硅酸盐学报

锌离子电池正极材料MnO₂/rGO的研究进展

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乔明涛 ¹ , 刘畅 ¹ , 苟倩誌 ² , 田玉蕾 ¹ , 魏剑 ¹

硅酸盐学报 | 综合评述 2026,54(3): 1148-1160

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硅酸盐学报 |综合评述 2026 , 54 (3) : 1148 -1160

锌离子电池正极材料MnO₂/rGO的研究进展

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乔明涛¹, 刘畅¹, 苟倩誌², 田玉蕾¹, 魏剑¹

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．西安建筑科技大学建筑设备科学与工程学院，西安 710055

通讯作者:

乔明涛（1989—），男，博士，副教授

苟倩誌（1993—），男，博士，副教授。

作者简介:

乔明涛（1989—），男，博士，副教授。

Research Progress of MnO₂/rGO as Cathode Materials for Zinc Ion Batteries

Mingtao QIAO¹, Chang LIU¹, Qianzhi GOU², Yulei TIAN¹, Jian WEI¹

Affiliations

^1.School of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 71055, China

^2.School of Building Services Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

Corresponding Author:

QIAO Mingtao (1989-), male, Ph.D., Associate Professor. E-mail: mtqiao@xauat.edu.cn

GOU Qianzhi (1993-), male, Ph.D., Associate Professor. E-mail: gqz813@xauat.edu.cn

QIAO Mingtao (1989-), male, Ph.D., Associate Professor. E-mail: mtqiao@xauat.edu.cn

出版时间: 2026-03-20 doi: 10.14062/j.issn.0454-5648.20250180

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摘要

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锌离子电池（ZIBs）因环境友好、成本低、容量高且氧化还原电位适宜等优点，在可再生能源中展现出广阔的应用前景。与锌负极相匹配的众多正极材料中，锰氧化物价态多样、价格低廉，成为当前最有潜力的正极材料。然而，锰氧化物仍存在着结构坍塌、电极溶解和副产物复杂等问题，同时，ZIBs的储能机理存在争议，严重制约了锰氧化物正极材料的进一步发展。还原氧化石墨烯（rGO）具有独特的二维结构和优异的柔韧性、导电性，使其可作为导电基底与锰基氧化物复合。这不仅提高了锰氧化物的比容量，还能改善MnO₂的比表面积，防止团聚。本文综述了MnO₂/rGO纳米复合材料在锌离子电池正极材料方面的研究进展；对比分析3种不同晶型MnO₂（α、δ和γ）的结构特点，探讨出最适合ZIBs的MnO₂晶型；揭示出最有益于电池循环稳定性的MnO₂/rGO制备方式；探寻储能机理中的共性规律；并对高性能ZIBs正极材料的发展方向与优化策略进行展望。

关键词

锌离子电池 / 二氧化锰 / 还原氧化石墨烯 / 储能机理

Abstract

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Limited lithium resources and potential safety/environmental issues restrict the further development of lithium-ion batteries (LIBs). There exists an urgent need to develop new green batteries. Compared with organic electrolytes, aqueous electrolytes are environmentally friendly, inexpensive, and have a high ionic conductivity. Among them, zinc ion batteries (ZIBs) using aqueous electrolytes become a focus of recent research due to their low manufacturing cost, safety and environmental friendliness, as well as their unique properties, such as high abundance of metallic zinc, suitable redox potential (-0.76 V vs. SHE), and high theoretical capacity (823 mA·h·g^-1). So far, the cathode materials suitable for storing zinc ions as ZIBs are manganese-based oxides, vanadium-based oxides, Prussian blue analogs, and organic compounds. Among these materials, vanadium oxides have relatively low redox potentials, Prussian blue analogs have insufficient theoretical specific capacity, and organic materials have poor electrical conductivity, resulting in a poor overall battery performance. In contrast, manganese oxides, with abundant resources, high operating voltage (i.e., 1.0-1.9 V vs. Zn/Zn²⁺), and high theoretical specific capacity (i.e., 308 mA·h·g^-1 for single-molecule reaction, and 616 mA·h·g^-1 for bimolecular reaction), become the most promising cathode materials for development. Meanwhile, manganese oxide faces short board problems such as low intrinsic electronic conductivity and electrode dissolution during charging and discharging, which hinder its further development. Reduced graphene oxide (rGO) has some advantages as a carbon material due to its ultra-high theoretical surface area (2630 m²·g^-1), high electrical conductivity and porosity. Therefore, MnO₂/graphene nanocomposites are prepared using rGO as a conductive substrate in combination with manganese oxides with a high theoretical specific capacity, solving the problem of poor durability performance of manganese oxides and achieving a high specific surface area as well as optimizing the electrical properties.

