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1、鋰電池研討動(dòng)力鋰離子電池現(xiàn)狀、安全性及壽命評(píng)測(cè)2011汽車動(dòng)力電池國(guó)際研討會(huì)INET,Tsinghua University2011年2月23-24日，上海何向明清華大學(xué)核研院新型能源與材料化學(xué)研究室Institute of New Energy Technology鋰電池研討內(nèi)容動(dòng)力電池現(xiàn)狀鋰離子動(dòng)力電池的安全性鋰離子動(dòng)力電池的使用壽命Institute of New Energy Technology,INET,Tsinghua University清華大學(xué)核研院鋰離子電池實(shí)驗(yàn)室介紹鋰電池研討The Great WallMingInstitute of Nuclear and New En

2、ergy TechnologyTsinghua UniversityLess than 50 minutes drive45 kmThe InstituteTsinghuaBeijingInstitute of New Energy Technology,INET,Tsinghua UniversityTombs鋰電池研討Lithium ionInstitute of New Energy Technology,INET,Tsinghua UniversityR&DbatteryFuel Cell 鋰電池研討Institute of New Energy Technology,INET,Tsi

3、nghua University燃料電池實(shí)驗(yàn)室鋰電池研討學(xué)術(shù)帶頭人：姜長(zhǎng)印、萬(wàn)春榮學(xué)術(shù)骨干（博士）：何向明、蒲薇華、應(yīng)皆榮、李建軍、劉靖、郭建偉、研究骨干（碩士）：武玉玲、馮麗娟、張麗春、孫文婷、陳敏實(shí)驗(yàn)室技師：陳克勤、常彩霞、李智敏、康建峰、楊兆衛(wèi)、史波鋰離子電池實(shí)驗(yàn)室王 莉、任建國(guó)、李建剛、高 劍 博士生、碩士生：10-15名Institute of New Energy Technology,INET,Tsinghua University鋰電池研討鋰離子電池研究概況材料合成，機(jī)理診斷，電極/電池工程化，數(shù)學(xué)模型電池模型Institute of New Energy Technology

4、,INET,Tsinghua University從納米尺度到微米尺度，再到毫米尺度性能電極結(jié)構(gòu)電池結(jié)構(gòu)結(jié)構(gòu)材料合成材料修飾表面/界面化學(xué)新工藝新材料安全性長(zhǎng)壽命電極制造電池制備電極模型高性能鋰電池電極模型鋰電池研討動(dòng)力鋰離子電池的現(xiàn)狀I(lǐng)nstitute of New Energy Technology,INET,Tsinghua University鋰電池研討目前市場(chǎng)上的混合動(dòng)力車Institute of New Energy Technology,INET,Tsinghua UniversityToyota HighlanderLexus RX400hHonda InsightLexus

5、GS450hToyota CamryHonda CivicToyota PriusHonda AccordSaturn VueChevy SilveradoFord Escapemore and more鋰電池研討混合動(dòng)力車ELECTRIC ACCESSORIESPETROLEUM ONLY76hp gasoline engine,67hp electric motor,1.5kWh batteryInstitute of New Energy Technology,INET,Tsinghua UniversityADVANCED ENGINE鋰電池研討Fuel Flexibility插電式混

6、合動(dòng)力車ELECTRIC ACCESSORIESADVANCED ENGINEPETROLEUMAND/ORELECTRICITYBATTERY RECHARGE76hp gasoline engine,67hp electric motor,9.0kWh battery(30mi)Institute of New Energy Technology,INET,Tsinghua University鋰電池研討Percentage of Vehicle Fleet In Use(%)Cumulative Fuel Consumed(gallons)5101520250010515202530Ti

7、me of Day(hr)Institute of New Energy Technology,INET,Tsinghua University03010050150200250300PHEV40 8647 total miles driven 共行駛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$3.45$0.48$0.72-5.45.16.59.1PHEV20

8、PHEV40HEVCV混合動(dòng)力車的實(shí)際節(jié)油效果40 400Conventional35 350鋰電池研討E-Transportation is the most significant technological revolutionafter the cellular and the internet.電動(dòng)交通是移動(dòng)電話和互聯(lián)網(wǎng)后的最重要的技術(shù)革命。Institute of New Energy Technology,INET,Tsinghua University電動(dòng)車對(duì)動(dòng)力電池的需求在持續(xù)增長(zhǎng)鋰電池研討 MW reserve power plants.兆瓦級(jí)儲(chǔ)能電站。Institute

