硅酸盐学报

普鲁士蓝材料在水系离子电池中的研究进展

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罗雯 ¹^,² , 许骥玉 ¹ , 傅凯 ² , 蔡红伟 ²

硅酸盐学报 | 综合评述 2026,54(3): 1161-1176

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硅酸盐学报 |综合评述 2026 , 54 (3) : 1161 -1176

普鲁士蓝材料在水系离子电池中的研究进展

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罗雯¹^,², 许骥玉¹, 傅凯², 蔡红伟²

作者信息

^1．武汉理工大学物理与力学学院，武汉 430070

^2．材料复合新技术国家重点实验室，武汉 430070

作者简介:

罗雯（1991—），女，博士，副教授。

Development on Prussian Blue for Aqueous Ion Batteries

Wen LUO¹^,², Jiyu XU¹, Kai FU², Hongwei CAI²

Affiliations

^1.School of Physics and Mechanics, Wuhan University of Technology, Wuhan 430070, China

^2.State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

LUO Wen (1991-), female, Ph.D., Associate Professor. E-mail: luowen_1991@whut.edu.cn

出版时间: 2026-03-20 doi: 10.14062/j.issn.0454-5648.20250176

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摘要

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水系离子电池由于具有低成本和高安全性等优点，在规模储能场景下被认为具有广阔的应用前景，近年来发展迅速。在各种水系离子电池电极材料体系中，普鲁士蓝类似物（PBAs, A₂T[M（CN）₆]，其中，A=Li, K, Na; T=Fe, Co, Ni, Mn, Cu，等；M=Fe, Mn, Co，等）由于其大的开放框架、丰富的离子嵌入位点和易于制备的特点，已经成为具有良好电化学性能的、有发展前景的材料之一。本文系统总结普鲁士蓝类似物材料的结构、合成策略以及其在水系锂离子、钠离子、钾离子、铵根离子和质子电池中的应用，同时，还指出了PBAs材料在未来作为水系离子电池电极材料发展中存在的关键挑战。

关键词

普鲁士蓝材料 / 电极材料 / 电化学储能 / 水系离子电池

Abstract

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Aqueous ion batteries have attracted recent attention due to their low cost, high safety, and environmental friendliness, making them a promising alternative to conventional lithium-ion batteries. Among the various electrode materials explored for aqueous ion batteries, Prussian blue analogues (PBAs), with the general formula A₂T[M(CN)₆] (where A = Li, Na, K; T = Fe, Co, Ni, Mn, Cu; and M = Fe, Mn, Co), emerge as a highly promising class of materials. PBAs are characterized by their large open frameworks, abundant ion insertion sites, and ease of synthesis, which contribute to their superior electrochemical performance. This review systematically summarizes the structural properties, synthesis strategies, and applications of PBAs in aqueous lithium-ion, sodium-ion, potassium-ion, and ammonium-ion batteries, while addressing the key challenges and future directions for their development.

The crystal structure of PBAs, determined by X-ray diffraction, consists of a face-centered cubic (FCC) framework, where Fe³⁺ and M²⁺ ions are octahedrally coordinated to the carbon and nitrogen atoms of cyanide groups, respectively. This structure creates a three-dimensional porous network capable of accommodating various guest ions. PBAs, which are derived via substituting Fe with other transition metals (i.e., Cr, V, Mn, Co, Ni, and Cu), retain the same structural framework, but exhibit enhanced electrochemical properties due to the presence of dual redox-active centers (i.e., Fe³⁺/Fe²⁺ and M³⁺/M²⁺). These redox pairs enable high theoretical capacities and reaction potentials, making PBAs suitable for high-performance battery applications.

However, PBAs often suffer from structural defects, such as Fe(CN)₆ vacancies, which can compromise their electrochemical stability. These vacancies, typically formed during rapid precipitation, can lead to a structural collapse during cycling, particularly in systems involving multi-electron reactions. To mitigate these issues, researchers have developed some strategies to synthesize low-defect PBAs with an improved structural integrity and cycling stability.

PBAs can be synthesized by various methods, i.e., co-precipitation, hydrothermal synthesis, and single-precursor approaches. Co-precipitation as one of the most common methods involves the reaction of Fe³⁺ salts with [Fe²⁺(CN)₆]^4- in aqueous solutions, resulting in the formation of PB or its analogues. Hydrothermal synthesis involves the production of well-crystallized PBAs with controlled morphologies at high temperatures and pressures. The single-precursor method, which relies on the slow release of Fe³⁺ or Fe²⁺ ions from [Fe(CN)₆]^4-or [Fe(CN)₆]^3- precursors, offers a route to highly mono-dispersive PBA nanoparticles.

