Issue 13, 2024

Reversible and irreversible reaction mechanisms of Li–CO2 batteries

Abstract

Li–CO2 batteries are considered a versatile solution for CO2 utilization. However, their development, including reversibility and efficiency, is impeded by an inadequate understanding of Li–CO2 electrochemistry, particularly the decomposition of carbon and the generation of by-product O2. Here, using typical Ru(0001) (reversible) and Ir(111) (irreversible) as model catalysts and employing state-of-the-art first-principles calculations, the rechargeable/reversible reaction mechanisms of Li–CO2 batteries are disclosed. We find that electrolyte, often neglected or oversimplified in Li–CO2 modelling, plays an essential role in CO2 activation and C–C coupling affects the generation pathways of discharge intermediates due to the sluggish kinetics. The results rationalize experimental observations, which are also examined by constant-potential modelling. Specifically, by exploring the kinetics of the charging process, we discover that the reversibility of Ru(0001) is attributed to its ability to suppress O–O coupling while co-oxidizing Li2CO3 and carbon. In contrast, Li2CO3 decomposition on Ir(111) preferentially produces O2, during which carbon can only be partially decomposed. These findings solve long-standing questions and highlight the necessity of describing the explicit solvent effect in modelling, which can promote further studies on Li–CO2 batteries.

Graphical abstract: Reversible and irreversible reaction mechanisms of Li–CO2 batteries

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Article information

Article type
Edge Article
Submitted
17 Jan 2024
Accepted
15 Feb 2024
First published
16 Feb 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 4804-4810

Reversible and irreversible reaction mechanisms of Li–CO2 batteries

X. Zhang, Y. Wang and Y. Li, Chem. Sci., 2024, 15, 4804 DOI: 10.1039/D4SC00383G

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