Electrode Reaction Mechanism of Ag2VO2PO4 Cathode

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• 作者：Ruibo Zhang ; Tesfaye A. Abtew ; Nicholas F. Quackenbush ; Linda W. Wangoh ; Matthew Huie ; Alexander B. Brady ; David Bock ; Harry Efstathiadis ; M. Stanley Whittingham ; Amy C. Marschilok ; Kenneth J. Takeuchi ; Esther S. Takeuchi ; Peihong Zhang ; Louis F. J. Piper
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：May 24, 2016
• 年：2016
• 卷：28
• 期：10
• 页码：3428-3434
• 全文大小：487K
• 年卷期：0
• ISSN：1520-5002

文摘

The high capacity of primary lithium-ion cathode Ag₂VO₂PO₄ is facilitated by both displacement and insertion reaction mechanisms. Whether the Ag extrusion (specifically, Ag reduction with Ag metal displaced from the host crystal) and V reduction are sequential or concurrent remains unclear. A microscopic description of the reaction mechanism is required for developing design rules for new multimechanism cathodes, combining both displacement and insertion reactions. However, the amorphization of Ag₂VO₂PO₄ during lithiation makes the investigation of the electrode reaction mechanism difficult with conventional characterization tools. For addressing this issue, a combination of local probes of pair-distribution function and X-ray spectroscopy were used to obtain a description of the discharge reaction. We determine that the initial reaction is dominated by silver extrusion with vanadium playing a supporting role. Once sufficient Ag has been displaced, the residual Ag⁺ in the host can no longer stabilize the host structure and V–O environment (i.e., onset of amorphization). After amorphization, silver extrusion continues but the vanadium reduction dominates the reaction. As a result, the crossover from primarily silver reduction displacement to vanadium reduction is facilitated by the amorphization that makes vanadium reduction increasingly more favorable.