物理化学学报

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金属硫化物基钾离子电池负极:储存机制和合成策略

杜忆忱, 张壮壮, 徐一帆, 包建春, 周小四   

  1. 南京师范大学化学与材料科学学院, 南京 210023
  • 收稿日期:2022-05-09 修回日期:2022-06-11 录用日期:2022-06-13 发布日期:2022-06-20
  • 通讯作者: 包建春, 周小四 E-mail:baojianchun@njnu.edu.cn;zhouxiaosi@njnu.edu.cn
  • 基金资助:
    国家自然科学基金(22075147, 22179063)资助项目

Metal Sulfide-Based Potassium-Ion Battery Anodes: Storage Mechanisms and Synthesis Strategies

Yichen Du, Zhuangzhuang Zhang, Yifan Xu, Jianchun Bao, Xiaosi Zhou   

  1. School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
  • Received:2022-05-09 Revised:2022-06-11 Accepted:2022-06-13 Published:2022-06-20
  • Contact: Jianchun Bao, Xiaosi Zhou E-mail:baojianchun@njnu.edu.cn;zhouxiaosi@njnu.edu.cn
  • Supported by:
    The project was supported by the National Natural Science Foundation of China (22075147, 22179063).

摘要: 钾离子电池由于其低成本和丰富的钾矿产资源,在能量存储和转化领域极具应用潜力。金属硫化物理论容量高且材料种类丰富,在众多钾离子电池负极材料中表现突出。然而,金属硫化物存在的缺点,如导电性差、离子扩散率低、界面/表面传输动力学缓慢等,限制了其在储钾过程中的性能表现。在这篇综述中,我们系统的讨论和总结了金属硫化物作为钾离子电池负极的电化学反应机制、所面临的挑战和合成方法。其中,重点讨论了其常见的合成方法,包括模板法、溶剂热/水热法、固相反应法、静电纺丝法和离子交换法。这篇综述意在通过优化合成策略设计合成理想的组分和结构,来解决钾电负极材料存在的问题,最终得到高性能的钾离子电池负极材料。最后我们还对基于金属硫化物的钾离子电池负极的发展方向进行了展望。

关键词: 储存机制, 合成方法, 挑战, 模板法, 水热/溶剂热法

Abstract: Rechargeable potassium-ion batteries (PIBs), with their low cost and the abundant K reserves, have been promising candidates for energy storage and conversion. Among all anode materials for PIBs, metal sulfides (MSs) show superiority owing to their high theoretical capacity and variety of material species. Nevertheless, the battery performance of MSs is hindered by many factors such as poor conductivity, low ion diffusivity, sluggish interfacial/surface transfer kinetics, and drastic volume changes. In this review, the electrochemical reaction mechanisms, challenges, and synthesis methods of MSs for PIBs are summarized and discussed. In particular, the most common synthesis methods of MSs for PIBs are highlighted, including template synthesis, hydro/solvothermal synthesis, solid-phase chemical synthesis, electrospinning synthesis, and ion-exchange synthesis. During the potassium storage process, the two-dimensional layered MSs follow the intercalation/extraction mechanism, and the MSs with inactive metal undergo the conversion reaction, whereas the metalactive MSs follow the conversion-alloying reaction mechanism. Given the inherent properties of MSs and the reactions they undergo during cycling, when used as anodes for PIBs, such materials experience a series of problems, including poor ion-/electron-transport kinetics, structural instability, and loss of active material caused by the dissolution of discharged polysulfide products and the occurrence of side reactions. These problems can be solved by optimizing the methods for synthesizing MSs with an ideal composition and structure. The template method can precisely prepare porous or hollowstructured materials, the hydro/solvothermal method can alter the thickness or size of the material by adjusting certain synthesis parameters, and the one-dimensional-structured material obtained via electrospinning often has a large specific surface area, all of which can shorten the transport pathway for potassium ions, thereby improving the performance of the battery. The ion-exchange method affords difficult-to-synthesize MSs via anion- or cation-exchange, in which the product inherits the structure of the starting material. The solid-phase synthesis method makes it possible to combine MSs with other materials. Combinations with materials such as carbon or other MSs helps to provide sufficient buffer space for the volume expansion of MSs during cycling, while promoting electron transport and improving the potassium-storage properties of the anodes. Therefore, this review aims to highlight the current defects of MS anodes and explore the construction of their ideal architecture for high-performance PIBs by optimizing the synthesis methods. Ultimately, we propose the possible future advancement of MSs for PIBs.

Key words: Storage mechanism, Synthesis strategy, Challenge, Template synthesis, Hydro/solvothermal synthesis

MSC2000: 

  • O646