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1、动力锂离子电池现状、安全性及寿命评测2011汽车动力电池国际研讨会INET, Tsinghua University2011年2月23-24日，上海何向明清华大学核研院新型能源与材料化学研究室Institute of New Energy Technology锂电池研讨内容动力电池现状锂离子动力电池的安全性锂离子动力电池的使用寿命Institute of New Energy Technology, INET, Tsinghua University清华大学核研院锂离子电池实验室介绍锂电池研讨The Great WallMingInstitute of Nuclear and New Ener
2、gy TechnologyTsinghua UniversityLess than 50 minutes drive45 kmThe InstituteTsinghuaBeijingInstitute of New Energy Technology, INET, Tsinghua UniversityTombs锂电池研讨Lithium ionInstitute of New Energy Technology, INET, Tsinghua UniversityR&DbatteryFuel Cell 锂电池研讨Institute of New Energy Technology, INET,
3、 Tsinghua University燃料电池实验室锂电池研讨学术带头人：姜长印、万春荣学术骨干（博士）：何向明、蒲薇华、应皆荣、李建军、刘靖 、 郭建伟、研究骨干（硕士）：武玉玲、冯丽娟、张丽春、孙文婷、陈敏实验室技师：陈克勤、常彩霞、李智敏、康建峰、杨兆卫、史波锂离子电池实验室王 莉、任建国、李建刚、高 剑 博士生、硕士生：10-15名Institute of New Energy Technology, INET, Tsinghua University锂电池研讨锂离子电池研究概况材料合成，机理诊断，电极/电池工程化，数学模型电池模型Institute of New Energy Te
4、chnology, INET, Tsinghua University从纳米尺度到微米尺度，再到毫米尺度性能电极结构电池结构结构材料合成材料修饰表面/界面化学新工艺新材料安全性长寿命电极制造电池制备电极模型高性能锂电池电极模型锂电池研讨动力锂离子电池的现状Institute of New Energy Technology, INET, Tsinghua University锂电池研讨目前市场上的混合动力车Institute of New Energy Technology, INET, Tsinghua UniversityToyota HighlanderLexus RX400hHonda
5、 InsightLexus GS450hToyota CamryHonda CivicToyota PriusHonda AccordSaturn VueChevy SilveradoFord Escapemore and more锂电池研讨混合动力车ELECTRIC ACCESSORIESPETROLEUM ONLY76hp gasoline engine, 67hp electric motor, 1.5kWh batteryInstitute of New Energy Technology, INET, Tsinghua UniversityADVANCED ENGINE锂电池研讨Fu
6、el Flexibility插电式混合动力车ELECTRIC ACCESSORIESADVANCED ENGINEPETROLEUMAND/ORELECTRICITYBATTERY RECHARGE76hp gasoline engine, 67hp electric motor, 9.0kWh battery (30mi)Institute of New Energy Technology, INET, Tsinghua University锂电池研讨Percentage of Vehicle Fleet In Use (%)Cumulative Fuel Consumed (gallons
7、)5101520250010515202530Time of Day (hr)Institute of New Energy Technology, INET, Tsinghua University03010050150200250300PHEV40 8647 total miles driven 共行驶8647英里58 mpg &140 Wh/miPHEVs:40% reduction inoperating costs$500 annual savings37 mpg76 mpg &211 Wh/miAssumes $2.41/gal and 9/kWh$1.58$1.21$2.48$3
8、.45$0.48$0.72-5.45.16.59.1PHEV20PHEV40HEVCV混合动力车的实际节油效果40 400Conventional35 350锂电池研讨E-Transportation is the most significant technological revolutionafter the cellular and the internet.电动交通是移动电话和互联网后的最重要的技术革命 。Institute of New Energy Technology, INET, Tsinghua University电动车对动力电池的需求在持续增长锂电池研讨 MW rese
9、rve power plants. 兆瓦级储能电站。 Institute of New Energy Technology, INET, Tsinghua University钛酸锂电池移动储能电站Electrovaya, International Battery, Ultralife, Valance, Saft. BYD磷酸铁锂电池固定储能电站规模储能是动力电池的又一重要市场 Manage fluctuations in electricity demand. 平抑电网波动。 Manufacturers to take a part: A123, Altairnano, Enerdel,
10、锂电池研讨different cell model120 different cell models Ultra High power 超高功率(20C)- 19 manufacturers,Market grow of 15% CAGR(复合年均增长率) peryear driven by the EV growing market, Cell costsare decreasing by 8% per year (Source: IIT).Institute of New Energy Technology, INET, Tsinghua University动力电池的现状 High po
11、wer 高功率(10C)- 84 manufacturers, 1500 锂电池研讨中日韩在动力电池制造方面占支配Far-East manufacturers dominate the market台湾Institute of New Energy Technology, INET, Tsinghua University锂电池研讨PouchInstitute of New Energy Technology, INET, Tsinghua University动力电池的包装方式Prismaticcells较好的传热安全性好使用寿命长cellsCylindricalcells锂电池研讨Cell
