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磷酸釩鹽在水系鋅離子電池中的應用

Application of vanadium phosphate in aqueous zinc-ion batteries

  • 摘要: 鋰離子電池因鋰資源儲量有限、分布不均及一定的安全問題,導致其在大型儲能領域的應用受限。水系鋅離子電池因其資源豐富、安全環保、易于組裝以及價格低廉等優勢在大規模儲能領域具有極大前景。但是由于鋅離子與正極材料基體具有較強的靜電吸附作用,導致其動力學緩慢以及部分正極材料在水系電解液中存在溶解等問題,限制了水系鋅離子電池的發展。在目前的正極材料中,磷酸釩鹽因其結構穩定、電壓平臺高、功率密度高等特點受到研究者的關注。然而,磷酸釩鹽作為水系鋅離子電池正極材料時,較差的電子電導率和溶解問題,制約其循環穩定性和倍率容量。本文綜述各類磷酸釩鹽及其衍生物的物相結構、合成方法、儲鋅性能和儲鋅機制,歸納提高電化學性能的方法如構建納米結構、調節電子結構、包覆導電材料、調控電解液等。最后,總結了磷酸釩鹽儲鋅正極材料現階段存在的挑戰,并對其未來的發展方向提出了展望。

     

    Abstract: With the increasing shortage of petroleum resources and serious environmental pollution, the demand for green technology development is growing stronger. Electrical energy storage is an excellent way to store intermittent clean energy and transport clean energy from one place to another. The lithium-ion battery (LIB) is broadly recognized as the first choice for electrical energy storage due to its high energy density, especially in smart electronics and electric cars. Nevertheless, the application of LIB in large-scale energy storage has been limited by various factors, including the limited and uneven distribution of lithium resources, safety issues and toxic organic electrolytes. The aqueous zinc-ion battery (AZIB) has been regarded as a potential substitute for LIB in large-scale energy storage devices because of the competitive theoretical volumetric capacity (5855 mA·h·cm?3) and gravimetric capacity (820 mA·h·g?1) of the Zn anode, the low electrochemical potential of Zn2+ (?0.76 V vs SHE), and the high ionic conductivity of the aqueous electrolyte, the ease of manufacturing (e.g., manufacture in an open-air environment), and the merits of rich resources, low cost and high safety. Finding a cathode material with high energy density and power density is proposed as a strategy to accelerate the progress of AZIB because the cathode material largely dominates the electrochemical properties and the cost of the battery. However, the strong electrostatic interaction between Zn2+ and the host material results in sluggish reaction kinetics, leading to inferior cycling performance and rate property. Some cathode materials are dissolved in aqueous electrolytes, which restrict the development of AZIB. In comparison to the reported AZIB cathodes, including vanadium-based materials, manganese-based materials, Prussian blue analogs, and organic materials, vanadium phosphates have received a lot of attention as cathodes due to their stable structures, high voltage plateaus, and high power densities. This review presents an overview of various vanadium phosphates such as Li3V2(PO4)3, Na3V2(PO4)3, VOPO4, Na3V2(PO4)2F3, NaVPO4F and their derivatives that are applied as cathodes for AZIB. The summary includes their phase structures, synthetic methods, electrochemical performance, electrochemical Zn2+ storage mechanisms and existing problems. The two major challenges in using vanadium phosphates as cathode materials for AZIB are low electronic conductivity and material dissolution problems, both of which result in inferior cycling performance and rate capacity. The resolution strategies for the mentioned challenges include designing the nanostructure, adjusting the electronic structure, coating with conductive materials, and regulating electrolytes to enhance electrochemical properties. Experimental techniques for studying electrochemical mechanisms are also proposed. Finally, the prospects for the future development of these cathodes in AZIB are advanced. It can be expected that this review has some significance for the development of new vanadium phosphates as cathode materials.

     

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