Materials Compatibility in Rechargeable Aluminum Batteries: Chemical and Electrochemical Properties between Vanadium Pentoxide and Chloroaluminate Ionic Liquids
Materials Compatibility in Rechargeable Aluminum Batteries: Chemical and Electrochemical Properties between Vanadium Pentoxide and Chloroaluminate Ionic Liquids
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DOI：
10.1021/acs.chemmater.9b01556
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发表时间：
2019-08
影响因子：
8.6
通讯作者：
Xiaoyu Wen;Yuhang Liu;A. Jadhav;Jian Zhang;D. Borchardt;Jiayan Shi;B. Wong;B. Sanyal;R. Messi
中科院分区：
文献类型：
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作者：
Xiaoyu Wen;Yuhang Liu;A. Jadhav;Jian Zhang;D. Borchardt;Jiayan Shi;B. Wong;B. Sanyal;R. Messi
为了证明电极/电解质稳定性在可充电铝电池中的重要性，我们研究了五氧化二钒（V2O5）与氯铝酸盐离子液体电解质之间的化学相容性，V2O5是一种被提议用于铝电池的正极材料。我们发现V2O5在电解液中可以与Lewis酸性物质（Al2Cl7 -）和Lewis中性物质（AlCl4 -）发生反应。结合电化学分析、拉曼光谱、液态和固态核磁共振（NMR）光谱以及密度泛函理论（DFT）计算，确定了反应产物。结果表明，V2O5与Al2Cl7 -发生化学反应，生成氯化钒（VOCl3）和无定形氧化铝。V2O5还与AlCl4 -发生化学反应，生成氯化二氧钒（VO2Cl）和一种新的与氯化铝配位的偏氰酸盐阴离子（AlCl3VO3 -）。这些产品进一步表现出电化学氧化还原活性。
To demonstrate the importance of electrode/electrolyte stability in rechargeable aluminum (Al) batteries, we investigate the chemical compatibility between vanadium pentoxide (V2O5), a proposed positive electrode material for Al batteries, and the common chloroaluminate ionic liquid electrolytes. We reveal that V2O5 reacts with both the Lewis acidic (Al2Cl7–) and the Lewis neutral species (AlCl4–) within the electrolyte. The reaction products are identified using a combination of electrochemical analyses, Raman spectroscopy, liquid-state and solid-state nuclear magnetic resonance (NMR) spectroscopy, and density functional theory (DFT) calculations. The results establish that V2O5 chemically reacts with Al2Cl7– to form vanadium oxychloride (VOCl3) and amorphous aluminum oxide. V2O5 also chemically reacts with AlCl4– to produce dioxovanadium chloride (VO2Cl) and a new species of metavanadate anion coordinated with aluminum chloride (AlCl3VO3–). These products furthermore exhibit electrochemical redox activi...