Acta Phys. -Chim. Sin. ›› 2021, Vol. 37 ›› Issue (3): 2005020.doi: 10.3866/PKU.WHXB202005020

• REVIEW • Previous Articles     Next Articles

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)

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

MSC2000: 

  • O646