Large Size Li-ion Batteries and Their Applications Xuejie Huang Institute of Physics, CAS, Beijing xjhuang@iphy.ac.cn
Group of Solid State Ionics in IOP 陈立泉院士 黄学杰研究员王兆翔研究员李泓研究员 胡勇胜 研究员 肖睿娟副研究员 张安讯高级技师 刘燕燕博士 赵文武博士 陈一霞博士 + 30 more graduate students
IOP-Phylion Phylion(Beijing-Suzhou) Electricity Storage Battery EV Battery Battery For gardening tools Battery for E-bike come into market Mass production of Large size LIB Mass Production of LiMn 2 O 4 Join Nation s EV Project Founded a pilot production line for HEV battery Study on Lithium-ion battery for vehicle, sponsored by Ford(China) Fund 1994 1999 2003 2004 2005 2008 2010
IOP/Phylion: Li-ion Batteries From R&D to Mass Production 星恒 : 从基础研究走向车用电池大规模量产 基础研究 R 材料 Materials 工程化 D 电芯 cells 规模制造 Mass Prod. 电池组 Batteies
1. LiB for ebikes 2. LiB for EVs 3. Next generation LiB for EVs
Chemistry of Li-ion Battery Cathode Voltage vs Graphite Specific Capacity Price Application Safety LiCoO 2 3.7V 140Ah/kg $35/kg Consumer Low LiNoCoMn 3.6V 155Ah/kg $24/kg Consumer Powertool LiNiCoAl 3.55V 170Ah/kg $26/kg Consumer Industial LiMn 2 O 4 3.8V 110Ah/kg $12/kg Powertool Vehicel LiFePO 4 3.2V 150Ah/kg $30/kg Powertool Vehicel mid Low/mid High High Voltage vs Graphite Specific Capacity Price Anode Graphite 0V 330Ah/kg $10/kg Hard Carbon 0.3V 250Ah/kg $40/kg Li 4 Ti 5 O 12 1.3V 160Ah/kg $25/kg Si Composite 0.2V 600-800Ah/kg NA Graphite is used for most of the commercial LiB.
Our strategy: Do the right thing at the right time. ( 正确的时间做正确的事 ) 1.LMO( 锰酸锂 )/Graphite Cell(e-bikes) 2003 2.LFP( 磷酸铁锂 )/Graphite(EVs) 2008 3.LMO+LMNCO? Safety, new separator/electrolyte
Cyclic Performance TEM Image specific capacity(mah/g) 200 B 180 160 140 120 100 0 5 10 15 20 cycle number C A (A) bare LiCoO 2 (B) Al 2 O 3 -coated LiCoO 2 heated at 300 o C (C) Al 2 O 3 -coated LiCoO 2 heated at 600 o C Al 2 O 3 -coated nano-licoo 2 heat treated at 300ºC
LiMn 2 O 4 Li Mn O LiMn 2 O 4
Thermal stability is much improved by the surface modification 1.2 1.0 expo DSC (mw/mg) 0.8 0.6 0.4 LiAl x Mn 2-x O 4 * * 0.2 0.0 * -0.2 0 50 100 150 200 250 300 350 400 Temperature( C) LMO/Li cell cycles at 60 C
LEVs Development in China
Cycling performance of LMO cells(100%dod, 1C rate) 容量 ( m A h ) 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600 1650 1700 1750 1800 1850 1900 1950 2000 S529 循环次数
电池组充电器充电工况放电衰减曲线 10 8 容量 (Ah) 6 4 2 0 工况放电 1 11 21 31 41 51 61 71 81 91 101 循环次数
