鋰離子電池安全性問題
發布時間:2012-02-15
中心議題:
1、使用安全型鋰離子電池電解質
目mu前qian鋰li離li子zi電dian池chi電dian解jie液ye使shi用yong碳tan酸suan酯zhi作zuo為wei溶rong劑ji,其qi中zhong線xian型xing碳tan酸suan酯zhi能neng夠gou提ti高gao電dian池chi的de充chong放fang電dian容rong量liang和he循xun環huan壽shou命ming,但dan是shi它ta們men的de閃shan點dian較jiao低di,在zai較jiao低di的de溫wen度du下xia即ji會hui閃shan燃ran,而er氟fu代dai溶rong劑ji通tong常chang具ju有you較jiao高gao的de閃shan點dian甚shen至zhi無wu閃shan點dian,因yin此ci使shi用yong氟fu代dai溶rong劑ji有you利li於yu抑yi製zhi電dian解jie液ye的de燃ran燒shao。目mu前qian研yan究jiu的de氟fu代dai溶rong劑ji包bao括kuo氟fu代dai酯zhi和he氟fu代dai醚mi。
阻(zu)燃(ran)電(dian)解(jie)液(ye)是(shi)一(yi)種(zhong)功(gong)能(neng)電(dian)解(jie)液(ye),這(zhe)類(lei)電(dian)解(jie)液(ye)的(de)阻(zu)燃(ran)功(gong)能(neng)通(tong)常(chang)是(shi)通(tong)過(guo)在(zai)常(chang)規(gui)電(dian)解(jie)液(ye)中(zhong)加(jia)入(ru)阻(zu)燃(ran)添(tian)加(jia)劑(ji)獲(huo)得(de)的(de)。阻(zu)燃(ran)電(dian)解(jie)液(ye)是(shi)目(mu)前(qian)解(jie)決(jue)鋰(li)離(li)子(zi)電(dian)池(chi)安(an)全(quan)性(xing)最(zui)經(jing)濟(ji)有(you)效(xiao)的(de)措(cuo)施(shi),所(suo)以(yi)尤(you)其(qi)受(shou)到(dao)產(chan)業(ye)界(jie)的(de)重(zhong)視(shi)。
使(shi)用(yong)固(gu)體(ti)電(dian)解(jie)質(zhi),代(dai)替(ti)有(you)機(ji)液(ye)態(tai)電(dian)解(jie)質(zhi),能(neng)夠(gou)有(you)效(xiao)提(ti)高(gao)鋰(li)離(li)子(zi)電(dian)池(chi)的(de)安(an)全(quan)性(xing)。固(gu)體(ti)電(dian)解(jie)質(zhi)包(bao)括(kuo)聚(ju)合(he)物(wu)固(gu)體(ti)電(dian)解(jie)質(zhi)和(he)無(wu)機(ji)固(gu)體(ti)電(dian)解(jie)質(zhi)。聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi),尤(you)其(qi)是(shi)凝(ning)膠(jiao)型(xing)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)的(de)研(yan)究(jiu)取(qu)得(de)很(hen)大(da)的(de)進(jin)展(zhan),目(mu)前(qian)已(yi)經(jing)成(cheng)功(gong)用(yong)於(yu)商(shang)品(pin)化(hua)鋰(li)離(li)子(zi)電(dian)池(chi)中(zhong),但(dan)是(shi)凝(ning)膠(jiao)型(xing)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)其(qi)實(shi)是(shi)幹(gan)態(tai)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)和(he)液(ye)態(tai)電(dian)解(jie)質(zhi)妥(tuo)協(xie)的(de)結(jie)果(guo),它(ta)對(dui)電(dian)池(chi)安(an)全(quan)性(xing)的(de)改(gai)善(shan)非(fei)常(chang)有(you)限(xian)。幹(gan)態(tai)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)由(you)於(yu)不(bu)像(xiang)凝(ning)膠(jiao)型(xing)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)那(na)樣(yang)包(bao)含(han)液(ye)態(tai)易(yi)燃(ran)的(de)有(you)機(ji)增(zeng)塑(su)劑(ji),所(suo)以(yi)它(ta)在(zai)漏(lou)液(ye)、zhengqiyaheranshaodengfangmianjuyougenghaodeanquanxing。