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

doi: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

Full Record
Other Related Research

Abstract

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 »« 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), 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.

Copy to clipboard


                    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.

Copy to clipboard


                    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.  doi:10.1021/acs.chemmater.7b02299.  https://www.osti.gov/servlets/purl/1405938.

Copy to clipboard


                    
@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},

  issn         = {0897-4756},

  number       = 21,

  volume       = 29,

  place        = {United States},

  year         = {2017},

  month        = {10}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acs.chemmater.7b02299

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Correlations between Transition-Metal Chemistry, Local Structure, and Global Structure in Li ₂ Ru _0.5 Mn _0.5 O ₃ Investigated in a Wide Voltage Window

Journal Article Lyu, Yingchun ; Hu, Enyuan ; Xiao, Dongdong ; ... - Chemistry of Materials

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 resultsmore »« less
Cited by 4
DOI: 10.1021/acs.chemmater.7b02299

Full Text Available
H ₃PO ₄ treatment to enhance the electrochemical properties of Li(Ni _1/3Mn _1/3Co _1/3)O ₂ and Li(Ni _0.5Mn _0.3Co _0.2)O ₂ cathodes

Journal Article Sahni, Karan ; Ashuri, Maziar ; He, Qianran ; ... - Electrochimica Acta

In this paper, Li(Ni _1/3Mn _1/3Co _1/3)O ₂ (NMC333) and Li(Ni _0.5Mn _0.3Co _0.2)O ₂ (NMC532) have been subjected to a phosphoric acid (H ₃PO ₄) solution treatment to form a thin Li ₃PO ₄ coating on their surfaces. The Li ₃PO ₄ coating formed is found to be very potent in enhancing the specific capacity of the first discharge as well as the rate capability and capacity retention in the subsequent charge/discharge cycles for both NMC333 and NMC532. The specific capacity of the first discharge for NMC532 has been increased drastically from ~160 mA h g ^–1 for pristinemore »« less
DOI: 10.1016/j.electacta.2019.01.153
Spin gaps in the ordered states of ${La}_{2} Li X O_{6} (X = Ru, Os)$ and their relation to the distortion of the cubic double perovskite structure in $4 d^{3}$ and $5 d^{3}$ magnets

Journal Article Maharaj, D. D. ; Sala, G. ; Marjerrison, C. A. ; ... - Physical Review B

Time-of-flight inelastic neutron scattering measurements have been carried out on polycrystalline samples of the 4d ³ and 5d ³ double pervoskite antiferromagnets La ₂LiRuO ₆ and La ₂LiOsO ₆. These reveal the development of an inelastic spin gap in La ₂LiRuO ₆ and La ₂LiOsO ₆ of ~1.8(8) and 6(1) meV, below their respective ordering temperatures TN, ~23.8 and 30 K. The bandwidths of the spin excitations are shown to be ~5.7(9)and12(1)meV, respectively, at low temperatures. Spin gaps are surprising in such magnets as the t _2g levels of Ru ⁵⁺ or Os ⁵⁺ are expected to be half-filled, resultingmore »« less
DOI: 10.1103/PhysRevB.98.104434
Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged Li _xNi _yMn _zCo _1-y-zO ₂ cathode materials

Journal Article Hwang, Sooyeon ; Kim, Seung Min ; Bak, Seong -Min ; ... - Chemistry of Materials

In this study, we use in-situ transmission electron microcopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged Li _xNi _yMn _zCo _1-y-zO ₂ (NMC) cathode materials of different composition (with y, z=0.8, 0.1 and 0.6, 0.2 and 0.4, 0.3), after they have been charged to their practical upper limit voltage (4.3V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (y, z =more »« less
Cited by 14
DOI: 10.1021/acs.chemmater.5b00709

Full Text Available
Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li ₇La ₃Zr ₂O ₁₂ Electrolyte and LiCoO ₂ Cathode

Journal Article Vardar, Gulin ; Bowman, William J. ; Lu, Qiyang ; ... - Chemistry of Materials

All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model systems of LiCoO ₂ (LCO) thin films deposited on cubic Al-doped Li ₇La ₃Zr ₂O ₁₂ (LLZO) pellets were studied as a function ofmore »« less
DOI: 10.1021/acs.chemmater.8b01713

Similar Records

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

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