Co3O4‑Catalyzed LiOH Chemistry in Li–O2 Batteries
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American Chemical Society (ACS)
https://doi.org/10.1021/acsenergylett.0c01940
https://doi.org/10.1021/acsenergylett.0c01940
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Li–O2 batteries (LOBs) operating via LiOH chemistry have attracted increasing interest because of the higher stability of LiOH in organic electrolytes, compared to Li2O2. Several catalysts have been shown to promote the formation of LiOH during discharge. However, LiOH has been difficult to reoxidize to form oxygen on charging. Here, we report that, in the presence of water, Co3O4 promotes the formation of LiOH on discharge via a 4 e–/O2 process with few side reactions, forming large (001) facet-exposed LiOH flakes. Hydroperoxide LiOOH was detected as a potential discharge intermediate. During charge, O2 evolution was detected along with LiOH decomposition up to 3.9 V; at higher voltages, products from parasitic reactions can be detected. This work provides new insights into the role of solid catalysts in LiOH chemistry in LOBs, and will help promote the development of reversible and long-lasting LiOH-based LOBs.
We thank EPSRC for the research funding under the grant EP/M009521/1 DJR00640, EP/P003532/1. J.L. thanks the EPSRC Underpinning Multi-User Equipment Call (EP/P030467/1) for electron microscopy facilities (SEM, TEM) located in the Department of Chemistry, University of Cambridge. J.L. thanks the Research Startup Fund from Harbin Institute of Technology, Shenzhen. S. D. acknowledges DST-Overseas Visiting Fellowship in Nanoscience and Technology (funded by Govt. of India, 2018-19). Y.J. acknowledges funding support from Faraday Institution NEXGENNA project. The X-ray photoelectron (XPS) data collection was performed at the EPSRC National Facility for XPS ("HarwellXPS"), operated by Cardiff University and UCL, under Contract No. PR16195. The authors thank Tao Liu, Evan Wenbo Zhao, James Ellison, Evelyna Wang for insightful discussions, Zachary Ruff for help with Raman spectroscopy, and Heather Greer for help with the TEM/SEM measurements.
We thank EPSRC for the research funding under the grant EP/M009521/1 DJR00640, EP/P003532/1. J.L. thanks the EPSRC Underpinning Multi-User Equipment Call (EP/P030467/1) for electron microscopy facilities (SEM, TEM) located in the Department of Chemistry, University of Cambridge. J.L. thanks the Research Startup Fund from Harbin Institute of Technology, Shenzhen. S. D. acknowledges DST-Overseas Visiting Fellowship in Nanoscience and Technology (funded by Govt. of India, 2018-19). Y.J. acknowledges funding support from Faraday Institution NEXGENNA project. The X-ray photoelectron (XPS) data collection was performed at the EPSRC National Facility for XPS ("HarwellXPS"), operated by Cardiff University and UCL, under Contract No. PR16195. The authors thank Tao Liu, Evan Wenbo Zhao, James Ellison, Evelyna Wang for insightful discussions, Zachary Ruff for help with Raman spectroscopy, and Heather Greer for help with the TEM/SEM measurements.