muqiandegantaijuhewudianjiezhishangbunengmanzujuhewulilizidianchideyingyongyaoqiu,rengxuyaojinyibudeyanjiucaiyouwangzaijuhewulilizidianchishangdedaoguangfanyingyong。xiangduiyujuhewudianjiezhi,wujigutidianjiezhijuyougenghaodeanquanxing,buhuifa,buranshao,gengjiabuhuicunzailouyewenti。ciwai,wujigutidianjiezhijixieqiangdugao,nairewendumingxiangaoyuyetidianjiezhiheyoujijuhewu,shidianchidegongzuowendufanweikuoda;將無機材料製成薄膜,更易於實現鋰離子電池小型化,並且這類電池具有超長的儲存壽命,能大大拓寬現有鋰離子電池的應用領域。
常chang規gui的de含han阻zu燃ran添tian加jia劑ji的de電dian解jie液ye具ju有you阻zu燃ran效xiao果guo,但dan是shi其qi溶rong劑ji仍reng是shi易yi揮hui發fa成cheng分fen,依yi然ran存cun在zai較jiao高gao的de蒸zheng氣qi壓ya,對dui於yu密mi封feng的de電dian池chi體ti係xi來lai說shuo,仍reng有you一yi定ding的de安an全quan隱yin患huan。而er以yi完wan全quan不bu揮hui發fa、不(bu)燃(ran)燒(shao)的(de)室(shi)溫(wen)離(li)子(zi)液(ye)體(ti)為(wei)溶(rong)劑(ji),將(jiang)有(you)希(xi)望(wang)得(de)到(dao)理(li)想(xiang)的(de)高(gao)安(an)全(quan)性(xing)電(dian)解(jie)液(ye)。離(li)子(zi)液(ye)體(ti)是(shi)在(zai)室(shi)溫(wen)及(ji)相(xiang)鄰(lin)溫(wen)度(du)下(xia)完(wan)全(quan)由(you)離(li)子(zi)組(zu)成(cheng)的(de)有(you)機(ji)液(ye)體(ti)物(wu)質(zhi),具(ju)有(you)電(dian)導(dao)率(lv)高(gao)、液態範圍寬、不揮發和不燃等特點,將離子液體用於鋰離子電池電解液中有望解決鋰離子電池的安全問題。
2、提高電極材料熱穩定性
lilizidianchideanquanwentishibuanquandianjiezhizhijiedaozhide,danconggenyuanshanglaishuo,shiyinweidianchibenshendewendingxingbugao,reshikongdechuxiandaozhide。erreshikongdefashengchuledianjiezhiderewendingxingyuanyin,dianjicailiaoderewendingxingyeshizuizhongyaodeyuanyinzhiyi,suoyitigaodianjicailiaoderewendingxingyeshitigaodianchianquanxingdezhongyaohuanjie,danshizhelisuoshuodedianjicailiaorewendingxingbudanbaokuoqizishenderewendingxing,yeyaobaokuoqiyudianjiezhicailiaoxianghuzuoyongderewendingxing。
通常負極材料熱穩定性是有其材料結構和充電負極的活性決定的。對於碳材料,球形碳材料,如中間相碳微球(MCMB)相(xiang)對(dui)於(yu)鱗(lin)片(pian)狀(zhuang)石(shi)墨(mo),具(ju)有(you)較(jiao)低(di)的(de)比(bi)表(biao)麵(mian)積(ji),較(jiao)高(gao)的(de)充(chong)放(fang)電(dian)平(ping)台(tai),所(suo)以(yi)其(qi)充(chong)電(dian)態(tai)活(huo)性(xing)較(jiao)小(xiao),熱(re)穩(wen)定(ding)性(xing)相(xiang)對(dui)較(jiao)好(hao),安(an)全(quan)性(xing)高(gao)。而(er)尖(jian)晶(jing)石(shi)結(jie)構(gou)的(de)Li4Ti5O12,xiangduiyucengzhuangshimodejiegouwendingxinggenghao,qichongfangdianpingtaiyegaodeduo,yincirewendingxinggenghao,anquanxinggenggao。yinci,muqianduianquanxingyaoqiugenggaodedonglidianchizhongtongchangshiyongMCMB或Li4Ti5O12代dai替ti普pu通tong石shi墨mo作zuo為wei負fu極ji。通tong常chang負fu極ji材cai料liao的de熱re穩wen定ding性xing除chu了le材cai料liao本ben身shen之zhi外wai,對dui於yu同tong種zhong材cai料liao,特te別bie是shi石shi墨mo來lai說shuo,負fu極ji與yu電dian解jie液ye界jie麵mian的de固gu體ti電dian解jie質zhi界jie麵mian膜mo(SEI)的熱穩定性更受關注,而這也通常被認為是熱失控發生的第一步。提高SEI膜的熱穩定性途徑主要有兩種:一是負極材料的表麵包覆,如在石墨表麵包覆無定形炭或金屬層;另一種是在電解液中添加成膜添加劑,在電池活化過程中,它們在電極材料表麵形成穩定性較高的SEI膜,有利於獲得更好的熱穩定性。