9、of New Energy Technology,INET,Tsinghua University鈦酸鋰電池移動(dòng)儲(chǔ)能電站Electrovaya,International Battery,Ultralife,Valance,Saft.BYD磷酸鐵鋰電池固定儲(chǔ)能電站規(guī)模儲(chǔ)能是動(dòng)力電池的又一重要市場(chǎng) Manage fluctuations in electricity demand.平抑電網(wǎng)波動(dòng)。Manufacturers to take a part:A123,Altairnano,Enerdel,鋰電池研討different cell model120 different cell model

10、s Ultra High power 超高功率(20C)-19 manufacturers,Market grow of 15%CAGR(復(fù)合年均增長(zhǎng)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動(dòng)力電池的現(xiàn)狀 High power 高功率(10C)-84 manufacturers,1500 鋰電池研討中日韓在動(dòng)力電池制造方面占支配Far

11、-East manufacturers dominate the market臺(tái)灣Institute of New Energy Technology,INET,Tsinghua University鋰電池研討PouchInstitute of New Energy Technology,INET,Tsinghua University動(dòng)力電池的包裝方式Prismaticcells較好的傳熱安全性好使用壽命長(zhǎng)cellsCylindricalcells鋰電池研討CellSizemmCapAhCyclelifeTemprangeWeightgrWeightenergydensityWh/KgVol

12、umeenergydensityWh/L-WeightconstantpowerdensityW/KgVolumepowert.densityW/LA123-AHR18700M1ULTRAD=18L=700.71000to90%-10to10038601291085523169A123-AHR32157M1HDD=32L=157101000to80%-30to603041082611085526148Saft-VL12VD=47L=17312500to80%-30to6064067144843718000功率最高的磷酸鐵鋰電池SeealsoInstitute of New Energy Tec

13、hnology,INET,Tsinghua University鋰電池研討Institute of New Energy Technology,INET,Tsinghua UniversityBeijing ChinaPowerel北京中潤(rùn)恒動(dòng)電池有限公司850 x560 x71200500 to80%?7000102211028213Lionik深圳市龍鋰實(shí)業(yè)有限公司255 x145 x55100500 to80%-20to 60360010518610551868單體電池容量最高的高功率動(dòng)力電池Cell Size Cap Cycle Temp Weight Weight Volume mm

14、 Ah life range gr energy energy density density density densityWh/Kg Wh/L W/Kg W/L.鋰電池研討CellVCapAhCyclelifeto80%WeightgrWeightenergydensityWh/KgVolumeenergydensityWh/LWeightpowerdensityW/KgVolumepower densityW/LAdvancedbatteryfactory3.31.210004392239552514372Q-LiteIndustrialICR18650HH3.71.3500401202

15、7530066885CENSEnergyTechCo18650P3.21.12000457821228447742AmericanLithiumIncNo-P.N3.21.5200034.314029027985806HenanBideliEnergyICR18650P3.71.45003813630627266129SamsungINR18650-15R3.61.55004512032620005443功率最高的18650電池Highcompetitivemarketwithalmost50differentcellmodelsInstitute of New Energy Technolo

16、gy,INET,Tsinghua University鋰電池研討CellVCapAhCyclelifeto80%Highoper.Temp.cWeightenergydensityWh/KgVolumeenergydensityWh/LWeightpowerdensityW/KgVolumeenpoweromdensityW/LSaftVL32600-1254.2420012512325961129AdvancedBatteryFactory3.2v/60ah3.660300090801276661060操作溫度最高的動(dòng)力電池EV needs batteries with up to 80C

17、hightemperature operating rangemInstitute of New Energy Technology,INET,Tsinghua University鋰電池研討CellI.DWh/KgChargeRateCycleLifeGPLbattery,GE-32AH-02,32AH939.38C500GAIAUHE-341440,7.5AH8416C500ToshibaSCiB6511.9C6000StandardChargeQuickChargeFastChargeUltraFastChargeC/3C/3,2C10C快速充電動(dòng)力電池短問(wèn)題的最經(jīng)濟(jì)的方法。road c

