硅酸盐学报

锰氧化物在水系电池中的研究进展与挑战

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杜玲玉 ¹ , 毕嵩山 ² , 牛志强 ²

硅酸盐学报 | 综合评述 2024,52(1): 273-291

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硅酸盐学报 |综合评述 2024 , 52 (1) : 273 -291

锰氧化物在水系电池中的研究进展与挑战

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杜玲玉¹, 毕嵩山², 牛志强²

作者信息

^1．烟台大学环境与材料工程学院，山东烟台 264005

^2．南开大学化学学院，天津 300071

通讯作者:

牛志强（1983—），男，博士，研究员。

作者简介:

杜玲玉（1991—），女，博士，讲师。

Progress and Challenges of Manganese Oxides in Aqueous Rechargeable Batteries

Lingyu DU¹, Songshan BI², Zhiqiang NIU²

Affiliations

^1.School of Environmental and Material Engineering, Yantai University, Yantai 264005, Shandong, China

^2.College of Chemistry, Nankai University, Tianjin 300071, China

Corresponding Author:

NIU Zhiqiang (1983-), male, Ph.D., Professor. E-mail: zqniu@nankai.edu.cn

DU Lingyu (1991-), female, Lecturer. E-mail: dulychem@nankai.edu.cn

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230454

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摘要

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水系二次电池因其安全性高、成本低以及对环境友好等特点，在大规模储能领域展现出广阔的应用前景。电极材料作为电池的关键组成部分，其性质直接影响电池电化学性能。锰氧化物具有晶体结构丰富、理论比容量高、氧化还原电位高、成本低等优势，被认为是最具发展潜力的正极材料之一。然而，锰氧化物存在导电性差、结构不稳定、锰溶解等问题，使电池面临倍率和循环性能差的严峻挑战，限制了其实际应用。此外，锰氧化物的反应机制较为复杂。针对上述问题，本文通过调研有关锰氧化物的文献，首先分析了其晶体结构类型和特点，进一步按照电解液酸度梳理归纳了锰氧化物在（弱）酸性和碱性条件下的反应机制，简要阐述了其在水系碱金属离子、多价金属离子以及非金属离子二次电池体系的研究进展，最后对未来高性能锰氧化物正极的发展方向进行了展望。

关键词

水系电池 / 锰氧化物 / 晶体结构 / 反应机制

Abstract

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Aqueous rechargeable batteries have great prospects in the field of large-scale energy storage due to their high safety, low cost, and environmental friendliness. As a key component of batteries, electrode materials play important roles on their electrochemical performance. Vanadium oxides, manganese oxides, Prussian blue analogues, and organic materials are often used as active materials in aqueous batteries. Among these materials, vanadium oxides possess a variety of compounds, high theoretical specific capacity, and superior cycling performance. However, their redox potential is relatively low, restricting the operating voltage of aqueous batteries. Moreover, these materials are toxic, which are not conducive in the large-scale applications. Compared with vanadium oxides, Prussian blue analogues have a higher redox potential and a stable structure, but they have some disadvantage of low theoretical specific capacity, resulting in the low energy density of batteries. In contrast, organic materials possess abundant sources, facile structure regulation, and superior sustainability. However, their poor conductivity and low compaction density make it difficult to prepare high-loading electrodes. Compared with the materials above, manganese oxides have the advantages of diverse crystal structures, high theoretical specific capacity, high redox potential, non-toxicity, and low cost, which are beneficial for constructing high-performance aqueous batteries. Therefore, manganese oxides are considered as a promising electrode material in aqueous batteries. Recent efforts are made in the design of manganese oxides-based aqueous batteries, but the corresponding comprehensive review on this topic is still sparse.

This review firstly analyzed the crystal structure types and characteristics of manganese oxides. According to the connection mode between MnO₆ units, the crystal structure of manganese oxides can be divided into one-dimensional tunneled structure (i.e., α-MnO₂, β-MnO₂, γ-MnO₂, R-MnO₂, Todorokite-MnO₂), two-dimensional layered structure (i.e., δ-MnO₂), and three-dimensional spinel structure (i.e., λ-MnO₂, Mn₃O₄, LiMn₂O₄, ZnMn₂O₄). The characteristics of corresponding crystal structure were summarized. Manganese oxides exhibited unique physical and chemical properties, endowing their wide application as electrode materials in aqueous batteries.

