边锋游戏

锂电池硅氧化物负极材料的最新研究进展
发布时间:2019-06-11 15:15:00
关键词:动力电池 锂电池

锂电池硅氧化物负极材料的最新研究进展


负极作为其关键构成成分之一,直接决定了锂离子电池的性能,目前市场上主要采用石墨类负极材料。然而,石墨类负极的两个致命缺陷:低能量密度(理论比容量 372mAh·g–1)和安全隐患(“析锂”现象)令其无法适用于动力电池。因此,寻找一种新型高容量、安全性好和长循环的材料来替换石墨类负极材料成为动力锂离子电池进一步发展的关键。


边锋游戏GUIYINQICHAOGAOBIRONGLIANG(LILUNZHI4200mAh·g–1)、DIQIANLIDIANWEI(300%),SHIHUOXINGCAILIAOFENHUA、DIANJINEIDIANJIECHUSHIXIAOYIJIXINGUXIANGDIANJIEZHICENGSEIZHONGFUSHENGCHENG,ZUIZHONGDAOZHIXUNHUANXINGNENGXUNSUSHUAITUI。WEIGAISHANGUIFUJIXUNHUANWENDINGXING,YANJIUZHEMENZUOLEGEZHONGGAIXING。


JINNIANLAI,YIZHONGYIJINGCHANYEHUADEGONGYEYUANLIAOGUIYANGHUAWU(SiOx,0<x≤2)YINQILERENMENDETEBIEGUANZHU,ZUICHANGJIANDERUYANGHUAYAGUI(SiO,x≈1),MUQIANYIJINGKAISHIYONGYULILIZIDIANCHIFUJICAILIAOBINGZHANXIANCHUJUDADEQIANLI。SiOxYUTANSHIMOLEICAILIAOXIANGBI,JUYOUJIAOGAODEBIRONGLIANG,YUSiDANZHIXIANGBIYONGYOULIANGHAODEXUNHUANWENDINGXING。WEICI,JINXIENIANLAIYANJIUZHEMENDUIGUIYANGHUAWUFUJICAILIAOZUOLEDALIANGDEYANJIUGONGZUO。


BENWENCONGSiOxDEJIEGOUYUDIANHUAXUECHULIJIZHIFANGMIANCHUFA,JIESHAOLESiOxDEJIEGOUYUDIANHUAXUEXINGNENGDEGUANXI,CHANMINGLESiOxCUNZAIDEZHUYAOTIAOZHANWENTI,BINGGUINALEJINQIYANJIUZHEMENDUIGUIYANGHUAWUFUJIDEZHUYAOGAIJINSILU,ZUIHOUDUISiOxFUJICAILIAOWEILAIFAZHANFANGXIANGJINXINGLEZHANWANG。


1、SiOx结构


边锋游戏SiOxCAILIAOZAOZAIJISHINIANQIANJIUYIBEIRENMENSUORENZHIBINGZAIXUDUOGONGNENGXINGYINGYONGZHONGSHIXIANSHANGYEHUA,RULIYONGQIBANDAOTISHUXINGERGUANGFANYUNYONGYUGEZHONGGUANGDIANZIQIJIAN,ZHIHOUCAIBEIYUNYONGYULILIZIDIANCHIFUJICAILIAO。


YINWEISiOxWEIYIZHONGWUDINGXINGJIEGOU,QIEZAISiOxZHONGSiDEHUAHEJIATAICUNZAIDUOYANGXING,YIXIECHANGGUICESHIJISHUSHOUDUANRUXSHEXIANYANSHE(XRD),XSHEXIANGUANGDIANZIPU(XPS)HEXSHEXIANRamanYANSHEDENGFENBIANLVYOUXIAN,JINNENGTIGONGWUDINGXINGSiOxDEPINGJUNJIEGOUXINXI,YINCI,DUIYUSiOxWEIGUANJIEGOUDEQUEDINGZHANGQIYILAIYIZHISHIGENANTI。SUIZHEKEJIDEBUDUANJINBU,DUISiOxDEJIEGOURENSHIYEZAIBUDUANSHENRU。


边锋游戏ZUIZAO,CHUXIANYOULIANGZHONGJINGDIANDEJIEGOUMOXING:SUIJIJIANHEMOXING(Random-bonding,RBMOXING)HESUIJIHUNHEMOXING(Random-mixture,RMMOXING)。QIZHONGRBMOXINGZHICHUSiOxDEJIEGOUWEIYIZHONGYOUSi-SiJIANYUSi-OJIANXINGCHENGDELIANXUSUIJIFENBUBINGGUANCHUANZHENGGEWANGLUODEDANXIANGJIEGOU;ERRMMOXINGZERENWEISiOxDEJIEGOUSHIYIZHONGYOUCHAOXIAOFANCHOU(<1nm)DESiHEDESiO2HUNHEWUZUCHENGDESHUANGXIANGJIEGOU。



