V while the charging current is taping to 0.05CA . And then discharged by 0.5C,1C,2C,3C,4C in turn.
No. Capacity Ratio0.5C 1C 2C 3C 4C 0.5C/20000mAh 1C/0.5C 2C/0.5C 3C/0.5C 4C/0.5C
1# 20526.1 20187.4 20009.2 20043.6 20003.3 102.63% 98.35% 97.48% 97.65% 97.45%2# 20598.9 20177 20000.2 20022.2 19950.1 102.99% 97.95% 97.09% 97.20% 96.85%3# 20409.0 20098.5 19983.9 19999.3 19971.2 102.05% 98.48% 97.92% 97.99% 97.85%
Spec ≥100% ≥97% ≥90% ≥80% ≥75%
2.5
2.7
2.9
3.1
3.3
3.5
3.7
3.9
4.1
4.3
0 5000 10000 15000 20000 25000
Volt
age/V
Capacity/mAh
HPD76130218AC-20000mAh Rate Discharge Performance
0.5C 1C 2C 3C 4C
2.5
2.7
2.9
3.1
3.3
3.5
3.7
3.9
4.1
4.3
4.5
0 5000 10000 15000 20000 25000
Voltage/V
Capacity/mAh
HPD76130218AC-20000mAh Temperature Discharge Performance
-20°C -10°C 0°C 25°C 55℃
Test Condition : •Cells charged by 1CA to 4.2V while the charging current is taping to 0.05CA at 25±5℃. Then stored under -20±2℃ , -10±2℃ , 0±2℃ for 24 hrs(and 55±2℃ for 4hrs), then discharge by 1C to 2.8V.
No. IMP(mΩ)
Voltage(V)
Capacity(mAh)
-20℃ 55℃Deformation BrokenCapacity(mAh) Ratio Capacity(mAh) Ratio
1# 1.7 4.184 20629.2 13022.5 63.10% 22144.8 107.35% NO NO2# 1.6 4.186 20693.4 13540.7 65.40% 22260.5 107.57% NO NO3# 1.7 4.188 20730.1 13670.9 65.95% 22233.8 107.25% NO NO
Spec ≥50% ≥95% ND/NB
Temperature Discharge Performance
60℃/30 Days Storage TestTest Condition : •Cells charged by 1CA to 4.2V while the charging current is taping to 0.05CA. Kept under 60±2℃ for 30 days, then rest at 25±5℃ for 2hrs. Discharged by 1C to 3.0V,standby for 10 minutes and then charged and discharged for 3 cycles.
CellNo
Original data After 60℃/ 30days
Full Charge state Hot state Cooling to Room Temperature Residual. Cap. Recovery. Cap.
OCV (V)
IMP/mohm
THK 1 /mm
initial cap. /mAh
THK 2/mm
Swelling/%
OCV (V)
Vol. drop/%
IMP/mohm
IMPIncreasing
/%
THK3 /mm
Swelling/% mAh △% mAh △%
1# 4.195 1.7 7.27 20828 7.73 6.33 4.09 2.57 1.8 5.88 7.43 2.20 18973 91.09 20418 98.032# 4.185 1.8 7.35 20881 7.72 5.03 4.084 2.47 2.0 11.11 7.46 1.50 19162 91.77 20654 98.913# 4.194 1.7 7.30 20905 7.74 6.03 4.089 2.50 1.9 11.76 7.46 2.19 19268 92.17 20489 98.01
Spec (Reference) Residual capacity ≥85%; Recovery capacity ≥90%
60%
70%
80%
90%
100%
110%
0 300 600 900 1200 1500 1800 2100 2400
Perce
ntage
76130218-20Ah 25℃ 1C/1C Cycle
1#
2#
3#
RT Cycle Life PerformanceTest Condition : •Charge @25℃: Charged by 1CA to 4.2V while the charging current is taping to 0.05CA. Rest for 10min.Discharge @25℃: Discharged by 1CA to 3.0V. Rest for10min
Criteria:80% after 2000cycles
Test Condition : •Charge @45℃/60℃: Charged by 1CA to 4.2V while the charging current is taping to 0.05CA. Rest for 10min.Discharge @45℃/60℃ :Discharged by 1CA to 3.0V. Rest for10min
60%
70%
80%
90%
100%
110%
0 300 600 900 1200 1500 1800
Perc
enta
ge
76130218-20Ah 45℃ 1C/1C Cycle
1#
2#
3#
60%
70%
80%
90%
100%
110%
0 300 600 900 1200 1500 1800
Perc
enta
ge
76130218-20Ah 60℃ 1C/1C Cycle
1#
2#
3#
HT Cycle Life Performance
Criteria:80% after 1000cycle. Criteria:80% after 800cycle.