The reaction mechanisms of manganese oxides are rather complex in aqueous batteries, especially for aqueous zinc-ion batteries, which were summarized according to the acidity of electrolytes. In alkaline Zn-MnO₂ batteries, MnO₂ is firstly converted into MnOOH, and then Mn(OH)₂ is formed. As the acidity of the electrolyte decreases, manganese oxides exhibit different electrochemical reactions, mainly including ion insertion-extraction, conversion, and dissolution-deposition (Mn²⁺/MnO₂). The different electrochemical reaction mechanisms of manganese oxides provide plentiful energy storage chemistry for the design of aqueous battery systems. However, there are also irreversible side reactions and structural distortions in manganese oxides during the cycling process, which hinder their further development.

The application of manganese oxides in aqueous batteries is briefly elaborated, including alkaline-metal-ions (such as Li⁺, Na⁺), multivalent-metal-ions (such as Zn²⁺, Mg²⁺, Al³⁺), and non-metallic-ions (such as H⁺, NH₄⁺) batteries. To address the poor conductivity, unstable structure, as well as manganese dissolution of manganese oxides, nanostructure design, hetero-element doping, defect engineering, and composite construction with other conductive materials are adopted to regulate the electronic structure and alleviate the Jahn-Teller distortion. As a result, the rate capability and cycling stability of manganese oxides-based aqueous batteries are significantly improved.

Summary and Prospects

Although significant progress has been achieved in the design of manganese oxides for the electrodes of aqueous batteries, great challenges still remain in the scientific researches and practical application. The reaction mechanisms of manganese oxides are relatively complex, compared with those of other electrode materials. The reaction processes are also different for the same crystal structure. It is thus necessary to conduct the systematic and comprehensive investigation. The detailed structure evolution of manganese oxides could be revealed during electrochemical reaction process through some advanced in-situ characterization techniques (i.e., electrochemical quartz crystal microbalance, cryo-electron microscopy, X-ray photon-electron spectroscopy). The poor structure stability and manganese dissolution of manganese oxides result in the capacity attenuation upon cycling. The precise structure optimization strategies are urgently needed to suppress the Jahn-Teller distortion and enhance structural stability, such as interface interaction regulation through introducing carbon materials and other functional materials into the composites, valence state adjustment of manganese elements through anionic doping. Furthermore, the development of novel electrolyte systems also plays a crucial role in the improvement of electrochemical performances for manganese oxides-based aqueous batteries. High-concentrated electrolytes, molecular-crowding electrolytes, hydrated-eutectic electrolytes, and organic/inorganic hybrid electrolytes could reduce free water content and water molecule activity, regulate the solvation structure, which would be beneficial for suppressing manganese dissolution and promoting reaction kinetics. In addition, the diverse reactions of manganese oxides could be also utilized by adjusting the pH value of the electrolytes, thus developing the electrochemical energy storage devices with a high voltage, high capacity, and high rate capability. The electrochemical performance of manganese oxide electrodes with a high mass loading could be improved by the synergistic effect of material structure design and electrolyte optimization. Finally, some controllable methods of manganese oxides in a largescale could be further developed for the industrial application of aqueous batteries.

Key words

aqueous batteries / manganese oxides / crystal structure / reaction mechanism

引用本文

杜玲玉, 毕嵩山, 牛志强. 锰氧化物在水系电池中的研究进展与挑战. 硅酸盐学报, 2024 , 52 (1) : 273 -291 . DOI: 10.14062/j.issn.0454-5648.20230454

Lingyu DU, Songshan BI, Zhiqiang NIU. Progress and Challenges of Manganese Oxides in Aqueous Rechargeable Batteries[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (1) : 273 -291 . DOI: 10.14062/j.issn.0454-5648.20230454

基金

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国家重点研究计划(2019YFA0705600)
国家自然科学基金(21875121)

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2024年第52卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230454

接收时间：2023-06-30
首发时间：2026-10-22
出版时间：2024-01-20

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收稿日期：2023-06-30
修回日期：2023-08-03

基金

国家重点研究计划(2019YFA0705600)

国家自然科学基金(21875121)

作者信息

^1．烟台大学环境与材料工程学院，山东烟台 264005

^2．南开大学化学学院，天津 300071

通讯作者:

牛志强（1983—），男，博士，研究员。

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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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