Research progress in Prussian blue-type cathode materials for aqueous multivalent metal-ion batteries

CHEN Zhijie; YAN Ruyu; WANG Bing; WANG Yankai; YANG Xiao; LIU Xiaofang

doi:10.19799/j.cnki.2095-4239.2025.1013

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Research progress in Prussian blue-type cathode materials for aqueous multivalent metal-ion batteries

Energy Storage Materials and Devices | 更新时间：2026-07-13

- Research progress in Prussian blue-type cathode materials for aqueous multivalent metal-ion batteries
- Energy Storage Science and Technology Vol. 15, Issue 6, Pages: 2148-2171(2026)
- 作者机构：
  
  安徽工业大学能源与环境学院，安徽马鞍山 243002
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2025.1013
  CLC： O 646
- Received：10 November 2025，
  
  Revised：2025-12-16，
  
  Published：28 June 2026
- 稿件说明：
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陈志杰, 颜如玉, 王冰, 等. 水系多价金属离子电池普鲁士蓝类正极材料的研究进展[J]. 储能科学与技术, 2026, 15(6): 2148-2171.

CHEN Zhijie, YAN Ruyu, WANG Bing, et al. Research progress in Prussian blue-type cathode materials for aqueous multivalent metal-ion batteries[J]. Energy Storage Science and Technology, 2026, 15(6): 2148-2171.
陈志杰, 颜如玉, 王冰, 等. 水系多价金属离子电池普鲁士蓝类正极材料的研究进展[J]. 储能科学与技术, 2026, 15(6): 2148-2171. DOI： 10.19799/j.cnki.2095-4239.2025.1013.

CHEN Zhijie, YAN Ruyu, WANG Bing, et al. Research progress in Prussian blue-type cathode materials for aqueous multivalent metal-ion batteries[J]. Energy Storage Science and Technology, 2026, 15(6): 2148-2171. DOI： 10.19799/j.cnki.2095-4239.2025.1013.

摘要

水系多价金属离子电池（aqueous multivalent metal-ion batteries，AMMBs）因成本低廉、资源丰富、环境友好以及本质安全等优点，有望成为替代锂离子电池进行大规模储能的前景技术。在构建此类电池时，开发兼具结构稳定性与快速离子传输能力的正极材料至关重要。结构稳定且能提供快速离子扩散通道的正极材料是构建AMMBs的关键。普鲁士蓝类似物（Prussian blue analogous，PBAs）具有开放三维框架结构、丰富的氧化还原位点及由可调控的元素组成，成为AMMBs应用前景广泛的正极材料。尽管如此，PBAs在实际应用中仍面临诸多挑战。为应对PBAs材料存在的结晶水/空位稳定性差、导电性较低等固有缺陷，以及在多价离子嵌入/脱出过程中引发的体积变化与结构相变等问题，本文系统总结了元素掺杂与比例调控、形貌与结构优化、复合策略以及结晶水与空位调控四类改性策略。在此基础上，本文进一步以金属离子的价态为分类依据，将PBAs在水系电池中的应用系统地划分为二价离子体系（Zn

、Mg

、Cu

、Ca

、Fe

）与三价离子体系（Al

），并总结了其在不同体系中的电化学性能，以期为AMMBs中PBAs正极材料的研究提供理论与实验参考。

Abstract

Aqueous multivalent metal-ion batteries (AMMBs) represent a promising alternative to lithium-ion batteries for large-scale energy stora

ge owing to their low cost

high natural abundance

environmental friendliness

and intrinsic safety. Cathode materials with stable structures and rapid ion-diffusion channels are crucial for the development of high-performance AMMBs. Prussian blue analogues (PBAs) are considered highly promising cathode materials for AMMBs because of their open three-dimensional framework

abundant redox-active sites

and tunable elemental composition. Despite these advantages

PBAs still face several challenges in practical applications. To address the inherent limitations of PBAs

such as poor crystallographic water/vacancy stability and low intrinsic electronic conductivity

as well as volume changes and structural phase transitions induced by the insertion/deinsertion of multivalent ions during the process

this review systematically summarizes four categories of modification strategies: element doping and stoichiometric tuning

morphology and structure optimization

composite material strategies

and crystallographic water/vacancy engineering. Based on these strategies

this study further classifies the applications of PBAs in aqueous batteries according to the valence states of metal ions

dividing them into divalent-ion systems (Zn

and Fe

) and trivalent-ion systems (Al

)

and summarizes their electrochemical performance in different systems. It provides theoretical and experimental guidance for future research on PBAs as cathode materials in AMMBs.

关键词

Keywords

references

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