納米復(fù)合材料在高性能鋰電池中的應(yīng)用

1、Nanocomposite Electrode Materials for High Energy Lithium Batteries Outline Status of Lithium Battery Industry in Taiwan High Capacity Li-rich Composite Cathode Materials High Capacity Si/Carbon NanocompositeAnode Materials Taiwan Lithium Battery Industry Cell 能元(E-ONE Moli) 有量(Amita) 必翔電能(Pihsiang)

2、 興能(SYNergy) 動能(EXAEnergy) 昇陽(PSI) etc. total 11s System EV 華創(chuàng)(Haitec) 勝榮(Kortus) 中華(China Motor) ES 中華(China Motor) 光陽工業(yè)(Kymco) 三陽(Sanyang) 益通(E-Ton) 必翔(Pihsiang) 山葉(Yamaha) etc. total 10s EB 巨大(Giant) 美利達(dá)(Merida). Power Scooter 必翔(Pihsiang) Battery Module/ Power Management Battery Module 新普(Simplo

3、) 順達(dá)科(DynaPack) 正崴(Foxlink) 能元(E-ONE Moli) 加百裕(Celxpert) 達(dá)振(CT Hitech) etc. total 20s Power Management 臺達(dá)電(Delta) 光寶(Liteon) 能元(E-ONE Moli) 致茂(Chroma) 達(dá)振(CT Hitech) Material Cathode 臺塑長園(Formosa Energy ) 立凱(Aleees) 尚志精密(Tatung) 宏瀨(Hirose) etc. total 10s Anode 中碳(China Steel Carbon) 義芳(Yee Fong ) Ele

4、ctrolyte 臺塑(Formosa) Separator 明基材料(BenQ Materials) Substrate 南亞(Nan Ya) 金居(Golden Copper) Li Battery Industry Supply Chain in Taiwan Taiwan Li-ion battery industry, with a domestic industrial chain of upstream materials, midstream electrode/module and downstream system , has successfully penetrated

5、 in power battery market. For energy saving and CO2 reduction, E-scooter and E-bus subsidization programs are applied in Taiwan. Additives 中碳(CSCC)高銀化學(xué) 榮碳(Long Time) (Formosa Plastic)(HOPAX) 明基材料 新永裕 Components Li-ion Battery Material Industry in Taiwan Material Industry: Cathode Materials 康普(Comax)

6、 鋰科(LICO) 鐵研(TAK) 宏森 臺塑鋰鐵 (Formosa Energy ) 立凱(Aleees ) 尚志(Tatung) 宏瀨(Hirose) 倍特利 Anode Separator Electrolyte Materials (Coin Chem.) 義芳(Yee Fong) (BenQ Materials) 前瞻能源 Battery Facility 宏全(Hon Chuan) 亞泰金屬(AMI) 沖壓精密(CIPC) 海金 長春 友煜(Unitronic) 臺日古河 固緯(Good Will) 金居(Golden Copper) 世宏 和勤(CFTC) 新德 聚鼎 LiFeP

7、O4 1. About the LFPpositive materials investment and production contain Formosa Energy ( invested 0.8 BNT$/annual capacity of 4800T), Aleees ( sales up to 200T in 2009 and additional 0.6 BNT$ investment/annual capacity of 3600T), Tatung ( 0.7 BNT$ investment/annual capacity of 4320T) and Hirose ( 0.

8、6 NT$ investment/annual capacity of 3600T). 2. The W.W. market share of LFPpositive material is higher than 43% (Taiwan:1800T/ W.W. 4200T) 臺塑 聚和 ITRI Where Taiwans High-tech Began Kodak Lithium Battery Standard Taiwan/ Ph. D. Joint Lab. Joint Program Optical UC Berkeley USA/ North Western U. Testing

9、 TCO Film Russia/ MSU-ITRI Joint Lab. Russia/ Ioffe Ukrain/ Inst. of TE Energy Harvesting Biomass Solar Tech Flexible Electronics Evonik Degussa Taiwan/ ITRI- NCU Joint Lab. International LC Simulation Rheology Simulation Fuel Cell LocalAcademia Taiwan/ ITRI-NTU Energy Material Eco Material Bio Mate

