边锋游戏

高浓盐电解液,后锂离子化学时代技术风口?
发布时间:2019-03-27 16:18:23
关键词:动力电池锂电池

高浓盐电解液,后锂离子化学时代技术风口?


传统的碳酸盐溶剂具有高挥发性和易燃性,存在严重的安全风险,而且LiPF6化学性质不稳定,这使得电解质对水分和温度变化高度敏感。即使与添加剂组合,电解质的电化学窗口也只能在4.4 V以内。下一代电池需要更高的能量密度(更高的电压或容量)和更宽的工作温度,并且必须满足用于智能电话,电动车辆,智能电网和更高的安全标准等,传统电解质的这些缺点阻碍了下一代电池的发展。因此,全世界都在努力探索新的电解质,如离子液体、高分子电解质、无机固体电解质和盐浓缩的电解质以超越传统的锂离子电解质。其中,浓缩电解质受到越来越多的关注。

 

在过去的几年中,通过简单地提高盐-溶剂组合中盐的浓度,实现了锂离子电池电解液的重大突破,在许多方面表现出出色的技术优势。这种极其简单而有效的策略可以克服限制现有锂离子电池的大部分障碍,而不需要牺牲制造效率,因此研究人员广泛感受到其具有的巨大工业发展潜力。近日,日本东京大学Atsuo Yamada教授回顾了高浓度电解质研究的进展,包括对其优缺点和未来前景的多角度分析,重点放在解决剩余技术障碍和科学问题的途径上,旨在提供及时和客观的信息,而不是重新强调许多技术优势。给予设计更实用的电池提供参考。

 

YI、CHUANTONGDIANJIEZHIHENONGSUODIANJIEZHIDEQUBIE                          

高浓盐电解液,后锂离子化学时代技术风口?

图1. 常规稀释电解质和盐浓缩电解质的概述。a)离子导电率取决于电解质组成和浓度。b)稀释和浓缩电解质及其相应的盐(LiTFSA)和溶剂(AN)的照片。c)基于盐,溶剂和浓度的电解质设计。稀释(d)和浓缩(e)LiTFSA/AN电解质的计算电子结构(投影态密度,pDOS)。

 

边锋游戏CHUANTONGDIANJIEZHIDEPEIFANG:ZAITANSUANYAYIZHI(EC)HEXIANXINGTANSUANZHIDEHUNHERONGJIZHONGJIARU1M(mol-1)LiPF6DEDAODERONGYE。ECSHIYIZHONGBIBUKESHAODECHENGFEN,KEYISHISHIMOFUJIDEDONGLIXUEWENDING; QIHAIYUANFENJIECHANWUKEYIBAOGUOSHIMOBIAOMIANXINGCHENGDAODIANDANDIANJUEYUANDEXIANG(GUTIDIANJIEZHIZHONGJIANXIANG,SEI),TAKEYIYOUXIAODIFANGZHIRONGJIGONGQIANRUSHIMOHUODIDIANWEIXIADIANJIEZHIDELIANXUFENJIE。LiPF6DUIAlJILIUTIDEDUNHUAZHIGUANZHONGYAO,AlJILIUTISHIYINJIZHONGBUKEHUOQUEDECHENGFEN,ZAIGAODIANWEIXIARONGYIBEIFUSHI; HENLIANGDESHUISHUIJIELiPF6CHANSHENGHF,SUIHOUYUAlFANYING,ZAIBIAOMIANXINGCHENGWENDINGDEAlF3BOMO。YOUHUADE1MNONGDUSHILILIZIDIANDAOLVZUIDADENONGDU。

 

边锋游戏ZENGJIAYANNONGDUJIANGDAOZHIYANGLIZIHEYINLIZI/RONGJIZHIJIANDEXIANGHUZUOYONGZENGQIANG,YIJIZIYOUTAIRONGJIFENZIDEHANLIANGJIANGDI。GAOYUYUZHI(TONGCHANG> ~3-5M,QUJUEYUYAN-RONGJIZUHE),YOULIRONGJIFENZIXIAOSHI,DAOZHIXINGCHENGYILEIJUYOUTESHUSANWEI(3D)RONGYEJIEGOUDEXINXINGDIANJIEYE(CHENGWEIGAODUNONGSUODIANJIEYE)。ZHEIZHONGNONGSUODIANJIEYEBIAOXIANCHUBUTONGYUCHANGGUIDIANJIEZHIDEWULIHUAXUEHEDIANHUAXUEXINGZHI。ZHEIDAIBIAOLEYIZHONGXINDEDIANJIEZHISHEJI,KEYIZAIBUYILAIECHELiPF6DEQINGKUANGXIADUNHUASHIMOFUJIHEAlJILIUTI,CONGERKAIFACHUGEZHONGBUHANECHELiPF6DEDIANJI。

 

边锋游戏ER、NONGSUOYANDIANJIEZHIDEYOUSHI

ZAIBENJIEZHONG,JIANYAOHUIGUHEZONGJIELENONGSUOYANDIANJIEZHIDEYOUSHI:

高浓盐电解液,后锂离子化学时代技术风口?

图2. 通过浓缩电解质实现出色的电池性能。a)中心圆(淡蓝色)包围由外圆包围的浓缩电解质的代表性结构,外圆包含决定物理化学和电化学性质的基本材料特性(浅棕色)。外六角形列出了各种先进的电池功能:高倍率,高稳定性,高压,高安全性,金属阳极实现,消除副反应。b)根据出版年份总结的浓缩电解质及相关技术成果

 

