电活性双酚A的合成及其锂离子电池防过充性能研究  

Synthesis of Electro-Active Bisphenol A Compounds and Overcharge Protection Performances in Lithium-Ion Batteries

作　　者：陈程 张灵志[1] CHEN Cheng;ZHANG Ling-Zhi(Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences,Guangzhou 510640,China)

机构地区：[1]中国科学院广州能源研究所

出　　处：《新能源进展》2019年第5期398-404,共7页Advances in New and Renewable Energy

基　　金：王宽成教育基金会资助项目(21573239);广州省科技计划项目(2015B010135008);广州市科技计划项目(201509010018)

摘　　要：对双酚A进行结构修饰,经甲醚化、氰基取代,设计合成了2,2-双-[4-(β-氰基乙氧基)苯基]丙烷(DBDCN)、2-[4-(β-氰基乙氧基)苯基]-2'-(4-甲氧基苯基)丙烷(DBMCN)和2,2-双-(4-甲氧基苯基)丙烷(DBMB),将三种化合物作为锂离子电池的防过充添加剂开展研究。在锂离子电池电解液1mol/LLiPF6/[碳酸乙烯酯(EC)+碳酸二乙酯(DEC)+碳酸甲乙酯(EMC)(1∶1∶1,体积比)]中分别添加0.1mol/L的DBDCN、DBMB和DBMCN,采用循环伏安、过充测试、电化学阻抗、恒流充放电和扫描电子显微镜等手段研究DBDCN、DBMB和DBMCN的防过充性能,并探讨添加剂与正极材料LiFePO4的相容性。这些化合物的氧化还原电位均为4.1V,显著提高了电池的过充保护。100%过充测试和5V截止电压测试结果表明,DBMB的防过充性能明显优于DBDCN和DBMCN。以0.5C倍率电流循环100圈,基础电解液和分别添加0.1MDBDCN、DBMB、DBMCN的电池放电比容量分别为134.5mA·h/g、135.3mA·h/g、132.8mA·h/g和127.0mA·h/g,容量保持率分别为87.7%、87.0%、89.5%和84.3%。结果表明,DBMB对电池防过充作用最明显。2,2-Bis-[4-(β-cyan-ethoxy)-phenyl]-propane (DBDCN), 2-[4-(β-cyan-ethoxy)-phenyl]-2'-(4-methoxyphenyl)propane (DBMCN) and 2,2-bis(4-methoxyphenyl)propane (DBMB) were synthesized by modifying bisphenol A through a Michael addition reaction using acrylonitrile or methyl etherification using dimethyl sulfate. These compounds were explored as new redox shuttle additives for overcharge protection in lithium-ion batteries. Cyclic voltammetry (CV), overcharge test, electrochemical impedance spectrum (EIS), charge-discharge cycle performance, and scanning electron microscopy (SEM) were carried out to investigate the electrochemical performances, and the compatibility of these additives in the electrolyte with LiFePO4 electrode. These three compounds had a working potential of 4.1 V (vs Li/Li+), and showed significantly improved overcharge protection performance when used as additive (0.1 M) in 1 mol/L LiPF6/[ethylene carbonate (EC)+ diethyl carbonate (DEC)+ ethylmethyl carbonate (EMC)(1:1:1, by volume)]. Among them, DBMB exhibited best overcharge protection performance in 100% overcharge at 5 V cutoff voltage. After 100 cycles at 0.5 C rate, the capacity retention for LiFePO4/Li cell, using the base electrolyte and the electrolyte with 0.1 M DBDCN, 0.1 M DBMB and 0.1 M DBMCN additive, were 87.7%, 87.0%, 89.5% and 84.3%, respectively.

关 键 词：锂离子电池 电解液 过充保护添加剂 双酚A 电聚合 

分 类 号：TK02[动力工程及工程热物理]