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Title: Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li 2Ru 0.5Mn 0.5O 3 Investigated in a Wide Voltage Window

Li 2Ru 0.5Mn 0.5O 3, a high capacity lithium rich layered cathode material for lithium-ion batteries, was subject to comprehen-sive diagnostic studies including in situ/ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), pair distribu-tion function (PDF) and high resolution scanning transmission electron microscopy (STEM) analysis, to understand the cor-relations between transition metal chemistry, structure and lithium storage electrochemical behavior. Ru-Ru dimers have been identified in the as-prepared sample and found to be preserved upon prolonged cycling. Presence of these dimers, which are likely caused by the delocalized nature of 4d electrons, is found to favor the stabilization of the structure in a lay-ered phase. The in situ XAS results confirm the participation of oxygen redox into the charge compensation at high charge voltage, and the great flexibility of the covalent bond between Ru and O may provide great reversibility of the global struc-ture despite of the significant local distortion around Ru. In contrast, the local distortion around Mn occurs at low discharge voltage and is accompanied by a “layered to 1T” phase transformation, which is found to be detrimental to the cycle per-formances. It is clear that the changes of local structure around individual transition metal cations respond separatelymore » and differently to lithium intercalation/deintercalation. Here, cations with the capability to tolerate the lattice distortion will benefit for maintaining the integrality of the crystal structure and therefore is able to enhance the long-term cycling performance of the electrode materials.« less
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [3] ; ORCiD logo [3] ;  [4] ;  [2] ; ORCiD logo [4] ; ORCiD logo [5] ;  [2] ; ORCiD logo [3]
  1. Chinese Academy of Sciences (CAS), Beijing (China); Shanghai Univ., Shanghai (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Chinese Academy of Sciences (CAS), Beijing (China); Collaborative Innovation Center of Quantum Matter, Beijing (China)
Publication Date:
Report Number(s):
BNL-114463-2017-JA
Journal ID: ISSN 0897-4756; R&D Project: MA453MAEA; VT1201000; TRN: US1702902
Grant/Contract Number:
SC0012704; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 21; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source; Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; National Synchrotron Light Source; lithium-ion batteries; cathode; lithium rich layered oxides
OSTI Identifier:
1405938
Alternate Identifier(s):
OSTI ID: 1461410

Lyu, Yingchun, Hu, Enyuan, Xiao, Dongdong, Wang, Yi, Yu, Xiqian, Xu, Guiliang, Ehrlich, Steven N., Amine, Khalil, Gu, Lin, Yang, Xiao -Qing, and Li, Hong. Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li2Ru0.5Mn0.5O3 Investigated in a Wide Voltage Window. United States: N. p., Web. doi:10.1021/acs.chemmater.7b02299.
Lyu, Yingchun, Hu, Enyuan, Xiao, Dongdong, Wang, Yi, Yu, Xiqian, Xu, Guiliang, Ehrlich, Steven N., Amine, Khalil, Gu, Lin, Yang, Xiao -Qing, & Li, Hong. Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li2Ru0.5Mn0.5O3 Investigated in a Wide Voltage Window. United States. doi:10.1021/acs.chemmater.7b02299.
Lyu, Yingchun, Hu, Enyuan, Xiao, Dongdong, Wang, Yi, Yu, Xiqian, Xu, Guiliang, Ehrlich, Steven N., Amine, Khalil, Gu, Lin, Yang, Xiao -Qing, and Li, Hong. 2017. "Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li2Ru0.5Mn0.5O3 Investigated in a Wide Voltage Window". United States. doi:10.1021/acs.chemmater.7b02299.
@article{osti_1405938,
title = {Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li2Ru0.5Mn0.5O3 Investigated in a Wide Voltage Window},
author = {Lyu, Yingchun and Hu, Enyuan and Xiao, Dongdong and Wang, Yi and Yu, Xiqian and Xu, Guiliang and Ehrlich, Steven N. and Amine, Khalil and Gu, Lin and Yang, Xiao -Qing and Li, Hong},
abstractNote = {Li2Ru0.5Mn0.5O3, a high capacity lithium rich layered cathode material for lithium-ion batteries, was subject to comprehen-sive diagnostic studies including in situ/ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), pair distribu-tion function (PDF) and high resolution scanning transmission electron microscopy (STEM) analysis, to understand the cor-relations between transition metal chemistry, structure and lithium storage electrochemical behavior. Ru-Ru dimers have been identified in the as-prepared sample and found to be preserved upon prolonged cycling. Presence of these dimers, which are likely caused by the delocalized nature of 4d electrons, is found to favor the stabilization of the structure in a lay-ered phase. The in situ XAS results confirm the participation of oxygen redox into the charge compensation at high charge voltage, and the great flexibility of the covalent bond between Ru and O may provide great reversibility of the global struc-ture despite of the significant local distortion around Ru. In contrast, the local distortion around Mn occurs at low discharge voltage and is accompanied by a “layered to 1T” phase transformation, which is found to be detrimental to the cycle per-formances. It is clear that the changes of local structure around individual transition metal cations respond separately and differently to lithium intercalation/deintercalation. Here, cations with the capability to tolerate the lattice distortion will benefit for maintaining the integrality of the crystal structure and therefore is able to enhance the long-term cycling performance of the electrode materials.},
doi = {10.1021/acs.chemmater.7b02299},
journal = {Chemistry of Materials},
number = 21,
volume = 29,
place = {United States},
year = {2017},
month = {10}
}