2003年,Wieder等提出了一种介于上述两种模型的“界面团簇混合型”模型,如图1所示。图中黑色区域代表Si团簇,白色区域代表SiO2团簇,而介于二者之间的浅灰色区域为SiOx过渡区域。该模型认为SiOx是由纳米Si团簇、纳米SiO2团簇以及环绕于二者之间的SiOx界面区域构成。该SiOx界面的结构与普通的超薄Si/SiO2界面层相当,但由于SiOx中Si及SiO2团簇尺寸小于2 nm, 而该界面区域的体积较大,因此不能忽视。



AkihikoYANJIUZUZAIPEIYOUTONGBUGAONENGXSHEXIANYANSHESHEBEIXIA,LIYONGAngstromSHUDIANZIYANSHEJISHUDUIWUDINGXINGSiOJIEGOUJINXINGBIAOZHENG。JIEGUOZHENGMING:CHULELILUNSHANGCUNZAIDEWUDINGXINGSiHEWUDINGXINGSiO2TUANCUZHIWAI,ZAISi/SiO2XIANGJIEMIANQUYUQUESHICUNZAISiO(Si:OBI≈1:1)XIANGJIANBIANJIECENG。ZHEIYIFAXIANTIGONGLELINGRENXINFUDEFEIJINGYIYANGHUAGUIYUANZICHIDUBUJUNYUNFENBUDESHIYANZHENGJU.


此外,他们通过计算机模拟构建出了1种异质结构模型,如图2所示,内部部分对应于1个非晶态的Si团簇,外部部分是非晶态的SiO2基质。蓝色、红色和绿色圆球分别表示非晶态SiO2中的Si和O以及Si簇中的Si,该模型很好地解释了非晶SiO材料的独特结构和性能。


2、SiOx储锂机制和电化学性能


边锋游戏YOUQIANMIANDEZHI,SiOxBINGFEIYOUDANYIXIANGZUCHENG,ERSHIYOUXUDUOJUNYUNFENBUDENAMIJISiTUANCU、SiO2TUANCUYIJIJIEYUSi/SiO2LIANGXIANGJIEMIANZHIJIANDESiOxGUODUXIANGZUCHENG,YINCIQICHULIJILIFEICHANGFUZA。MiyachiDENGFAXIANSiOSHOUCILIHUACHANWUWEILixSi、LIGUISUANYANHELi2O,QIZHONGBUFENLIGUISUANYANJUYOUKENIXING。Jun Kyu LeeDENGRENWEISiOQIANLIXINGCHENGLi2OHELixSi,SiO2QIANLIXINGCHENGLi4SiO4HE LixSi。ERChenDENGRENWEISiO2QIANLIGUOCHENGZHONGBUJINXINGCHENGLi4SiO4HELixSi,HAIXINGCHENGLi2OHE Li2Si2O5。


边锋游戏OhzukuDENGZHENGMINGSiOZAISHOUCIQIANLIGUOCHENGZHONGXINGCHENG Li4SiO4 HE LixSi,QIZHONGYOUBUFEN SiO2BUCANYUFANYING。Yamamura DENGFAXIANJIEJINGXINGDESiO2BUJUBEIQIANLIDIANHUAXUEHUOXING。



2016NIAN,YasudaDENGYUNYONGLi-Si-OSANYUANXIANGTU,CONGRELIXUEJIAODUFENXILESiOSHOUCITUOQIANLIDEYANBIANGUOCHENG,JUTIRUTU3SUOSHI:


(1)点①–⑦,初始阶段SiO中的SiO2组分连续锂化为 Li2Si2O5、Li2SiO3、Li4SiO4且与Si共存;(2)点⑦–?,Si连续合金化为Li12Si7、Li7Si3、Li13Si4并与Li4SiO4共存;(3)点?–?,Li4SiO4分解成Li13Si4和Li2O; (4)点?–?,Li13Si4逐步锂化形成Li22Si5并与Li2O共存;(5)点?,为锂沉积过程。根据上述锂化过程,可以得出SiO在不同平衡条件下的理论容量和首次充放电效率,平衡点?的理论容量和首次充放电效率分别为1480mAh·g–1和70.9%,平衡点?的理论容量和首次充放电效率分别为2584mAh·g–1和81.0%,平衡点?的理论容量为3283 mAh·g–1、首次充放电效率为 84.4%。 


边锋游戏SiOxFUJICAILIAODEDIANHUAXUEXINGNENGYUQICHULIJIZHIXIXIXIANGGUAN。JungDENGTONGGUODIYIXINGYUANLIFENZIDONGLIXUEMONIDECHU,ZAICHONGFANGDIANGUOCHENGZHONG,Li2OJIZHIHUANRAOZAILixSiHEZHOUWEIKECHONGDANGZHELILIZIDEKUAISUKUOSANTONGDAO,YINCIQIANLISHISiOxFUHANDELi2OJIZHINENGGOUSHIQIZAIXUNHUANHEBEILVXINGNENGFANGMIANZUIYOUHUA,CIWAI,LixSiHEZHOUWEIDELi2OHELi4SiO4JIZHIHAIKEYIYOUXIAODEHUANCHONGTIJIPENGZHANG。RANER,Li2OHELi4SiO4XIANGWEIDUOXINGXIANG,QICHANSHENGXIAOHAOLEDIANJIEYE YIJICONGZHENGJITUOCHUDELi,QIECIGUOCHENGBUKENI,ZAOCHENGSHOUCIKENIRONGLIANGDEYANZHONGDIUSHI。



