物理化学学报 >> 2026, Vol. 42 >> Issue (10): 100226.doi: 10.1016/j.actphy.2025.100226

所属专题： 二次电池先进正极材料

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可充电镁金属电池无机正极材料研究进展

朱彩霞1, 李婷3, 徐飞2,*(), 董程远4, 张逸捷1, 方永进1, 曹余良1,*()   

  1. 1 武汉大学化学与分子科学学院, 电化学电源湖北省重点实验室, 湖北 武汉 430072
    2 武汉大学动力与机械学院, 水力机械过渡过程教育部重点实验室, 湖北 武汉 430072
    3 中南民族大学催化与能源材料化学教育部重点实验室, 湖北省催化与材料科学重点实验室, 湖北省超支化聚合物合成与应用研发中心, 湖北 武汉 430074
    4 清华大学车辆与运载学院, 北京 100084
  • 收稿日期:2025-10-15 修回日期:2025-11-12 录用日期:2025-11-27 发布日期:2026-09-03
  • 通讯作者: Email: xufei2058@whu.edu.cn (徐飞)ylcao@whu.edu.cn (曹余良)

Recent advances in inorganic cathodes for rechargeable magnesium metal batteries

Caixia Zhu1, Ting Li3, Fei Xu2,*(), Chengyuan Dong4, Yijie Zhang1, Yongjin Fang1, Yuliang Cao1,*()   

  1. 1 College of Chemistry & Molecular Science, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, Hubei Province, China
    2 Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, Hubei Province, China
    3 Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education, Hubei Key Laboratory of Catalysis and Materials Science, Hubei R&D Center of Hyperbranched Polymers Synthesis and Applications, South-Central Minzu University, Wuhan 430074, Hubei Province, China
    4 School of Vehicle and Mobility, Tsinghua University, Beijing 100084, China
  • Received:2025-10-15 Revised:2025-11-12 Accepted:2025-11-27 Published:2026-09-03
  • Contact: Email: xufei2058@whu.edu.cn (Fei Xu)ylcao@whu.edu.cn (Yuliang Cao)

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摘要：

在可持续发展需求驱动下，开发后锂离子电化学储能体系已成为当前的研究焦点。可充电镁金属电池(RMBs)凭借金属镁负极资源丰度高、体积比容量大及无枝晶沉积的安全特性，展现出突出的下一代储能技术潜力。近年来镁兼容电解液的突破性进展有效破解了负极钝化和低库仑效率等难题，推动RMBs研究迈入新阶段。然而，二价镁离子的强极化效应与高电荷密度特征，使其与正极材料间产生强静电力作用，导致缓慢的固态扩散动力学，这成为制约RMBs能量密度与循环稳定性的核心瓶颈。本文系统梳理了RMBs无机正极材料的最新进展，重点针对聚阴离子化合物、氧化物、硫化物和硒化物四大类材料体系展开分析，探究了材料结构、电化学性能与镁离子存储机制之间的关联，既讨论了重大进展也分析了持续存在的问题，从聚阴离子化合物的循环寿命到氧化物的动力学障碍，再到硫属化合物的穿梭效应等等。在此基础上，总结了应对这些挑战的有效材料工程策略，包括缩短扩散路径的纳米结构设计、增强导电性的复合工程、促进离子传输的层间扩展、创造活性位点的缺陷调控、非晶化处理以及稳定晶体结构的元素掺杂等。针对特定材料局限性，合理整合上述策略对突破当前性能瓶颈至关重要。期望未来研究重点发展先进原位/工况表征技术，探索新型正极材料设计范式，并致力于电极-电解质体系的协同匹配。本综述旨在为设计高性能RMBs正极材料提供理论支持，推动可充电镁金属电池的技术进步与实际应用。

关键词: 可充电镁金属电池, 无机正极, 氧化物, 硫化物, 硒化物

Abstract:

Advancing electrochemical energy storage beyond lithium-ion technologies has become increasingly critical in response to sustainable development. Rechargeable magnesium metal batteries (RMBs), recognized for their inherent advantages in resource abundance, potential for higher volumetric capacity, and enhanced safety characteristics due to the dendrite-free plating of magnesium, stand out as highly promising for next-generation energy storage. Recent breakthroughs in magnesium-compatible electrolytes have effectively overcome longstanding issues of anode passivation and low coulombic efficiency, thereby accelerating RMB research into a new stage of development. However, the practical application of RMBs continues to face significant challenges, predominantly centered on cathode materials. These challenges primarily stem from the strong polarization and high charge density of divalent Mg2+ ions, which lead to strong electrostatic interactions with the host cathode materials, resulting in sluggish solid-state diffusion kinetics that limit achievable energy density and cycling stability. To systematically address these hurdles and promote the development of cathode materials, this review provides a comprehensive summary of recent progress in inorganic cathode materials for RMBs, focusing on four major categories: polyanionic compounds, oxides, sulfides, and selenides. For each class, we delve into the relationships between crystal structure, electrochemical performance, and Mg2+ storage mechanism, discussing both significant advances and persistent issues. Each material class faces distinct limitations, from short lifespan in polyanionic compounds to kinetic barriers in oxides and shuttle effects in chalcogenides. From this survey, we summarize effective material engineering strategies to address these challenges, which include nanostructural design to shorten diffusion pathways, composite engineering to enhance conductivity, interlayer expansion to facilitate ion transport, defect modulation to create active sites, amorphization, and elemental doping to stabilize crystal structures. The rational integration of these strategies tailored to specific material limitations is crucial for breaking the current performance ceiling. Future research should emphasize advanced in situ/operando characterization, explore new cathode design paradigms, and pursue synergistic electrode-electrolyte pairings. This review aims to provide theoretical fundamentals for the rational design of high-performance cathode materials, promoting the technological advancement and practical application of RMBs.

Key words: Rechargeable magnesium metal battery, Inorganic cathode, Oxide, Sulfide, Selenide