Research Progress of Advanced Lithium Ion Polymer...

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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: peter.cheng@highpowertech.com

.Mobile: +86-13537680342/15922000360

.Tel: +86-755-61862699 ext 836

.Fax:+86-755-29522241

.Web: www.highpowertech.com

.Nasdaq:HPJ