Unraveling the Reaction Interfaces and Intermediates of Ru-Catalyzed LiOH Decomposition in DMSO-Based Li−O2 Batteries
Unraveling the Reaction Interfaces and Intermediates of Ru-Catalyzed LiOH Decomposition in DMSO-Based Li−O2 Batteries
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揭示 DMSO 锂 O2 电池中 Ru 催化 LiOH 分解的反应界面和中间体
DOI：
10.1021/acs.jpclett.1c03470
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发表时间：
2022
影响因子：
5.7
通讯作者：
Tao Liu
中科院分区：
文献类型：
--
作者：
Linbin Tang;Junjian Li;Yue Zhang;Zongyan Gao;Junchao Chen;Tao Liu
LiOH在非水电解质中的分解研究不仅拓展了对非质子介质中四电子析氧反应的基本认识，而且对开发涉及LiOH生成/分解的高性能锂空气电池至关重要。在这项工作中，我们已经表明，在湿DMSO电解质中的钌金属催化剂的LiOH的分解发生在催化剂-电解质界面，通过电位触发的溶解-再沉淀过程启动。本文设计的原位UV-vis方法提供了直接的实验证据，表明羟基自由基是在几种非水电解质中形成的常见反应中间体;该方法适用于研究其他电池系统。我们的研究结果强调，对非水电解质的羟基自由基的反应性是一个主要的因素限制在LiOH分解过程中的O2演变。将抑制羟基反应的催化剂与更能抵抗羟基自由基攻击的电解质偶联有助于改善该反应的可逆性。
Investigation of LiOH decomposition in nonaqueous electrolytes not only expands the fundamental understanding of four-electron oxygen evolution reaction in aprotic media, also is crucial to development of high-performance lithium-air batteries involving the formation/decomposition of LiOH. In this work, we have shown that the decomposition of LiOH by ruthenium metal catalysts in a wet DMSO electrolyte occurs at the catalyst-electrolyte interface, initiating via a potential-triggered dissolution-reprecipitation process. The in-situ UV-vis methodology devised herein provides direct experimental evidence that hydroxyl radical is a common reaction intermediate formed in several nonaqueous electrolytes; this method is applicable to study other battery systems. Our results highlight that the reactivity of hydroxyl radical towards nonaqueous electrolyte represents a major factor limiting O2 evolution during LiOH decomposition. Coupling catalysts restraining hydroxyl reactivity with electrolytes more resistant to hydroxyl radical attack could help improve the reversibility of this reaction.