边锋游戏SiOxCAILIAODEDIANHUAXUEXINGNENGYUQIYANGHANLIANG(xZHI)YEMIQIEXIANGGUAN,JangDENGTANJIULESiOxFUJICAILIAODEDIANHUAXUEXINGNENGSUIYANGHANLIANG(xZHI)DEBIANHUA,RUTU4SUOSHI,SUIZHExZHIDEZENGDA,DIANJICAILIAODEXUNHUANWENDINGXINGZENGJIA,DANSHISHOUCICoulombXIAOLVHERONGLIANGJIANGDI。


因此,概括来讲,对于SiOx材料,其中的氧有利也有弊。一方面,随着x值升高,电化学活性储锂相(a-Si)减少,不可逆相Li2O和Li4SiO4增加,因此比容量逐渐下降,首次Coulomb效率降低;然而从另一方面来讲,生成的不可逆Li2O相增加,动力学加快,并且伴随着体积膨胀产生的应力得到有效释放,因此电化学性能得到提升。 


3、SiOx存在的主要问题


SiOx循环性能的衰减


ZAIGUI/LIHEJINHUAGUOCHENGZHONG,BANSUIZHEJUDADETIJIXIAOYING。SUIRANOYUANZIDECUNZAIHUIZAIYUANWEISHENGCHENGDUOXINGHUANCHONGJIZHIXIANG,DANSHIZONGTITIJIXIAOYINGRENGRANJIAODA,CHANSHENGDEJIXIEYINGLIHUISHIDEHUOXINGCAILIAOFENHUABINGYUJILIUTIZHIJIANFASHENGDIANJIECHUSHIXIAO;LINGWAI,SiOxDEBENZHENGDIANDAOLVDI,BULIYUCAILIAODIANHUAXUEXINGNENGDEFAHUI;CIWAI,SiOxFUJIYUYOUXIEDIANJIEYEDEPIPEIXINGYEBUSHIHENHAO,YIBEILIYANFENJIECHANSHENGDEWEILIANGHF FUZHUDENG。YOUYUYISHANGYINSUDEGONGTONGYINGXIANG,ZUIZHONGDAOZHILESiOxFUJICAILIAODEXUNHUANXINGNENGYANZHONGSHUAIJIAN。


SiOx首次Coulomb效率低


边锋游戏ZAIDIANCHIYUNXINGGUOCHENGZHONG,YOUYUYOUJIDIANJIEZHIRELIXUEDEBUWENDINGXING,SHIQIZAIDIDIANWEIRUFUJIGONGZUODIANWEICHUHUIFASHENGFENJIEERZAIDIANJIBIAOMIANXINGCHENGGUTIDIANJIEZHIJIEMIANXIANG(SEI),ZHEIZHONGBUKENISEIDEXINGCHENGXIAOHAOLEDIANJIEYEHEZHENGJICAILIAOTUOCHUDELi,DAOZHIHUOXINGZHENGJICAILIAORONGLIANGDEMINGXIANSUNSHIHEDIDEDIYIXUNHUANCoulombXIAOLV(CE)。


YULILIZIQIANRUSHIFANYINGFUJICAILIAO(RUSHIMO)XIANGBI,SEICENGDESHENGCHENGDUIYUGAORONGLIANGHEJINHUAFUJICAILIAO(BAOKUOGUIJI、XIJI、JINSHUYANGHUAWUDENG)ZEGENGWEIYANZHONG。CIWAI,ZAISHOUCIQIANLISHI,SiOxZHONGDEYANGYUANZIYEHUIHEDIANJIEYEZHONGDELi+FASHENGBUKENIFANYINGSHENGCHENGDUOXINGXIANGDELi2OHELi4SiO4,ZAICIJIAJULEQISHOUCIBUKENIRONGLIANG,ZUIZHONGJIEGUODAOZHISiOxFUJICAILIAOSHOUXIAODIDEWENTI,CONGERYANZHONGZHIYUELESiOxFUJICAILIAOZAIGAOBINENGLILIZIDIANCHIZHONGDEYINGYONG。


4、SiOx负极材料的改性


YOUQIANMIANKEZHI,SUIRANSiOxCAILIAOJIAODANZHISiYONGYOUGENGHAODEXUNHUANWENDINGXING,RANERJIANGQISHIJIYUNYONGYULILIZIDIANCHIFUJIRENGRANCUNZAIJIAODUOWENTI。WEILEGAISHANSiOxFUJICAILIAODEDIANHUAXUEXINGNENG,JINNIANLAIYANJIUZHEMENJINXINGLEDALIANGDEGONGZUODUIQIJINXINGGAIXINGHEYOUHUA,GUINAQILAIZHUYAOYOUYIXIAJIBUFEN:SiOxDEQIHUA、YUQITACAILIAODEFUHE、YULIUHUANCHONGKONGJIAN、YULIHUAJISHUDEYUNYONGYIJIQITAGAIXINGCUOSHI。