Focusing on the research progress of MnO₂/rGO nanocomposites in the anode of zinc ion batteries (ZIBs), this review firstly analyzes the structural characteristics of different crystallines MnO₂ (δ, α, γ) to explore the most suitable MnO₂ crystalline for ZIBs. The lattice constant of each unit is 2.3 Å through the connection shared by octahedral [MnO₆] edge and corner sharing connection. The 2D lamellar structure δ-MnO₂ has a relatively wide interlayer spacing (7 Å), and the large distances can accommodate moderate impurity cations. The tunnel structure of α-MnO₂ has large dimensions (i.e., 4.6 Å × 4.6 Å), which can accommodate most of the metal ions and water molecules, and the γ-MnO₂ consists of randomly arranged of 1×1 (2.3 Å× 2.3 Å) and 1×2 (2.3 Å × 4.6 Å) tunnels, which are characterized by hollow, porous, and 1D structures. This review also analyzes the composite mode and performance of different crystallines of MnO₂/rGO to reveal the MnO₂/rGO preparation mode that is most beneficial to the cycling stability of the batteries, explore the common law in the energy storage mechanism, and look forward to the direction of the development of the high-performance ZIBs cathode materials and optimization strategies.

Summary and prospects

1) α-MnO₂ has superior stability and specific capacity. It is attributed to the double-chain structure of α-MnO₂, with a larger average cross-sectional area of tunneling, which is favorable for ion storage. The lamellar structure of δ-MnO₂ is prone to structural deterioration during cycling, leading to the irreversible growth of new phases, and the crystal structure of γ-MnO₂ consists of a random arrangement of 1 × 1 and 1 × 2 tunneling structures, which is unstable and prone to the transformation of the crystalline structure, restricting the insertion/extraction of Zn²⁺.

2) The in-situ-constructed α-MnO₂/rGO belongs to the optimum cathode materials for zinc ion batteries. The in-situ growth method enables the α-MnO₂ arrays to be anchored in the rGO surface layer (110). The Mn atoms on the crystalline surface and the rGO substrate are bonded by Mn-O-C covalent bonds, and the interface is in atomic-level contact, which reduces the charge transfer resistance, promotes the coordination adsorption of Zn²⁺, decreases the activation energy of extraction and blunts the active sites on the surface of rGO, and inhibits the occurrence of side reaction such as a hydrogen precipitation reaction.

3) The energy storage mechanism of MnO₂/rGO cathode material is mainly based on H⁺/Zn²⁺ insertion/extraction, supplemented by other energy storage mechanisms. In the process of H⁺ extraction, the exposure of surface active sites and short diffusion paths are crucial, so the specific surface area and interfacial proton affinity of rGO need to be optimized as a priority. Zn²⁺ extraction is limited by the ionic size and volumetric strain, so it is necessary to strengthen the conductive network and the structural stability and to design a suitable pore structure.

To further enhance the electrochemical performance of zinc ion batteries, the MnO₂/rGO composites still need to be further investigated from the following two aspects in the future:

1) Although the rGO composite strategy improves the performance of MnO₂ to a certain extent, the electrochemical performance of MnO₂/rGO composites can be further enhanced to meet the demands of high-efficiency and long-life zinc ion batteries if combined with a variety of strategies, such as pre-insertion of guest ions, defect engineering, and nanomodulation.

2) MnO₂/rGO cathode materials still face a problem of MnO₂ dissolution, leading to the loss of active material and reducing the battery capacity. Common solutions are to add Mn²⁺ salts to the electrolyte or to use solid-state electrolytes, which are costly and unfavorable for mass production applications. Therefore, exploring low-cost MnO₂ dissolution inhibition strategies will become an important aspect in zinc ion battery research, while the development of flexible, wearable, and high-security electronic devices will be the future development of zinc ion batteries.

Key words

zinc ion battery / manganese dioxide / reduced graphene oxide / energy storage mechanism

引用本文

乔明涛, 刘畅, 苟倩誌, 田玉蕾, 魏剑. 锌离子电池正极材料MnO₂/rGO的研究进展. 硅酸盐学报, 2026 , 54 (3) : 1148 -1160 . DOI: 10.14062/j.issn.0454-5648.20250180

Mingtao QIAO, Chang LIU, Qianzhi GOU, Yulei TIAN, Jian WEI. Research Progress of MnO₂/rGO as Cathode Materials for Zinc Ion Batteries[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (3) : 1148 -1160 . DOI: 10.14062/j.issn.0454-5648.20250180

基金

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国家自然科学基金青年项目(52302112)
陕西省教育厅重点科学研究计划(22JY037; 22JY039)

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2026年第54卷第3期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250180

接收时间：2025-03-17
首发时间：2026-10-27
出版时间：2026-03-20

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出版历史

收稿日期：2025-03-17
修回日期：2025-04-03

基金

国家自然科学基金青年项目(52302112)

陕西省教育厅重点科学研究计划(22JY037; 22JY039)

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．西安建筑科技大学建筑设备科学与工程学院，西安 710055

通讯作者:

乔明涛（1989—），男，博士，副教授

苟倩誌（1993—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250180

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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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