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正(zheng)極(ji)材(cai)料(liao)和(he)電(dian)解(jie)液(ye)的(de)熱(re)反(fan)應(ying)被(bei)認(ren)為(wei)是(shi)熱(re)失(shi)控(kong)發(fa)生(sheng)的(de)主(zhu)要(yao)原(yuan)因(yin),提(ti)高(gao)正(zheng)極(ji)材(cai)料(liao)的(de)熱(re)穩(wen)定(ding)性(xing)尤(you)為(wei)重(zhong)要(yao),在(zai)產(chan)業(ye)界(jie)正(zheng)極(ji)材(cai)料(liao)的(de)開(kai)發(fa)也(ye)更(geng)受(shou)關(guan)注(zhu),除(chu)了(le)有(you)其(qi)價(jia)格(ge)較(jiao)高(gao)、利(li)潤(run)較(jiao)大(da)的(de)原(yuan)因(yin)外(wai),它(ta)在(zai)電(dian)池(chi)安(an)全(quan)性(xing)中(zhong)的(de)重(zhong)要(yao)地(di)位(wei)也(ye)是(shi)其(qi)備(bei)受(shou)關(guan)注(zhu)的(de)一(yi)個(ge)重(zhong)要(yao)原(yuan)因(yin)。與(yu)負(fu)極(ji)材(cai)料(liao)一(yi)樣(yang),正(zheng)極(ji)材(cai)料(liao)的(de)本(ben)質(zhi)特(te)征(zheng)決(jue)定(ding)了(le)其(qi)安(an)全(quan)特(te)征(zheng)。LiFePO4由於具有聚陰離子結構,其中的氧原子非常穩定,受熱不易釋放,因此不會引起電解液的劇烈反應或燃燒;而其他過渡金屬氧化物正極材料,受熱或過充時容易釋放出氧氣,安全性差。而在過渡金屬氧化物當中,LiMn2O4在充電態下以λ-MnO2形式存在,由於它的熱穩定性較好,所以這種正極材料也相對安全性較好。此外,也可以通過體相摻雜、表麵處理等手段提高正極材料的熱穩定性。
- 鋰離子電池安全性問題
- 使用氟代溶劑有利於抑製電解液的燃燒
- 在常規電解液中加入阻燃添加劑
1、使用安全型鋰離子電池電解質
目mu前qian鋰li離li子zi電dian池chi電dian解jie液ye使shi用yong碳tan酸suan酯zhi作zuo為wei溶rong劑ji,其qi中zhong線xian型xing碳tan酸suan酯zhi能neng夠gou提ti高gao電dian池chi的de充chong放fang電dian容rong量liang和he循xun環huan壽shou命ming,但dan是shi它ta們men的de閃shan點dian較jiao低di,在zai較jiao低di的de溫wen度du下xia即ji會hui閃shan燃ran,而er氟fu代dai溶rong劑ji通tong常chang具ju有you較jiao高gao的de閃shan點dian甚shen至zhi無wu閃shan點dian,因yin此ci使shi用yong氟fu代dai溶rong劑ji有you利li於yu抑yi製zhi電dian解jie液ye的de燃ran燒shao。目mu前qian研yan究jiu的de氟fu代dai溶rong劑ji包bao括kuo氟fu代dai酯zhi和he氟fu代dai醚mi。
阻(zu)燃(ran)電(dian)解(jie)液(ye)是(shi)一(yi)種(zhong)功(gong)能(neng)電(dian)解(jie)液(ye),這(zhe)類(lei)電(dian)解(jie)液(ye)的(de)阻(zu)燃(ran)功(gong)能(neng)通(tong)常(chang)是(shi)通(tong)過(guo)在(zai)常(chang)規(gui)電(dian)解(jie)液(ye)中(zhong)加(jia)入(ru)阻(zu)燃(ran)添(tian)加(jia)劑(ji)獲(huo)得(de)的(de)。阻(zu)燃(ran)電(dian)解(jie)液(ye)是(shi)目(mu)前(qian)解(jie)決(jue)鋰(li)離(li)子(zi)電(dian)池(chi)安(an)全(quan)性(xing)最(zui)經(jing)濟(ji)有(you)效(xiao)的(de)措(cuo)施(shi),所(suo)以(yi)尤(you)其(qi)受(shou)到(dao)產(chan)業(ye)界(jie)的(de)重(zhong)視(shi)。