SiOx的歧化


RENMENTONGCHANGSHIYONGDEGUTISiOxSHIYOUWUDINGXINGSiHEGEZHONGJIATAIDEGUIYANGHUAWUGOUCHENGDE,ZAIGAOWENXIA,QIRELIXUEXINGZHIFEICHANGBUWENDING,RONGYIFASHENGQIHUASHENGCHENGSiHESiO2。


MamiyaDENGYANJIUFAXIAN,JIANGWUDINGXINGSiOZHIYU850℃DUOXINGQIFENZHONGGAOWENDUANSHAOFASHENGQIHUAFANYING,HUIXINGCHENGPINGJUNLIJINGWEI4~5nmDENAMIDANJINGGUI,QIESUIZHEDUANSHAOSHIJIANDEYANZHANG,NAMIJINGGUIDESHULIANGZHUJIANZENGJIA,DANKELICHICUNBAOCHIBUBIAN。RUOSHENGGAODUANSHAOWENDUZHI1000℃YISHANG,DANJINGGUIDESHENGCHENGSULVZEXUNSUJIAKUAI,KELICHICUNYEZHUJIANBIANDA。ZAINAMIJINGGUISHENGCHENGDETONGSHIBANSUIZHESi4+DEZHUJIANZENGJIA,Si+、Si2+HESi3+DEZHUJIANJIANSHAO,QISHOUCIQIANLIPINGTAIZHUJIANXIANGDANZHISiKAOJIN,ERSiOxDEDIANHUAXUEXINGNENGZHUJIANTISHENG。


ParkDENGYANJIUFAXIAN,SiOxFUJICAILIAOZAI1000℃QIHUAHOUBIZAI800℃QIHUAHOUJUYOUGENGHAODEXUNHUANXINGHEKENIXING,SHENGCHENGDENAMIJINGSiJUNYUNFENSANZAIWUDINGXINGSiOxJIZHIZHONG。DANSHIJIANGQIHUAWENDUJINYIBUTIGAODAO1200℃,ZECHANWUDIANHUAXUEXINGNENGKAISHIXIAJIANG,CAICEYUANYINSHIGUOLIANGDESi4+WUDINGXINGGUIYANGHUA WUDESHENGCHENGZUAILELi+DECHUANSHU。


边锋游戏TONGYANG,HwaDENGGUANCHADAO,ZAI1200℃RECHULIDEQIHUASiOxJIHUMEIYOURONGLIANG,YINWEINAMIJINGSiBEIWUDINGXINGSiO2JINJINBAOWEIERWUFAYULi+FASHENGFANYING,DANSHIZAIQIHUAHOUTONGGUOGAONENGQIUMOFANGFAKEJIANGNAMIJINGSiHEWUDINGXINGSiO2BAOLUCHULAI,BINGYINCIGAISHANQIDIANHUAXUEXINGNENG。


SUIRANQIHUASHIYIZHONGKEYITONGGUOGAIBIANSiOxZHONGDEHUAXUECHENGFENHEZENGQIANGQINEIBUHUANCHONGJIZHIJINERTIGAOQIXUNHUANXINGNENGDEYOUXIAOFANGFA,DANSHIQIRENGXUYAOJINXINGJINYIBUDEWAICHULILAI“JIHUO”,RUGAONENGQIUMOHEKESHIDENGLAIPOHUAIQIWAIBUZHIMIDEWUDINGXINGGUIYANGHUAWUBAOFUJIZHI,BINGJIANGNEIBUNAMIJINGGUIBAOLUCHULAI。


与其他材料的复合


TANCAILIAOYINJUYOUWENDINGXINGHAO、TIJIBIANHUAXIAOHEDAODIANXINGYOUYIDENGYOUDIANERCHANGBEIYONGYUHESiOxFUHE。JIANGTANCAILIAOZUOFUHECAILIAO,SHOUXIANKEYITISHENGSiOxDEDAODIANXING,QICIKECHONGDANGDUOXINGHUANCHONGCENGJIANXIAOQITIJIXIAOYING,CIWAI,RUZUICHANGYONGDESHOUFATANBAOFUDENGHAINENGYOUXIAODEJIANGDISiOxYUDIANJIEYEDEJIECHUMIANJI,CONGERTIGAOCoulombXIAOLV。


边锋游戏GENJUFUHETANCAILIAODEBUTONG,KEJIANGQIGAIKUOWEILIANGLEI:SiOxYUCHUANTONGTANCAILIAOHESiOxYUXINXINGTANCAILIAODEFUHE。CHUANTONGTANCAILIAOBIJIAOCHANGJIAN,RUYOUSHIMO、TANHEIHEWUDINGXINGTANDENG。ERXINXINGTANCAILIAOZESHIHOUXINGQIDEJUYOUTESHUJIEGOUHUOGONGNENGTANCAILIAO,RUTANNAMIGUAN、TANNAMIXIANWEIHESHIMOXIDENG。XIANGDUIBI,XINXINGTANCAILIAOYOUYUJUBEICHAODADEBIBIAOMIANJIHEDUOWEIDAODIANWANGLUO,DUISiOxFUJIDEDIANHUAXUEXINGNENGTISHENGGENGWEIXIANZHU。


