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。
shiyonggutidianjiezhi,daitiyoujiyetaidianjiezhi,nenggouyouxiaotigaolilizidianchideanquanxing。gutidianjiezhibaokuojuhewugutidianjiezhihewujigutidianjiezhi。juhewudianjiezhi,youqishiningjiaoxingjuhewudianjiezhideyanjiuqudehendadejinzhan,muqianyijingchenggongyongyushangpinhualilizidianchizhong,danshiningjiaoxingjuhewudianjiezhiqishishigantaijuhewudianjiezhiheyetaidianjiezhituoxiedejieguo,taduidianchianquanxingdegaishanfeichangyouxian。gantaijuhewudianjiezhiyouyubuxiangningjiaoxingjuhewudianjiezhinayangbaohanyetaiyirandeyoujizengsuji,suoyitazailouye、蒸zheng氣qi壓ya和he燃ran燒shao等deng方fang麵mian具ju有you更geng好hao的de安an全quan性xing。目mu前qian的de幹gan態tai聚ju合he物wu電dian解jie質zhi尚shang不bu能neng滿man足zu聚ju合he物wu鋰li離li子zi電dian池chi的de應ying用yong要yao求qiu,仍reng需xu要yao進jin一yi步bu的de研yan究jiu才cai有you望wang在zai聚ju合he物wu鋰li離li子zi電dian池chi上shang得de到dao廣guang泛fan應ying用yong。相xiang對dui於yu聚ju合he物wu電dian解jie質zhi,無wu機ji固gu體ti電dian解jie質zhi具ju有you更geng好hao的de安an全quan性xing,不bu揮hui發fa,不bu燃ran燒shao,更geng加jia不bu會hui存cun在zai漏lou液ye問wen題ti。此ci外wai,無wu機ji固gu體ti電dian解jie質zhi機ji械xie強qiang度du高gao,耐nai熱re溫wen度du明ming顯xian高gao於yu液ye體ti電dian解jie質zhi和he有you機ji聚ju合he物wu,使shi電dian池chi的de工gong作zuo溫wen度du範fan圍wei擴kuo大da;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
鋰li離li子zi電dian池chi的de安an全quan問wen題ti是shi不bu安an全quan電dian解jie質zhi直zhi接jie導dao致zhi的de,但dan從cong根gen源yuan上shang來lai說shuo,是shi因yin為wei電dian池chi本ben身shen的de穩wen定ding性xing不bu高gao,熱re失shi控kong的de出chu現xian導dao致zhi的de。而er熱re失shi控kong的de發fa生sheng除chu了le電dian解jie質zhi的de熱re穩wen定ding性xing原yuan因yin,電dian極ji材cai料liao的de熱re穩wen定ding性xing也ye是shi最zui重zhong要yao的de原yuan因yin之zhi一yi,所suo以yi提ti高gao電dian極ji材cai料liao的de熱re穩wen定ding性xing也ye是shi提ti高gao電dian池chi安an全quan性xing的de重zhong要yao環huan節jie,但dan是shi這zhe裏li所suo說shuo的de電dian極ji材cai料liao熱re穩wen定ding性xing不bu但dan包bao括kuo其qi自zi身shen的de熱re穩wen定ding性xing,也ye要yao包bao括kuo其qi與yu電dian解jie質zhi材cai料liao相xiang互hu作zuo用yong的de熱re穩wen定ding性xing。
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deLi4Ti5O12,相(xiang)對(dui)於(yu)層(ceng)狀(zhuang)石(shi)墨(mo)的(de)結(jie)構(gou)穩(wen)定(ding)性(xing)更(geng)好(hao),其(qi)充(chong)放(fang)電(dian)平(ping)台(tai)也(ye)高(gao)得(de)多(duo),因(yin)此(ci)熱(re)穩(wen)定(ding)性(xing)更(geng)好(hao),安(an)全(quan)性(xing)更(geng)高(gao)。因(yin)此(ci),目(mu)前(qian)對(dui)安(an)全(quan)性(xing)要(yao)求(qiu)更(geng)高(gao)的(de)動(dong)力(li)電(dian)池(chi)中(zhong)通(tong)常(chang)使(shi)用(yong)MCMB或Li4Ti5O12daitiputongshimozuoweifuji。tongchangfujicailiaoderewendingxingchulecailiaobenshenzhiwai,duiyutongzhongcailiao,tebieshishimolaishuo,fujiyudianjieyejiemiandegutidianjiezhijiemianmo(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。
