Influence of Ionic Coordination on the Cathode Reaction Mechanisms of Al/S Batteries
Influence of Ionic Coordination on the Cathode Reaction Mechanisms of Al/S Batteries
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DOI：
10.1021/acs.jpcc.1c08426
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发表时间：
2022-01-05
影响因子：
3.7
通讯作者：
Garcia-Lastra, Juan Maria
中科院分区：
文献类型：
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作者：
Bhowmik, Arghya;Carrasco-Busturia, David;Garcia-Lastra, Juan Maria
由于缺乏对铝/硫电池电化学反应途径的了解，阻碍了实际方法的发展，以减轻这种吸引人的二次电池系统的不可逆性和不良循环性能，从理论上讲，这种系统具有可扩展性、廉价性和高能量密度。与Li/S系统不同，Al/S电池使用离子液体（ILs）作为电解质。IL的选择，即IL是基于传统的emimci电解质还是基于氯化铝与尿素（或其衍生物）的深共晶混合物，对电池的电化学储能性能有很大影响。为了阐明Al/S电池的化学性质，本文介绍了计算电化学研究工作，以确定最有利的反应途径和热力学稳定的反应中间体。我们还讨论了离子种类（源自含铝深共晶电解质）与多硫化物中间体的配位对Al/S体系反应途径和电化学行为的影响。还报道了各种反应中间体的光谱特征，并通过与实验观察的比较进行了验证。
The lack of knowledge on electrochemical reaction pathways for Al/S batteries prevents the development of practical approaches to mitigate the irreversibility and poor cycling performances of this appealing secondary battery system, which is, in theory, scalable, inexpensive, and energy-dense. Different from the Li/S system, Al/S batteries use ionic liquids (ILs) as electrolytes. The choice of the IL, i.e., whether the IL is based on a conventional EMImCI-based electrolyte or in a deep eutectic mixture of aluminum chloride with urea (or any of its derivatives), strongly affects the electrochemical energy-storage performance of the cell. To shed some light on the Al/S battery chemistry, here, we present the computational electrochemistry research work to determine the most favorable reaction pathways and thermodynamically stable reaction intermediates. We also discuss the effect of the coordination of ionic species (originated from aluminum-containing deep eutectic electrolytes) with polysulfide intermediates, which lead to alterations in the reaction pathway and electrochemical behavior of the Al/S system. The spectroscopic signatures from various reaction intermediates are also reported and validated via comparison with experimental observations.