2.1 GAOBEILV

边锋游戏YamadaDENGRENFAXIANHANYOUGAODULIJIEDEYAN(LIRU,LiN(SO2F)2,BIAOSHIWEILiFSA)HEDIZHANDURONGJI(LIRU,YIJING(AN))DENONGSUODIANJIEZHIKESHIXIANGAOBEILVDEDIANJIFANYING。JIYUJIEGUOFENXI,LiFSAYANHEDIZHANDURONGJIYINGGAISHIGAOBEILVFANYINGDEXIANJUETIAOJIAN,YINWEITAMENKEYIZUIDAXIANDUDIJIANSHAOGAONONGDUXIAZHANDUDEZENGJIA,CONGERZAILi+ZENGJIADEQINGKUANGXIABAOCHIKEJIESHOUDELIZIDIANDAOLVSHUIPING。RANER,NONGSUODIANJIEZHIZHONGDEBUXUNCHANGDEJIEMIANBILIZIDIANDAOLVGENGZHONGYAO。FENXISUOYOUDEJIEGUO,FAXIANSHIMODIANJISHANGDESEIJUYOUYUCHANGGUIECYANSHENGDESEIFEICHANGBUTONGDEZUCHENG;NONGSUODIANJIEZHIDEJIEMIANLAIZIYAN(BUSHITONGCHANGZAICHANGGUIXISHIDIANJIEZHIZHONGGUANCHADAODERONGJI),QIGAOBEILVNENGLIYINGGAIYUQIXINGCHENGDEDETESHUSEIJIEMIANXIANGGUANLIAN。

 

2.2 GAONENGLIANGMIDU

为了获得高能量密度,锂离子电池边锋游戏必须使用高压(例如5V级)或高容量(例如硫和锂金属)电极。然而,这些电极与常规的LiPF 6的电解液的兼容性很差。例如,化学性质不稳定的LiPF6易与微量水或H+反应生成HF,在高电压下腐蚀电极材料中的过渡金属。用LiFSA或LiN(SO2CF3)2(LiTFSA)代替LiPF6,但这些电解质不能钝化Al集流体。通过应用盐浓缩策略可以解决这种困境。Matsumoto等人首次报道,当LiTFSA浓度从1.0M增加到1.8M时,LiTFSA基电解质中Al溶解的起始电位从3.8变为4.3V。Wang等人开发了一种超浓缩电解液,5.5M LiFSA/DMC,显着改善了5V LiNi0.5Mn1.5O4/石墨电池的充放电循环。X射线光谱测量表明,在石墨电极表面沉积的过渡金属可以忽略,这证明浓缩电解质有效地抑制了铝和过渡金属在~5V时的正极溶解。


GAOYAXINGNENGKEGUIYINYUNONGSUODIANJIEZHIDETESHURONGYEJIEGOU:(1)HENSHAOYOUZIYOUZHUANGTAIRONGJIFENZIKEYIXIEDIAOLAIZIZHENGJIDEJINSHUYANGLIZI,(2)JINYIBUZENGQIANGDE3DWANGLUOYIZHILEJINSHUYANGLIZIKUOSANDAOBENTIDIANJIEZHIXIANG。LEISIDEJIZHIYESHIYONGYUSuoHEUenoDENGRENSHIYONGNONGSUODIANJIEZHILAIYOUXIAODIYIZHIDUOLIUHUAWUCONGLIUDIANJIZHONGRONGJIE,BINGHUODELEJUYOUXIANZHUGAISHANDEXUNHUANXINGNENGDEGAORONGLIANGLILIUDIANCHI。CIWAI,YULi+PEIWEIDERONGJIFENZIXIANSHICHUBIQIZIYOUZHUANGTAIDEFENZIGENGGAODEYANGHUAWENDINGXING,ZHEISHIYOUYUQIZUIGAOZHANJUFENZIGUIDAO(HOMO)SHUIPINGXIANGXIAYIDONG。YINCI,NONGSUODEDIANJIEZHIKEYIJIANSHAORONGJIYANGHUABINGYINCIZAIGAODIANYAXIACHANSHENGH+。

 

QICI,NONGSUODIANJIEZHIYESHIYONGYULIJINSHUFUJI。QIANDENGRENZAILi||CuDIANCHIZHONGSHIJIA4M LiFSA/DME,SHIXIAN500XIAOSHIDEWENDINGGONGZUO(ZAI4mA/cm 2XIA 1000GEXUNHUAN)HEGAOKULUNXIAOLV(> 98%)。NONGSUODIANJIEZHIDEZHISHAOYOULIANGGEYOUDIAN:SHOUXIAN,GAONONGDUDELi+ KEYIYIGENGJUNYUNDEFANGSHICUJINLiDIANDU/BOLI,BIMIANZHIJINGSHENGZHANG;QICI,NONGSUODEDIANJIEZHICHANSHENGWENGUSEI,QIYIZHIDIANJIEZHIHELiJINSHUZHIJIANDEFUFANYINGYIJIZHIJINGSHENGZHANG。

 

ZUIHOU,NONGSUODIANJIEZHIYESHIYONGYULI-O2HENa-O2GEDIANCHI。XUANZEHESHIDEYAN-RONGJIZUHE(LIRU,LiTFSA/NaTFSAYUERJIAJIYAFENG,ANHUOMI)SHIDEO2ZHENGJIHELi/NaFUJIDEKENIYUNXINGCHENGWEIKENENG。

 

2.3 XUNHUANWENDING

SHANGYONGLILIZIDIANCHIBIXUNENGGOUWENDINGDIXUNHUANDUONIAN,ZHEIYAOQIUDIANCHINEIBUDEFUFANYINGBIXUZUIXIAOHUA。SUIRANNONGSUODIANJIEZHIJUYOUXUDUOCHUANTONGDIANJIEZHISUOBUJUBEIDECHUSEGONGNENG,DANRENGXUKAOCHAHANYOUNONGSUODIANJIEZHIDEDIANCHIDEZHANGQIWENDINGXING。ZUIJIN,SHIMO||LiHEYINGTAN||NaDIANCHIZAINONGSUODIANJIEZHIZHONGCESHICHAOGUOYINIAN(CHAOGUO1,000CIXUNHUAN),RONGLIANGSHUAIJIANKEHULVEBUJI,BIAOMINGNONGSUODIANJIEZHIZHONGDESEIsFEICHANGWENDING,NENGGOUCUJINLILIZIHENALIZIDIANCHIDEZHANGQIXUNHUAN。ZHIDEZHUYIDESHI,SHIYONGCHANGGUIDIANJIEZHIDENALIZIDIANCHIBURULILIZIDIANCHIWENDING,YINWEIECYANSHENGDESEIZAICHANGGUINa+DIANJIEZHIZHONGGENGYIRONG。HANYOUNONGSUODIANJIEZHIDEYINGTANDIANCHIXIANSHICHUBIHANYOUCHANGGUIDIANJIEZHIDEGENGHAODEXUNHUANXINGNENG,ZHENGMINGYINLIZIYANSHENGDEWUJISEIBIECYANSHENGDEYOUJI-WUJIZAHUASEIGENGWENJIAN。NONGSUODIANJIEZHIDEZHEIZHONGTEZHENGJIANGYOUZHUYUKAIFAGAODUWENDINGDEDIANCHI,QIEBUXIANYULILIZI。