12、SizemmCapAhCyclelifeTemprangeWeightgrWeightenergydensityWh/KgVolumeenergydensityWh/L-WeightconstantpowerdensityW/KgVolumepowert.densityW/LA123-AHR18700M1ULTRAD=18L=700.71000to90%-10to10038601291085523169A123-AHR32157M1HDD=32L=157101000to80%-30to603041082611085526148Saft-VL12VD=47L=17312500to80%-30to
13、6064067144843718000功率最高的磷酸铁锂电池SeealsoInstitute of New Energy Technology, INET, Tsinghua University锂电池研讨Institute of New Energy Technology, INET, Tsinghua UniversityBeijing ChinaPowerel北京中润恒动电池有限公司850 x560 x71200500 to80%?7000102211028213Lionik深圳市龙锂实业有限公司255 x145 x55100500 to80%-20to 6036001051861055
14、1868单体电池容量最高的高功率动力电池Cell Size Cap Cycle Temp Weight Weight Volume mm Ah life range gr energy energy density density density densityWh/Kg Wh/L W/Kg W/L.锂电池研讨CellVCapAhCyclelifeto80%WeightgrWeightenergydensityWh/KgVolumeenergydensityWh/LWeightpowerdensityW/KgVolumepower densityW/LAdvancedbatteryfactor
15、y3.31.210004392239552514372Q-LiteIndustrialICR18650HH3.71.35004012027530066885CENSEnergyTechCo18650P3.21.12000457821228447742AmericanLithiumIncNo-P.N3.21.5200034.314029027985806HenanBideliEnergyICR18650P3.71.45003813630627266129SamsungINR18650-15R3.61.55004512032620005443功率最高的18650电池Highcompetitivem
16、arketwithalmost50differentcellmodelsInstitute of New Energy Technology, INET, Tsinghua University锂电池研讨CellVCapAhCyclelifeto80%Highoper.Temp.cWeightenergydensityWh/KgVolumeenergydensityWh/LWeightpowerdensityW/KgVolumeenpoweromdensityW/LSaftVL32600-1254.2420012512325961129AdvancedBatteryFactory3.2v/60
17、ah3.660300090801276661060操作温度最高的动力电池EV needs batteries with up to 80C hightemperature operating rangemInstitute of New Energy Technology, INET, Tsinghua University锂电池研讨CellI.DWh/KgChargeRateCycleLifeGPLbattery,GE-32AH-02,32AH939.38C500GAIAUHE-341440,7.5AH8416C500ToshibaSCiB6511.9C6000StandardChargeQ
18、uickChargeFastChargeUltraFastChargeC/3C/3,2C10C快速充电动力电池短问题的最经济的方法。road charging stations.Current Market Ultra fast charging cellUltrafastchargeStationInstitute of New Energy Technology, INET, Tsinghua University快速充电 (up to 5 min, 80% capacity) 是解决电动车续驶里程锂电池研讨Toshiba Super Charge Lithium IonBattery -
19、 SCiB Lithium Manganese oxide Spinel cathode - LMO Lithium Titanate Oxide anode LTO Recharge to 90% of full capacity in less than 5 minutes. Excellent safety because of high level anode stability. 6000 cycles of full D.O.D to 90% of initial capacity. Low temperature discharge from -30C. SCIB is curr
20、ently available on the Schwinn Tailwind electric bike.2.4Voc65 Wh/Kg131 wh/l650 W/Kg1316 W/lInstitute of New Energy Technology, INET, Tsinghua UniversityVW&Toshiba锂电池研讨 1stWill dominate the rechargeable market for the near and midfuture. 2ndGeneration Li-Ion Chemistries Better performance- Up to 300
21、 Wh/kg with fast recharge.- Wider operating temperature range.- Fast Charging. Improved safety. Reduced cost.锂空气电池？Institute of New Energy Technology, INET, Tsinghua University下一代锂离子电池动力电池20Generation Li-Ion Chemistries 锂电池研讨动力电池的安全性问题将影响其市场命运If it is not safe it will not surviveInstitute of New Ene
