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Reaction heterogeneity in LiNi0.8Co0.15Al0.05O2 induced by surface layer
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Grenier, Antonin, Liu, Hao, Wiaderek, Kamila M., Lebens-Higgins, Zachary W., Borkiewicz, Olaf J., Piper, Louis F. J., Chupas, Peter J. and Chapman, Karena W. (2017) Reaction heterogeneity in LiNi0.8Co0.15Al0.05O2 induced by surface layer. Chemistry of Materials, 29 (17). pp. 7345-7352. doi:10.1021/acs.chemmater.7b02236 ISSN 0897-4756.
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Official URL: http://dx.doi.org/10.1021/acs.chemmater.7b02236
Abstract
Through operando synchrotron powder X-ray diffraction (XRD) analysis of layered transition metal oxide electrodes of composition LiNi0.8Co0.15Al0.05O2 (NCA), we decouple the intrinsic bulk reaction mechanism from surface-induced effects. For identically prepared and cycled electrodes stored in different environments, we demonstrate that the intrinsic bulk reaction for pristine NCA follows solid-solution mechanism, not a two-phase as suggested previously. By combining high resolution powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and surface sensitive X-ray photoelectron spectroscopy (XPS), we demonstrate that adventitious Li2CO3 forms on the electrode particle surface during exposure to air through reaction with atmospheric CO2. This surface impedes ionic and electronic transport to the underlying electrode, with progressive erosion of this layer during cycling giving rise to different reaction states in particles with an intact versus an eroded Li2CO3 surface-coating. This reaction heterogeneity, with a bimodal distribution of reaction states, has previously been interpreted as a “two-phase” reaction mechanism for NCA, as an activation step that only occurs during the first cycle. Similar surface layers may impact the reaction mechanism observed in other electrode materials using bulk probes such as operando powder XRD.
Item Type: | Journal Article | ||||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Engineering > WMG (Formerly the Warwick Manufacturing Group) | ||||||||
Journal or Publication Title: | Chemistry of Materials | ||||||||
Publisher: | ACS Publications | ||||||||
ISSN: | 0897-4756 | ||||||||
Official Date: | 12 September 2017 | ||||||||
Dates: |
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Volume: | 29 | ||||||||
Number: | 17 | ||||||||
Page Range: | pp. 7345-7352 | ||||||||
DOI: | 10.1021/acs.chemmater.7b02236 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Restricted or Subscription Access |
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