10、rial 6 students BASF Dow Fuel Cell IC Materials Battery SONY Electronic Material Nokia Precision Coating International &Academia Cooperation Anti UV/ Self Cleaning Nano Coating Behr Taiwan, China Bureau of Standard Swiss/ Fribourg U. Dispersion Tohoku U. Kyoto U. Nano Materials Testing Clay AIST Nan

11、oblending PALS Calibration LCD Rubbing Cloth Electrode and Jelly Roll Conducting Mechanism Simulation Safety Verification Performance TestModule TestCell Fab.Safety Test Anode / Cathode synthesis micro-structure Design High V electrolyte Capacity control Material Development Paste control Thermal/El

12、ectrical Design/ simulation Safety control sealing Cell Design Recipe of Material System Mathematical Model and Capacity and Energy Density Specific Power High Current Capability Cycle life and Storage/Shelf Life Impedance Analysis Failure Mechanism Thermal /Electrical conduction Mechanical design/s

13、imulation SOC Information Cell Equalization Protection Battery Module Design Mechanical Abuse Performance Test Electrical Abuse Abnormal Environment From Cell toApplication Lithium Ion Battery Verification Platform in ITRI Anode Material High-Rate Charge High Capacity Cathode Material High Capacity

14、High Voltage Separator Low Cost Safety Electrolyte Safety High Voltage Innovation and Goal for Each Li Battery Materials High Capacity Li-rich Composite Cathode Material Voltage(V) Capacity (mAh/g) 0100200300400 Capacity(mAh/g) 2.0 3.0 4.0 5.0 A104231S2 0.5C D(2-4.8V):211.31 mAh/g Qirr=55 Q=250 0102

15、03040506070 50 0 100 200 150 250 Cycle number 0.2C/0.2D 0.6 LiLi1/3Mn2/3O2 0.4 LiNi0.4Co0.2Mn0.4O2 A10423-1S mixer c-rate retest(0.1C/0.1C*2-0.2C/0.2C*1-0.2C/0.5C) (11) For C(0.1C-1st:2-4.8V):305.12 mAh/g For D(0.1C-1st:2-4.8V):250.54 mAh/g For C(0.1C-2nd:2-4.8V):253.76 mAh/g For D(0.1C-2nd:2-4.8V):

16、248.77 mAh/g 0.2C C(2-4.8V):243.22 mAh/g 0.2C D(2-4.8V):228.02 mAh/g 0.2C C(2-4.8V):232.41 mAh/g Electrochemical Properties of Composite Cathode Tap density=1.78 Voltage(V) Z Capacity(mAh/g) 11 050100150200250300350400 0 50 100 150 200 250 80% Cycle no. Tap density= 2.1 g/cm3 0.2C/0.5C 0501001502002

17、50300350 2.0 4.0 3.5 3.0 2.5 4.5 Capacity(mAh/g) 0.1C(4.8V):309.36 0.1D(4.8V):231.71 0.1C(4.6V):211.31 0.1D(4.6V):210.59 0.2C:198.76 0.2D:192.08 0.2C:193.71 0.5D:179.58 0.2C:179.31 1D:168.18 0.2C:167.83 2D:151.45 0.2C:151.64 3D:138.72 Irriversible :77.65 A1-0626-5S .76 204080100120 10 0 30 20 40 50

18、60 70 Z 5cycle 85cycle 60 () () AC impedance D50 21 m d100 nm 0Rs Rsei Rct Rct Rsei Li1.2Ni0.16Co0.08Mn0.56O2 Electrochemical Properties of Composite Cathode Nanocomposite powders increase RT the rate capability of composite cathode 5.0 Voltage ( V ) 050100150200250 5.0 4.5 4.0 3.5 3.0 2.5 2.0 0.2C

19、/ 0.5C 10th 210.60 0.2C / 0.5C 100th 194.53 0.2C / 0.5C 200th 182.71 0.2C / 0.5C 350th 171.14 (mAh/g) Capacity( mAh/g ) Cycle Life of Composite Cathode Long cycle life and voltage decay issue for composite cathode 0.6 LiLi1/3Mn2/3O2 0.4 LiNi0.4Co0.2Mn0.4O2 Voltage(V) Z 050100150200250300350 2.0 4.0