22、rgy Technology, INET, Tsinghua University动力电池的安全性问题 锂电池研讨锂离子电池的安全性Institute of New Energy Technology, INET, Tsinghua University锂电池研讨Institute of New Energy Technology, INET, Tsinghua University锂电池研讨Institute of New Energy Technology, INET, Tsinghua University安全性问题引起的损失锂电池研讨Institute of New Energy Te
23、chnology, INET, Tsinghua UniversitySafety cases锂电池研讨Institute of New Energy Technology, INET, Tsinghua UniversitySafety cases锂电池研讨安全性的概念滥用安全性 abuse thermal runaway Mechanical 机械的 crush, nail penetration 挤压、针刺 Electrical 电的 short circuit, overcharge 短路、过充 Thermal 热的 thermal ramp, simulated fire 热箱、火烧
24、现场安全性 field failure thermal runaway Manufacturing defects 由制造瑕疵引起 Loose connection, separator damage, foreign debris 连接问题、隔膜损坏、粉尘 Can develop into an internal short circuit 随机发生，引起内短路 Can lead to overheating and thermal runaway 引起过热与热失控Institute of New Energy Technology, INET, Tsinghua University锂电池
25、研讨Institute of New Energy Technology, INET, Tsinghua University滥用安全性锂电池研讨Institute of New Energy Technology, INET, Tsinghua University现场（随机）安全性锂电池研讨两种安全性概念的差异现场安全性滥用安全性Institute of New Energy Technology, INET, Tsinghua University Predictable 可预测的 Common to all cells 对每一个电池 Can/should be evaluatedat
26、the cell level 可以通过测试进行评估 Time constants relativelylong 发生过程较长 Can be augmented byprotection devices 可以通过保护措施进行改善 Not predictable 不可预测的 One-in-a-million (or less) 随机小概率发生 Difficult to evaluate at thecell level, or through QC 无法通过测试进行评估，也不能通过质量管理来完全消除 can occur quickly 发生很突然 PTC, CID, shutdownseparat
27、ors, electroniccontrols not are effective 目前所有的安全性措施，均不能完全消除锂离子电池安全隐患锂电池研讨 发生安全事故的锂离子电池，之前均通过UL安全认证。 发生原因基本上是不可预测的内短路所造成。而这种内短路似乎是不能完全消除。 引起安全事故的电池在制造时，均是合格品。 目前滥用安全性标准的测试结果，与发或者不发生安全性事故，之间没有任何联系。Institute of New Energy Technology, INET, Tsinghua University锂离子电池安全性 对于笔记本电脑电池，发生概率在几百万分之一。锂电池研讨 Major
28、effort has been payed to improve the ways weaddress safety in lithium-ion batteries, however 在人们如此重视锂离子电池安全性的今天，严重的安全性问题还时有发生。 The battery community does not have adequate teststo evaluate safety as it relates to the safety incidentsthat have taken place or could take place. 人们还没有找到合适的方法来预测和评测这类安全隐患
29、问题 我们在做工作，希望“十二五”结束时，这个问题得到一定程度的解决。Institute of New Energy Technology, INET, Tsinghua University锂离子电池的安全性serious safety incidents can always occur. 锂电池研讨Energy Released (J)热失控的机 Institute of New Energy Technology, INET, Tsinghua University249.9378292.573.716400.90300200100700600500400Anode/Binder An
30、ode/Solvent SEIDecompnCathodeBreakdownSeparatorOxidnCathodeSolvent Oxdn JouleHeatingCathode锂离子电池安全性9008000.8 Ah 钴酸锂手机电池826.2 锂电池研讨Institute of New Energy Technology, INET, Tsinghua University负极材料的安全性改进锂电池研讨Institute of New Energy Technology, INET, Tsinghua University正极材料锂电池研讨Institute of New Energy
31、Technology, INET, Tsinghua UniversityHeat release锂电池研讨Safety of cathode Materials Institute of New Energy Technology, INET, Tsinghua University锂电池研讨隔膜隔膜关闭的温度范围 Strength and physical integrity抗压机械强度 Shrinkage allowance热收缩率Institute of New Energy Technology, INET, Tsinghua University影响电池安全性的重要指标 Shutd
32、own performance锂电池研讨电解质Solvent，non-flamableSalts，high decomposition temperatureAdditives，Flame-RetardantGel electrolyteInstitute of New Energy Technology, INET, Tsinghua University锂电池研讨P(VdF-HFP)凝胶电解质在 Institute of New Energy Technology, INET, Tsinghua University凝胶电解质 凝胶电解质的放热量与放热速率黄倩，厦门大学博士论文燃烧过程中的
