High Capacity Rechargeable Magnesium-Ion Batteries Based on a Microporous Molybdenum–Vanadium Oxide Cathode

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• 作者：Watchareeya Kaveevivitchai ; Allan J. Jacobson
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：July 12, 2016
• 年：2016
• 卷：28
• 期：13
• 页码：4593-4601
• 全文大小：530K
• 年卷期：0
• ISSN：1520-5002

文摘

The three-dimensional microporous framework of the oxide Mo_2.5+yVO_9+δ (containing Mo^5+/6+ and V^4+/5+) is defined by three-, six-, and seven-membered ring channels. Due to the oxidation–reduction properties of Mo and V ions and the large open tunnels that can provide a diffusion pathway for small ions, Mo_2.5+yVO_9+δ has been found to intercalate both Li⁺ ions, reported previously, and also Mg²⁺ ions in Mg-ion batteries. Cathodes composed of Mo_2.5+yVO_9+δ were discharged and charged in Mg-ion cells at current densities ranging from 2 mA/g (C/70) to 10 mA/g (C/12). Mg²⁺ ions can be inserted into and extracted from Mg_xMo_2.5+yVO_9+δ between ∼3.33 and 1.73 V vs Mg/Mg²⁺ at room temperature, with up to 3.49 Mg²⁺ ions per formula unit intercalated into the framework, corresponding to a capacity of 397 mAh/g (1st discharge) which is among the highest capacities reported for Mg-based batteries. Powder X-ray diffraction was used to determine the lattice parameters of Mg_xMo_2.5+yVO_9+δ (0 < x ≤ 3) compositions prepared by chemical insertion using (C₄H₉)₂Mg. Our findings suggest that in order to overcome the significant shortcomings observed in the traditional Mg-ion Chevrel cathodes (low operating voltage and specific capacity), oxide-based intercalation cathodes can be used instead of the chalcogenides. The slow Mg diffusion kinetics caused by strong Coulombic interactions of the multivalent cations are offset by using a microporous oxide to allow easy migration and minimize steric effects. The combination of Mo and V ions, which can change oxidation state by more than one, can reduce volume expansion and help with charge redistribution during insertion of Mg²⁺ ions to maintain electroneutrality. This approach based on a microporous molybdenum–vanadium oxide suggests the possibility of using other porous mixed metal oxides for the development of advanced secondary multivalent-ion batteries.