 

2.4 ANQUANXINGGAO

GUANYUANQUANXING,NONGSUODIANJIEZHIYUCHUANTONGDEDIANJIEZHIXIANGBIJUYOUHENDADEYOUSHI。SHOUXIAN,NONGSUODIANJIEYEKEYIWANQUANPAICHUYIRANRONGJI,QUEBAOQIBUYIRAN;DIER,TATIGONGLEQIANGDADEYINLIZIYANSHENGDESEI,BIMIANLECHANGJIANDEFEIYIRANRONGJICHADEDUNHUANENGLI;DISAN,TAZENGQIANGLEYANGLIZIHERONGJIFENZIZHIJIANDEXIANGHUZUOYONG,JIANGDILERONGJIDEGUYOUHUIFAXING。SUOYOUNONGSUODIANJIEZHIDEGONGTONGJIBENTEZHENG,KEHULVEBUJIDEZHENGQIYA,GENGSHAODEYOUJIRONGJIXIANGDUILIANGHEGENGGAODEFEIDIAN,WEISHEJIGENGANQUANDEDIANCHIXITONGTIGONGLEJIANSHIDEJICHU。

 

YUYOUJIDIANJIEZHIBUTONG,HANSHUIDIANJIEZHIBENZHISHANGSHIBUYIRANDE,SHIANQUANDIANCHIDELIXIANGXUANZE。RANER,YOUYUSHUIDEGUYOUZHAIDIANHUAXUECHUANGKOU(<1.23V),TAMENDEYINGYONGSHOUDAOXIANZHI。JINQIYANJIUBIAOMING,TONGGUOYANNONGSUOCELVEKEYISHIXIANDIANJIEZHIDIANHUAXUECHUANGKOUDETISHENG,GOUJIANJUYOUGAONENGLIANGMIDU、GAODUANQUANDEDIANCHI。

 

SAN、NONGSUOYANDIANJIEZHIDEJISHUWENTIHEQITAWENTI

边锋游戏ZAIBENJIEZHONG,ZONGJIELEGAONONGDUDIANJIEYEDESHIJIYINGYONG、KEXUENANTIHEJISHUWENTI。

 

边锋游戏3.1 SHIJIYINGYONGZHONGDEGONGYIHECHENGBENWENTI

NONGSUODIANJIEYEHAIYOULIANGGEZUAIQISHANGYEHUADEZHUYAOQUEDIAN:GAOZHANDUHEGAOCHENGBEN。SHANGYEXISHIDIANJIEYEZAISHIWENXIADEZHANDUWEI~3mPa·s,SHIYONGZHEIZHONGDIZHANDUDIANJIEYE,SHANGYONGLILIZIDIANCHIYEXUYAOCHIXUYUE24XIAOSHIDELAOHUACHULI,YISHIGEMOHEDIANJIHUODEZUGOUDERUNSHI。RANER,NONGSUODIANJIEYEDEZHANDUYUEWEICHUANTONGXISHIDIANJIEYEDESHIBEIHUOGENGDUO,DANGCAIYONGLEISIDEZHIZAOGONGYISHI,JIANGXIANZHUYANZHANGRUNSHISHIJIAN。CIWAI,WEILETIGAOZHENGGEDIANCHIXITONGDENENGLIANGMIDU,SHANGYONGDIANCHIDEDIANJIZHENGBIANDEYUELAIYUEHOU,GENGHOUDEDIANJISHIYONGNONGSUODEDIANJIEZHISHIJIANGJINYIBUYANZHANGRUNSHISHIJIAN。

 

边锋游戏MUQIANSHANGYONGLILIZIDIANJIEYEDECHENGBENZHUYAOQUJUEYULiPF6YANNONGDU。MUQIANSHANGYEXIDIANJIEZHI1.0M LiPF6/EC:DMC(1:1(TIJI))ZHONG,LiPF6ZAIDIANJIEZHIZHONGDEZHONGLIANGHANLIANGSHI12%,DANQIZAIZHENGTIDIANJIEYECHENGBENZHONGZHANLE70%YISHANG。GENJUZHONGGUOSHICHANG2018NIAN3YUEDESHUJU,LiPF6YANDEJIAGEBITANSUANYANRONGJIDEJIAGEGAOYUE18BEI。ZAINONGSUODIANJIEYEZHONG,YANSHIZHUYAOCHENGFEN,ZHEIBUKEBIMIANDIZENGJIALEDIANJIEYEDECHENGBEN。LIRU,YOU5.5MLiFSA / DMCZUCHENGDENONGSUODIANJIEZHIYEDEYANHANLIANGDADAO70wt%,JIHUSHI1.0M LiPF 6ZHONGDE 6BEI。YINCI,JIASHEZAIDAGUIMOSHENGCHANZHIHOULiFSADEJIAGEJIANGDIDAOLiPF 6DEJIAGE,QIANZHEDECHENGBENJIANGBIHOUZHEDECHENGBENGAO6BEI,CHENGBENDEXIANZHEZENGJIADAIBIAOLENONGSUODIANJIEYESHANGYEHUADEZHONGDATIAOZHAN。

 

3.2 KEXUEWEIZHIWENTI

NONGSUODIANJIEZHIDEKEXUEJICHUJUYOUFENGFUDEXINGAINIAN(DANZHUYAOSHIWEIZHIDE),YINWEIZAIRONGYEJIEGOU,DIANZIJIEGOU,YUNSHUJIZHIHESEIXINGCHENGJIZHIFANGMIANYUZHONGSUOZHOUZHIDEXISHITIXICUNZAIJIAODAPIANCHA。

 