33、放热总量非常接近于纯液态电解液体系。并且随着P(VdF-HFP)在凝胶电解质中浓度的增加，其相应的热释放速率逐渐降低。采用P(VdF-HFP)凝胶电解质比液态电解液更为安全 PMMA凝胶电解质体系中，情况却是相反:其燃烧反应的放热总量和热释放速率都随PMMA的加入而显著增大。锂电池研讨锂离子电池的安全性是一个复杂的系统问题 动力电池安全性是一个系统问题。 从单纯的电池材料改性（正极、负极、电解质、隔膜）是不能完全解决安全性问题，但可以大幅度地提高。Institute of New Energy Technology, INET, Tsinghua University锂电池研讨Institut
34、e of New Energy Technology, INET, Tsinghua University正极材料包覆锂电池研讨钴酸锂包覆磷酸铝5-10nm AlPO4过充电前过充电后自制安全性手机电池过充电试验未燃烧、未爆炸。市售品牌电过充电池电芯Institute of New剧烈燃Technology, INET, Tsinghua UniversityEnergy 烧锂电池研讨高性能高安全性动力电池采用正极材料表面与界面控制技术、电解质添加剂等技术，制备出高安全性动力电池。20V过充150热箱5小时以上标称容量12Ah，三元氧化物正极材料。电池比能量大于160wh/kg，比功率大于12
35、00W/kg，Institute of New Energy Technology, INET, Tsinghua University安全很好的倍率性能锂电池研讨目前市售三元动力电池的过充电 充电到5.2V时，发生剧烈燃烧Institute of New Energy Technology, INET, Tsinghua University锂电池研讨目前市售三元动力电池 充电到4.15V，加热到120，发生剧烈燃烧Institute of New Energy Technology, INET, Tsinghua University锂电池研讨 动力电池的使用寿命与成本 如何评测动力电池的
36、使用寿命 现场检测电池的寿命状态（SOH）Institute of New Energy Technology, INET, Tsinghua University锂离子动力电池的使用寿命锂电池研讨 PHEV battery likely to deep-cycle each day driven: 15 yrs equates to 4000-5000 deep cycles Also need to consider combination of high and low frequency cycling and calendarwlife 电池电池循环寿命70%50%4000Data
37、presented by Christian Rosenkranz (Johnson Controls) at EVS 20, 2006Institute of New Energy Technology, INET, Tsinghua University锂电池研讨52% EVInstitute of New Energy Technology, INET, Tsinghua University$4,005$2,865$2,919$3,002$1,998$1,992$2,004$2,020$2,079$2,407$2,454$2,433$5,117$8,433$663$-$2,000$4,
38、000$6,000$10,000$8,000$14,000$12,000$18,000$16,000CVHEVPHEV20PHEV40transmissionengine25%电池占电动车成本比例Projected Retail Powertrain Costs - Midsize Sedans1) including manufacturer and dealer markups2) all component costs assume projected statuscharger/plugbattery 40%motor/inverter60%锂电池研讨动力电池的使用寿命 电池的成本占整
39、个电动车成本的2560%。是一个非常重要的零部件。 车的使用寿命：10-15年 动力电池目前的使用寿命是3-7年，LG化学声称可以有10-15年的寿命保证。 因此大幅度地延长动力锂离子电池的使用寿命，使之达到与电动车的寿命相当，是目前动力锂离子电池发展的关键问题。 需要动力电池使用寿命评测技术做支撑。Institute of New Energy Technology, INET, Tsinghua University锂电池研讨Ohmic Resistance Ohmic Resistance Ohmic Resistance temperature large1.51.3 HighdeCy
40、cles50100 150 200 250 300 350 400 450CyclesInstitute of New Energy Technology, INET, Tsinghua University1.21.111.11Effects of charging/discharging depth2.521.510050100 150 200 250 300 350 400 450Cycles050100 150200250 300350 400 450ep影响动力电池的使用寿命的因素 温度 电流 充放电深度动力电池的使用寿命评测Effects of charge current Eff
41、ects of 1.61.71.51.61.41.41.2 1.31.8 2 1.7 1.9 锂电池研讨Internal ResistanceVoltage VCurrent AR=V/I动力电池的使用寿命评测Degradation35003.75Remaining lifeInstitute of New Energy Technology, INET, Tsinghua UniversityTemperature of a battery3.653.63.553.83.70772500-500-1500-2500450025001500Voltage response/VCurrent/A
42、DayPresentBattery*BMS: Battery Management System*PLC: Programmable Logic Controller-Battery Temperature-Battery Voltage-Battery CurrentBMS* Controller(PLC*)-Internal resistancedegradation rate-Remaining batterylife (Estimated)Monitor(ex. Based on an Internal resistance degradation rate)1623 2510 3410 4197 5022Time stDrate kt x 1Degradation rateof Internal resistance Target Accuracy: 10%Lifetime judgmentcriteriaDegradation rate(Present)1(Estimated)(ex. Based on the detection of an internal resistance status) 锂电池研讨Institute of New Energy Technology, INET, Tsinghua University58锂电池研讨
