稀土元素改性钒基固溶体储氢合金研究进展  

Research Progress on Rare Earth Element Modified V-Based Solid Solution Hydrogen Storage Alloys

作　　者：任权兵 钟鸣 郑波 冯兰 丁南 尹东明[2] 程勇[2] 王立民[2] REN Quan-Bing;ZHONG Ming;ZHENG Bo;FENG Lan;DING Nan;YIN Dong-Ming;CHENG Yong;WANG Li-Min(Jiangxi Jiangwu Haoyun High-tech Co.,Ltd.,Nanchang 330095,China;State Key Laboratory of Rare Earth Resources Utilization,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)

机构地区：[1]江西江钨浩运科技有限公司,南昌330095 [2]中国科学院长春应用化学研究所,稀土资源利用国家重点实验室,长春130022

出　　处：《应用化学》2023年第12期1601-1612,共12页Chinese Journal of Applied Chemistry

基　　金：国家重点研发计划(No.2021YFB4000604);吉林省科技发展计划项目(Nos.20230201125GX,20230201140GX)资助。

摘　　要：钒基固溶体储氢合金具有体心立方(BCC)结构,储氢质量分数在3.8%以上,充放电容量为1052 mA·h/g,优于AB2和AB5等系列合金,并且在常温常压下表现出较高的氢溶解度和扩散系数,因此在氢储运系统以及氢能源供应等领域具有广阔的应用前景,但钒基固溶体合金存在着活化难度大、放氢条件苛刻、循环寿命短以及对氧敏感易氧化等问题。研究表明,稀土对多种固态储氢材料均有很好的改性作用,将稀土元素通过元素替代或掺杂的方式加入到钒基固溶体合金中,有助于生成高活性的稀土或稀土氧化物第二相,可明显改善材料的吸放氢热力学、循环稳定性以及抗毒化性质,同时可减少材料内的氧含量,提高材料的活化特性。电化学性能方面,稀土元素的添加能显著提升合金电极的循环稳定性、耐腐蚀能力以及高倍率放电性能。因此,稀土元素取代是实现钒基固溶体储氢材料实际应用的一项行之有效的方法。本文报道了近30年稀土改性钒基固溶体储氢合金的研究现状,重点总结了稀土元素的作用机制,并对今后重点研究方向进行了展望。V-based solid solution hydrogen storage alloys possess BCC structures and have the weight hydrogen storage capacity of above 3.8%and the charge/discharge capacity of 1052 mA·h/g,which is superior to series alloys such as AB2 type and AB5 type.They exhibit high hydrogen solubility and diffusion coefficients at ambient temperature and pressure,therefore,and have a broad application prospect in the field of hydrogen storage and transport system as well as hydrogen energy supply.However,V-based solid solution alloys suffer from difficult activation,harsh hydrogen release conditions,short cycle life and oxygen sensitivity and oxidation.Studies have shown that rare earths have a positive effect on modifying various solid-state hydrogen storage materials.The inclusion of rare earth elements in V-based solid solution alloys through elemental substitution or doping produces a vigorously active second phase of rare earths or rare earth oxides,substantially enhancing the material's capacity for hydrogen absorption and desorption,cycling durability,and anti-toxicity characteristics.Simultaneously,it decreases the oxygen content and enhances the activity properties of materials.In terms of electrochemical performance,the addition of rare earth elements can significantly improve the cycle stability,corrosion resistance and high rate discharge performance of the alloy electrode.Therefore,rare earth element substitution is a well-established method for achieving practical applications of V-based solid solution hydrogen storage materials.This report presents the recent research status of rare earth-modified V-based solid solution hydrogen storage alloys,with a focus on summarizing the rare earth elements'mechanism of action and providing an outlook for future key research directions.

关 键 词：钒基固溶体合金 稀土元素 储氢性能 

分 类 号：O614[理学—无机化学]