20、3.5 3.0 2.5 4.5 Capacity(mAh/g) 0.1C(4.8V):288.50 0.1D(4.8V):251.83 0.1C(4.6V):239.69 0.1D(4.6V):238.32 0.2C:227.64 0.2D:218.27 0.2C:215.57 0.5D:199.56 0.2C:197.95 1D:181.17 0.2C:180.21 2D:156.11 0.2C:155.83 3D:135.26 Irriversible :37.12 020406080100120 40 30 20 10 0 50 60 Z 85cycle () () AC impedan

21、ce Performance of Composite Cathode by Surface Nanocoating Reduce the irreversible capacity loss of composite cathode by VOx nanocoating VOx-coated 0.6 LiLi1/3Mn2/3O2 0.4 LiNi0.4Co0.2Mn0.4O2 .95 RT 5.0 70 5cycle Heat Flow (mW/mg) 14 240245250255260 -30 -35 DSC profiles of pristine & VOxsurface-coate

22、d 0.6 LiLi1/3Mn2/3O2 0.4 LiNi0.4Co0.2Mn0.4O2 5 0 -5 -10 -15 -20 -25 o 0.4A-0.6B 0.4A-0.6B-VOx pristine surface-coated Voltage(V) Z M-doped 0.6 LiLi1/3Mn2/3O2 0.4 LiNi0.4Co0.2Mn0.4O2 050100150200250300350 2.0 3.5 3.0 2.5 4.5 4.0 5.0 Capacity(mAh/g) 0.1C(4.8V):310.38 0.1D(4.8V):263.37 0.1C(4.6V):240.8

23、9 0.1D(4.6V):241.06 0.2C:227.16 0.2D:219.63 0.2C:217.46 0.5D:204.77 0.2C:203.73 1D:190.66 0.2C:190.00 2D:170.90 0.2C:171.50m 3D:156.93m Irriversible :47.01 A1-0626-20Cr.74RT 0204080100120 40 30 20 10 0 60 50 70 5cycle 85cycle 60 Z() () AC impedance Performance of Composite Cathode by Metal Doping Re

24、duce the voltage decay of composite cathode by metal doping Average Voltage Voltage(V) Pristine 16 050100150200250 2.0 4.0 3.5 3.0 2.5 4.5 5.0 Capacity(mAh/g) 10cycle 30cycle 50cycle 84cycle A2-0709-1S.35RT 020406080100120140160180 3.25 3.40 3.35 3.30 3.45 3.50 Cycle Pristine 0729-1CrM-doped Perform

25、ance of Composite Cathode by Metal Doping Reduce the voltage decay of composite cathode by metal doping Pristine vs. M-doped High Capacity Si/Carbon NanocompositeAnode Material Composite Cathode(+) Capacity250mAh/g SiAlloy/Carbon CompositeAnode() Capacity1000mAh/g New Entry Barrier 18 Energy Density

26、350 Wh/Kg Energy Density280 Wh/Kg LiNiCo(M)O2(+) Capacity180mAh/g Nano Si/Carbon NanocompositeAnode() Capacity600mAh/g Energy Density:200 Wh/Kg LiNiCoMnO2(+) Capacity:165mAh/g Capacity limitation for traditional anode materials Graphite() Capacity:350mAh/g Cylindrical Li Battery(18650) CompositeAnod

27、e Materials for High Energy Density Li Battery High-capacity anode material is the key material for high-energy density Li battery High Energy Li Battery Approach: Nanostructure (nano-Si) alleviates cracking problem Core-Shelled structure reinforces structural integrity Uniform pores absorb volume e

28、xpansion of nano-Si Reduce the irreversible capacity loss of Si/Carbon nanocomposite anode by carbon coating layer. High-Capacity Si/Carbon NanocompositeAnode Material Irreversible capacity loss1,450mAh (80%) Cell Discharge Capacity of NanocompositeAnode Material LiFePO4-Graphite (Si/C + Graphite) 1

29、8650 power Cell Capacity increase more than 35% Electrochemical Properties of NanocompositeAnode Material LiFePO4-Si/C + Graphite 18650 Cell after test Safety Test - Overcharge LiFePO4-Si/C + Graphite 18650 Cell Standard: 3C charge for 3 hours，the cell shall not explode or catch fire Result: Pass Test data Before test Standard: Before test after test The cell is to be crushed between 2 flat surface, the crushing is to be continued to 131kN, the sample shall no explode or catch fire Result: Pass Test data Safety Test - Crush LiFePO4-Si/C + Graphite 18650 Cell after test Safety Test Sho