Understanding LiOH Formation in a Li-O <inf>2</inf> Battery with LiI and H <inf>2</inf> O Additives
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Authors
Jónsson, E
Temprano, I
Shao, Y
Carretero-González, J
Kerber, RN
Publication Date
2019Journal Title
ACS Catalysis
ISSN
2155-5435
Publisher
American Chemical Society (ACS)
Volume
9
Issue
1
Pages
66-77
Type
Article
This Version
AM
Metadata
Show full item recordCitation
Liu, T., Kim, G., Jónsson, E., Castillo-Martinez, E., Temprano, I., Shao, Y., Carretero-González, J., et al. (2019). Understanding LiOH Formation in a Li-O <inf>2</inf> Battery with LiI and H <inf>2</inf> O Additives. ACS Catalysis, 9 (1), 66-77. https://doi.org/10.1021/acscatal.8b02783
Abstract
LiI-promoted LiOH formation in Li-O2 batteries with wet ether electrolytes has been investigated by Raman, nuclear magnetic resonance spectroscopy, operando pressure tests and molecular dynamics simulations. We find that LiOH formation is a synergistic effect involving both H2O and LiI additives, whereas with either alone Li2O2 forms. LiOH is generated via a nominal four-electron oxygen reduction reaction, the hydrogen coming from H2O and the oxygen from both O2 and H2O, and with fewer side reactions than typically associated with Li2O2 formation; the presence of fewer parasitic reactions is attributed to the proton donor role of water which can coordinate to O2- and the higher chemical stability of LiOH. Iodide plays a catalytic role in decomposing H2O2/HO2- thereby promoting LiOH formation, its efficacy being highly dependent on the water concentration. This iodide catalysis becomes retarded at high water contents due to the formation of large water-solvated clusters, and Li2O2 forms again.
Keywords
LiI, Li-O-2 batteries, LiOH formation, four-electron oxygen reduction, water clusters, molecular dynamics
Sponsorship
EPSRC
Funder references
Engineering and Physical Sciences Research Council (EP/M009521/1)
European Commission Horizon 2020 (H2020) Future and Emerging Technologies (FET) (696656)
Identifiers
External DOI: https://doi.org/10.1021/acscatal.8b02783
This record's URL: https://www.repository.cam.ac.uk/handle/1810/287103
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