Deciphering CO₂ Reduction Reaction Mechanism in Aprotic Li–CO₂ Batteries using In Situ Vibrational Spectroscopy Coupled with Theoretical Calculations

Zhiwei Zhao; Long Pang; Yuwei Su; Tianfu Liu; Guoxiong Wang; Chuntai Liu; Jiawei Wang; Zhangquan Peng

doi:10.1021/acsenergylett.1c02773

journal article·2022-02-11

Deciphering CO₂ Reduction Reaction Mechanism in Aprotic Li–CO₂ Batteries using In Situ Vibrational Spectroscopy Coupled with Theoretical Calculations

Zhiwei Zhao, Long Pang, Yuwei Su, Tianfu Liu, Guoxiong Wang, Chuntai Liu, Jiawei Wang, Zhangquan Peng

ACS Energy Letters· Volume 7· Issue 2

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Abstract

The aprotic Li–CO2 battery represents a sustainable technology by virtue of energy storage capability and CO2 recyclability. However, the CO2 reduction reaction (CO2RR) mechanism underpinning the operation of Li–CO2 batteries is not yet completely understood. Herein, using in situ surface-enhanced Raman spectroscopy coupled with density functional theory calculations, we obtain direct spectroscopic evidence of the CO2RR (i.e., CO2–, CO, and Li2CO3) and propose a surface-mediated discharge pathway (i.e., 2Li+ + 2CO2 + 2e– → CO + Li2CO3) in Li–CO2 batteries. We also highlight the significant effect of the electrocatalysts’ near-Fermi-level d-orbital states on the CO2RR activity through a systematic comparative study of model electrocatalysts. Moreover, deep CO2RR via “4Li+ + 3CO2 + 4e– → 2Li2CO3 + C” may be difficult to proceed because of the sluggish chemical steps involved (e.g., dimerization of two CO2– intermediates). This work provides molecular insights into the CO2RR mechanism in a Li+-aprotic medium and will be beneficial for next-generation Li–CO2 batteries.

Source: openalex_inverted_index · Quality: baseline

Research context

Energy storage Catalysis & surfaces

OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · CO2 Reduction Techniques and Catalysts

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Key Laboratory of Materials Processing and Mold (Zhengzhou University), Ministry of Education, National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002, China

School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, China

Tianmu Lake Institute of Advanced Energy Storage Technologies Co. Ltd., Liyang 213300, China

Funding

Royal Society · Ministry of Science and Technology of the People's Republic of China · National Natural Science Foundation of China

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