LINGWAI,HAIKEYIJIANGSiOxYUJINSHUJINXINGFUHE。YIFANGMIAN,JINSHUCAILIAOJUYOULIANGHAODEDAODIANXING,KEZENGQIANGGUIHEJINCAILIAODEDONGLIXUEXINGNENG;LINGYIFANGMIAN,JINSHUKEYICHONGDANGZHICHENGGUJIA,GAISHANGUITIJIXIAOYING,YINCINENGYOUXIAOGAISHANSiOxFUJIDEDIANHUAXUEXINGNENG。


MiyachiDENGYANJIUFAXIAN25%DEFe、TiHUONiCHANZAGAIXINGDESiOSHOUCICoulombXIAOLVDEDAOXIANZHUTI SHENG,GAODA84%~86%,TONGSHIKENITUOQIANLIRONGLIANGDEDAOTIGAO,TONGGUOXPSCESHIBIAOMINGJINSHUYUANSUBINGBUCANYUFANYING,DANCHANZAHOUDESiYUANSUZAIKENITUOLIGUOCHENGZHONGHUAHEJIABIANHUABODONGDA(YOU0JIADAO+4JIAZAIDAO0JIA)。


边锋游戏TangDENGYANJIUCHAOJINGXINiNAMIKELIFUHE iO2SHIFAXIAN,NiNAMIKELICHICUNYUEXIAO,SiO2/NiDETUOQIANLIRONGLIANGYUEGAO,QIEXUNHUANWENDINGXINGYUEHAO。DANGRANHAIYOUYIXIEQITACAILIAOFUHE,RUZhangDENGTONGGUOQIUMOFAZHIBEICHUSn2Fe@SiOxFUHECAILIAO,DAFUDUTIGAOLESiOxLIHUAFANYINGDEKENIXING,QISHOUXIAOGAODA78%,QIEZAI200mA·g–1DIANLIUXIA,JUYOU700mAh·g–1DEGAOWENDINGRONGLIANG,CoulombXIAOLVCHAOGUO99%,ZAI1000mA·g–1DEGAOBEILVXIACHAOZHANGSHOUMINGKECHAOGUO1000GEXUNHUAN。


预留缓冲空间


SiOxZAITUOQIANLIGUOCHENGZHONGRENGRANJINGLILEJIAODADETIJIPENGZHANG,YINCITONGGUOTIGONGEWAIDEZIYOUKONGJIANRUXINGCHENGDUOKONGHUOZHONGKONGHE-QIAOJIEGOUDENG,KEYOUXIAODIHUANJIEQITIJIPENGZHANG。CIWAI,DUOKONGKAIFANGDEJIEGOUYEYOULIYULi+DEKUAISUSHUYUN,CONGERTIGAOQIBEILVXINGNENG。


LeeDENGCAIYONGDIANOUZHIHUANFANYINGHEJINSHUFUZHUDIANHUAXUESHIKEXIANGJIEHEDEFANGFAHECHENGSANWEIDUOKONGSiOCAILIAO,SHOUXIANTONGGUODIANOUFANYINGZAISiOBIAOMIANCHENJIQICUIHUAJIZUOYONGDENAMIYINKELI,RANHOUDUICHENJIYINDESiOxKELIJINXINGDIANHUAXUESHIKE,HECHENGDUOKONGSiOKELI,GAICAILIAOBIAOXIANCHUYOUYIDEDIANHUAXUEXINGNENG,BAOKUOGAODEBIRONGLIANG(1520mAh·g–1)、WENDINGDEXUNHUANXINGNENG(50QUAN,1490mAh·g–1)HEGAODEBEILVXINGNENG(3C,74%)。


YUCHUANTONGDETONGGUOHFKESHISiO2CONGERDEDAODUOKONGSiFUJICAILIAODEFANGFAXIANGFAN,YuDENGDUIJING900℃REQIHUACHULIHOUDESiOJINXINGNaOHCHULI,JIEGUOSHIJIANGJINGTISiKESHIERSiOxBAOLIUXIALAI,CONGERDEDAOLEDUOKONGSiOxCAILIAO,TONGGUOKONGZHIKESHISHIJIANKEDEDAOBUTONGKESHICHENGDUDEDUOKONGSiOxCAILIAO,QIEGAIFUJICAILIAOTONGYANGYEBIAOXIANCHUYOUYIDEDIANHUAXUEXINGNENG,0.2CXIAXUNHUAN100QUANHOU,KENIRONGLIANGWENDINGZAI1240mAh·g–1YISHANG。


