水系锌离子电池正极材料的研究进展  

Research Progress of Cathode Materials for Aqueous Zinc Ion Battery

作　　者：曹鹏飞 刘雅婷 陈妮 汤文静 李福枝[1] 夏勇 孙翱魁 CAO Pengfei;LIU Yating;CHEN Ni;TANG Wenjing;LI Fuzhi;XIA Yong;SUN Aokui(School of Packaging and Materials Engineering,Hunan University of Technology,Zhuzhou 412007,Hunan,China;School of Metallurgy and Environment,Central South University,Changsha 410083,China)

机构地区：[1]湖南工业大学包装材料工程学院,湖南株洲412007 [2]中南大学冶金与环境学院,长沙410083

出　　处：《材料导报》2022年第23期31-43,共13页Materials Reports

基　　金：国家自然科学基金(51704108);湖南省教育厅科学研究项目(18B293,19K028);湖南省普通高等学校教学改革研究项目(HNJG-2020-0572);湖南省学位与研究生教育改革研究重点项目(2019JGZD067)。

摘　　要：水系锌离子电池(ZIBs)是近年发展起来的一种新型二次电池,具有能量密度高、功率密度高、放电过程高效安全、电池材料无毒廉价、制备工艺简单等优点,在电动汽车和储能电网等新兴的大规模储能领域具有很高的应用价值和发展前景。目前,阻碍水系锌离子电池进一步发展的主要因素之一就是缺乏合适的正极材料。Zn^(2+)及其水合离子半径大,在嵌入/脱附时,会引发正极材料不可逆形变甚至结构坍塌,导致电池容量快速衰减;正极材料导电性较差、充放电过程中电极极化较大,使得正极充电电压与析氧电压部分重合,充电过程中正极材料会对水进行催化产生氧气,导致电池胀气失效;二价的Zn^(2+)与正极材料的晶体结构之间的静电相互作用过强,导致Zn^(2+)嵌入容量小等。因此,开发在Zn^(2+)存储过程中既能提供高容量又能保持良好结构稳定性的正极材料至关重要。针对水系锌离子电池正极材料存在的缺陷,研究人员采用多种改性方法以改良其性能:(1)引入客体粒子,通过引入金属离子、有机分子和水分子等客体粒子,使主体框架发生结构性变化,获得更稳定的骨架;(2)制备本征混合价态材料,混合价态能够适应充放电过程中正极材料的体积变化和价态变化;(3)引入氧空位,增加活性位点,促进Zn^(2+)扩散动力学,提升材料容量;(4)与导电材料复合,改善材料整体导电性,提升结构稳定性;(5)纳米结构改性,赋予材料更高比表面积,缩短Zn^(2+)扩散距离,增大电化学反应接触面积。本文对水系锌离子电池的优点及储能机理进行了简要介绍,基于正极材料在水系锌离子电池中的关键作用,综述了几种常见的正极材料(如锰氧化物、钒氧化物、普鲁士蓝类似物),且对各类正极材料的结构、性能及缺陷进行了梳理,重点讨论了掺杂客体粒子、复合导电材料、制备本征混合价态和构造纳米结Aqueous zinc ion batteries(ZIBs),a new type of aqueous secondary batteries proposed in recent years,show great practical value and developmental prospects in the field of scale energy storage including electric vehicle and energy storage grid owing to their high energy density and high power density,safe and efficient discharge processes,cheap and nontoxic electrode materials and simple manufacturing process.At present,one of the main factors hindering the further development of ZIBs is the lack of suitable cathode materials.Due to the large ion radius of Zn^(2+)and its hydrated ions,it will cause irreversible deformation or structural collapse of the cathode electrode material during insertion/desorption process,resulting in a rapid decline in battery capacitance.The poor conductivity of the cathode electrode material and serious electrode polarization during charging and discharging cause the charging voltage of cathode partially overlaps with the oxygen evolution voltage.As a result,the cathode electrode material will catalyze the water to produce oxygen,causing the battery flatulence to invalid during the charging process.Moreover,the strong electrostatic interaction between the divalent Zn^(2+)and the crystal structure of the cathode electrode material leads to unsatisfactory Zn^(2+)insertion capacitance.Therefore,it is crucial to develop a cathode material that can provide high capacity and maintain good structural stability during Zn^(2+)insertion/desorption process.In view of the shortcomings of the cathode material of the ZIBs,a variety of modification methods are used to improve their performance:(Ⅰ)guest particles,such as metal ions,organic molecules and water molecules,are introduce in to the host so a more stable frame can be obtained through its structural changes;(Ⅱ)intrinsic mixed valence materials are prepared because of their better adaptability to the volume changes and valence changes of the cathode electrode material during charging and discharging;(Ⅲ)introduce oxygen vacancies to incre

关 键 词：水系锌离子电池 储能机理 正极材料 锰氧化物 钒氧化物 普鲁士蓝类似物 改性方法 

分 类 号：O646.21[理学—物理化学]