Pyun Jangwook, Lee Hyungjin, Lee Hyeonjun, Kwon Hyeju, Lee Hyeongseok, Hong Seung-Tae, Lee Woo-Jae, Chae Munseok S
Department of Nanotechnology Engineering, Pukyong National University, Busan, 48547, Republic of Korea.
Department of Energy Science and Engineering, DGIST, Daegu, 42988, Republic of Korea.
Small. 2025 Aug;21(31):e2504200. doi: 10.1002/smll.202504200. Epub 2025 Jun 5.
Mn-based energy storage systems are gaining attention as promising candidates for next-generation aqueous batteries, owing to their higher theoretical energy density and capacity compared to conventional Zn-based systems. This advantage is primarily attributed to the lower standard redox potential of the Mn anode (-1.19 V vs SHE) relative to that of Zn (-0.76 V vs SHE). In this study, an Mn⁺/H⁺ hybrid aqueous battery system utilizing LiV₃O₈ is presented as the cathode material, which delivers a high specific capacity of 204.58 mAh g and excellent capacity retention of 76.2% after 7,000 cycles. The charge storage mechanism of LiV₃O₈ is thoroughly investigated through structural characterization, as well as diffusion pathway and energy barrier analyses. Proton insertion is identified as the dominant charge carrier and is found to induce the formation of Mn(OH)₂ on the electrode surface, as confirmed by spectroscopic techniques. Notably, the Mn//LiV₃O₈ cell achieved an operating voltage of 1.1-0.2 V higher than that of the conventional Zn//LiV₃O₈ cell. This study underscores the potential of Mn⁺/H⁺ hybrid systems as next-generation aqueous batteries and offers a comprehensive understanding of the associated reaction mechanisms, providing valuable guidance for the future design of Mn-based aqueous energy storage technologies.
基于锰的储能系统作为下一代水系电池的有前景候选者正受到关注，这是因为与传统的锌基系统相比，它们具有更高的理论能量密度和容量。这一优势主要归因于锰负极相对于锌负极（相对于标准氢电极，锌为-0.76 V，锰为-1.19 V）较低的标准氧化还原电位。在本研究中，提出了一种利用LiV₃O₈作为正极材料的Mn⁺/H⁺混合水系电池系统，该系统具有204.58 mAh g的高比容量，并且在7000次循环后具有76.2%的优异容量保持率。通过结构表征以及扩散途径和能垒分析，对LiV₃O₈的电荷存储机制进行了深入研究。质子插入被确定为主要的电荷载体，并发现其会在电极表面诱导形成Mn(OH)₂，这已通过光谱技术得到证实。值得注意的是，Mn//LiV₃O₈电池的工作电压比传统的Zn//LiV₃O₈电池高1.1 - 0.2 V。本研究强调了Mn⁺/H⁺混合系统作为下一代水系电池的潜力，并提供了对相关反应机制的全面理解，为未来基于锰的水系储能技术的设计提供了有价值的指导。
