Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li2Ru0.5Mn0.5O3 Investigated in a Wide Voltage Window

doi:https://doi.org/10.1021/acs.chemmater.7b02299

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

Abstract

Li2Ru0.5Mn0.5O3, a high capacity lithium-rich layered cathode material for lithium-ion batteries, was subject to comprehensive diagnostic studies, including in situ/ex situ X-ray diffraction, X-ray absorption spectroscopy (XAS), pair distribution function, and high resolution scanning transmission electron microscopy analysis, to understand the correlations between transition-metal chemistry, structure, and lithium storage electrochemical behavior. Ru-Ru dimers were 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 layered 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 structure despite 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 performances. It is clear that the changes of local structure around individual transition-metal cations respond separately and differently to lithium intercalation/ deintercalation. Cations with the capability to toleratemore »« less

Authors:

^[1]; Hu, Enyuan ^[2]; Xiao, Dongdong ^[3]; Wang, Yi ^[3];

^[3]; Xu, Guiliang ^[4]; Ehrlich, Steven N. ^[2];

^[4];

^[5]; Yang, Xiao -Qing ^[2];

^[3]

Chinese Academy of Sciences (CAS), Beijing (China); Shanghai Univ., Shanghai (China)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Chinese Academy of Sciences (CAS), Beijing (China)
Argonne National Lab. (ANL), Argonne, IL (United States)
Chinese Academy of Sciences (CAS), Beijing (China); Collaborative Innovation Center of Quantum Matter, Beijing (China)

Publication Date:: 2017-10-20

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); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

OSTI Identifier:: 1405938

Alternate Identifier(s):: OSTI ID: 1461410

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

Resource Type:: Journal Article: 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)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; National Synchrotron Light Source; lithium-ion batteries; cathode; lithium rich layered oxides

Citation Formats


                    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., 2017. 
        Web.  doi:10.1021/acs.chemmater.7b02299.

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                    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.  https://doi.org/10.1021/acs.chemmater.7b02299

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                    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. Fri .  
        "Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li2Ru0.5Mn0.5O3 Investigated in a Wide Voltage Window".  United States.  https://doi.org/10.1021/acs.chemmater.7b02299.  https://www.osti.gov/servlets/purl/1405938.

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@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 comprehensive diagnostic studies, including in situ/ex situ X-ray diffraction, X-ray absorption spectroscopy (XAS), pair distribution function, and high resolution scanning transmission electron microscopy analysis, to understand the correlations between transition-metal chemistry, structure, and lithium storage electrochemical behavior. Ru-Ru dimers were 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 layered 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 structure despite 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 performances. It is clear that the changes of local structure around individual transition-metal cations respond separately and differently to lithium intercalation/ deintercalation. Cations with the capability to tolerate the lattice distortion will be beneficial 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},

  url          = {https://www.osti.gov/biblio/1405938},
  journal      = {Chemistry of Materials},

  issn         = {0897-4756},

  number       = 21,

  volume       = 29,

  place        = {United States},

  year         = {2017},

  month        = {10}

}

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https://doi.org/10.1021/acs.chemmater.7b02299

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Works referencing / citing this record:

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides
journal, January 2020

Han, Miao; Jiao, Junyu; Liu, Zepeng
Advanced Energy Materials, Vol. 10, Issue 8
https://doi.org/10.1002/aenm.201903634

Improving the Electrochemical Performance of Li ₂ RuO ₃ through Chemical Substitution: A Case Study of ( x )LiCoO ₂ ‐(1‐ x )Li ₂ RuO ₃ Solid Solution ( x ≤0.4)
journal, December 2019

Neelakantaiah, Ramesha R.; Dasari, Bosu Babu; Ette, Pedda Masthanaiah
ChemElectroChem, Vol. 7, Issue 1
https://doi.org/10.1002/celc.201902059

Cracks Formation in Lithium-Rich Cathode Materials for Lithium-Ion Batteries during the Electrochemical Process
journal, October 2018

Cheng, Tao; Ma, Zhongtao; Gu, Run
Energies, Vol. 11, Issue 10
https://doi.org/10.3390/en11102712

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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

Abstract

Citation Formats

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides journal, January 2020

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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

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides
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