LILUNMONIHESHIYANGUANGPUJISHUXIANGJIEHEYONGYUJIESHILiTFSA/ANRONGYEDERONGYEJIEGOUHEDIANZIJIEGOU(TU1d,e)。FAXIANZAIXISHIDEDIANJIEZHIZHONG,SUOYOUDEYANDOUHENHAODIRONGJIEBINGRONGJIHUAYIXINGCHENGRONGJIFENLIDELIZIDUI。ZAIDADUOSHUQINGKUANGXIA,ZHUYAOSHIRONGJIFENZIJUEDINGLUMO。YINCI,RONGJIFENZIZHUYAOBEIHAIYUANBINGYOUZHUYUSEIXINGCHENG。SUIZHENONGDUZENGJIA,RONGJIHUABIANDE“BUWANMEI”,BINGQIEJIECHULIZIDUI(CIP)HEJUJITI(AGG)DEBILIZENGJIA。TONGSHI,YOULIRONGJIFENZIDESHULIANGJIJUJIANSHAO。YULi +DEGUANGFANXIEDIAODAOZHIYINLIZIGUIDAOSHUIPINGXIANGXIAYIDONG。ZUIZHONG,LUMOYOUYINLIZIZHUDAO。YINCI,YINLIZIZHUYAOBEIHAIYUANHEFENJIEYIXINGCHENGYINLIZIYANSHENGDESEI。SHIYANJIEGUOFAXIANZHEIZHONGYINLIZIYANSHENGDESEIJUYOUDIDEJIEMIANDIANZU,ZHEIYOULIYUSHIXIANKUAISUCHONGDIAN/FANGDIANFANYING。

高浓盐电解液,后锂离子化学时代技术风口?

图3. 离子传输机制。a)不同浓度和30℃的非水(LiFSA/DMC)和水(LiTFSA/H2O和Li(TFSA)0.7(BETA)0.3·2H2O水合物熔体)电解液的Walden图。Walden图显示了电解液溶液的摩尔电导率(Λ)和粘度(η)之间的关系。b)常规稀释电解液中载体型机理的示意图和浓缩电解液中的跳跃型机理。c)浓缩电解质中的离子迁移机制:LiBOB/AN中的溶剂辅助跳跃,NaFSA/DME中的配体交换机制以及LiTFSA/H2O中富含H2O的3D渗透通道的形成。

 

边锋游戏NONGSUODIANJIEZHIDELINGYIGEZHONGYAOTEZHENGSHIQITEYOUDELIZICHUANSHUJIZHI。ZAICHUANTONGDERONGYEHUAXUEZHONG,(RONGJIHUA)LIZIDEYUNDONGXIANSHICHUZUNSHOUSITUOKESI - AIYINSITANDINGLV(TU3),RUGUOWUZHONGBICIDULIDIYIDONG,ZHEISHIYIGEHENHAODEJINSI。XIANRAN,ZAIJUYOUJUJIRONGYEJIEGOUDENONGSUODIANJIEZHIZHONG,CHUANSHUJIZHIBUHUIJIANDANDEZUNXUNGAIDINGLV。YINCI,YOUYANJIUZHETICHULEYIZHONGGENGFUZADEJIZHI,JIYUZHOUWEIFENZIXIANGGUANDELIZIYUNDONG。SHUANG(CAOSUAN)PENGSUANLI(LiBOB)/ANHENaFSA/DMEXITONGDELILUNYANJIUJIESHILE“RONGJIFUZHULILIZIKUOSAN”,BINGQIELEISIDI,TONGGUORONGJIHEYINLIZIZHIJIANDEJIAOHUANFANYINGZAISHIJIANCHIDUSHANGJINXINGNALIZIYUNDONGDAYUEWEIca.50 PSHE60-120 PS(TU3)。ZHEIXIECHUANSHUJIZHIJIBENSHANGBIAOSHIWEIDUOTIGUOCHENG,BINGQIEKEGUIYINYUNONGSUODIANJIEYEZHONGLIZIDEKUAISUCHUANSHUHEGAOLi+DECHUANSHUSHULIANG。YUJIZHEIXIEJIZHISHICHANGJIANDEBINGQIEKEKUOZHANDAOQITANONGSUOXITONG。HAITICHULEZAIYANBAOSHUIDIANJIEZHIZHONGYETICHULEGENGDACHIDUDESHUYUNXULIE。FUHANYINLIZIDEQUYUDEYINRULEFUHANH2ODE3DSHENTOUWANGLUOCHENG,Li+ZAIQIZHONGDEKUAISUCHUANSHUSHIKENENGDE(TU3)。

 

边锋游戏CHONGFENLEJIESEIXINGCHENGDEXIANGJIANJIEGOUHEFANYINGSHIYIGEJUDADETIAOZHAN。ZAIDIANJI/DIANJIEZHIJIEMIANCHUFASHENGDEYIBANXIANXIANGSHIDIANHUAXUESHUANGCENGDEXINGCHENGHEYANGHUA/HAIYUANFANYING。RANER,DADUOSHUJIEMIANRONGYEJIEGOUHEFANYINGSHANGWEIWANQUANCHANMING,YINWEIZAIFUZASEIXINGCHENGDESHIYANYUANWEIGUANCHAHUOJISUANMONIZHONGCUNZAIXIANZHEKUNNAN,BAOKUODIANJIDIANWEIXIAOYING。ZUIXINDEMONIJISHUTICHULEYIZHONG“JINANJIZHI”,QIZHONGJIANSHAODECHENGFENSHOUXIANXIANGWAIQIANYIDAO“JINAN”QUYU(JULIBIAOMIANJISHINAMI)RANHOUJUJICHENJIZAIDIANJIBIAOMIANSHANG。GAIJIZHIYUNONGSUODIANJIEZHIDEDIANZIJIEGOUJISUANYIZHI,DANHAIXUYAOJINYIBUDESHIYANYANZHENG。

 

