Understanding LiOH Chemistry in a Ruthenium-Catalyzed Li-O2 Battery

被引：87

作者：

Liu, Tao ^{[1
]}

Liu, Zigeng ^{[1
]}

Kim, Gunwoo ^{[1
]}

Frith, James T. ^{[2
]}

Garcia-Araez, Nuria ^{[2
]}

Grey, Clare P. ^{[1
]}

机构：

[1] Univ Cambridge, Dept Chem, Lensfield Rd, Cambridge CB2 1EW, England

[2] Univ Southampton, Dept Chem, Highfield Campus, Southampton SO17 1BJ, Hants, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 50期

基金：

英国工程与自然科学研究理事会; “创新英国”项目;

关键词：

dimethyl sulfone; Li-O-2; batteries; LiOH; oxygen reduction/evolution; ruthenium catalysis; LITHIUM-OXYGEN BATTERIES; AIR BATTERY; DIMETHYL-SULFOXIDE; SUPEROXIDE; REDUCTION; SOLVENTS; WATER;

D O I：

10.1002/anie.201709886

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Non-aqueous Li-O-2 batteries are promising for next-generation energy storage. New battery chemistries based on LiOH, rather than Li2O2, have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru-catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4e(-) oxygen reduction reaction, the H in LiOH coming solely from added H2O and the O from both O-2 and H2O. On charging, quantitative LiOH oxidation occurs at 3.1V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2O2, LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long-lived battery. An optimized metal-catalyst-electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.

引用

页码：16057 / 16062

页数：6

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