18、harging stations.Current Market Ultra fast charging cellUltrafastchargeStationInstitute of New Energy Technology,INET,Tsinghua University快速充電(up to 5 min,80%capacity)是解決電動(dòng)車?yán)m(xù)駛里程鋰電池研討Toshiba Super Charge Lithium IonBattery-SCiB Lithium Manganese oxide Spinel cathode-LMO Lithium Titanate Oxide anode LT

19、O 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 currently available on the Schwinn Tailwind electric bike.2.4Voc65 Wh/Kg131 wh/l650 W/Kg1316

20、W/lInstitute of New Energy Technology,INET,Tsinghua UniversityVW&Toshiba鋰電池研討 1stWill dominate the rechargeable market for the near and midfuture.2ndGeneration Li-Ion Chemistries Better performance-Up to 300 Wh/kg with fast recharge.-Wider operating temperature range.-Fast Charging.Improved safety.R

21、educed cost.鋰空氣電池？Institute of New Energy Technology,INET,Tsinghua University下一代鋰離子電池動(dòng)力電池20Generation Li-Ion Chemistries 鋰電池研討動(dòng)力電池的安全性問(wèn)題將影響其市場(chǎng)命運(yùn)If it is not safe it will not surviveInstitute of New Energy Technology,INET,Tsinghua University動(dòng)力電池的安全性問(wèn)題 鋰電池研討鋰離子電池的安全性Institute of New Energy Technology,

22、INET,Tsinghua University鋰電池研討Institute of New Energy Technology,INET,Tsinghua University鋰電池研討Institute of New Energy Technology,INET,Tsinghua University安全性問(wèn)題引起的損失鋰電池研討Institute of New Energy Technology,INET,Tsinghua UniversitySafety cases鋰電池研討Institute of New Energy Technology,INET,Tsinghua Universi

23、tySafety cases鋰電池研討安全性的概念濫用安全性 abuse thermal runaway Mechanical 機(jī)械的 crush,nail penetration 擠壓、針刺 Electrical 電的 short circuit,overcharge 短路、過(guò)充 Thermal 熱的 thermal ramp,simulated fire 熱箱、火燒現(xiàn)場(chǎng)安全性 field failure thermal runaway Manufacturing defects 由制造瑕疵引起 Loose connection,separator damage,foreign debris

24、 連接問(wèn)題、隔膜損壞、粉塵 Can develop into an internal short circuit 隨機(jī)發(fā)生，引起內(nèi)短路 Can lead to overheating and thermal runaway 引起過(guò)熱與熱失控Institute of New Energy Technology,INET,Tsinghua University鋰電池研討Institute of New Energy Technology,INET,Tsinghua University濫用安全性鋰電池研討Institute of New Energy Technology,INET,Tsinghu

25、a University現(xiàn)場(chǎng)（隨機(jī)）安全性鋰電池研討兩種安全性概念的差異現(xiàn)場(chǎng)安全性濫用安全性Institute of New Energy Technology,INET,Tsinghua University Predictable 可預(yù)測(cè)的 Common to all cells 對(duì)每一個(gè)電池 Can/should be evaluatedat the cell level 可以通過(guò)測(cè)試進(jìn)行評(píng)估 Time constants relativelylong 發(fā)生過(guò)程較長(zhǎng) Can be augmented byprotection devices 可以通過(guò)保護(hù)措施進(jìn)行改善 Not predic

26、table 不可預(yù)測(cè)的 One-in-a-million(or less)隨機(jī)小概率發(fā)生 Difficult to evaluate at thecell level,or through QC 無(wú)法通過(guò)測(cè)試進(jìn)行評(píng)估，也不能通過(guò)質(zhì)量管理來(lái)完全消除 can occur quickly 發(fā)生很突然 PTC,CID,shutdownseparators,electroniccontrols not are effective 目前所有的安全性措施，均不能完全消除鋰離子電池安全隱患鋰電池研討 發(fā)生安全事故的鋰離子電池，之前均通過(guò)UL安全認(rèn)證。發(fā)生原因基本上是不可預(yù)測(cè)的內(nèi)短路所造成。而這種內(nèi)短路似乎是不