JINQI,ParkDENGBAODAOLEYIZHONGTONGGUOYOUSHUIMOBANFAZHIBEITANBAOFUDUOKONGSiOxCAILIAOYONGYUGAORONGLIANGCHULICAILIAO,GAIFUJICAILIAOJUYOU730mAh·g–1DEGAORONGLIANGTONGSHIYONGYOUCHAOGAODEXUNHUANWENDINGXINGJI100CIXUNHUANDIANJICAILIAOMEIYOUMINGXIANDECHICUNBIANHUA。


SUIRANMUQIANZHIBEIDUOKONGSiOxDEFANGFAZHONGDUO,RANER,KEYIXITONGGUILVXINGDUIDUOKONGJIEGOUYIJIKONGBANJINGJIFENBUDEKONGZHIHAIWEICHENGXING,QIETONGCHANGDUIDUOKONGHUOZHONGKONGJIEGOUSiOxFUJICAILIAODEZHIBEIBUZHOUFANSUO,CHANLIANGDI,WAIJIAZAIQUCHUMOBANHUOKESHIGUOCHENGZHONGHUIZAOCHENGBUFENJIEGOUDETANTA,YINCIDUIDUOKONGSiOxDEZHIBEIJISHANGYEHUAYINGYONGHAIXUGENGSHENRUYANJIU,YIBIANDADAOJIANDAN GAOXIAODEZHIBEIMUDE。


预锂化技术


LILIZIDIANCHIGUIFUJICAILIAODEYULIHUASHIMIBUQIBIAOMIANXINGCHENGGUTIDIANJIEZHIJIEMIANXIANG(SEI)SUOZAOCHENGDELISUNSHIDEYIZHONGZHONGYAOCELVE。DUIYUSiOxFUJICAILIAO,YOUYUYANGDEYINRUJIADALEDUIDIANJIEZHIZHONGHEYOUZHENGJICAILIAOSHIFANGDELILIZIXIAOHAO,ZAOCHENGLIDEYANZHONGSUNSHI,YINCIYULIHUAJISHUDUIYUGUIYANGHUAWU(SiOx)FUJICAILIAODEXINGNENGGAISHANYOUWEIXIANZHU。


边锋游戏YULIHUAJISHUGAIKUOLAISHUOKEFENWEIYIXIAJILEI:


(1) JIANDANDEWULIHUNHE,RUKulovaDENGTONGGUOGUIHEJINSHULIZAIDIANJIEYEZHONGDEZHIJIEJIECHUFANGFAHUANJIANGUIFUJISHOUCIBUKENIRONGLIANGSUNSHI;


(2) WENDINGDEJINSHULIFEN,RUForneyDENGZAIDIANCHIZUZHUANGGUOCHENGZHONG,JIANGWENDINGDELIJINSHUFENMOJUNYUNDEFENSANZAIGUITANFUJIJIPIANBIAOMIAN,TONGGUOKONGZHILIJINSHUFENMODEYONGLIANGHEDIAOJIEYALIDUIGAORONGLIANGGUI/TANNAMIGUAN(Si-CNT)FUJIJINXINGYOUXIAOYULI,TAMENYONGGAIFANGFAXIAOCHULE20%~40%CIBUKENIRONGLIANGSUNSHI,BINGSHIDEGAONENGLIANGMIDUNCA/Si-CNT QUANDIANCHIZAI20%SHENDUFANGDIANSHIDADAO>1000CIXUNHUAN;


边锋游戏(3) DUANLUFA,RUKimDENGCAIYONGDIANJIECHUDUANLUFADUISiOx(x~1)JIPIANJINXINGYULIHUA,TONGGUODIAOJIEDUANLUDAOXIANDIANZUJIDUANLUSHIJIANSHIXIANDUISHOUCICoulomb XIAOLVDEJINGQUEDIAOKONG,YANJIUFAXIAN100ΩDIANZUDUANLU30minKEYISHISHOUCICoulombXIAOLVCONG73.6%TISHENGZHI 94.9%;


边锋游戏(4) YULIHUATIANJIAJI,RUCuiYANJIUZUCAIYONGYEJINFASHIRONGRONGLiYUSiOHUOSiO2FANYINGXINGCHENG LixSi/Li2OFUHECAILIAO,YOUYULi-OJIANXIANGBIYULi-SiGENGWENDING,Li2OBAOFUDELixSiJUYOUGAODUDESHIWENWENDINGXING,YINCIKEZUOWEIGAOWENDINGXINGYULIHUATIANJIAJIYONGYUYUGUIYANGHUAWUFUJICAILIAOFUHETISHENGSHOUCICHONGFANGDIANXIAOLV。ZUIJIN,CuiZUYOUYANFALEYIZHONGGENGJIANBIANDEFANGFAJIANGHECHENGDELi22Z5HEJINHE Li22Z5-Li2OFUHECAILIAO(Z=Si、Ge、SnDENG)ZUOWEIYULIHUASHIJIDUIXIANGYINGDIⅣZHUZUYUANSUJINXINGYULIHUA,JIEGUOBIAOMING,CIFANGFADAFUDUDIJIANGDISHOUCIBUKENIRONGLIANGDESUNSHI,LINGCAILIAORONGLIANGJIEJINLILUNBIRONGLIANG。


