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通过碳酸亚丙酯还原形成用于锂阳极的固体电解质界面

Solid electrolyte interphase formation by propylene carbonate reduction for lithium anode.

作者信息

Qian Qinlai, Yang Yifu, Shao Huixia

机构信息

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China.

出版信息

Phys Chem Chem Phys. 2017 Nov 1;19(42):28772-28780. doi: 10.1039/c7cp04839d.

Abstract

The naturally formed solid electrolyte interphase (SEI) of lithium (Li) with organic electrolytes is fragile and can result in repeated exposure of fresh Li metal to the electrolyte during plating/stripping cycles. Building an artificial SEI layer is an effective way to enhance its stability and improve the electrochemical deposition behavior of Li. Using non-Li metal substrate to construct Li metal electrode is a more applicable method than using direct Li metal anode. In this study, the possibility of electrochemical reduction of propylene carbonate (PC) as an artificial SEI formation reaction for Li metal anode was evaluated. The results show that PC reduction can be divided into two stages: in the potential region higher than 0.85 V (vs. Li/Li), the soluble free radical anion CH-ĊH-CH-OCO is formed and can be re-oxidized. In the potential region between 0.85 and 0.55 V (vs. Li/Li), the insoluble reduction products CHCH(-OCOLi)CH-OCOLi and LiCO are formed and construct the SEI film. By controlling the PC reduction rate with limited current, the morphology and construction of the SEI film could be improved, and thus the Li plating/stripping cycling efficiency could be enhanced. This can be considered a fundamental concept for high quality artificial SEI formation.

摘要

锂(Li)与有机电解质自然形成的固体电解质界面(SEI)很脆弱,在锂电镀/剥离循环过程中会导致新鲜锂金属反复暴露于电解质中。构建人工SEI层是增强其稳定性和改善锂电化学沉积行为的有效方法。使用非锂金属基底构建锂金属电极比使用直接锂金属阳极更适用。在本研究中,评估了碳酸丙烯酯(PC)电化学还原作为锂金属阳极人工SEI形成反应的可能性。结果表明,PC还原可分为两个阶段:在高于0.85 V(相对于Li/Li)的电位区域,形成可溶性自由基阴离子CH-ĊH-CH-OCO,且该自由基阴离子可被再氧化。在0.85至0.55 V(相对于Li/Li)的电位区域,形成不溶性还原产物CHCH(-OCOLi)CH-OCOLi和LiCO,并构建SEI膜。通过用有限电流控制PC还原速率,可以改善SEI膜的形态和结构,从而提高锂电镀/剥离循环效率。这可被视为高质量人工SEI形成的基本概念。

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