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中国物理学会期刊

水系锰基储能体系中的电子-晶格耦合、界面电荷转移与非平衡输运

Aqueous manganese-based energy storage systems: Electron-lattice coupling, interfacial charge transfer, and non-equilibrium transport

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  • 水系锰基储能体系兼具高安全性、低成本与较高理论容量, 是面向规模储能的重要候选体系. 然而, 多价离子强水合、强静电相互作用及锰氧化物可变价结构, 使其储能过程同时受电子-晶格耦合、固液界面电荷转移和多孔电极非平衡输运支配. 本文从物理学视角梳理水系锰基电极中的3个关键问题: Mn3+轨道简并诱发的Jahn-Teller畸变及其晶格动力学后果; 界面极化场、局域电荷分布与溶剂化结构对Zn2+脱溶剂化和电荷转移能垒的调控; 高载量电极中活化、溶解-沉积、相重构与离子输运受限的耦合机制. 在此基础上, 本文进一步总结多电位阶跃、原位谱学、电化学阻抗与物理建模在动力学参数解析中的作用. 最后, 针对多价离子关联输运、宽温储能物理和真实工况下界面稳定性等问题进行展望, 以期为水系锰基储能体系的物理理解与材料设计提供参考.

     

    Aqueous manganese-based energy storage systems offer high safety, low cost, and relatively high theoretical capacity, making them promising candidates for large-scale energy storage. However, owing to the strong hydration of multivalent ions, intense electrostatic interactions, and the multiple accessible valence states of manganese oxides, their electrochemical storage processes are jointly governed by electron-lattice coupling, charge transfer across solid-liquid interfaces, and non-equilibrium transport in porous electrodes. From a physics perspective, this review focuses on three key issues: the Jahn-Teller distortion associated with the orbital degeneracy of high-spin Mn3+ and its consequences for lattice stability and structural evolution; the regulation of Zn2+ desolvation and charge-transfer barriers by interfacial polarization fields, local charge distributions, and solvation structures; and the coupled mechanisms of electrochemical activation, dissolution-deposition, phase reconstruction, and ion-transport limitations in high mass loading electrodes. These processes are integrated into a multiscale framework linking orbital occupation and local lattice strain to interfacial kinetics and macroscopic electrode transport. On this basis, the roles of multi-potential-step measurements, in situ spectroscopy, electrochemical impedance spectroscopy, and physics-based modeling in extracting kinetic parameters and identifying reaction pathways are summarized. The analysis further indicates that optimizing aqueous manganese-based energy storage requires coordinated regulation of Mn valence states, lattice stability, interfacial solvation structures, and coupled electron/ion transport, rather than isolated improvement of a single performance metric. Finally, future challenges involving correlated multivalent-ion transport, operation over a wide temperature range, and interfacial stability under practically relevant conditions are discussed, with the aim of advancing the fundamental understanding and rational design of aqueous manganese-based energy-storage systems.

     

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