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Title: Identifying the Critical Role of Li Substitution in P2-Na x[Li yNi zMn 1-y-z]O 2 (0 < x, y, z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries

Abstract

Li-substituted layered P2–Na 0.80[Li 0.12Ni 0.22Mn 0.66]O 2 is investigated as an advanced cathode material for Na-ion batteries. Both neutron diffraction and nuclear magnetic resonance (NMR) spectroscopy are used to elucidate the local structure, and they reveal that most of the Li ions are located in transition metal (TM) sites, preferably surrounded by Mn ions. To characterize structural changes occurring upon electrochemical cycling, in situ synchrotron X-ray diffraction is conducted. It is clearly demonstrated that no significant phase transformation is observed up to 4.4 V charge for this material, unlike Li-free P2-type Na cathodes. The presence of monovalent Li ions in the TM layers allows more Na ions to reside in the prismatic sites, stabilizing the overall charge balance of the compound. Consequently, more Na ions remain in the compound upon charge, the P2 structure is retained in the high voltage region, and the phase transformation is delayed. Ex situ NMR is conducted on samples at different states of charge/discharge to track Li-ion site occupation changes. Surprisingly, Li is found to be mobile, some Li ions migrate from the TM layer to the Na layer at high voltage, and yet this process is highly reversible. Novel design principles for Namore » cathode materials are proposed on the basis of an atomistic level understanding of the underlying electrochemical processes. These principles enable us to devise an optimized, high capacity, and structurally stable compound as a potential cathode material for high-energy Na-ion batteries.« less

Authors:
; ; ; ; ; ; ; ; ;  [1]
  1. Cambridge
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGNNSFDOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1118040
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 26; Journal Issue: (2) ; 01, 2014; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Xu, Jing, Lee, Dae Hoe, Clément, Raphaële J., Yu, Xiqian, Leskes, Michal, Pell, Andrew J., Pintacuda, Guido, Yang, Xiao-Qing, Grey, Clare P., Meng, Ying Shirley, UCSD), Lyon-France), and BNL). Identifying the Critical Role of Li Substitution in P2-Nax[LiyNizMn1-y-z]O2 (0 < x, y, z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries. United States: N. p., 2014. Web. doi:10.1021/cm403855t.
Xu, Jing, Lee, Dae Hoe, Clément, Raphaële J., Yu, Xiqian, Leskes, Michal, Pell, Andrew J., Pintacuda, Guido, Yang, Xiao-Qing, Grey, Clare P., Meng, Ying Shirley, UCSD), Lyon-France), & BNL). Identifying the Critical Role of Li Substitution in P2-Nax[LiyNizMn1-y-z]O2 (0 < x, y, z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries. United States. doi:10.1021/cm403855t.
Xu, Jing, Lee, Dae Hoe, Clément, Raphaële J., Yu, Xiqian, Leskes, Michal, Pell, Andrew J., Pintacuda, Guido, Yang, Xiao-Qing, Grey, Clare P., Meng, Ying Shirley, UCSD), Lyon-France), and BNL). Wed . "Identifying the Critical Role of Li Substitution in P2-Nax[LiyNizMn1-y-z]O2 (0 < x, y, z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries". United States. doi:10.1021/cm403855t.
@article{osti_1118040,
title = {Identifying the Critical Role of Li Substitution in P2-Nax[LiyNizMn1-y-z]O2 (0 < x, y, z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries},
author = {Xu, Jing and Lee, Dae Hoe and Clément, Raphaële J. and Yu, Xiqian and Leskes, Michal and Pell, Andrew J. and Pintacuda, Guido and Yang, Xiao-Qing and Grey, Clare P. and Meng, Ying Shirley and UCSD) and Lyon-France) and BNL)},
abstractNote = {Li-substituted layered P2–Na0.80[Li0.12Ni0.22Mn0.66]O2 is investigated as an advanced cathode material for Na-ion batteries. Both neutron diffraction and nuclear magnetic resonance (NMR) spectroscopy are used to elucidate the local structure, and they reveal that most of the Li ions are located in transition metal (TM) sites, preferably surrounded by Mn ions. To characterize structural changes occurring upon electrochemical cycling, in situ synchrotron X-ray diffraction is conducted. It is clearly demonstrated that no significant phase transformation is observed up to 4.4 V charge for this material, unlike Li-free P2-type Na cathodes. The presence of monovalent Li ions in the TM layers allows more Na ions to reside in the prismatic sites, stabilizing the overall charge balance of the compound. Consequently, more Na ions remain in the compound upon charge, the P2 structure is retained in the high voltage region, and the phase transformation is delayed. Ex situ NMR is conducted on samples at different states of charge/discharge to track Li-ion site occupation changes. Surprisingly, Li is found to be mobile, some Li ions migrate from the TM layer to the Na layer at high voltage, and yet this process is highly reversible. Novel design principles for Na cathode materials are proposed on the basis of an atomistic level understanding of the underlying electrochemical processes. These principles enable us to devise an optimized, high capacity, and structurally stable compound as a potential cathode material for high-energy Na-ion batteries.},
doi = {10.1021/cm403855t},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = (2) ; 01, 2014,
volume = 26,
place = {United States},
year = {2014},
month = {2}
}