shiyonggutidianjiezhi,daitiyoujiyetaidianjiezhi,nenggouyouxiaotigaolilizidianchideanquanxing。gutidianjiezhibaokuojuhewugutidianjiezhihewujigutidianjiezhi。juhewudianjiezhi,youqishiningjiaoxingjuhewudianjiezhideyanjiuqudehendadejinzhan,muqianyijingchenggongyongyushangpinhualilizidianchizhong,danshiningjiaoxingjuhewudianjiezhiqishishigantaijuhewudianjiezhiheyetaidianjiezhituoxiedejieguo,taduidianchianquanxingdegaishanfeichangyouxian。gantaijuhewudianjiezhiyouyubuxiangningjiaoxingjuhewudianjiezhinayangbaohanyetaiyirandeyoujizengsuji,suoyitazailouye、蒸zheng氣qi壓ya和he燃ran燒shao等deng方fang麵mian具ju有you更geng好hao的de安an全quan性xing。目mu前qian的de幹gan態tai聚ju合he物wu電dian解jie質zhi尚shang不bu能neng滿man足zu聚ju合he物wu鋰li離li子zi電dian池chi的de應ying用yong要yao求qiu,仍reng需xu要yao進jin一yi步bu的de研yan究jiu才cai有you望wang在zai聚ju合he物wu鋰li離li子zi電dian池chi上shang得de到dao廣guang泛fan應ying用yong。相xiang對dui於yu聚ju合he物wu電dian解jie質zhi,無wu機ji固gu體ti電dian解jie質zhi具ju有you更geng好hao的de安an全quan性xing,不bu揮hui發fa,不bu燃ran燒shao,更geng加jia不bu會hui存cun在zai漏lou液ye問wen題ti。此ci外wai,無wu機ji固gu體ti電dian解jie質zhi機ji械xie強qiang度du高gao,耐nai熱re溫wen度du明ming顯xian高gao於yu液ye體ti電dian解jie質zhi和he有you機ji聚ju合he物wu,使shi電dian池chi的de工gong作zuo溫wen度du範fan圍wei擴kuo大da;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
鋰li離li子zi電dian池chi的de安an全quan問wen題ti是shi不bu安an全quan電dian解jie質zhi直zhi接jie導dao致zhi的de,但dan從cong根gen源yuan上shang來lai說shuo,是shi因yin為wei電dian池chi本ben身shen的de穩wen定ding性xing不bu高gao,熱re失shi控kong的de出chu現xian導dao致zhi的de。而er熱re失shi控kong的de發fa生sheng除chu了le電dian解jie質zhi的de熱re穩wen定ding性xing原yuan因yin,電dian極ji材cai料liao的de熱re穩wen定ding性xing也ye是shi最zui重zhong要yao的de原yuan因yin之zhi一yi,所suo以yi提ti高gao電dian極ji材cai料liao的de熱re穩wen定ding性xing也ye是shi提ti高gao電dian池chi安an全quan性xing的de重zhong要yao環huan節jie,但dan是shi這zhe裏li所suo說shuo的de電dian極ji材cai料liao熱re穩wen定ding性xing不bu但dan包bao括kuo其qi自zi身shen的de熱re穩wen定ding性xing,也ye要yao包bao括kuo其qi與yu電dian解jie質zhi材cai料liao相xiang互hu作zuo用yong的de熱re穩wen定ding性xing。
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deLi4Ti5O12,相(xiang)對(dui)於(yu)層(ceng)狀(zhuang)石(shi)墨(mo)的(de)結(jie)構(gou)穩(wen)定(ding)性(xing)更(geng)好(hao),其(qi)充(chong)放(fang)電(dian)平(ping)台(tai)也(ye)高(gao)得(de)多(duo),因(yin)此(ci)熱(re)穩(wen)定(ding)性(xing)更(geng)好(hao),安(an)全(quan)性(xing)更(geng)高(gao)。因(yin)此(ci),目(mu)前(qian)對(dui)安(an)全(quan)性(xing)要(yao)求(qiu)更(geng)高(gao)的(de)動(dong)力(li)電(dian)池(chi)中(zhong)通(tong)常(chang)使(shi)用(yong)MCMB或Li4Ti5O12daitiputongshimozuoweifuji。tongchangfujicailiaoderewendingxingchulecailiaobenshenzhiwai,duiyutongzhongcailiao,tebieshishimolaishuo,fujiyudianjieyejiemiandegutidianjiezhijiemianmo(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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