27、能完全消除。引起安全事故的電池在制造時(shí)，均是合格品。目前濫用安全性標(biāo)準(zhǔn)的測(cè)試結(jié)果，與發(fā)或者不發(fā)生安全性事故，之間沒(méi)有任何聯(lián)系。Institute of New Energy Technology,INET,Tsinghua University鋰離子電池安全性 對(duì)于筆記本電腦電池，發(fā)生概率在幾百萬(wàn)分之一。鋰電池研討 Major effort has been payed to improve the ways weaddress safety in lithium-ion batteries,however 在人們?nèi)绱酥匾曚囯x子電池安全性的今天，嚴(yán)重的安全性問(wèn)題還時(shí)有發(fā)生。The batter

28、y community does not have adequate teststo evaluate safety as it relates to the safety incidentsthat have taken place or could take place.人們還沒(méi)有找到合適的方法來(lái)預(yù)測(cè)和評(píng)測(cè)這類安全隱患問(wèn)題 我們?cè)谧龉ぷ?，希望“十二五”結(jié)束時(shí)，這個(gè)問(wèn)題得到一定程度的解決。Institute of New Energy Technology,INET,Tsinghua University鋰離子電池的安全性serious safety incidents can always

29、 occur.鋰電池研討Energy Released(J)熱失控的機(jī) Institute of New Energy Technology,INET,Tsinghua University249.9378292.573.716400.90300200100700600500400Anode/Binder Anode/Solvent SEIDecompnCathodeBreakdownSeparatorOxidnCathodeSolvent Oxdn JouleHeatingCathode鋰離子電池安全性9008000.8 Ah 鈷酸鋰手機(jī)電池826.2 鋰電池研討Institute of N

30、ew Energy Technology,INET,Tsinghua University負(fù)極材料的安全性改進(jìn)鋰電池研討Institute of New Energy Technology,INET,Tsinghua University正極材料鋰電池研討Institute of New Energy Technology,INET,Tsinghua UniversityHeat release鋰電池研討Safety of cathode Materials Institute of New Energy Technology,INET,Tsinghua University鋰電池研討隔膜隔膜

31、關(guān)閉的溫度范圍 Strength and physical integrity抗壓機(jī)械強(qiáng)度 Shrinkage allowance熱收縮率Institute of New Energy Technology,INET,Tsinghua University影響電池安全性的重要指標(biāo) Shutdown performance鋰電池研討電解質(zhì)Solvent，non-flamableSalts，high decomposition temperatureAdditives，F(xiàn)lame-RetardantGel electrolyteInstitute of New Energy Technology,

32、INET,Tsinghua University鋰電池研討P(VdF-HFP)凝膠電解質(zhì)在 Institute of New Energy Technology,INET,Tsinghua University凝膠電解質(zhì) 凝膠電解質(zhì)的放熱量與放熱速率黃倩，廈門大學(xué)博士論文燃燒過(guò)程中的放熱總量非常接近于純液態(tài)電解液體系。并且隨著P(VdF-HFP)在凝膠電解質(zhì)中濃度的增加，其相應(yīng)的熱釋放速率逐漸降低。采用P(VdF-HFP)凝膠電解質(zhì)比液態(tài)電解液更為安全 PMMA凝膠電解質(zhì)體系中，情況卻是相反:其燃燒反應(yīng)的放熱總量和熱釋放速率都隨PMMA的加入而顯著增大。鋰電池研討鋰離子電池的安全性是一個(gè)復(fù)雜的

33、系統(tǒng)問(wèn)題 動(dòng)力電池安全性是一個(gè)系統(tǒng)問(wèn)題。從單純的電池材料改性（正極、負(fù)極、電解質(zhì)、隔膜）是不能完全解決安全性問(wèn)題，但可以大幅度地提高。Institute of New Energy Technology,INET,Tsinghua University鋰電池研討Institute of New Energy Technology,INET,Tsinghua University正極材料包覆鋰電池研討鈷酸鋰包覆磷酸鋁5-10nm AlPO4過(guò)充電前過(guò)充電后自制安全性手機(jī)電池過(guò)充電試驗(yàn)未燃燒、未爆炸。市售品牌電過(guò)充電池電芯Institute of New劇烈燃Technology,INET,Tsi

