TY  - JOUR
AU  - Petit, Yann K.
AU  - Mourad, Eleonore
AU  - Prehal, Christian
AU  - Leypold, Christian
AU  - Windischbacher, Andreas
AU  - Mijailović, Daniel
AU  - Slugovc, Christian
AU  - Borisov, Sergey M.
AU  - Zojer, Egbert
AU  - Brutti, Sergio
AU  - Fontaine, Olivier
AU  - Freunberger, Stefan A.
PY  - 2021
UR  - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4903
AB  - 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.
PB  - Nature Research
T2  - Nature Chemistry
T1  - Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation
EP  - 471
IS  - 5
SP  - 465
VL  - 13
DO  - 10.1038/s41557-021-00643-z
ER  - 

@article{
author = "Petit, Yann K. and Mourad, Eleonore and Prehal, Christian and Leypold, Christian and Windischbacher, Andreas and Mijailović, Daniel and Slugovc, Christian and Borisov, Sergey M. and Zojer, Egbert and Brutti, Sergio and Fontaine, Olivier and Freunberger, Stefan A.",
year = "2021",
abstract = "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.",
publisher = "Nature Research",
journal = "Nature Chemistry",
title = "Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation",
pages = "471-465",
number = "5",
volume = "13",
doi = "10.1038/s41557-021-00643-z"
}

Petit, Y. K., Mourad, E., Prehal, C., Leypold, C., Windischbacher, A., Mijailović, D., Slugovc, C., Borisov, S. M., Zojer, E., Brutti, S., Fontaine, O.,& Freunberger, S. A.. (2021). Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. in Nature Chemistry
Nature Research., 13(5), 465-471.
https://doi.org/10.1038/s41557-021-00643-z

Petit YK, Mourad E, Prehal C, Leypold C, Windischbacher A, Mijailović D, Slugovc C, Borisov SM, Zojer E, Brutti S, Fontaine O, Freunberger SA. Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. in Nature Chemistry. 2021;13(5):465-471.
doi:10.1038/s41557-021-00643-z .

Petit, Yann K., Mourad, Eleonore, Prehal, Christian, Leypold, Christian, Windischbacher, Andreas, Mijailović, Daniel, Slugovc, Christian, Borisov, Sergey M., Zojer, Egbert, Brutti, Sergio, Fontaine, Olivier, Freunberger, Stefan A., "Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation" in Nature Chemistry, 13, no. 5 (2021):465-471,
https://doi.org/10.1038/s41557-021-00643-z . .