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Title: Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer

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 vs 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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, United States
  2. Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, United States
  3. Energy and Global Security Directorate, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1392465
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 17
Country of Publication:
United States
Language:
English

Citation Formats

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. Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b02236.
Grenier, Antonin, Liu, Hao, Wiaderek, Kamila M., Lebens-Higgins, Zachary W., Borkiewicz, Olaf J., Piper, Louis F. J., Chupas, Peter J., & Chapman, Karena W. Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer. United States. doi:10.1021/acs.chemmater.7b02236.
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. Tue . "Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer". United States. doi:10.1021/acs.chemmater.7b02236.
@article{osti_1392465,
title = {Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer},
author = {Grenier, Antonin and Liu, Hao and Wiaderek, Kamila M. and Lebens-Higgins, Zachary W. and Borkiewicz, Olaf J. and Piper, Louis F. J. and Chupas, Peter J. and Chapman, Karena W.},
abstractNote = {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 vs 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.},
doi = {10.1021/acs.chemmater.7b02236},
journal = {Chemistry of Materials},
number = 17,
volume = 29,
place = {United States},
year = {Tue Aug 15 00:00:00 EDT 2017},
month = {Tue Aug 15 00:00:00 EDT 2017}
}