普鲁士蓝类钠离子电池正极材料导电性研究进展

doi:10.19799/j.cnki.2095-4239.2023.0895

摘要/Abstract

摘要：

发展具有快充性能(即超高倍率性能)的钠离子电池是目前储能领域研究的重点和热点。普鲁士蓝及其类似物(PBAs)具有有利于钠离子储存和扩散的开放式三维骨架结构，已经被证明作为钠离子电池正极材料具有巨大的潜力。然而，目前所制备的PBAs大多数存在结构缺陷和结晶水，以及其本身较差的电子电导率，导致其倍率性能不理想。本文针对PBAs导电性差的问题，从离子导电和电子导电两个方面进行讨论，首先分析了PBAs中结构缺陷以及结晶水的存在对离子导电的影响以及其本身价键结构对电子电导的影响。综述了近期对于提高PBAs导电性的相关研究：①改变晶体结构，通过减少PBAs晶体内部缺陷及结晶水，从而降低钠离子迁移距离及减少阻碍；②设计特殊的PBAs晶体结构，能有效减少钠离子传输路径；③采用复合导电材料，能构建新的电子运输途径。最后对提高PBAs导电性的三种策略进行了总结和展望，指出应该在优化PBAs结构的基础上，复合导电材料，同时增强离子电导和电子电导，以期达到最佳的倍率性能。

关键词: 钠离子电池, 普鲁士蓝类似物, 倍率性能, 结构优化

Abstract:

The development of sodium-ion batteries with fast charge performance (ultra-high rate performance) is a research hotspot in the field of energy storage. Prussian blue analogues (PBAs), which have an open three-dimensional skeleton structure conducive to sodium-ion storage and diffusion, have great potential as anode materials for sodium-ion batteries. However, most existing PBAs have structural defects, crystal water, and poor electronic conductivity, resulting in unsatisfactory rate performance. In this study, the problem of poor electrical conductivity of PBAs is analyzed from two perspectives: ionic and electronic conduction. First, the influence of structural defects in PBAs, the presence of crystal water on ionic conduction, and the influence of the valence bond structure on electronic conduction are analyzed. Recent literature on improving the electrical conductivity of PBAs is also reviewed. ①Improving the crystal structure reduces the internal defects and crystal water of PBAs, thereby reducing the migration distance of sodium ions and obstacles. ②The design of special PBA crystal structures can effectively reduce the sodium-ion transport path. ③Composite conductive materials can build new electronic transport routes. In addition, three strategies to improve the conductivity of PBAs are described. Based on our analysis, to optimize the structure of PBAs and achieve optimal rate performance, composite conductive materials should be strengthened to enhance ionic and electronic conductance.

Key words: sodium ion battery, Prussian blue analogs, rate capability, structure optimization

中图分类号:

TM 911

赵毅伟, 张福华, 颜顺, 丁坤, 蓝海枫, 刘辉. 普鲁士蓝类钠离子电池正极材料导电性研究进展[J]. 储能科学与技术, 2024, 13(5): 1474-1486.

Yiwei ZHAO, Fuhua ZHANG, Shun YAN, Kun DING, Haifeng LAN, Hui LIU. Research progress on the conductivity of Prussian blue sodium-ion battery cathode materials[J]. Energy Storage Science and Technology, 2024, 13(5): 1474-1486.

图/表 10

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参考文献 44

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Samples	Cyclability/(cycles,retention%@mA/g)	Rata capacity/(mAh/g@mA/g)	Refs
Na_1.81Fe[Fe(CN)₆]_0.83·2.04H₂O	3700,79.7%@700	77@1400	[11]
Na_1.70Fe_2.15(CN)₆	500,63.4%@85	75@850	[18]
Na_1.58Fe[Fe(CN)₆]_0.87·2.38H₂O	3000,64.9%@750	90.6@1500	[20]
Na_1.76FeFe(CN)₆	2000,82.5%@500	80@2000	[22]
Na_1.11NiFe(CN)₆·0.71H₂O	5000,83.2%@500	70.9@4000	[25]
Na_1.38Ni_0.07Mn_0.93[Fe(CN)₆]_0.82·□_0.18·1.4H₂O	600,82.3%@50	52@3200	[26]
(K_0.47Fe₄ [Fe(CN)₆]_3.14)@(MoSO_1.7)_0.44·18H₂O	10000,98%@10000	85@10000	[30]
Na_0.647Fe[Fe(CN)₆]_0.93·□_0.07·2.6H₂O	2000,90%@2000	77.5@9000	[32]
PBGO	800,91.3%@500	68.0@4000	[35]
PB@PANI	500,93.4%@100	102.5@1000	[38]
NaFeFe(CN)₆@Ti₃C₂T _x	1000,69.7%@1000	92.0@1000	[41]
Na_1.6Mn[Fe(CN)₆]_0.9@Na₃(VOPO₄)₂F	500,84.3%@100	91.4@1000	[42]
Na_1.36FeFe(CN)₆@PDA	500,77.4%@200	72.6@5000	[43]

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