Despite the widespread use of lithium-ion batteries, their application in aqueous systems is limited due to the poor compatibility of PBAs with hydrated Li⁺ ions. The small ionic radius of Li⁺ leads to a structural instability in PBAs, thus having a rapid capacity decay. However, recent studies have explored the use of salt-in-water electrolytes to improve the reversibility of Li⁺ insertion in PBAs, offering a potential pathway for their application in aqueous lithium-ion batteries.

Aqueous sodium-ion batteries with their low cost and natural abundance of sodium emerge as a viable alternative to lithium-ion batteries. PBAs, particularly those based on Fe, Mn, and Co, have the excellent performance in sodium-ion batteries due to their ability to accommodate larger Na⁺ ions. For instance, FeFe-PBAs and MnFe-PBAs exhibit high specific capacities and long cycle lives, making them attractive candidates for grid-scale energy storage. However, the presence of structural vacancies remains a challenge as they can lead to capacity fading during cycling.

Aqueous potassium-ion batteries face some challenges due to the large ionic radius of K⁺, which can cause significant volume changes during cycling. PBAs with their large interstitial spaces are well-suited for K⁺ insertion and demonstrate high reaction potentials and excellent cycling stability. For instance, K₂NiFe(CN)₆ has a remarkable performance with a high capacity retention over thousands of cycles. In addition, mixed-ion systems, such as Na⁺/K⁺ hybrid batteries, are also developed to leverage the advantages of both ions, further enhancing the performance of PBAs in potassium-ion batteries.

Aqueous ammonium-ion batteries, though less explored, offer unique advantages due to the large ionic radius of NH₄⁺, which matches well with the interstitial spaces in PBAs. This compatibility results in high reaction potentials and stable cycling. Recent studies have demonstrated that PBAs such as CuFe-PBAs can achieve high specific capacities and excellent cycle life in NH₄⁺batteries, particularly when paired with Zn anodes. However, the development of full-cell configurations remains a challenge due to the limited availability of NH₄⁺-compatible anodes.

Aqueous proton batteries, though less common, have shown a potential due to the unique transport mechanism of protons in PBAs. Protons can rapidly diffuse through the hydrogen-bonded water networks within the PBA structure, enabling a high-rate performance. PBAs such as Na₀·₄(VO)₃[Fe(CN)₆]₂·12H₂O demonstrate high capacities and excellent cycling stability in acidic electrolytes, making them promising candidates for high-power applications.

Despite the development of PBAs for aqueous ion batteries, several challenges still remain. The presence of structural vacancies and water in the PBA framework can lead to a capacity fading and a structural instability during cycling. Future research should focus on understanding the mechanisms of vacancy formation and developing strategies to eliminate these defects. In addition, the optimization of electrolyte composition and the enhancement of electronic conductivity in PBAs are also critical for improving their performance in practical applications.

In conclusion, PBAs represent a versatile and promising class of materials for aqueous ion batteries, offering high capacities, long cycle lives, and superior rate capabilities. PBAs have a potential to play a key role in the development of next-generation energy storage systems via addressing the existing challenges and further exploring their electrochemical properties.

Key words

Prussian blue analogues materials / electrode material / electrochemical energy storage / aqueous ion batteries

引用本文

罗雯, 许骥玉, 傅凯, 蔡红伟. 普鲁士蓝材料在水系离子电池中的研究进展. 硅酸盐学报, 2026 , 54 (3) : 1161 -1176 . DOI: 10.14062/j.issn.0454-5648.20250176

Wen LUO, Jiyu XU, Kai FU, Hongwei CAI. Development on Prussian Blue for Aqueous Ion Batteries[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (3) : 1161 -1176 . DOI: 10.14062/j.issn.0454-5648.20250176

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国家自然科学基金重大研究计划培育项目(92472108)

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2026年第54卷第3期

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doi: 10.14062/j.issn.0454-5648.20250176

接收时间：2025-03-14
首发时间：2026-10-27
出版时间：2026-03-20

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收稿日期：2025-03-14
修回日期：2025-03-25

基金

国家自然科学基金重大研究计划培育项目(92472108)

作者信息

^1．武汉理工大学物理与力学学院，武汉 430070

^2．材料复合新技术国家重点实验室，武汉 430070

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250176

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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