SUIRANDAOMUQIANWEIZHIYONGYOUDEYULIHUAJISHUSHOUDUANFENGFUDUOYANG,DANSHIRENGRANCUNZAIYIDINGDEWENTI。DUANJIEJISHUZUIWEIJIANBIAN,KEJINGZHUNDIAOKONGYULIHUACHENGDU,DANSHIQIFANYINGTIAOJIANBIXUYANGEKONGZHIYANGQIHESHUIDEHANLIANG,JIAOSHIYONGYUSHIYANSHIJIEDUANDEYINGYONGERWUFASHIXIANDAGUIMOYINGYONG。WENDINGDEJINSHULIFENJISHU,KESHIXIANJIAODAGUIMOYINGYONG,DANSHIYEXUYAOYANGEKONGZHISHIYANTIAOJIAN,DUIYIQISHEBEIYAOQIUGAO,QIECUNZAIYIDINGDEANQUANYINHUAN,YOUQISHIZAIJINSHULIFENDEGAOSUHUNLIAOGUOCHENGZHONG。TONGGUOTIANJIAYULIHUATIANJIAJIKEYIYOUXIAOTIGAO SiOxFUJICAILIAODESHOUCICoulombXIAOLV,DANSHICHUANTONGDEYULIHUASHIJICUNZAIKERANXINGJIAOGAO、HUAXUEWENDINGXINGJIAOCHAHEYUQITADIANJIZUCHENGCHENGFEN(RUDIANJIEYE、ZHANJIEJIYIJIQITATIANJIAJIDENG)XIANGRONGXINGCHADENGWENTI,RONGYIDAOZHIANQUANYINHUANDEFASHENG。


边锋游戏JINNIANLAI,GAOWENDINGXINGQIEGAOXIAOXINXINGYULIHUATIANJIAJICHENGWEIYANJIUREDIAN,RANER,DUIQIWENDINGXINGHEYUQITACAILIAODEXIANGRONGXINGHAIXUJINYIBUDETISHENG,CIWAI,QIHECHENGCHENGBENRENGXUJINYIBUDEJIANGDI。


其它改性措施


边锋游戏CHUHUOXINGCAILIAOZHIWAI,QITARUDAODIANJI、ZHANJIEJIHEDIANJIEYEDENGYESHIDIANCHIZHONGYAOZUCHENGBUFEN,DUIQITAZUFENDEGAIXINGYEKEYIYOUXIAODEGAISHANSiOxFUJIDEDIANHUAXUEXINGNENG。


SiOxCAILIAODIANDAOLVDI,SHILIANGDEDAODIANJIKEYIBAOZHENGDIANZITONGGUODIANJIPIANLIUTONGJINRUWAIDIANLUCONGERJIDADIGAISHANQIDIANHUAXUEXINGNENG。HESiOxDIANJICAILIAOYIYANG,DAODIANJIYEZAIYIZHIBUDUANDIJINBU,CONGZUIKAISHIDELINGWEIDIANZHUANGDAODIANJITANHEI,DAOHOULAIDEYIWEIXIANWEIZHUANGDEDAODIANTANXIANWEIHETANNAMIGUAN,ZAIDAOZUIJINHUOREDEERWEIPIANZHUANGSHIMOXICAILIAO,GENGJINYIBUDEZENGJIALEDIANJICAILIAOKELIZHIJIANDEJIECHU,TIGAOLEDAODIANXING。JINQIYOUYANJIUBIAOMING,MOUXIETESHUXINGMAODEDAODIANJIZAIDIANJIPIANZHONGKEQIDAOWENDINGDIANJIJIEGOUDEZUOYONG,QIEBUTONGDEDIANJITIXIKEXUAN ZEGEZIZUISHIYINGDEDAODIANJI。


JUDADETIJIXIAOYINGRONGYISHISiOxJIFUJIDIANJIJIEGOUTANTACONGERSHIQUDIANJIECHU,ZHANJIEJIDESHIYONGKEYIYOUXIAODEBAOZHENGDIANJIJIEGOUDEWANZHENGXING。CHUANTONGZHANJIEJIJUPIANFUYIXI(PVDF)YUSiOxDIANJIDEGONGZUOXINGNENGHENCHA,YINCIXUDUOGENGJIAGAOXIAODEXINXINGZHANJIEJIZHUJIANBEIRENMENYANFAHELIYONG,RUSUOJIAJIXIANWEISUNA(CMC)、JUBINGXISUAN(PAA)、JUYIXICHUN(PVA)HEJUXIANYAAN(PI)DENG,ZHEIXIEJIEHEJIKETONGGUOYU SiOxBIAOMIANDESiO2CENGXINGCHENGLAOGUDEQINGJIANHUOGONGJIAJIANDADAOZENGQIANGYUFUJICAILIAODEZHANFUHEJIEHEDEXIAOGUO,CONGERTIGAOLEXUNHUANSHOUMING。


