Issue 11, 2024

Bidirectional electron transfer boosts Li–CO2 electrochemistry

Abstract

The activation mechanism for the CO2 reactant remains a crucial and controversial question in the field of Li–CO2 batteries, which is primarily attributed to the catalyst injecting electrons into CO2 while ignoring the reverse electron transfer. Here, extending classical unidirectional activation theory, a novel “bidirectional electron transfer (BET)” mechanism was unraveled to well establish a fundamental understanding of the interplay between the metal active sites and CO2 redox. By means of spin-polarized density functional theory (DFT) calculations, the number of bidirectional transferred electrons was confirmed to be a good indicator to characterize the adsorption strength of CO2 in the presence of TM/Ti17B18 (TM = V, Cr, Mn, Fe, Co, Ni or Cu) as aprotic Li–CO2 battery catalysts. Of particular interest is that the selective nucleation of Li2CO3 and reverse dissociation with carbon products were achieved on these catalysts with abundant metal active sites. The results obtained from the constant charge method and constant potential implicit solvent method together demonstrate that Fe/Ti17B18 delivers dramatically boosted bifunctional activity towards Li–CO2 redox benefiting from its appropriate BET behavior with CO2, in sharp contrast to pristine TiB monolayers. The current findings provide intriguing insights into the CO2 activation mechanisms and potential-dependent Li–CO2 electrochemical performance.

Graphical abstract: Bidirectional electron transfer boosts Li–CO2 electrochemistry

Supplementary files

Article information

Article type
Paper
Submitted
26 Dec 2023
Accepted
05 Feb 2024
First published
07 Feb 2024

J. Mater. Chem. A, 2024,12, 6515-6526

Bidirectional electron transfer boosts Li–CO2 electrochemistry

P. Shu, Q. Peng, T. Luo, J. Ding, X. Gong, J. Zhou, Y. Yu, X. Qi and Z. Sun, J. Mater. Chem. A, 2024, 12, 6515 DOI: 10.1039/D3TA08035H

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