Zhao Yazhen, Chen Shaopeng, Zhou Miao, Pan Ming, Sun Yukun, Zhang Duo, Zhang Shuxin, Wang Yaru, Li Mengyang, Zeng Xiaoqin, Yang Jun, Wang Jiulin, NuLi Yanna
School of Chemistry and Chemical Engineering, Shanghai Electrochemical Energy Devices Research Center, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
State Key Laboratory of Metal Matrix Composite, Shanghai Jiao Tong University Shanghai 200240, P. R. China.
ACS Nano. 2024 Aug 20;18(33):22356-22368. doi: 10.1021/acsnano.4c06653. Epub 2024 Aug 7.
Rechargeable magnesium metal batteries (RMBs) have shown promising prospects in sustainable energy storage due to the high crustal abundance, safety, and potentially large specific capacity of magnesium. However, their development is constrained by the lack of effective cathode materials that can achieve high capacity and stable magnesium storage at a practically reasonable rate. Herein, we construct a three-dimensional (3D) iron(III)-dihydroxy-benzoquinone (Fe(DHBQ)) metal-organic framework (MOF) material with dual redox centers of Fe cations and DHBQ anions for reversible storage of Mg in RMBs. Spectroscopic analysis and density functional theory (DFT) calculations reveal the redox chemistry of both Fe ions and carbonyls from DHBQ ligands during electrochemical processes. Benefiting from the rational structure, the Fe(DHBQ)∥Mg cells exhibit a high reversible capacity of 395.3 mAh/g, large energy density of 463.5 Wh/kg, and high power density of 2456.0 W/kg. Moreover, the high electronic conductivity (8.35 × 10 S/cm) and favorable diffusion path of Mg in Fe(DHBQ) endow the cells with exceptional cycling stability and rate capability with a long life of 5000 cycles at 2000 mA/g. The dual redox-active MOF demonstrates a category of advanced cathode materials for high-performance RMBs.
由于镁在地壳中的丰度高、安全性好且比容量可能较大，可充电镁金属电池（RMBs）在可持续储能方面展现出了广阔的前景。然而，它们的发展受到缺乏有效阴极材料的限制，这些材料需要在实际合理的速率下实现高容量和稳定的镁存储。在此，我们构建了一种具有铁阳离子和二羟基苯醌（DHBQ）阴离子双氧化还原中心的三维（3D）铁（III）-二羟基苯醌（Fe(DHBQ)）金属有机框架（MOF）材料，用于在RMBs中可逆存储镁。光谱分析和密度泛函理论（DFT）计算揭示了电化学过程中Fe离子和DHBQ配体羰基的氧化还原化学。得益于合理的结构，Fe(DHBQ)∥Mg电池展现出395.3 mAh/g的高可逆容量、463.5 Wh/kg的大能量密度和2456.0 W/kg的高功率密度。此外，Fe(DHBQ)中高的电子电导率（8.35×10 S/cm）和有利的镁扩散路径赋予电池卓越的循环稳定性和倍率性能，在2000 mA/g下具有长达5000次循环的长寿命。这种双氧化还原活性MOF展示了一类用于高性能RMBs的先进阴极材料。
