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Oxidative decomposition mechanisms of lithium carbonate on carbon substrates in lithium battery chemistries

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  • Deqing Cao

    (Nanjing Tech University)

  • Chuan Tan

    (Nanjing Tech University)

  • Yuhui Chen

    (Nanjing Tech University)

Abstract

Lithium carbonate plays a critical role in both lithium-carbon dioxide and lithium-air batteries as the main discharge product and a product of side reactions, respectively. Understanding the decomposition of lithium carbonate during electrochemical oxidation (during battery charging) is key for improving both chemistries, but the decomposition mechanisms and the role of the carbon substrate remain under debate. Here, we use an in-situ differential electrochemical mass spectrometry-gas chromatography coupling system to quantify the gas evolution during the electrochemical oxidation of lithium carbonate on carbon substrates. Our results show that lithium carbonate decomposes to carbon dioxide and singlet oxygen mainly via an electrochemical process instead of via a chemical process in an electrolyte of lithium bis(trifluoromethanesulfonyl)imide in tetraglyme. Singlet oxygen attacks the carbon substrate and electrolyte to form both carbon dioxide and carbon monoxide—approximately 20% of the net gas evolved originates from these side reactions. Additionally, we show that cobalt(II,III) oxide, a typical oxygen evolution catalyst, stabilizes the precursor of singlet oxygen, thus inhibiting the formation of singlet oxygen and consequent side reactions.

Suggested Citation

  • Deqing Cao & Chuan Tan & Yuhui Chen, 2022. "Oxidative decomposition mechanisms of lithium carbonate on carbon substrates in lithium battery chemistries," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-32557-w
    DOI: 10.1038/s41467-022-32557-w
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    References listed on IDEAS

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    1. Nika Mahne & Bettina Schafzahl & Christian Leypold & Mario Leypold & Sandra Grumm & Anita Leitgeb & Gernot A. Strohmeier & Martin Wilkening & Olivier Fontaine & Denis Kramer & Christian Slugovc & Serg, 2017. "Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries," Nature Energy, Nature, vol. 2(5), pages 1-9, May.
    2. Doron Aurbach & Bryan D. McCloskey & Linda F. Nazar & Peter G. Bruce, 2016. "Advances in understanding mechanisms underpinning lithium–air batteries," Nature Energy, Nature, vol. 1(9), pages 1-11, September.
    3. Won-Jin Kwak & Hun Kim & Yann K. Petit & Christian Leypold & Trung Thien Nguyen & Nika Mahne & Paul Redfern & Larry A. Curtiss & Hun-Gi Jung & Sergey M. Borisov & Stefan A. Freunberger & Yang-Kook Sun, 2019. "Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen," Nature Communications, Nature, vol. 10(1), pages 1-8, December.
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    Cited by:

    1. Heng Zhu & Ximei Lv & Yuexu Wu & Wentao Wang & Yuping Wu & Shicheng Yan & Yuhui Chen, 2024. "Carbonate-carbonate coupling on platinum surface promotes electrochemical water oxidation to hydrogen peroxide," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    2. Yingqi Liu & Zhiyuan Zhang & Junyang Tan & Biao Chen & Bingyi Lu & Rui Mao & Bilu Liu & Dashuai Wang & Guangmin Zhou & Hui-Ming Cheng, 2024. "Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries," Nature Communications, Nature, vol. 15(1), pages 1-11, December.

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