Li–O2 batteries can provide greater gravimetric energy than Li-ion batteries but suffer from poor efficiency and cycle life due to the instability of aprotic electrolytes. In this study, we show that the apparent four-electron oxygen reduction to form Li2O in Li–O2 batteries with molten nitrate is facilitated by the electrochemical reduction of nitrate to nitrite, and subsequent chemical oxidation of nitrite to nitrate by molecular oxygen, instead of a four-electron oxygen reduction aided by disproportionation of Li2O2 generated from two-electron reduction of molecular oxygen. By examining a series of transition metal catalysts using experiments and computation, optimizing the surface binding of nitrate to enhance the kinetics of the electrochemical reduction of nitrate to nitrite, as well as increasing the kinetics of nitrite oxidation by O2 was shown to increase the discharge voltage and render the observed high-rate capability for NiO-based surfaces in Li–O2 batteries.

Zhu, Y., Leverick, G., Giordano, L., Feng, S., Zhang, Y., Yu, Y., et al. (2022). Nitrate-mediated four-electron oxygen reduction on metal oxides for lithium-oxygen batteries. JOULE, 6(8), 1887-1903 [10.1016/j.joule.2022.06.032].

Nitrate-mediated four-electron oxygen reduction on metal oxides for lithium-oxygen batteries

Giordano L.;
2022

Abstract

Li–O2 batteries can provide greater gravimetric energy than Li-ion batteries but suffer from poor efficiency and cycle life due to the instability of aprotic electrolytes. In this study, we show that the apparent four-electron oxygen reduction to form Li2O in Li–O2 batteries with molten nitrate is facilitated by the electrochemical reduction of nitrate to nitrite, and subsequent chemical oxidation of nitrite to nitrate by molecular oxygen, instead of a four-electron oxygen reduction aided by disproportionation of Li2O2 generated from two-electron reduction of molecular oxygen. By examining a series of transition metal catalysts using experiments and computation, optimizing the surface binding of nitrate to enhance the kinetics of the electrochemical reduction of nitrate to nitrite, as well as increasing the kinetics of nitrite oxidation by O2 was shown to increase the discharge voltage and render the observed high-rate capability for NiO-based surfaces in Li–O2 batteries.
Articolo in rivista - Articolo scientifico
catalysts; lithium nitrate; lithium nitrite; lithium oxide; lithium-oxygen battery; molten-salt electrolyte; nitrate redox; redox mediator;
English
5-ago-2022
2022
6
8
1887
1903
none
Zhu, Y., Leverick, G., Giordano, L., Feng, S., Zhang, Y., Yu, Y., et al. (2022). Nitrate-mediated four-electron oxygen reduction on metal oxides for lithium-oxygen batteries. JOULE, 6(8), 1887-1903 [10.1016/j.joule.2022.06.032].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/422519
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