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

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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:

; Hu, Enyuan ^[2]; Xiao, Dongdong ^[3]; Wang, Yi ^[3]; ; Xu, Guiliang ^[4]; Ehrlich, Steven N. ^[2]; ; ; Yang, Xiao -Qing ^[2];

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:: Fri Oct 20 00:00:00 EDT 2017

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1405938

Report Number(s):: BNL-114463-2017-JA
Journal ID: ISSN 0897-4756; R&D Project: MA453MAEA; VT1201000; TRN: US1702902

Grant/Contract Number:: SC0012704

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.  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, 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.

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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 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         = {Fri Oct 20 00:00:00 EDT 2017},

  month        = {Fri Oct 20 00:00:00 EDT 2017}

}

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DOI: 10.1021/acs.chemmater.7b02299

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Three-layer Aurivillius phases containing magnetic transition metal cations: Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, M=Ru{sup 4+}, Ir{sup 4+}, Mn{sup 4+}, x{approx}0.5

Sharma, Neeraj ; Ling, Chris D. ; Wrighter, Grant E. ; ... - Journal of Solid State Chemistry

We report the synthesis of Aurivillius-type phases incorporating magnetic M {sup 4+} cations (M=Mn, Ru, Ir), based on the substitution of M {sup 4+} for Ti{sup 4+} in Bi{sub 2}Sr{sub 2}(Nb,Ta){sub 2}TiO{sub 12}. Key to incorporating these magnetic transition metal cations appears to be the partial substitution of Sr{sup 2+} for Bi{sup 3+} in the {alpha}-PbO-type layer of the Aurivillius phase, leading to a concomitant decrease in the M {sup 4+} content; i.e., the composition of the prepared compounds was Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, x{approx}0.5. Thesemore »« less
DOI: 10.1016/j.jssc.2006.10.031
Three-layer Aurivillius phases containing magnetic transition metal cations : Bi{sub 2-x}Sr{sub 2+x}(Nb,Ta){sub 2+x}M{sub 1-x}O{sub 12}, M = Ru{sub 4+}, Ir{sub 4+}, Mn{sub 4+}, x {approx} 0.5.

Sharma, N. ; Wrighter, G. E. ; Chen, P. Y. ; ... - J. Solid State Chem.

We report the synthesis of Aurivillius-type phases incorporating magnetic M{sup 4+} cations (M=Mn, Ru, Ir), based on the substitution of M{sup 4+} for Ti{sup 4+} in Bi{sub 2}Sr{sub 2}(Nb,Ta){sub 2}TiO{sub 12}. The key to incorporating these magnetic transition metal cations appears to be the partial substitution of Sr{sup 2+} for Bi{sup 3+} in the {alpha}-PbO-type layer of the Aurivillius phase, leading to a concomitant decrease in the M{sup 4+} content; i.e., the composition of the prepared compounds was Bi{sub 2-x}Sr{sub 2+x}(Nb,Ta){sub 2+x}M{sub 1-x}O{sub 12}, x {approx} 0.5. These compounds only exist over a narrow range of x, between an apparentmore »« less
DOI: 10.1016/j.jssc.2006.10.031
LiLaPO{sub 4}-coated Li[Ni{sub 0.5}Co{sub 0.2}Mn{sub 0.3}]O{sub 2} and AlF{sub 3}-coated Li[Ni{sub 0.5}Co{sub 0.2}Mn{sub 0.3}]O{sub 2} blend composite for lithium ion batteries

Song, Han Gab ; Park, Yong Joon, E-mail: yjpark2006@kyonggi.ac.kr - Materials Research Bulletin

A blended composite of LiLaPO{sub 4}-coated Li[Ni{sub 0.5}Co{sub 0.2}Mn{sub 0.3}]O{sub 2} and AlF{sub 3}-coated Li[Ni{sub 0.5}Co{sub 0.2}Mn{sub 0.3}]O{sub 2} was tested as the cathode of lithium secondary batteries. The rate capability, cyclic performance, and thermal stability of the blended electrode were characterized and compared with pristine, AlF{sub 3}-coated, and LiLaPO{sub 4}-coated electrodes. The blended sample showed good cyclic performance and thermal stability, which implies that blending these two cathode coatings were effective in obtaining their advantages and lessening their weaknesses.
DOI: 10.1016/J.MATERRESBULL.2012.04.127
Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O and Co-O bonded interactions for tephroite, Mn ₂SiO ₄, fayalite, Fe ₂SiO ₄ and Co ₂SiO ₄ olivine and selected organic metal complexes: Comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides

Gibbs, Gerald V. ; Downs, R. T. ; Cox, David F. ; ... - Journal of Physical Chemistry. C

Bond critical point, bcp, and local energy density properties for the electron density, ED, distributions, calculated with first principle quantum mechanical methods for divalent transition metal Mn-, Co- and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn ₂SiO ₄, fayalite, Fe ₂SiO ₄ and Co ₂SiO ₄ olivine, each determined with high energy synchrotron single crystal X-ray diffraction data. Trends observed between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp, local total energy density, H(rmore »« less
DOI: 10.1021/jp804280j
Synthesis and electrochemical properties of layer-structured 0.5Li(Ni{sub 0.5}Mn{sub 0.5})O{sub 2}{emdash}0.5Li(Li{sub 1/3}Mn{sub2/3})O{sub 2} solid mixture.

Kang, S.-H. ; Amine, K. ; Chemical Engineering - J. Power Sources

A 1:1 mixture of electrochemically active Li(Ni{sub 0.5}Mn{sub 0.5})O{sub 2} and electrochemically inactive Li(Li{sub 1/3}Mn{sub 2/3})O{sub 2}, i.e. Li(Li{sub 0.17}Ni{sub 0.25}Mn{sub 0.58})O{sub 2}, has been synthesized by a sol-gel method. The mixture was calcined at 900 {sup o}C in air for 24 h and cooled at three different rates: quenched into liquid nitrogen, 2 {sup o}C/min, and 0.5 {sup o}C/min. It was found that the crystallographic structure and electrochemical properties of Li(Li{sub 0.17}Ni{sub 0.25}Mn{sub 0.58})O{sub 2} highly depend on the cooling rate. The sample quenched into liquid nitrogen exhibited a long irreversible plateau at ca. 4.5 V during the firstmore »« less
DOI: 10.1016/S0378-7753(03)00804-8

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