Overcharge Test(1C/5.0V) 5pcs Passed
Test Items
Nail penetration 5pcs Passed
Safety Performance
Heating test (130℃/30min.) 5pcs Passed
Short-circuit(55℃) 5pcs Passed
Crush test 5pcs Passed
Impact Test 5pcs Passed
Sample Size Test After Conclusion
High Power Density Power Battery Performance Cell model: HPD10161221AD Dimension: Max10.5*165*223
Chemical system: NCM with special coating technology (145mAh/g)/Graphite
Operation voltage: 3.0~4.2V, nominal voltage 3.7V@1C
Capacity: 18.0Ah(1C,min.),18.5Ah(1C,aver.),3.0V cut down
Cell energy density: 130Wh/Kg
Cell power density: 2700W/Kg
Standard charge/discharge rate:1.0C/1.0C
Charge & discharge parameter: 4.2V to 0.05C cut off, 3.0V cut down
Cell cycle Life: 1.0C charge/1.0C discharge or 4.0C charge/5.0C discharge
•Room temp. 2000 cycles 80% residual capacity 10% swelling rate(4C/5C)
•High temp. 1000 cycles 80% residual capacity 10% swelling rate (45 ℃,1C/1C)
Safety: GB/T 31485
Test Condition : •Charge by 1CA CC-CV to 4.2V while the charging current is taping to 0.05CA. And discharged 5% of the 1C capacity at constant current of 1CA. The discharge repeats 20 times. Cells rest 60 minutes after every discharge. OCV shall be recorded after every pause.
SOC(%)
OCV(V)
SOC(%)
OCV(V)
100 4.185 45 3.720 95 4.126 40 3.700 90 4.072 35 3.681 85 4.022 30 3.664 80 3.976 25 3.643 75 3.932 20 3.616 70 3.890 15 3.593 65 3.848 10 3.568 60 3.806 5 3.540 55 3.772 0 3.503 50 3.744
3
3.2
3.4
3.6
3.8
4
4.2
0 20 40 60 80 100O
CV(V
)SOC(%)
OCV-SOC Profile
OCV Table & Curve
No. CC-CV Capacity(mAh) CC-Capacity(mAh) CC-Ratio1C 2C 3C 5C 1C 2C 3C 5C 1C 2C 3C 5C
1# 18479.3 18595.4 18635.2 18654.1 17238.3 16604.9 15979.3 15496.4 93.28% 89.30% 85.75% 83.07%
2# 18416.6 18523.2 18587.3 18640.7 17553.1 16764.7 16021.6 15430.6 95.31% 90.51% 86.20% 82.78%
3# 18290.0 18312.5 18339.4 18410.3 17082.1 16511.4 15773.5 15290.1 93.40% 90.16% 86.01% 83.05%
Spec 5C,CC capacity ≥ 80% 5C CC-CV capacity
Test Condition : •Cells discharged by 1CA to 3.0V. And then charged by 1C,2C,3C,5C, 8C to 4.2V with 0.05CA cut-off in turn.
Rate Charge Performance
3.43.53.63.73.83.9
44.14.24.3
0 3600 7200 10800 14400 18000 21600
Volta
ge/V
SOC/%
Rate Charge Performance
1C
2C
3C
5C
0 20 40 60 80 100 1200
20406080
100120140160
0 3880 7760 11640 15520 19400 23280Ti
me/
min
.SOC/%
Time- SOC Profile
1C
2C
3C
5C
0 20 40 60 80 100
No. Capacity(mAh) Ratio1C 3C 5C 8C 1C 3C 5C 8C
1# 18489.6 17863.8 17032.1 16922.3 100.00% 96.62% 92.12% 91.52%2# 18458.7 17867.5 17026.9 16918.4 100.00% 96.80% 92.24% 91.66%3# 18619.3 17933.5 17443.4 17109.1 100.00% 96.32% 93.68% 91.89%
Spec 8C capacity≥88% initial capacity
Test Condition : •Cells charged by 1CA to 4.2V while the charging current is taping to 0.05CA . And then discharged to 3.0V by 1C,2C,3C,5C, 8C in turn.