使(shi)用(yong)固(gu)體(ti)電(dian)解(jie)質(zhi),代(dai)替(ti)有(you)機(ji)液(ye)態(tai)電(dian)解(jie)質(zhi),能(neng)夠(gou)有(you)效(xiao)提(ti)高(gao)鋰(li)離(li)子(zi)電(dian)池(chi)的(de)安(an)全(quan)性(xing)。固(gu)體(ti)電(dian)解(jie)質(zhi)包(bao)括(kuo)聚(ju)合(he)物(wu)固(gu)體(ti)電(dian)解(jie)質(zhi)和(he)無(wu)機(ji)固(gu)體(ti)電(dian)解(jie)質(zhi)。聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi),尤(you)其(qi)是(shi)凝(ning)膠(jiao)型(xing)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)的(de)研(yan)究(jiu)取(qu)得(de)很(hen)大(da)的(de)進(jin)展(zhan),目(mu)前(qian)已(yi)經(jing)成(cheng)功(gong)用(yong)於(yu)商(shang)品(pin)化(hua)鋰(li)離(li)子(zi)電(dian)池(chi)中(zhong),但(dan)是(shi)凝(ning)膠(jiao)型(xing)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)其(qi)實(shi)是(shi)幹(gan)態(tai)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)和(he)液(ye)態(tai)電(dian)解(jie)質(zhi)妥(tuo)協(xie)的(de)結(jie)果(guo),它(ta)對(dui)電(dian)池(chi)安(an)全(quan)性(xing)的(de)改(gai)善(shan)非(fei)常(chang)有(you)限(xian)。幹(gan)態(tai)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)由(you)於(yu)不(bu)像(xiang)凝(ning)膠(jiao)型(xing)聚(ju)合(he)物(wu)電(dian)解(jie)質(zhi)那(na)樣(yang)包(bao)含(han)液(ye)態(tai)易(yi)燃(ran)的(de)有(you)機(ji)增(zeng)塑(su)劑(ji),所(suo)以(yi)它(ta)在(zai)漏(lou)液(ye)、zhengqiyaheranshaodengfangmianjuyougenghaodeanquanxing。muqiandegantaijuhewudianjiezhishangbunengmanzujuhewulilizidianchideyingyongyaoqiu,rengxuyaojinyibudeyanjiucaiyouwangzaijuhewulilizidianchishangdedaoguangfanyingyong。xiangduiyujuhewudianjiezhi,wujigutidianjiezhijuyougenghaodeanquanxing,buhuifa,buranshao,gengjiabuhuicunzailouyewenti。ciwai,wujigutidianjiezhijixieqiangdugao,nairewendumingxiangaoyuyetidianjiezhiheyoujijuhewu,shidianchidegongzuowendufanweikuoda;將無機材料製成薄膜,更易於實現鋰離子電池小型化,並且這類電池具有超長的儲存壽命,能大大拓寬現有鋰離子電池的應用領域。
常chang規gui的de含han阻zu燃ran添tian加jia劑ji的de電dian解jie液ye具ju有you阻zu燃ran效xiao果guo,但dan是shi其qi溶rong劑ji仍reng是shi易yi揮hui發fa成cheng分fen,依yi然ran存cun在zai較jiao高gao的de蒸zheng氣qi壓ya,對dui於yu密mi封feng的de電dian池chi體ti係xi來lai說shuo,仍reng有you一yi定ding的de安an全quan隱yin患huan。而er以yi完wan全quan不bu揮hui發fa、不(bu)燃(ran)燒(shao)的(de)室(shi)溫(wen)離(li)子(zi)液(ye)體(ti)為(wei)溶(rong)劑(ji),將(jiang)有(you)希(xi)望(wang)得(de)到(dao)理(li)想(xiang)的(de)高(gao)安(an)全(quan)性(xing)電(dian)解(jie)液(ye)。離(li)子(zi)液(ye)體(ti)是(shi)在(zai)室(shi)溫(wen)及(ji)相(xiang)鄰(lin)溫(wen)度(du)下(xia)完(wan)全(quan)由(you)離(li)子(zi)組(zu)成(cheng)的(de)有(you)機(ji)液(ye)體(ti)物(wu)質(zhi),具(ju)有(you)電(dian)導(dao)率(lv)高(gao)、液態範圍寬、不揮發和不燃等特點,將離子液體用於鋰離子電池電解液中有望解決鋰離子電池的安全問題。
2、提高電極材料熱穩定性
