Sun Yuwei, Wang Chen, Gao Ling, Wang Tan, Huang Yunhui, Fu Jing
School of Materials Science and Engineering, Tongji University, Shanghai, 201804, P.R. China.
School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, P.R. China.
Angew Chem Int Ed Engl. 2025 Sep 15;64(38):e202512463. doi: 10.1002/anie.202512463. Epub 2025 Aug 1.
Acidic aqueous metal─MnO rechargeable batteries enable high-capacity energy storage via a two-electron MnO/Mn redox chemistry but suffer from severe anode corrosion and poor reversibility in acidic environments. Here, we report an acidic In─MnO battery (IMB) system that employs anion-regulated interfacial chemistry to enable reversible deposition-dissolution reactions at both electrodes. The In/In redox couple offers a favorable potential that mitigates acidic corrosion while matching the MnO two-electron redox. Systematic investigation of anion effects reveals that concentrated Cl anions restructure the In solvation, forming stable chloro-complexes that lower dissociation energy and promote uniform Indium (In) deposition. Conversely, SO -rich electrolytes impede In plating but enhance MnO crystallization and MnO/Mn reversibility. Through tailored Cl/SO ratios and an anion-decoupled dual-electrolyte configuration, the battery operates at ∼1.7 V with 72.3% energy efficiency (EE) and over 1500 cycles at 5 mA cm. Furthermore, we demonstrate an electrode-less IMB using a Bi substrate at the anode, where in situ alloying-driven In deposition enables over 2000 stable cycles at 4 mA cm (2 mAh cm), delivering a compelling energy density of 484.5 Wh kg and a high cumulative areal capacity of 4120 mAh cm. This work establishes a design paradigm coupling anion-regulated interfacial chemistry with substrate engineering for high-performance acidic IMB.
酸性水系金属-二氧化锰可充电电池通过双电子MnO/Mn氧化还原化学实现高容量储能，但在酸性环境中会遭受严重的阳极腐蚀且可逆性较差。在此，我们报道了一种酸性铟-二氧化锰电池（IMB）系统，该系统采用阴离子调控的界面化学，使两个电极都能发生可逆的沉积-溶解反应。In/In氧化还原对提供了一个有利的电位，可减轻酸性腐蚀，同时与MnO的双电子氧化还原相匹配。对阴离子效应的系统研究表明，高浓度的Cl-阴离子会重构In的溶剂化结构，形成稳定的氯配合物，降低离解能并促进均匀的铟（In）沉积。相反，富含SO的电解质会阻碍In的电镀，但会增强MnO的结晶和MnO/Mn的可逆性。通过调整Cl/SO的比例和采用阴离子解耦的双电解质配置，该电池在~1.7 V下运行，能量效率（EE）为72.3%，在5 mA cm下可循环超过1500次。此外，我们展示了一种在阳极使用Bi衬底的无电极IMB，其中原位合金化驱动的In沉积在4 mA cm（2 mAh cm）下可实现超过2000次的稳定循环，提供了令人瞩目的484.5 Wh kg的能量密度和4120 mAh cm的高累积面积容量。这项工作建立了一种将阴离子调控的界面化学与衬底工程相结合的设计范式，用于高性能酸性IMB。