>5M 10Ah cells to market for e-bikes UL1642 Safety test 2004-11-19 3C/10V overcharge 2. 150 C hot box 3. Nail penetration 4. Crush 5. Short Circuit 6. Dropping Crush force:13kn. Battery packs were not deformed. And no obvious change of voltage & temp
Suzhou Phylion is the second largest e-bilke LiB producer. 15
1. LiB for ebikes 2. LiB for EVs 3. Next generation LiB for EVs
FeO6 LiFePO 4 LiFePO 4 作为正极材料 [1] O 碳包覆 [2] Li ( b ) 1997 1999 b a PO4 b c ( a ) b c ( c ) J. B. Goodenough M. Armand [1] A. K. Padhi, et al., J. Electrochem. Soc.144 (1997) 1188. [2] N. Ravet, et al., E S Fall Meeting, Hawaii (1999) Abs. 127,
2 Log Conductivity ( S/cm) 0-2 -4-6 -8 E a =0.035eV Li 0.964 Fe 0.958 Na 0.047 PO 4-d LiFePO 4 E a =0.639eV -10 0.0016 0.0020 0.0024 0.0028 0.0032 1/T(1/K) Arrhenius plots of dc conductivity of LiFePO 4 and Li 0.964 Fe 0.958 Na 0.047 PO 4-δ
N doped LiFePO 4 DOS(states/eV) 30 25 20 15 10 5 0 10 20 30 40 50-9 -6-3 0 3 6 E-Ef(eV) 4 Eg=3.7eV DOS(1/eV/f.u.) 30 25 20 15 10 5 0 5 10 15 20 25 30-5 -4-3 -2-1 0 1 2 3 4 5 4 E-Ef(eV) Eg=1.3eV 3 3 5 unoccupied states Fe 3+ 3d 5 Fe 2+ 3d 6 E-Ef(eV) 2 1 0 2 1 0-1 -1-2 -2 L G X UK G L G X U K G
40Ah LFP cells(120wh/kg, 1000W/Kg) Dimensions Nominal Voltage 3.2V Impedance (1KHz AC( Power density Energy density Operating temperature range 32mm x 100mm x 192mm 2mΩ 1000W/Kg 120Wh/Kg Charge 0~45 Discharge -20~45 Storage temperature range -10~35 1C Discharge capacity 40Ah (C 1 ) Rate Capability 5C >90%C 1 Cycle life >2000(100%DOD)
Rate performances of 40Ah LFP cell at 25 C 180A charge 4.1 3.9 3.7 Voaltage(V) 3.5 3.3 3.1 2.9 2.7 Capacity(Ah) 2.5 0 5 10 15 20 25 30 35 40 45 50 300A discharge Voltage(V) 3.7 3.5 3.3 3.1 2.9 2.7 2.5 2.3 2.1 1.9 Capacity (Ah) 0 5 10 15 20 25 30 35 40 45 50
40Ah LFP cell 1C cycling performance at room temp. 40 Ah LFP cell 1C cycling performance at room temp. 120.0% 100.0% Residual Capacity 80.0% 60.0% 40.0% 20.0% 0.0% 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 Normal temp.1c Cycle times
40AhLFP battery pack cycling performance at room temp. 10 in series LFP battery pack 20A charge &32A discharge cycle curve Capacity (Ah) 50 45 40 35 30 25 20 15 10 5 Cycle times 0 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700
50Ah LFP Cell 容量规格 (Ah)( 磷酸铁锂 ) 50 十一五指南要求 完成情况 功率密度 (W/kg) 700 800 能量密度 (Wh/kg) 110 130 最大放电倍率 6C(30s) 6C( 30s) 最大充电倍率 4C(60s) 4C( 60s) 单体电池电阻 (mω) 3.0 1.0 单体电压偏差 (V) 0.02 0.02 单体容量偏差 (%) 2 <2 使用温度范围 ( ) -25-60 -25-60 搁置温度范围 ( ) -40-80 -40-60 荷电保持能力 ( 常温下搁置 28 天 ) 90% 92%~95% SOC 估算误差 (%) 5 5 安全性通过行标或规范要求 UL1642 电池组循环寿命 ( 万公里 ) 15 测试中 可靠性 在环境相对湿度 100% 条件下, 动力蓄电池组能够正常工作 ; 满足整车行驶 3 万公里型式试验的相关要求
