物理化学学报 >> 2021, Vol. 37 >> Issue (3): 2005020.doi: 10.3866/PKU.WHXB202005020

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客体预嵌策略提升水系锌离子电池正极材料电化学性能

黄江涛1, 周江1,2,*(), 梁叔全1,2,*()   

  1. 1 中南大学材料科学与工程学院，长沙 410083
    2 中南大学电子封装及先进功能材料湖南省重点实验室，长沙 410083
  • 收稿日期:2020-05-08 录用日期:2020-07-02 发布日期:2020-07-13
  • 通讯作者: 周江,梁叔全 E-mail:zhou_jiang@csu.edu.cn;lsq@csu.edu.cn
  • 作者简介:周江，1987年生。中南大学本科(2011)，中南大学-新加坡南洋理工大学联合培养博士(2015)。先后在新加坡南洋理工大学、美国麻省理工学院从事科学研究工作。现为中南大学材料科学与工程学院特聘教授，博士生导师。目前主要从事水系锌电池研究
    梁叔全，1962年生。2000年在中南大学获博士学位。现为中南大学材料科学与工程学院二级教授，博士生导师、享受国务院特殊津贴专家、湖南省优秀教师，芙蓉学者特聘教授成就奖获得者。主要从事材料的合成、结构分析与性能研究
  • 基金资助:
    国家自然科学基金(51932011);国家自然科学基金(51972346);国家自然科学基金(51802356);国家自然科学基金(51872334);中南大学创新驱动项目(2020CX024)

Guest Pre-Intercalation Strategy to Boost the Electrochemical Performance of Aqueous Zinc-Ion Battery Cathodes

Jiangtao Huang1, Jiang Zhou1,2,*(), Shuquan Liang1,2,*()   

  1. 1 School of Materials Science & Engineering, Central South University, Changsha 410083, China
    2 Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province, Central South University, Changsha 410083, China
  • Received:2020-05-08 Accepted:2020-07-02 Published:2020-07-13
  • Contact: Jiang Zhou,Shuquan Liang E-mail:zhou_jiang@csu.edu.cn;lsq@csu.edu.cn
  • About author:Shuquan Liang. Email: lsq@csu.edu.cn (S. L.)
    Jiang Zhou. Email: zhou_jiang@csu.edu.cn (J.Z.)

  • Supported by:
    the National Natural Science Foundation of China(51932011);the National Natural Science Foundation of China(51972346);the National Natural Science Foundation of China(51802356);the National Natural Science Foundation of China(51872334);the Innovation Driven Program of Central South University, China(2020CX024)

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摘要：

随着人们对电子通讯器件、新能源汽车以及电网级储能技术的需求日益增长，开发安全、高效且兼具环保、低成本等优点的二次电池显得至关重要。近年来，水系锌离子电池因其高安全性、高容量、低成本以及环境友好等优点受到了广泛关注。在与锌负极相匹配的众多正极材料中，具有多电子转移特性的钒基和锰基材料表现出了广阔的应用前景。然而这些正极材料在电池循环过程通常面临着结构坍塌、组分溶解、衍生副反应、反应动力学缓慢等问题，严重制约了其商业化进程。近年来，大量研究表明，客体离子或分子预嵌正极宿主结构可以有效缓解上述问题，提升水系锌离子电池正极材料的电化学性能。本文综述了客体预嵌策略应用于水系锌离子电池钒、锰基正极材料的研究进展，对该策略所解决的问题以及其局限性进行了讨论和总结，并对未来水系锌离子电池钒基和锰基正极材料的研究发展方向进行了展望。

关键词: 水系锌离子电池, 正极材料, 客体预嵌, 钒基材料, 锰基材料

Abstract:

The growing demand for electric vehicles, communication devices, and grid-scale energy storage systems urgently calls for the development of rechargeable batteries. Although lithium-ion batteries have dominated the new energy market for decades, there are challenges limiting their development, such as the high cost of lithium, as well as the toxicity and flammability of the organic electrolyte. In recent years, aqueous zinc-ion batteries (ZIBs) have gained much attention due to their advantages of high safety, high capacity, low cost, and nontoxicity. Materials based on multivalent vanadium and manganese have shown great potential for application as cathodes that are compatible with the metallic zinc anode in ZIBs. However, the commercialization of ZIBs has been hindered by the choice of cathodes, since the cathode materials show unsatisfactory energy densities and suffer from severe structural collapse, dissolution of the electrode components, sluggish reaction kinetics and detrimental side reactions during cycling. This stalemate was broken when a Zn2+/H2O co-inserted V2O5 (Zn0.25V2O5·nH2O) material was first reported in 2016, and it showed much higher cycling stability and capacity than those of V2O5. The Zn2+ and water molecules pre-intercalated into the interlayer served as pillars to maintain the crystal structure and increase the interplanar spacing, leading to high structural stability and fast Zn2+ diffusion. Since then, several guest ions (Li+, Na+, K+, Ca2+, NH4+, PO43-, N3-, etc.) and molecules (H2O, polyethylene dioxythiophene (PEDOT), polyaniline (PANI, etc.) have been widely used to improve the electrochemical performance of aqueous ZIB cathodes, especially with manganese-based and vanadium-based materials. It is demonstrated that pre-intercalation of the guest ions or molecules can effectively optimize the electronic structure, regulate the interplanar spacing, and improve the reaction kinetics of the host. The local coordination structure of the host with pre-intercalated guest ions/molecules directly influences the zinc-ion storage performance. For example, sodium vanadates with a tunneled structure generally show better cycling stability than those with a layered structure due to their stronger Na-O bonds, since the O atoms on their layer surfaces are only single-connected. Manganese dissolution could be greatly suppressed by intercalation of the large potassium ions into tunneled α-MnO2, where solid K-O bonds act as pillars to be connected with Mn polyhedrons, and thus strengthen the structure. New mechanisms underlying reduction/displacement reactions could also be revealed in vanadates upon the introduction of Ag+ and Cu2+. Thus, we believe that guest pre-intercalation is a promising method for optimizing the zinc-ion storage performance of the appropriate cathodes and is worthy for further exploration. Here we have reviewed the recent advances in manganese-based and vanadium-based cathodes via the guest pre-intercalation strategy, discussed the related advantages and challenges. The future research direction for these two kinds of aqueous ZIB cathodes is also prospected.

Key words: Aqueous zinc-ion battery, Cathode material, Guest pre-intercalation, Vanadium-based material, Manganese-based material