磷化铁掺杂硫化聚丙烯腈储锂动力学行为

兰州理工大学学报 ›› 2023, Vol. 49 ›› Issue (5): 10-19.

磷化铁掺杂硫化聚丙烯腈储锂动力学行为

刘文武^*1,2, 徐志强^1,2, 雷怡潇^1,2, 郑雅文^1,2, 达世纪^1,2, 吴有智^1,2

1.兰州理工大学材料科学与工程学院, 甘肃兰州 730050;
2.兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室, 甘肃兰州 730050

收稿日期:2023-04-06 出版日期:2023-10-28 发布日期:2023-11-07
通讯作者: 刘文武(1987-),男,博士,甘肃兰州人,副研究员.Email:wwliu@lut.edu.cn
基金资助:
国家自然科学基金(52262035),金昌科技局科技计划项目(2022GY003)

Kinetic behavior of lithium storage in ferric phosphide doped sulfide polyacrylonitrile

LIU Wen-wu^1,2, XU Zhi-qiang^1,2, LEI Yi-xiao^1,2, ZHENG Ya-wen^1,2, DA Shi-ji^1,2, WU You-zhi^1,2

1. School of Materials Science and Engineering, Lanzhou Univ. of Tech., Lanzhou 730050, China;
2. State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou Univ. of Tech., Lanzhou 730050, China

Received:2023-04-06 Online:2023-10-28 Published:2023-11-07

摘要/Abstract

摘要： 通过高温磷化法合成磷化铁掺杂硫化聚丙烯腈(FeP@SPAN).在FeP@SPAN材料中构建的P—S化学配位,在放电过程中增强亲核试剂S^2－的HOMO能级与亲电试剂Li⁺的LUMO能级匹配度,降低了还原产物Li₂S的成键轨道σ能级,加快了正极储锂反应动力学行为.探讨了FeP@SPAN正极材料的物相结构、电化学性能和在电池运行过程中对氧化还原动力学的影响.结果表明:FeP通过P—S键与SPAN连接,并且FeP的引入对SPAN形貌的影响可以忽略不计.FeP@SPAN作为电池的正极,有效提高了电池的导电性,降低了正极的阻抗,缓解了多硫化物的溶解,提高了氧化还原动力学.较初始的SPAN正极,FeP@SPAN正极电池在0.2 A/g的电流密度下初始容量可达到1 285.8 mAh/g.在1 A/g电流密度下经过500次循环后,仍能够保持615.2 mAh/g的容量,平均每圈容量衰减为0.079%.

关键词: 磷化铁, 锂-有机硫电池, 电化学性能

Abstract: Fe-phosphide doped sulfide polyacrylonitrile (FeP@SPAN) was synthesized by high-temperature phosphating. The P—S chemical coordination constructed in FeP@SPAN enhances the compatibility between the HOMO level of the nucleophile S^2－ and the LUMO level of the electrophilic reagent Li⁺ during the discharge process, reduces the bonding orbital σ level of the reduction product Li₂S, and speeds up the kinetic behavior of lithium storage reaction in the positive electrode. The phase structure, electrochemical properties, and effects of FeP@SPAN cathode material on redox kinetics during battery operation were investigated. The results showed that FeP is connected with SPAN through the P—S bond, and the influence of FeP on the morphology of SPAN can be ignored. FeP@SPAN, as the positive electrode of the battery, effectively improves the conductivity of the battery, reduces the impedance of the positive electrode, alleviates the dissolution of polysulfide, and improves the redox kinetics. Compared with the initial SPAN positive electrode, the FeP@SPAN positive battery has an initial capacity of 1 285.8 mAh/g at A current density of 0.2 A/g, and can still maintain the capacity of 615.2 mAh/g after 500 cycles at1 A/g current density with the average capacity attenuation per cycle of 0.079%.

Key words: FeP, Lithium-organic sulfur battery, electrochemical performance

中图分类号:

TB34

刘文武, 徐志强, 雷怡潇, 郑雅文, 达世纪, 吴有智. 磷化铁掺杂硫化聚丙烯腈储锂动力学行为[J]. 兰州理工大学学报, 2023, 49(5): 10-19.

LIU Wen-wu, XU Zhi-qiang, LEI Yi-xiao, ZHENG Ya-wen, DA Shi-ji, WU You-zhi. Kinetic behavior of lithium storage in ferric phosphide doped sulfide polyacrylonitrile[J]. Journal of Lanzhou University of Technology, 2023, 49(5): 10-19.

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