边锋游戏HAIXUYAOJIEJUEYIXIEXUANERWEIJUEDEWENTI,LIRUZHEIXIEJIZHIDEPUBIANXING(JIYANHERONGJIYILAIXING)YIJIGENGDAGUIMOHESEIBOMOZHONGDERONGYEJIEGOUHECHUANSHUJIZHI。ERQIEHAIYOUQITAWEIZHIJIZHIHAIWEINENGZHUYIDAO,YINWEIQIJINWEIZHISHIYONGDEFENXIFANGFAXIANYU10-100 psDESHIJIANCHIDUHEGAODA104 -105GEYUANZIDEKONGJIANCHIDU。CIWAI,LILUNJISUANZHONGSHIZHONGCUNZAIJIANMOXIANZHIHEJINSI。YINCI,KAOLVDAOFENZIZHIJIANDESUOYOUXIANGHUZUOYONGJUYOUCONGTOUKAISHIDEZHUNQUEXING,DIANHUAXUEHUANJINGDEJIEHE,LIRUDIANJIDIANWEIHE/HUOHUAXUEFANYINGDEPINGGU,SHIJINYIBUYANJIUDEGUANJIAN。

 

SI、NONGSUOYANDIANJIEZHIDEFAZHANFANGXIANG

ZAIBENJIEZHONG,JIESHAOLEYOUGUANSHANGSHUWENTIDEGUANDIAN。


4.1 YAN/RONGJITANSUO

NONGSUODIANJIEYEZUIXIANZHUHEZUIJIBENDETEDIANSHIQIQIANZAISHEJIDEDUOYANGXING,ZHEIYUSHANGYEXISHIDIANJIEYE(XUYAOLiPF6HEEC)DEGUDINGSHEJIXINGCHENGXIANMINGDUIBI。NONGSUODIANJIEYEKEYIZAIMEIYOUECHUOQITAYOUJITANSUANYANDEBANGZHUXIADUNHUASHIMOHEQITAFUJI,BINGQIEJISHIZAIBUCUNZAIF-GONGTIDEQINGKUANGXIAYEKEYIDUNHUAAlJILIUTI。ZHIQIANRENWEIDUIDIANCHIDIANJIEZHIWUXIAODEGEZHONGYAN-RONGJIZUHEKEYONGYUNONGSUODIANJIEYEZHONG(TU1a,c)。ZHEIZHONGSHEJIDUOYANGXINGKEYIYIBUGONGNENGHUADIANCHIDIANJIEZHI,ERBUHUIXISHENGTAMENYUDIANJIDEJIANRONGXING。YINCI,ZHIDETANSUOGEZHONGXINDEYAN-RONGJIZUHEYIKAIFAQIANSUOWEIYOUDEDIANJIEZHIGONGNENG。GENGZHONGYAODESHILIZIDIANDAOLVQIANGLIEYILAIYUYAN-RONGJIZUHE,CONGZHEIGEJIAODULAIKAN,SHEJIGAODAODIANDENONGSUODIANJIEYEYOUXIANGDANGDADEKONGJIAN。WUXIANZHIDEYAN - RONGJIZUHEYEJIANGYOULIYUSHEJIYONGYUXIAYIDAIYANGHELIUDIANCHI。

 

4.2 XISHIDEGAINIAN

高浓盐电解液,后锂离子化学时代技术风口?

图4. 用低极性溶剂稀释浓缩电解质。a)三种电解质溶液结构示意图:常规稀释电解质,浓缩电解质和稀释浓缩电解质。b)比较三种电解质的性质和性能。

 

边锋游戏YANNONGSUODIANJIEZHIGAOZHANDUHEGAOCHENGBENDEQUEDIAN,BIXUZAISHIJIYINGYONGZHONGJIAYIJIEJUE。YIZHONGJIEJUEFANGANKEYISHIYINRUDUOXINGRONGJIYI“XISHI”NONGSUODEDIANJIEZHI。LIXIANGDEXISHIJIYINGJUYOUJIGETEZHENG:(1)DIZHANDU,KEYOUXIAOJIANGDIDIANJIEZHIDEZHANDU; (2)CHENGBENDI,KEJIANGDIDIANJIEYEDEZONGCHENGBEN; (3)SHIDANGDEJIEDIANCHANGSHUHEPEIWEIXINGNENG,SHINONGSUODIANJIEZHIJUYOUGAORONGJIEDU,TONGSHIBUGAIBIANNONGSUODIANJIEZHIDEJUBUPEIWEIHUANJING(CANJIANTU4aZHONGDEJIEGOUFANGAN); (4)ZUGOUDEDUOXING/WENDINGXING,BUHUISUNHAINONGSUODIANJIEZHIDEDIANHUAXUECHUANGKOU;(5)BUYIRANHEDIHUIFAXING,BUSUNHAINONGSUODIANJIEZHIDEANQUANXING。

 

4.3 HOULILIZIHUAXUESHIDAI

高浓盐电解液,后锂离子化学时代技术风口?

表1. 比较用于电池的几种有希望的金属离子的特性

 

MUQIAN,BAODAODEDADUOSHUNONGSUODIANJIEZHIDOUJIZHONGZAILILIZISHANG。ZAIXIAYIJIEDUAN,ZHIDEJIANGZHEIYIGAINIANKUOZHANDAOJUYOUFENGFUZIYUANDEHOULILIZIDIANCHI,LIRUNa +,K +,Mg2 +HEAl3+TIXI。YOUYULi+HEQITALIZIZHIJIANDEGUYOUCHAYI,ZHEIZHONGHOULIDIANCHIDEDIANJIEZHIDEYANJIUYUDAOGEZHONGKUNNAN/TIAOZHAN。QIZHONG,NaHEKYINJUYOUJIEJINLiDEDIANWEI,ZAIZHEIYANGDEXITONGZHONGMEIYOURONGJISHIRELIXUEWENDINGDE,SHUYUSEIYILAIXINGZU;XIANGFAN,MgHEAlDEDIANWEIMINGXIANGAOYULi,ZAIZHEIYANGDEXITONGZHONG,YIXIEDIANJIEYESHIWENDINGDEERMEIYOUHAIYUANFENJIE,SHUYUSEIFEIYILAIXINGZU。


