钾离子电池聚阴离子正极材料的研究进展

doi:10.19799/j.cnki.2095-4239.2023.0257

摘要/Abstract

摘要：

钾离子电池(PIBs)由于钾金属资源丰富、成本低廉、环境友好及能量密度高等优点，已成为替代锂离子电池(LIBs)的理想新型储能体系。尽管近年来PIBs在负极领域的研究已经取得了显著进展，但正极材料的研究缓慢，其设计和应用面临可逆比容量低、循环稳定性差、能量密度不理想等问题。因此，发现和设计正极材料对构建用于实际应用的钾离子(K⁺)电池至关重要。由于聚阴离子材料在LIBs和钠离子电池(NIBs)中的成功应用，近年来，人们也将研究集中于PIBs的聚阴离子材料。聚阴离子材料具有氧化还原电位高、发生有利的感应效应、安全性高、热稳定性和结构稳定性良好等优点，可以实现较为稳定的容量存储，但是其可逆容量低、导电性差等问题仍需解决。本篇综述针对钾离子电池聚阴离子正极材料的研究进行了综述和讨论，以探究聚阴离子正极材料发展设计潜力和研究空间为目的，集中讨论了磷酸盐、氟磷酸盐、焦磷酸盐、硫酸盐类材料的机理和结构的发展现状，总结了当前聚阴离子类正极材料设计的主要理念，并对聚阴离子正极材料的改性研究提出了一些建议和前景。

关键词: 聚阴离子, 正极材料, 磷酸盐, 钾离子电池, 氟磷酸盐

Abstract:

Potassium-ion batteries (PIBs) have become an ideal new energy storage system to replace lithium-ion batteries (LIBs) due to their abundant potassium resources, low cost, environmental friendliness and high energy density. Although the research of PIBs in the field of anode has made significant progress in recent years, the research on cathode materials is slow, and its design and application are faced with problems such as low reversible specific capacity, poor cycle stability, and unsatisfactory energy density. Therefore, the discovery and design of cathode materials is critical to building potassium-ion (K⁺) batteries for practical applications. Due to the successful application of polyanionic materials in LIBs and sodium-ion batteries (NIBs), in recent years, people have also focused on polyanionic materials focusing on PIBs. Polyanionic materials have the advantages of high redox potential, produces a favorable induction effect, high security, thermal stability and structural stability well, and can achieve relatively stable capacity storage, but their low reversible capacity and poor conductivity need to be solved. This review reviews and discusses the research of polyanionic cathode materials for potassium-ion batteries, with the purpose of exploring the development design potential and research space of polyanionic cathode materials, focuses on the development status of phosphate, fluorophosphate, pyrophosphate and sulfate materials, summarizes the main concepts of the current polyanionic cathode material design, and puts forward some suggestions and prospects for the modification of polyanionic cathode materials.

Key words: polyanion, cathode materials, phosphate, potassium ion batteries, fluorophosphates

中图分类号:

TM 911.3

李尚倬, 龙禹彤, 刘朝孟, 高宣雯, 骆文彬. 钾离子电池聚阴离子正极材料的研究进展[J]. 储能科学与技术, 2023, 12(5): 1348-1363.

Shangzhuo LI, Yutong LONG, Zhaomeng LIU, Xuanwen GAO, Wenbin LUO. Advances toward polyanionic cathode materials for potassium-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(5): 1348-1363.

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Materials	Structure	Theoretical capacity /(mAh/g)	Actual capacity /(mAh/g)	Average dischargepotential (vs. K⁺/K) /V
KVPO₄F	KTiOPO₄(KTP)-type orthorhombic (Pna2₁)	131	90	4.13
KVOPO₄	KTP-type orthorhombic (Pna2₁)	133	80	4
KVP₂O₇	KAlP₂O₇-type monoclinic (P2₁/c)	102	61	4.15
K₃V₂(PO₄)₃	Unknown	106	54	3.5
K₃V₂(PO₄)₂F₃	Orthorhombic (Cmcm)	115	104	3.7
Amorphous-FePO₄	—	178	156	2.64
Orthorhombic KFeSO₄F	KTP-type orthorhombic (Pna2₁)	128	100	3.6
Monoclinic KFeSO₄F	Layered monoclinic (C2/c)	128	50	3.5(vs. Li)

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