Rate Discharge Performance
2.5
2.8
3.1
3.4
3.7
4
4.3
0 3720 7440 11160 14880 18600
Voltage
/V
SOC/%
Rate Discharge Performance
1C
3C
5C
8C
0 20 40 60 80 100
Test Condition : •Cells Charged by 1CA to 4.2V while the charging current is taping to 0.05CA at 25±5℃. Then stored under -20±2℃ for 24 hrs(or 55±2℃ for 5 hrs), then discharge by 1CA to 2.5V.
No. IMP(mΩ)
Voltage(V)
Capacity(mAh)
-20℃ 55℃Deformation Broken
Capacity(mAh) Ratio Capacity(mAh) Ratio1# 0.75 4.177 18295.3 13205.1 72.18% 19220.1 105.05% NO NO2# 0.76 4.179 18448.6 13189.3 71.49% 19284.5 104.53% NO NO3# 0.78 4.181 18453.8 13213.5 71.60% 19422.2 105.25% NO NO
Spec ≥70% ≥95% ND/NB
Temperature Discharge Performance
2
2.5
3
3.5
4
4.5
0 3500 7000 10500 14000 17500
Volta
ge/V
SOC/%
Temperature Discharge Performance
-20℃
25℃
55℃
0 20 40 60 80 100
HPPC Performance Test Condition : •Cells Charged by 1CA to 4.2V while the charging current is taping to 0.05CA at 25±5℃. Then measure 5C/10s discharge power at every 10% SOC, rest 1hr between every two pulse.
1000
1500
2000
2500
3000
3500
4000
4500
90% 80% 70% 60% 50% 40% 30% 20%
Pow
er D
ensit
y(W
/kg)
HPPC Performance
1#
2#
3#
Temperature Increment Analysis Test Condition (45 ℃) :• Charge by CC=4C to 4.20V then CV=4.20V to current drop to 0.05C and then discharge by CC=5.0C to 3.0V.
60%
70%
80%
90%
100%
110%
0 300 600 900 1200 1500 1800 2100 2400
Percen
tage
10161221-18Ah 25℃ 4C/5C Cycle
1#
2#
3#
Test Condition : •Charge @25℃: Charged by 4CA to 4.2V while the charging current is taping to 0.05CA•Rest for 10min.•Discharge @25℃: Discharged by 5CA to 3.0V. Rest for 10min
RT Cycle Life Performance(4C/5C)
Criteria:80% after 2000cycle.
60%
70%
80%
90%
100%
110%
0 300 600 900 1200 1500 1800 2100 2400
Perce
ntage
10161221-18Ah 25℃ 1C/1C Cycle
1#
2#
3#
Test Condition : •Charge @25℃: Charged by 1CA to 4.2V while the charging current is taping to 0.05CA•Rest for 10min.•Discharge @25℃: Discharged by 1CA to 3.0V. Rest for 10min
RT Cycle Life Performance(1C/1C)
Criteria:80% after 2000cycle.
60%
70%
80%
90%
100%
110%
0 300 600 900 1200 1500
Perce
ntage
10161221-18Ah 45℃ 1C/1C Cycle
1#
2#
3#
HT Cycle Life PerformanceTest Condition : •Charge @45℃: Charged by 1CA to 4.2V while the charging current is taping to 0.05CA•Rest for 10min.•Discharge @45℃: Discharged by 1CA to 3.0V. Rest for 10min
Criteria:80% after 1000cycle.
Overcharge Test(1C/5.0V) 5pcs Passed
Test Items
Nail penetration 5pcs Passed
Safety Performance
Heating test (130℃/30min.) 5pcs Passed
Short-circuit(55℃) 5pcs Passed
Crush test 5pcs Passed
Impact Test 5pcs Passed
Sample Size Test After Conclusion
Highpower International: Chen Qiduo, Liu Chan, Yu Lijuan, etc.
Acknowledge
Contact Information.Peter Cheng
.Email: [email protected]
.Mobile: +86-13537680342/15922000360
.Tel: +86-755-61862699 ext 836
.Fax:+86-755-29522241
.Web: www.highpowertech.com
.Nasdaq:HPJ
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