lilizidianchideanquanwentishibuanquandianjiezhizhijiedaozhide,danconggenyuanshanglaishuo,shiyinweidianchibenshendewendingxingbugao,reshikongdechuxiandaozhide。erreshikongdefashengchuledianjiezhiderewendingxingyuanyin,dianjicailiaoderewendingxingyeshizuizhongyaodeyuanyinzhiyi,suoyitigaodianjicailiaoderewendingxingyeshitigaodianchianquanxingdezhongyaohuanjie,danshizhelisuoshuodedianjicailiaorewendingxingbudanbaokuoqizishenderewendingxing,yeyaobaokuoqiyudianjiezhicailiaoxianghuzuoyongderewendingxing。
通常負極材料熱穩定性是有其材料結構和充電負極的活性決定的。對於碳材料,球形碳材料,如中間相碳微球(MCMB)相(xiang)對(dui)於(yu)鱗(lin)片(pian)狀(zhuang)石(shi)墨(mo),具(ju)有(you)較(jiao)低(di)的(de)比(bi)表(biao)麵(mian)積(ji),較(jiao)高(gao)的(de)充(chong)放(fang)電(dian)平(ping)台(tai),所(suo)以(yi)其(qi)充(chong)電(dian)態(tai)活(huo)性(xing)較(jiao)小(xiao),熱(re)穩(wen)定(ding)性(xing)相(xiang)對(dui)較(jiao)好(hao),安(an)全(quan)性(xing)高(gao)。而(er)尖(jian)晶(jing)石(shi)結(jie)構(gou)的(de)Li4Ti5O12,xiangduiyucengzhuangshimodejiegouwendingxinggenghao,qichongfangdianpingtaiyegaodeduo,yincirewendingxinggenghao,anquanxinggenggao。yinci,muqianduianquanxingyaoqiugenggaodedonglidianchizhongtongchangshiyongMCMB或Li4Ti5O12代dai替ti普pu通tong石shi墨mo作zuo為wei負fu極ji。通tong常chang負fu極ji材cai料liao的de熱re穩wen定ding性xing除chu了le材cai料liao本ben身shen之zhi外wai,對dui於yu同tong種zhong材cai料liao,特te別bie是shi石shi墨mo來lai說shuo,負fu極ji與yu電dian解jie液ye界jie麵mian的de固gu體ti電dian解jie質zhi界jie麵mian膜mo(SEI)的熱穩定性更受關注,而這也通常被認為是熱失控發生的第一步。提高SEI膜的熱穩定性途徑主要有兩種:一是負極材料的表麵包覆,如在石墨表麵包覆無定形炭或金屬層;另一種是在電解液中添加成膜添加劑,在電池活化過程中,它們在電極材料表麵形成穩定性較高的SEI膜,有利於獲得更好的熱穩定性。
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正(zheng)極(ji)材(cai)料(liao)和(he)電(dian)解(jie)液(ye)的(de)熱(re)反(fan)應(ying)被(bei)認(ren)為(wei)是(shi)熱(re)失(shi)控(kong)發(fa)生(sheng)的(de)主(zhu)要(yao)原(yuan)因(yin),提(ti)高(gao)正(zheng)極(ji)材(cai)料(liao)的(de)熱(re)穩(wen)定(ding)性(xing)尤(you)為(wei)重(zhong)要(yao),在(zai)產(chan)業(ye)界(jie)正(zheng)極(ji)材(cai)料(liao)的(de)開(kai)發(fa)也(ye)更(geng)受(shou)關(guan)注(zhu),除(chu)了(le)有(you)其(qi)價(jia)格(ge)較(jiao)高(gao)、利(li)潤(run)較(jiao)大(da)的(de)原(yuan)因(yin)外(wai),它(ta)在(zai)電(dian)池(chi)安(an)全(quan)性(xing)中(zhong)的(de)重(zhong)要(yao)地(di)位(wei)也(ye)是(shi)其(qi)備(bei)受(shou)關(guan)注(zhu)的(de)一(yi)個(ge)重(zhong)要(yao)原(yuan)因(yin)。與(yu)負(fu)極(ji)材(cai)料(liao)一(yi)樣(yang),正(zheng)極(ji)材(cai)料(liao)的(de)本(ben)質(zhi)特(te)征(zheng)決(jue)定(ding)了(le)其(qi)安(an)全(quan)特(te)征(zheng)。LiFePO4由於具有聚陰離子結構,其中的氧原子非常穩定,受熱不易釋放,因此不會引起電解液的劇烈反應或燃燒;而其他過渡金屬氧化物正極材料,受熱或過充時容易釋放出氧氣,安全性差。而在過渡金屬氧化物當中,LiMn2O4在充電態下以λ-MnO2形式存在,由於它的熱穩定性較好,所以這種正極材料也相對安全性較好。此外,也可以通過體相摻雜、表麵處理等手段提高正極材料的熱穩定性。
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