34、nghua UniversityEnergy 燒鋰電池研討高性能高安全性動(dòng)力電池采用正極材料表面與界面控制技術(shù)、電解質(zhì)添加劑等技術(shù)，制備出高安全性動(dòng)力電池。20V過(guò)充150熱箱5小時(shí)以上標(biāo)稱容量12Ah，三元氧化物正極材料。電池比能量大于160wh/kg，比功率大于1200W/kg，Institute of New Energy Technology,INET,Tsinghua University安全很好的倍率性能鋰電池研討目前市售三元?jiǎng)恿﹄姵氐倪^(guò)充電 充電到5.2V時(shí)，發(fā)生劇烈燃燒Institute of New Energy Technology,INET,Tsinghua Univer

35、sity鋰電池研討目前市售三元?jiǎng)恿﹄姵?充電到4.15V，加熱到120，發(fā)生劇烈燃燒Institute of New Energy Technology,INET,Tsinghua University鋰電池研討 動(dòng)力電池的使用壽命與成本 如何評(píng)測(cè)動(dòng)力電池的使用壽命 現(xiàn)場(chǎng)檢測(cè)電池的壽命狀態(tài)（SOH）Institute of New Energy Technology,INET,Tsinghua University鋰離子動(dòng)力電池的使用壽命鋰電池研討 PHEV battery likely to deep-cycle each day driven:15 yrs equates to 4000-

36、5000 deep cycles Also need to consider combination of high and low frequency cycling and calendarwlife 電池電池循環(huán)壽命70%50%4000Data presented by Christian Rosenkranz(Johnson Controls)at EVS 20,2006Institute of New Energy Technology,INET,Tsinghua University鋰電池研討52%EVInstitute of New Energy Technology,INET,

37、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$4,000$6,000$10,000$8,000$14,000$12,000$18,000$16,000CVHEVPHEV20PHEV40transmissionengine25%電池占電動(dòng)車成本比例Projected Retail Powertrain Costs-Midsize Sedans1)including manufacturer and dealer

38、markups2)all component costs assume projected statuscharger/plugbattery 40%motor/inverter60%鋰電池研討動(dòng)力電池的使用壽命 電池的成本占整個(gè)電動(dòng)車成本的2560%。是一個(gè)非常重要的零部件。車的使用壽命：10-15年 動(dòng)力電池目前的使用壽命是3-7年，LG化學(xué)聲稱可以有10-15年的壽命保證。因此大幅度地延長(zhǎng)動(dòng)力鋰離子電池的使用壽命，使之達(dá)到與電動(dòng)車的壽命相當(dāng)，是目前動(dòng)力鋰離子電池發(fā)展的關(guān)鍵問(wèn)題。需要?jiǎng)恿﹄姵厥褂脡勖u(píng)測(cè)技術(shù)做支撐。Institute of New Energy Technology,INE

39、T,Tsinghua University鋰電池研討Ohmic Resistance Ohmic Resistance Ohmic Resistance temperature large1.51.3 HighdeCycles50100 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 4

40、50Cycles050100 150200250 300350 400 450ep影響動(dòng)力電池的使用壽命的因素 溫度 電流 充放電深度動(dòng)力電池的使用壽命評(píng)測(cè)Effects of charge current Effects of 1.61.71.51.61.41.41.2 1.31.8 2 1.7 1.9 鋰電池研討Internal ResistanceVoltage VCurrent AR=V/I動(dòng)力電池的使用壽命評(píng)測(cè)Degradation35003.75Remaining lifeInstitute of New Energy Technology,INET,Tsinghua Univer

41、sityTemperature of a battery3.653.63.553.83.70772500-500-1500-2500450025001500Voltage response/VCurrent/ADayPresentBattery*BMS:Battery Management System*PLC:Programmable Logic Controller-Battery Temperature-Battery Voltage-Battery CurrentBMS*Controller(PLC*)-Internal resistancedegradation rate-Remai

42、ning 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)鋰電池研討Institute of New Energy Technology,INET,Tsinghua University58