Asymmetric Mn 2+ Cluster Electrolyte for High‐Performance Mn‐Metal Batteries

作者：Jian Zhang, Fang Chen, Jixing Yu, Qing Lang, Zhiyi Liu, L. Chen, Gang Wang · 发表于：Advanced Functional Materials · 年份：2025 · DOI：10.1002/adfm.202515536 · 被引用次数：4 · 研究领域：Advanced Battery Materials and Technologies、Advanced battery technologies research、Advancements in Battery Materials

Abstract Due to the high natural abundance and low redox potential, Mn metal is an attractive anode material for post‐Li batteries. A key challenge of Mn‐metal batteries (MnMBs) lies at the unsatisfying ionic conductivity of the present non‐aqueous electrolyte. In this work, an asymmetric tetramethylene sulfone (TMS)‐coordinated Mn 2 (µ‐Cl)Cl 2 (TMS) x (TFSI) y n + (TFSI: bistrifluoromethanesulfonimide) cluster electrolyte is reported for MnMBs. Benefitting from the asymmetric solvation structure of Mn 2+ and high‐dielectric constant TMS, the concentration is improved over 1 m with a high ionic conductivity of 4.68 mS cm −1 . Impressively, reversible Mn plating‐stripping is realized under high current rates (up to 8 mA cm −2 ), high areal capacity (1–10 mAh cm −2 ), and even in a wide temperature range (−40 to 60 °C). The electrolyte composition is parsed as TMS‐coordinated Mn 2 Cl 3 + , AlCl 2+ , AlCl 2 + , and Al(TFSI) 3 Cl − . A hybrid MnMBs is thus proposed based on AlCl 2+ insertion/extraction at an organic cathode and Mn plating‐stripping. The hybrid battery delivers a specific capacity over 100 mAh g −1 , a high output voltage of 1.0 V, excellent rate performance and a long cycle life (>2000 cycles) at both low and high temperatures (−30 and 60 °C), much superior over state‐of‐the‐art MnMBs. The work demonstrates the significance of the cluster structure of Mn 2+ and their influence on Mn‐ion electrolyte and MnMBs.