微车用电器盒外观 2010 上海世博会纯电动 Bus 和燃料电池 PHEV 采用锂离子电池 磷酸铁锂电池包 微车用电池包外观 锰酸锂电池包
HEV and EV with Phylion s Battery in Expo 2010
1. LiB for ebikes 2. LiB for EVs 3. Next generation LiB for EVs
新能源汽车电池目标 (China EV LiB Goal) 2015 2020 能量密度型电池组 EV Battery 能量密度达到 120 瓦时 / 公斤, 功率密度达到 1 千瓦 / 公斤, 循环寿命达到 2000 次, 电池成本达到 2.0 元 / 瓦时以下 >120Wh/Kg,>1KW/Kg, >2000 Cycles, <2.0RMB/Wh 能量密度达到 200 瓦时 / 公斤, 功率密度达到 1.5 千瓦 / 公斤, 循环寿命达到 3000 次, 电池成本达到 1.0 元 / 瓦时以下 >200Wh/Kg,>1.5KW/Kg, >3000 Cycles, <1.0RMB/Wh
Next generation LiB for EVs? Power (2000W/Kg) Cost ($300/KWh) Energy (200Wh/Kg) Safety Temp. range (-30-60 C) Life (10~15y) Present Goal
New Cathode Materials 例如 : 层状氧化物 : xli 2 MnO 3 (1-x)Li 1+y Mn 2-y O 4 比容量大于 250mAh/g
-2000 voltage LiFe 1-x Mn x PO 4 4.4 4.2 4.0 3.8 3.6 3.4 3.2 1 21 3.0 45 2.8 0 20 40 60 80 100 120 140 160 Capacity mah/g 1st 21st 45th 1600 1400 1200 1000 800 600 400 200 dq/dv 0-200 -400-600 -800-1000 -1200-1400 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 2000 1500 1000 500 dq/dv0-500 -1000-1500 -2000-2500 -3000 Voltage ----discharge ----charge 3.0 3.5 4.0 Voltage 1500 1000 45th 500 dq/dv 0-500 -1000-1500
LiFe 1-x Co x PO 4 Voltage, V 5.0 4.5 4.0 3.5 3.0 2.5 2.0 5.0 4.5 4.0 3.5 3.0 2.5 2.0 0 20 40 60 80 100 120 140 160 180 LiCoPO 4 Co0.8 Co0.5 Co0.2 LiFePO 4 A B Co0.8 Co0.5 Co0.2 LiFePO4 Co0.2 LiCoPO 4 Co0.8 Co0.5 0 20 40 60 80 100 120 140 160 180 Capacity, mah/g
nano-si/c After discharging Electrochem. agglomeration
capacity(mah/g) 1400 1200 1000 800 600 400 200 0 Si Composite Anode materials 0 0 2 4 6 8 10 12 14 16 18 20 cycle number 100 90 80 70 60 50 40 30 20 10
New Electrolytes LiFSI is stable to 300 C LiFSI is stable with H 2 O TGA Endo DSC T m = 142 o C Li F O S O O N LiFSI S O F HF or H 2 O (ppm) 6000 5000 4000 3000 2000 1000 0 0 5 10 15 20 Time (day) HF (LiFSI) H 2 O (LiFSI) HF (LiPF 6 ) H 2 O (LiPF 6 ) Dec. Exo 0 100 200 300 400 500 Temperature ( o C) 1.0 M LiFSI 电解液加 0.3% 的水, 20 天后水未与盐反应转化为 HF 1.0 M LiPF 6 电解液同样加 0.3% 的 水,3 天后水几乎完全反应转化为 HF 1. L. F. Li, S. S. Zhou, H. B. Han, H. Li, J. Nie, M. Armand, Z. B. Zhou, and X. J. Huang, Transport and Electrochemical Properties and Spectral Features of Non-Aqueous Electrolytes Containing LiFSI in Linear Carbonate Solvents JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 158(2)A74-A82, 2011 35
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