Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation

被引：54

作者：

Petit, Yann K. ^{[1
]}

Mourad, Eleonore ^{[1
]}

Prehal, Christian ^{[1
]}

Leypold, Christian ^{[1
]}

Windischbacher, Andreas ^{[2
]}

Mijailovic, Daniel ^{[1
,3
]}

Slugovc, Christian ^{[1
]}

Borisov, Sergey M. ^{[4
]}

Zojer, Egbert ^{[2
]}

Brutti, Sergio ^{[5
]}

Fontaine, Olivier ^{[6
,7
,8
]}

Freunberger, Stefan A. ^{[1
,8
]}

机构：

[1] Graz Univ Technol, Inst Chem & Technol Mat, Graz, Austria

[2] Graz Univ Technol, Inst Solid State Phys, Graz, Austria

[3] Univ Belgrade, Fac Technol & Met, Belgrade, Serbia

[4] Graz Univ Technol, Inst Analyt Chem & Food Chem, Graz, Austria

[5] Univ Roma La Sapienza, Dipartimento Chim, Rome, Italy

[6] Univ Montpellier, Inst Charles Gerhardt Montpellier, Montpellier, France

[7] Vidyasirimedhi Inst Sci & Technol VISTEC, Sch Energy Sci & Engn, Rayong, Thailand

[8] IST Austria Inst Sci & Technol Austria, Klosterneuburg, Austria

来源：

NATURE CHEMISTRY | 2021年 / 13卷 / 05期

基金：

欧洲研究理事会;

关键词：

D O I：

10.1038/s41557-021-00643-z

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Aprotic alkali metal-O-2 batteries face two major obstacles to their chemistry occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides and parasitic reactions that are caused by the highly reactive singlet oxygen (O-1(2)). Redox mediators are recognized to be key for improving rechargeability. However, it is unclear how they affect O-1(2) formation, which hinders strategies for their improvement. Here we clarify the mechanism of mediated peroxide and superoxide oxidation and thus explain how redox mediators either enhance or suppress O-1(2) formation. We show that charging commences with peroxide oxidation to a superoxide intermediate and that redox potentials above similar to 3.5 V versus Li/Li+ drive O-1(2) evolution from superoxide oxidation, while disproportionation always generates some O-1(2). We find that O-1(2) suppression requires oxidation to be faster than the generation of O-1(2) from disproportionation. Oxidation rates decrease with growing driving force following Marcus inverted-region behaviour, establishing a region of maximum rate.

引用

页码：465 / +

页数：10

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