边锋游戏Na+HEK+JUYOUYULi+LEISIDEDIANCHIHUAXUEXINGZHI,TAMENDEDIANJIEYEFAZHANKEYIZUNXUNCONGCHANGGUILi+DIANJIEYEHUODEDELEIJIZHISHI。DANSHI,Na+DIANJIEYECHANSHENGDESEIGENGYIRONGYUNa+DIANJIEZHIRONGYE,ZHEIHUIDAOZHIJIAOGAODEZIFANGDIAN,DUINa+DIANCHIDEZHANGQIWENDINGXINGCHANSHENGFUMIANYINGXIANG。YINCIZAIZHEIFANGMIAN,YANNONGSUOCELVEJUYOUXIANZHUDEYOUSHI,YINWEIYOUYINLIZIYANSHENGDEWUJISEIGENGBUYIRONGJIE,CONGERYIZHIFUFANYING。DAOMUQIANWEIZHI,BAODAODEK+DIANJIEZHIXIANGDANGSHAO,JIAYANTONGCHANGBINaHELiYANJUYOUGENGCHADERONGJIEDU,YINCI,XUANZESHIDANGDEYAN(GAODULIJIEDE)HERONGJI(GAOJIXING)SHINONGSUODEK+DIANJIEYEDEZHUYAOKAOLVYINSU。Mg2+HEAl3+DIANJIEYEDEFAZHANBUTONGYUCHUANTONGDELi+DIANJIEYE,CHANGGUITANSUANZHIRONGJIHUIDUNHUABIAOMIANMO,QIDUIGEZIDEYANGLIZIBUDAODIAN,SHIMgHUOAlJINSHUFUJIKUAISUSHIHUO。


JINJISHINIANLAI,ZHUYAONULISHEJIKAIFAYUJINSHUFUJIXIANGRONGQIEBUCHANSHENGDUNHUAMODEWENDINGDIANJIEZHI。BAODAODEMg2 +DIANJIEZHITONGCHANGJUYOUYOUMEIYAN,AlCl3HEMIRONGJIZUCHENGDEFUZAZUHEWU,ERAl3+DIANJIEZHIZHUYAOSHIAlCl3HELIZIYETIDEHUNHEWU。SUIRANZHEIXIEDIANJIEYEKEYIJINXINGKENIDEJINSHUDIANDU/BOLI,DANTAMENDEFUJIWENDINGXINGCHA,YIFUSHIJILIUTIHECHUANSHUSULVDI。YINGYONGYANNONGSUOCELVEYIJIXUANZEHESHIDEYANHERONGJIKEYICHANSHENGTONGYONGDEMg2+HUOAl3+DIANJIEZHI,QITONGGUOHELIDIAOJIEDIANJIEZHIRONGYEDEHOMO-LUMOXINGZHIYUJINSHUFUJIHEGAOYAZHENGJIJIANRONG。ZHEIZHONGCELVEYEKENENGYOUZHUYUJIANSHAOJILIUTIDEFUSHIBINGZENGJIACHUANSHUSULV,YINWEINONGSUODIANJIEZHIBUHANZIYOUTAIRONGJIFENZIHUOYINLIZI。

 

4.4 LIZICHUANSHUJIZHI

LIZICHUANSHUYUDIANCHIDEBEILVNENGLIZHIJIEXIANGGUAN。XISHIDIANJIEZHIZHONGDECHANGGUIZAILIUZILEIXINGJIZHI(TU3b)TIGONGLEYIZHONGJIANDANDEZHIDAOYUANZE,TONGGUOZUIDAHUAJUYOURONGJIHUACENGDELIJIEZIYOULIZIDEZAILIUZIMIDUHEQIANYILV,KEYISHIXIANGENGHAODELIZICHUANSHUXINGNENG。RANER,GAIZHINANBUSHIYONGYUNONGSUODIANJIEZHI,YINWEIYANWUZHONGGENGDUODIYIDIHETAICUNZAI(LIRUCIPHEAGG)。MUQIAN,DUICHUANSHUJIZHIDERENSHIHAIYUANYUANBUNENGRANGRENMANYI。KAOLVDAOCIPsHEAGGsZHONGXIANGGUANDELi+-YINLIZIZHUANGTAI,Li+KENENGSHITONGGUOLewisJIBENWEIDIANCONGYIGEYINLIZITIAOYUEDAOLINGYIGEYINLIZI,DANZHEIYIJIZHISHANGWEIDEDAOSHIYANHELILUNSHANGDEZHENGMING(TU3b)。

 

BENWENJIESHAOLEYOUGUANLIZICHUANSHUJILIDEWEILAIYANJIUDEJIGEZHONGYAOGUANDIAN。SHOUXIAN,ZHIDEZHUYIDESHI,GENJUWaldenTU(TU3a),YIXIENONGSUODIANJIEZHIBEIGUILEIWEI“CHAOLIZIRONGYE”,BIAOMINGLIZIYUNDONGYUZHANDU(LIUDONGXING)FENLI,ZHEIBIAOMINGTIAOYUEXINGLIZICHUANSHULEISIYUWUJIGUTILIZIDAOTI。QICI,YINGGAIZHONGXINGUANZHULIZIDIANDAOLVSUIYAN-RONGJIZUHEDEJUDABIANHUA(TU1a),RONGJIFENZIHEYINLIZIZAIYUEBIANJILIZHONGJUNQIZHEZHONGYAOZUOYONG,NONGQINGTAMENDEZUOYONGJIANGSHIGAODAODIANXINGNONGSUODIANJIEYEDESHEJIGENGJIAHELI。ZUIHOU,GAOLi+QIANYISHU(t+)YAOYUANYUANCHAOGUO0.7,BINGQIEXUYAOJINXINGSHENRUYANJIU。GAOQIANYISHUYIWEIZHELi +BIYINLIZIYIDONGDEKUAIDEDUO,YUCHUANTONGXISHIDIANJIEZHIZHONGJIAOMANDELi+QIANYISHUXINGCHENGXIANMINGDUIBI(t+≈0.2-0.4)。ZHEIZHONGGAOt+DEYIGEGUANJIANYINSUYINGGAIZHEZHONGTAOLUNTIAOYUEXINGJIZHIHE/HUOFEIJUNXIANGRONGYEJIEGOU,ZHEIKENENGWEIKAIFAJUYOUJIEJINTONGYIt+DELIXIANGYETIDIANJIEZHITIGONGYUANZEZHIDAO。