ZUIJIN,XUDUOGENGJIAYOUYIDEZHANJIEJIBEIYANFACHULAI,RUWangDENGBAODAODEGAOLASHENDAODIANJIAO(CG),MunaokaDENGYANFADEZIYUJUHEWU(SHP),ZhuDENGYANFADEJIAOLIANBINGXIXIANAN(c-PAM)DENG,GENGJIAGAOXIAODIBAOZHENGLESiOxCAILIAODEXUNHUANWENDINGXING。


ZAICHONGDIANGUOCHENGZHONG,DIANJIEZHIRONGYEDEHAIYUANFENJIEHUIDAOZHISEICENGDESHENGZHANG,BUTONGDEDIANJIEYETIANJIAJIZHIJIEYINGXIANGSUOXINGCHENGDESEICENGWUHUAXINGZHI(ZHIMIDU、RENXINGHEWENDINGXINGDENG)BUTONG,YINCIYANFAGAOXIAODEDIANJIEYETIANJIAJIDUISiOxFUJIDEDIANHUAXUEXINGNENGTISHENGFEICHANGZHONGYAO。MUQIANSHIYONGJIAODUOYIXIEDIANJIEYETIANJIAJIZHUYAOYOUSHUANGFUHUANGXIANYAANLIYAN(LiFSI)、FUDAITANSUAN YIXIZHI(FEC)、TANSUANCIYIZHI(EC)、TANSUANYAYIXIZHI(VC)HEGUIYANGWANDENG,ZHEIXIEDIANJIEYETIANJIAJIKEYIZAIDIANJICAILIAOBIAOMIANXINGCHENGZHIMIDUNHUABAOHUMO,RU LiF、Li2O、YIXIELi+DAODIANYANHEHANFULEIJUHEWUDENG,CONGERGAISHANDIANCHIDEDIANHUAXUEXINGNENG。


SUIRANDIANJIEYETIANJIAJIDESHIYONGNENGXIANZHUDETIGAOSiOxFUJICAILIAODERONGLIANGBAOCHILVHECoulombXIAOLV,RANERQIZAIKAILUDIANYAXIADUIDIANJICAILIAODEJIECHUDONGLIXUEJIQIDUIJIEGOUYINGXIANGDEBENZHIRENGRANLINGRENFEIJIE,YINCIHAIXUGENGJINYIBUDETANJIU。


5、结论与展望


SiOxCAILIAOSHIYIZHONGJIJUYOUQIANLIDELILIZIDIANCHIFUJICAILIAO,TIGONGGAORONGLIANGDECHAOXINAMISiTUANCUJUNYUNFENSANZAISiOxJIZHIZHONG,QIEZAISHOUCIQIANLIGUOCHENGZHONG,YUANWEISHENGCHENGDELi4SiO4HELi2ODUOXINGXIANGBAOFUZAINAMISiTUANCUWAIWEI,GEJUELESiYUDIANJIEYEDEJIECHU,QIDAOLEHUANCHONGTIJIXIAOYINGHEBAOHUDIANHUAXUEHUOXINGDENAMISiTUANCUDESHUANGZHONGZUOYONG,YINCILINGQIZONGHEJUBEIGAORONGLIANGHEZHANGXUNHUANDENGXINGNENG。


SiOxFUJICAILIAODEDIANHUAXUEXINGNENGYUxZHIJINMIXIANGGUAN,SUIZHExZHISHENGGAO,YIFANGMIAN,DIANHUAXUEHUOXINGCHULIXIANG(a-Si)JIANSHAO,SHENGCHENGDEBUKENIXIANGLi2OHELi4SiO4ZENGJIA,YINCIBIRONGLIANGZHUJIANXIAJIANG,SHOUCICoulombXIAOLVYEZHUJIANJIANGDI;RANERLINGYIFANGMIAN,SUIZHESHENGCHENGDEBUKENILi2OXIANGZENGJIA,DONGLIXUEJIAKUAI,BANSUIZHETIJIPENGZHANGCHANSHENGDEYINGLIDEDAOYOUXIAOSHIFANG,YINCIDIANHUAXUEXINGNENGDEDAOTISHENG。


SUIRANSiOxFUJICAILIAOJUYOUHENQIANGDEYOUSHI,RANERSHIXIANSHIYONGHUASHUIPINGRENGRANCUNZAIJIAODUOWENTI,ZUITUCHUDEYOURONGLIANGSHUAIJIANYANZHONGHESHOUCICoulombXIAOLVDILIANGDAWENTI。YINCI,WEILEJINYIBUTIGAOSiOxDIANJICAILIAODESHIYONGXING,DALIANGDEYANJIUGONGZUORENGRANPOQIEXUQIU。


边锋游戏QIYI,JIANHUAYOUHUASiOxCAILIAODEGAIXINGFANGANBINGJIANGDIQIHECHENGCHENGBEN;

边锋游戏QIER,YANFAGENGJIACHENGSHUHESHIYONGDEYULIHUAJISHU;

边锋游戏QISAN,ZHENDUISiOxCAILIAOPIPEICHUGENGJIAHESHIDEDAODIANJI,NIANJIEJIHEDIANJIEYETIANJIAJIDENG。


稿件来源: 锂电联盟会长
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