ZrO_(2)包覆对层状氧化物正极材料储钠性能的改善  

Improved sodium storage performance of layered oxide cathode materials via ZrO_(2) coating

作　　者：孙阳[1] 王红[1] 车海英[1,2] 廖小珍 李林森[1] 崔桂嘉[1] 杨为民 马紫峰[1,2] Yang SUN;Hong WANG;Haiying CHE;Xiaozhen LIAO;Linsen LI;Guijia CUI;Weimin YANG;Zifeng MA(Shanghai Electrochemical Energy Devices Research Center,Department of Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China;Zhejiang Natrium Energy Co.,Ltd.,Shaoxing,Zhejiang 312000,China;Sinopec Shanghai Research Institute of Petrochemical Technology,Shanghai 201208,China)

机构地区：[1]上海交通大学化学工程系,上海电化学能源器件工程技术研究中心,上海200240 [2]浙江钠创新能源有限公司,浙江绍兴312000 [3]中国石油化工股份有限公司上海石油化工研究院,上海201208

出　　处：《过程工程学报》2022年第1期72-78,共7页The Chinese Journal of Process Engineering

基　　金：国家重点研发计划(编号:2016YFB0901505);国家自然科学基金资助项目(编号:21676165,21938005,21506123);上海市青年科技启明星计划(编号:17QB1404600);上海市科技创新行动计划(编号:19DZ1205500)。

摘　　要：层状氧化物正极材料具有良好的结构稳定性和较高的充放电比容量,是一类理想的钠离子电池正极材料。本工作研究了层状氧化物正极材料NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)表面修饰对其电化学性能的影响,采用固相球磨法在正极材料表面包覆一层纳米ZrO_(2),采用形貌、结构、电化学方法等研究了包覆后性能改进机理。研究结果表明,ZrO_(2)在NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)表面形成一层惰性保护层,有效隔开了电解液与正极材料的接触,缓解了电解液的分解速度,抑制了金属离子的溶出速度,从而显著改善了电池的循环性能以及高温性能。在ZrO_(2)包覆修饰后,55℃下正极材料相比于未包覆的正极材料有明显提升,100次循环后容量保持率达到83.6%,高于未包覆的75.2%。此外,包覆后的NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)正极材料在空气环境存储后,稳定性得到明显提高。Lithium ion batteries have been successfully applied in portable electronic products,the application of lithium ion batteries is expanding to the fields such as large scale energy storage grid and electric vehicles.However,the considerably increased demand of lithium ion batteries might yield problems in the future with the limit of Li resources.Compared with lithium,sodium is abundant in the earth.Based on its resource and cost advantages,sodium ion batteries hold promise for low-cost energy storage and could be key for smart electric-grid of the future.To date,a large variety of cathode materials with satisfactory performance have been proposed.These cathode materials include layered transition metal oxides,Prussian blue analogues,polyanionic-type compounds and organic-based materials.Layered transition metal oxides Na_(x)MO_(2)(M=Mn,Fe,Ni,Co,Ti,V,Cr)have been extensively investigated because of their higher capacities and industrial feasibility.Up to now,layered transition metal oxide NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)has been established as a promising cathode materials for practical sodium ion batteries.Many works have also focused their efforts on NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)over the years and studied its synthesis method,large scale synthesis,electrochemical reaction mechanism,coating,doping and thermal stability.In this work,ZrO_(2)coating NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)cathode was prepared by a solid state method,and the coating effect was evaluated by electrochemical measurements as well as morphological,structural,and chemical composition analyses.The results showed that ZrO_(2)formed an inert protective layer on the surface of NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2),which effectively separated the contact between electrolyte and cathode material,alleviated the decomposition rate of electrolyte and inhibited the dissolution rate of metal ions,so as to significantly improve the cycle performance and high temperature performance of the battery.After ZrO_(2)coating modification,the cathode material was significan

关 键 词：钠离子电池 层状氧化物正极材料 ZrO_(2)包覆 高温性能 空气稳定性 

分 类 号：TB306[一般工业技术—材料科学与工程] TM912[电气工程—电力电子与电力传动]