YIBANLAISHUO,FENXIYETIJIEZHIZHONGLIZIYUNDONGDESHIYANFANGFAYUGUTIJIEZHIZHONGLIZIYUNDONGDESHIYANFANGFAXIANGBISHIYOUXIANDE。YINCI,LILUNFANGFASHIJIESHILIZISHUYUNJILIDEJIAOHAOXUANZE。JINNIANLAI,YUELAIYUEDUODELILUNHUAXUEJIAJIANGXIANJINJISUAN/MONIFANGFAYINRUDIANCHIDIANJIEZHILINGYUYIN,ZHEIJIANGCHANSHENGXINDELIXUELIJIE。ZUIJIN,YIZHONGXIANJINDEMIDUFANHANJINSHUFU(DFTB)FENZIDONGLIXUEFANGFABEIYINGYONGYUNONGSUODIANJIEZHI(>103GEYUANZI)DEDAGUIMOMONI,YUMIDUFANHANLILUN(DFT)FENZIDONGLIXUEFANGFAXIANGBI,MEIYOUXIANZHUDEJINGDUSUNSHI。

 

4.5 GONGNENGXINGJIEMIAN

高浓盐电解液,后锂离子化学时代技术风口?

图5. SEI在浓缩电解液中形成过程。通过混合蒙特卡罗/分子动力学(MC/MD)方法模拟5MLiFSA/AN,以证明阴离子衍生的SEI是如何形成的。a)初始状态(0 MC/MD循环)。b)优先将FSA-还原为绿色FS2O4N-阴离子(100MC/MD循环)。c)在FSA -表面(500 MC/MD循环)逐次还原AN。d)最终平衡状态以形成稳定的SEI(2000MC/MD循环)。

 

YINLIZIYANSHENGDESEIXIANGZAIHENDACHENGDUSHANGJUEDINGLENONGSUODIANJIEZHIDEYIXIEGONGNENG。YUANZIYINLIZIDESEIXINGCHENGYOUXIANHAIYUANYULi+PEIWEIDEYANYINLIZI,YANYINLIZIDEXUANZEZHIJIEZHUDAOSEI。YINCI,NONGQINGGOUCHENGZHEIZHONGXINDEYINLIZIYANSHENGDESEIDEGONGNENG、XINGCHENGJIZHIHEJIBENZUFENYIBIANDEYUELAIYUEZHONGYAO。


SHOUXIAN,BIXUJINYIBUSHENRUTAOLUNSEIXINGCHENGJIZHI。DADUOSHUWENXIANJIANGYINLIZIYOUXIANJIANSHAOGUIYINYULi+-YINLIZIPEIWEIDAOZHIYINLIZILUMOSHUIPINGXIAJIANG,ZHEISHI2014NIANZAIDFTFENZIDONGLIXUEMONIDEJICHUSHANGSHOUCITICHUDE。ZHEIYITIYIDAIBIAOLEJIANGWEIGUANPEIWEITAIYUDIANHUAXUEFANYINGLIANXIQILAIDEYIGEZHONGYAOFANGMIAN。RANER,GENGHONGGUANDEFANGMIAN,RUDIANJIDEPINGHENGDIANWEIHESEIWUZHONGDERONGJIEDU,BUYINGGAIBEIHUSHI。YOUYUNONGSUODIANJIEZHIZHONGLi+HUOXINGZENGJIA,ZHENGFUJIDEPINGHENGFANYINGDIANWEIYEGENJUNENGSITEFANGCHENGXIANGSHANGYIDONG,ZHEIKENENGGAIBIANZHUYAODIANHUAXUEFANYINGTUJING。CIWAI,NONGSUODIANJIEZHIZHONGDESEIRONGJIEDUHUIJIANGDI,WEILEJIEJUEZHEIGEWENTI,HUNHEMonte Carlo /FENZIDONGLIXUEFANGFAKENENGSHIYIZHONGQIANGYOULIDEGONGJU。YONGYUXIUSHIHUOJINYIBUGONGNENGHUAZHONGJIANXIANGDEDIANJIEZHITIANJIAJIYEZHIDEYANJIU。


边锋游戏QICI,BIXUCAIYONGGEZHONGSHIYANFANGFALAICONGDUOFANGMIANDEJIAODULAIBIAOZHENGSEI。MUQIAN,DADUOSHUGUANCESHITONGGUOXSHEXIANGUANGDIANZINENGPU,FULIYEBIANHUANHONGWAIGUANGPU,SAOMIAODIANZIXIANWEIJINGHETOUSHEDIANZIXIANWEIJINGZAIBIAOMIANFENXIZHONGHUODEDE,DANMEIYOUZHENGJUBIAOMINGSEIZAICONGDIANCHIZHONGTIQUHOUBAOLIUQIYUANSHIZUCHENGHUOXINGTAI,QIEXSHEXIANFUSHEHUOAr+JIANSHEHUIJIANGDIANJISHANGCANLIUDELiTFSAHUOLiFSAYANFENJIECHENGLiF。YUANWEIHUOXIANCHANGYUANWEIFENXIDUIYUHUODEGENGZHUNQUEDEXIANGJIANHUAXUEXINXIJUYOUZHONGYAOZUOYONG。


ZUIHOU,ZUIJUTIAOZHANXINGDERENWUSHIGAIKUOSEIHUAXUEYUQIGONGNENGZHIJIANDEXIANGGUANXING。MUQIAN,LiFSAYANSHENGDESEIJUYOUCHAOGAODEDEWENDINGXINGHEKUAISUFANYINGDONGLIXUE,DADUOSHUYANJIURENYUANRENWEILiFSHIZHEIXIETEZHENGDEZHUYAOGONGXIANZHE,DANSHILiFRUHEDAOZHIZHEILIANGGETEZHENGRENGRANSHIYIGEXUANERWEIJUEDEWENTI。JINGUANLiPF6YESHILIANGHAODEF-GONGTI,DANLiPF6YANSHENGDESEIBURULiFSAYANSHENGDESEIWENDING。CONGZHEIGEJIAODULAIKAN,BUYINGHUSHIFSADEQITAZUFEN(SHUON)HE/HUOFENZIJIEGOUTEZHENG。SHIBIELiFSAYANSHENGDESEIDEGUANJIANCHENGFENJIANGSHICHAOZHEGENGHAODEDIANCHIDESHEJIMAICHUDEZHONGYAOYIBU。

 

4.6 LIANGHUAJISUANFANGFA

高浓盐电解液,后锂离子化学时代技术风口?

