新型硅氧碳氮负极材料合成及可控化学预锂化  

Synthesis of Novel Silicon Oxycarbonitride Anode Material and Controllable Chemical Prelithiation

作　　者：赵欣悦[1,2,3] 胡金龙 燕禾 段先健 吴春蕾 王跃林 张灵志 ZHAO Xinyue;HU Jinlong;YAN He;DUAN Xianjian;WU Chunlei;WANG Yuelin;ZHANG Lingzhi(Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences,Guangzhou 510640,China;CAS Key Laboratory of Renewable Energy,Guangzhou 510640,China;Guangdong Provincial Key Laboratory of Renewable Energy,Guangzhou 510640,China;Guangzhou Huifu Research Institute Co.LTD.,Guangzhou 510663,China)

机构地区：[1]中国科学院广州能源研究所,广州510640 [2]中国科学院可再生能源重点实验室,广州510640 [3]广东省可再生能源重点实验室,广州510640 [4]广州汇富研究院有限公司,广州510663

出　　处：《新能源进展》2024年第6期664-670,共7页Advances in New and Renewable Energy

基　　金：东莞市重点领域研发项目(20221200300112);中科院科技服务网络计划(STS)东莞专项项目(20211600200331);汇富公司横向研发项目(E249070401)。

摘　　要：以3-氨丙基三乙氧基硅烷(APTES)与戊二醛(GA)为原料,通过水解和醛胺缩合反应生成前驱体,再高温热解制备碳氮氧化硅(SiOCN)负极材料。采用联苯锂(Li-BP)为锂化剂,2-甲基四氢呋喃(2-MeTHF)为还原溶剂的化学预锂化方法提高SiOCN负极极片的首次库仑效率。通过调控锂化试剂的反应时间很容易控制极片的预锂化程度。化学预锂化在电极表面优先形成固体电解质界面膜,在1mol/L锂化试剂浸渍30s,SiOCN/Li半电池首次库仑效率由73.6%提高到90.4%,循环稳定性与原始极片相当,1 A/g电流密度下的充电比容量为604 mA·h/g,195圈充放电循环容量保持率为98.5%。与NCM811正极匹配全电池,电池的首次效率从46.3%提高到78.6%。预锂化处理的SiOCN负极材料具有高首次库仑效率、高容量和长循环稳定性,在高能量密度锂电池中具有很好的应用前景。A novel silicon oxycarbonitride(SiOCN)anode material is synthesized through an aldimine condensation of 3-aminopropyl triethoxysilane(APTES)with glutaraldehyde(GA)and simultaneous hydrolysis of APTES,followed by subsequent thermal pyrolysis.A chemical prelithiation method using lithium-biphenyl(Li-BP)as the lithiation reagent and a 2-methyl tetrahydrofuran(2-MeTHF)solution as the reducing solvent is designed to enhance the initial Coulombic efficiency(ICE)for SiOCN anodes.The prelithiation extent can be easily controlled by tuning the reaction time.A solid electrolyte interface layer is formed during chemical prelithiation.After dipping in 1 mol/L lithium reagent for 30 s,prelithiated SiOCN/Li half-cell ICE can be increased from 73.6% to 90.4%.Compared with the original cell,the prelithiated SiOCN/Li half-cell exhibits equivalent cycling performance,delivering a stable specific capacity of 604 mA·h/g after 195 cycles with a retention rate of 98.5% at 1 A/g current density.When matched with an NCM811 cathode,the full cell exhibits an improved ICE from 46.3% to 78.6%.The pre-lithium SiOCN anode shows a performance of high ICE,high capacity and long cycle stability,which promises great application in high-energy lithium batteries.

关 键 词：锂离子电池 硅氧碳氮 联苯锂 预锂化 

分 类 号：TK02[动力工程及工程热物理]