过渡金属硫化物Co9S8的制备及电化学性能研究进展

doi:10.16085/j.issn.1000-6613.2023-0790

摘要/Abstract

摘要：

过渡金属硫化物Co₉S₈由于具有比电容高、倍率性能好、循环寿命长、生产成本较低等特点，是一类极有潜在应用前景的石墨替代储能材料。但Co₉S₈存在充放电过程中体积膨胀大和导电性差等问题，导致充放电过程中材料结构易破坏，容量衰减快，还不能完全满足实际市场需求。本文基于Co₉S₈不同类型复合材料在各领域的最新研究，综述了Co₉S₈材料在实际应用中通过结构设计（形貌和颗粒大小调控）、多组分掺杂以及表面包覆等策略克服该材料存在的缺陷，通过对现有研究的归纳与总结，简述针对过渡金属硫化物Co₉S₈的主要改性手段，并对其今后的研究重点提出可行性建议。

关键词: 过渡金属硫化物, 结构改性, 元素掺杂, 电化学性能

Abstract:

Transition metal sulfide Co₉S₈ is a highly promising alternative energy storage material for graphite due to its high capacitance, good rate performance, long cycle life and low production cost. However, Co₉S₈ has problems such as large volume expansion and poor conductivity during the charging and discharging process, which leads to easy damage to the material structure and fast capacity decay during the charging and discharging process, and cannot fully meet the actual market demand. According to the latest research on different types of Co₉S₈ composite materials in various fields, this article reviewed the practical applications of Co₉S₈ materials. Through the induction and summary of existing research, the main modification methods for transition metal sulfide Co₉S₈ were briefly described, and the feasible suggestions were put forward for its future research focus.

Key words: transition metal sulfides, structural modification, element doping, electrochemical performance

中图分类号:

TQ125.1

李莹莹, 刘安, 姜乐妍, 李晖, 陈春钰, 居殿春. 过渡金属硫化物Co₉S₈的制备及电化学性能研究进展[J]. 化工进展, 2024, 43(6): 3114-3127.

LI Yingying, LIU An, JIANG Leyan, LI Hui, CHEN Chunyu, JU Dianchun. Progress in the preparation and electrochemical properties of transition metal sulfide Co₉S₈[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3114-3127.

图/表 18

参考文献 60

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方法	条件	优点
溶剂热法	有机物或者其他非水溶媒将原料分散或溶解在溶剂里，在密封条件下通过高压达到超临界状态使前体变得活跃而发生相关反应	具有结晶度高、尺寸均匀、形貌良好
电沉积法	在条件一定的电解液中，发生电化学沉积的结果	具有简便、经济、可避免各种黏结剂的优点
硫化法	通过氧化物制备硫化物或将硫化物离子固定到材料或分子中的过程。通常，先制备前体溶液，通过配备有和控制压力的管式反应器进行热硫化过程	可避免各种黏结剂的优点
离子交换法	溶液中离子与交换剂反应基团作用能力相对较大，交换剂中的被交换基团离子则由于作用力不足而进入溶液中	具有条件温和、成本低等优点

方法	条件	优点
溶剂热法	有机物或者其他非水溶媒将原料分散或溶解在溶剂里，在密封条件下通过高压达到超临界状态使前体变得活跃而发生相关反应	具有结晶度高、尺寸均匀、形貌良好
电沉积法	在条件一定的电解液中，发生电化学沉积的结果	具有简便、经济、可避免各种黏结剂的优点
硫化法	通过氧化物制备硫化物或将硫化物离子固定到材料或分子中的过程。通常，先制备前体溶液，通过配备有和控制压力的管式反应器进行热硫化过程	可避免各种黏结剂的优点
离子交换法	溶液中离子与交换剂反应基团作用能力相对较大，交换剂中的被交换基团离子则由于作用力不足而进入溶液中	具有条件温和、成本低等优点

参数	Co₉S₈/C-S^[26]	MoF-Co₉S₈@C^[27]	Co₉S₈/rGO^[28]	N-C@Co₉S₈@G^[29]
结构
空间维度	0-D	3-D	3-D	2-D
成本	中等	中等	低	高
比电容	高	高	高	高
循环稳定性	高	高	中等	高

参数	Co₉S₈/C-S^[26]	MoF-Co₉S₈@C^[27]	Co₉S₈/rGO^[28]	N-C@Co₉S₈@G^[29]
结构
空间维度	0-D	3-D	3-D	2-D
成本	中等	中等	低	高
比电容	高	高	高	高
循环稳定性	高	高	中等	高

改性方法	过程	性能
碳包覆改性	无机/碳复合材料作为硫载体；引入碳来改善极性材料的电导率和孔体积	有效分散活性金属复合纳米粒子；缓冲材料以抑制粉化，还作为导电基质以促进电荷转移；提高了电极的导电性、结构稳定性，在延长循环过程中有效地保持了结构的完整性
氧化物掺杂改性	将氧化物与Co₉S₈杂合	复合材料具有氧化物和Co₉S₈纳米材料二者的优点即高的比容量和良好的循环性能

过渡金属硫化物Co₉S₈的制备及电化学性能研究进展

Progress in the preparation and electrochemical properties of transition metal sulfide Co₉S₈

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改性方法	过程	性能
铝元素掺杂	在复合材料中嵌入Al掺杂的Co₉S₈纳米粒子	提高硫化钴导电性；克服其反应过程中的堆积和团聚，从而固定与电解质离子的电化学反应动力学
硫元素掺杂	使用具有孔结构的碳材料作为硫的包封主体	防止多硫化物溶解，并提供足够的空间以容纳必要的体积膨胀；解决了由于硫的低导电性、中间体多硫化锂的溶解、严重的体积膨胀引起的快速容量衰减
铁元素掺杂	拓扑化学脱嵌方法	优化该材料的固有活性
氮、硫双掺杂	调整碳材料中的电子结构，氮、硫原子来取代sp²碳原子	产生协同效应或产生新的电荷分布特性，从而大大提高催化活性；提高了材料的导电性，提供更多的活性位点

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