图6. 电解液分析的计算方法。a)适用于各种时间尺度和原子数的模拟方法。b)可以通过每种方法分析的电解质性质。

 

TONGGUOZIXIXUANZEHESHIDEFANGFA,KEYITONGGUOFENZIDONGLIXUEMONIFENXIDIANJIEZHIRONGYEDEDONGLIXUE,RUTU6aSUOSHI。JIEZHUXIANJINDECHAOJIJISUANJIJIEHEXIANXINGSUOFANGFANGFAHE/HUOGAOXIAODEBINGXINGHUAJISHU,KEYISHIXIANRONGYEJIEGOUYIJICHUANSHUXIANXIANGDEDUOCHIDUYUANZIFENXI(RENGRANXIANYU<105GEYUANZI)。 DFTFENZIDONGLIXUEKEYIYINGYONGYUJUYOU~102-103GEYUANZIDENINGJUYEXIANG,TONGGUODIANHEMIDULAIQUEDINGQIDIANZIJIEGOU,DIANHEMIDUYUFUZAJIEGOUWEIYIYIDUIYINGDE。XIANGBIZHIXIA,JINGDIANDEFENZIDONGLIXUEKEYICHULIGAODA104-105GEYUANZIDEDAGUIMOXITONG,DANSHILICHANGHUIXIANZHUYINGXIANGZHUNQUEXING。DFTBFENZIDONGLIXUEFANGFASHIYIZHONGZHONGJIANJISHU,TAZAIJINGDUHESHIJIAN/KONGJIANCHIDUFANGMIANJIANGDFTHEJINGDIANFENZIDONGLIXUEMONILIANXIQILAI,YINGYONGYUJUYOUHUAXUEFANYINGDEDAXITONG。TONGGUOCHENGGONGXUANZEHESHIDEFENZIDONGLIXUEMONI,YIZHANSHILENONGSUODIANJIEZHIZHONGTEYOUDEDIANZIJIEGOUHECHUANSHUJIZHI,RURONGJIFUZHUTIAOYUE,PEITIJIAOHUANHE3DSHENTOUTONGDAO(TU3c)。HUNHEMENGTEKALUO/FENZIDONGLIXUESHIYIZHONGKAICHUANGXINGDEFANGFA,YONGYUFENXIGENGDUODEHONGGUANSEIXINGCHENGGUOCHENG。ZAIGAIFANGFAZHONG,TONGGUOLIANGZILIXUEYUXIANJISUANYIZUKENENGDEJIBENFANYING,ZHEIXIEFANYINGYUJINGDIANFENZIDONGLIXUEMONIDEJIEGOUSUISHIJIANDEBODONGHEFENZIYUNDONGXIANGJIEHE,TIGONGLESEIXINGCHENGDEZHIJIEKESHIHUA,BINGTUCHULEXISHIHENONGSUODIANJIEYEZHONGSEIXINGCHENGDECHAYI。ZUIXINXIANJINFANGFADEDUOCHIDU(ZAISHIJIANHEKONGJIANJIANMOFANGMIAN)NENGLIDUIYUWANQUANLIJIEYANNONGSUODIANCHIDIANJIEZHIGUYOUDEDUTETEZHENGSHIBIBUKESHAODE。

 

WU、ZONGJIE

高浓盐电解液,后锂离子化学时代技术风口?


边锋游戏NONGSUODIANJIEYEZHONGMEIYOUYOULIRONGJIFENZIDETEZHENGJUBUPEIWEIJIEGOUHEYINLIZIYANSHENGDEGONGNENGXINGSEIDEXINGCHENG,KEYIZAIHENDACHENGDUSHANGKEFUMUQIAN1M LiPF6/ECTIXIDEDADUOSHUJISHUZHANGAI。JIANGZHEIZHONGSHEJILINIANYANSHENDAOHANSHUIXITONGKEYITIGONGCHAOGUO4 VDEKUANWENDINGDIANWEICHUANGKOU。CHULEZENGQIANGDERELIXUEWENDINGXINGWAI,HAISHIYANGLIZIDETIAOYUEYUNSHUCHENGWEIKENENG,QIZHONGQIANYISHUJIEJINYU1。ZAIXUDUOQINGKUANGXIA,YINLIZIYANSHENGDESEIKEYIJIASUDIANHEZHUANYIGUOCHENGBINGCUJINJINSHUDIANJISHANGDEJUNYUNCHENJI/RONGJIE。ERXIANJINDEFENZIDONGLIXUEMONIFANGFA,KEYIZHENDUIFASHENGZAIBUTONGSHIJIANCHIDUHEBUTONGYUANZISHULIANGDEXIANXIANGJINXINGYOUHUA,YOUZHUYURANGWOMENGENGJIASHENRUDELEJIEJUYOUQIANZAIYUANZICHIDUXIANGHUZUOYONGDETI/JIEMIANDIANHUAXUEGONGNENG。ZHEIZHONGJIANDANDANFEICHANGYOUXIAODEDIANJIEYECELVEDEYINGXIANGBUXIANYUGAIJINMUQIANDEDIANJIEYETIXI,ERQIEHAIYOUCHAOGUOCHUANTONGJUHEWUHUOTAOCIDIANJIEZHIDEJISHUYOUSHI。TONGGUOJIEJUENONGSUODIANJIEZHIDECHENGBENHEZHANDUXIANGGUANDESHENGYUZHANGAI,YIJITONGGUOZHEIZHONGJIANDANJISHUHUODEDEYUELAIYUEDUODEHOUXUANDIANJICAILIAO,KEYIWEIXIANJINDIANCHIXITONGTUPODEDAXIAJIANSHIJICHU。


稿件来源: 能源学人
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