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Title: Investigating Li 2NiO 2–Li 2CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

Abstract

Li 2Ni 1–xCu xO 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2Ni 1–xCu xO 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, and charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.

Authors:
 [1];  [2];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1379866
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 21; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Xu, Jing, Renfrew, Sara, Marcus, Matthew A., Sun, Meiling, McCloskey, Bryan D., and Tong, Wei. Investigating Li2NiO2–Li 2CuO2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b01799.
Xu, Jing, Renfrew, Sara, Marcus, Matthew A., Sun, Meiling, McCloskey, Bryan D., & Tong, Wei. Investigating Li2NiO2–Li 2CuO2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries. United States. doi:10.1021/acs.jpcc.7b01799.
Xu, Jing, Renfrew, Sara, Marcus, Matthew A., Sun, Meiling, McCloskey, Bryan D., and Tong, Wei. 2017. "Investigating Li2NiO2–Li 2CuO2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries". United States. doi:10.1021/acs.jpcc.7b01799.
@article{osti_1379866,
title = {Investigating Li2NiO2–Li 2CuO2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries},
author = {Xu, Jing and Renfrew, Sara and Marcus, Matthew A. and Sun, Meiling and McCloskey, Bryan D. and Tong, Wei},
abstractNote = {Li2Ni1–xCuxO2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li2Ni1–xCuxO2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, and charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.},
doi = {10.1021/acs.jpcc.7b01799},
journal = {Journal of Physical Chemistry. C},
number = 21,
volume = 121,
place = {United States},
year = 2017,
month = 5
}

Journal Article:
Free Publicly Available Full Text
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  • Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr4+ to Cr3+ and Cr6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr1/3Fe1/3Mn1/3O2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g-1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) → (P3 + O3'') → O3'' phase-transition pathway formore » NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na+ deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr4+ to Cr3+ and Cr6+ can be effectively suppressed by Fe3+ and Mn4+ substitution. These results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO6 octahedral distortion and recovery.« less
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