Mitigating oxygen release in anionic-redox-active cathode materials by cationic substitution through rational design

Thomas A. Wynn, Chengcheng Fang, Minghao Zhang, Haodong Liu, Daniel M. Davies, Xuefeng Wang, Derek Lau, Jungwoo Z. Lee, Bo Yuan Huang, Kuan Zong Fung, Chung Ta Ni, Ying Shirley Meng

研究成果: Article

摘要

When substituting excess lithium in the transition metal layer, oxygen extends its role as a framework in classical layered oxide cathodes, exhibiting electrochemical activity and enhancing the reversible capacities of layered oxides through anionic redox mechanisms. However, oxygen activity comes with instability in the form of oxygen loss, which is associated with irreversible voltage decay and capacity fade. To understand this irreversible loss and to increase the stability of lattice oxygen, density functional theory is applied to calculate oxygen vacancy formation energies in lithium rich transition metal layered oxides for a variety of dopants, noting increased stability upon doping with 4d elements Mo and Ru. Driven by these findings, Mo is co-doped with Co into Li[Li0.2Ni0.2Mn0.6]O2, showing notably reduced voltage decay and capacity fade without sacrificing energy density and cycle life, and the evidence of Mo incorporation is presented. Calculations suggest that this is due to a modified charge density distribution around anions upon incorporation of Mo, altering the local band structure and impeding oxygen vacancy formation, while maintaining the anionic activity available for redox.

原文English
頁(從 - 到)24651-24659
頁數9
期刊Journal of Materials Chemistry A
6
發行號47
DOIs
出版狀態Published - 2018 一月 1

指紋

Cathodes
Substitution reactions
Oxides
Oxygen
Oxygen vacancies
Lithium
Transition metals
Doping (additives)
Electric potential
Charge density
Chemical elements
Band structure
Density functional theory
Anions
Life cycle
Negative ions
Oxidation-Reduction

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

引用此文

Wynn, Thomas A. ; Fang, Chengcheng ; Zhang, Minghao ; Liu, Haodong ; Davies, Daniel M. ; Wang, Xuefeng ; Lau, Derek ; Lee, Jungwoo Z. ; Huang, Bo Yuan ; Fung, Kuan Zong ; Ni, Chung Ta ; Meng, Ying Shirley. / Mitigating oxygen release in anionic-redox-active cathode materials by cationic substitution through rational design. 於: Journal of Materials Chemistry A. 2018 ; 卷 6, 編號 47. 頁 24651-24659.
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abstract = "When substituting excess lithium in the transition metal layer, oxygen extends its role as a framework in classical layered oxide cathodes, exhibiting electrochemical activity and enhancing the reversible capacities of layered oxides through anionic redox mechanisms. However, oxygen activity comes with instability in the form of oxygen loss, which is associated with irreversible voltage decay and capacity fade. To understand this irreversible loss and to increase the stability of lattice oxygen, density functional theory is applied to calculate oxygen vacancy formation energies in lithium rich transition metal layered oxides for a variety of dopants, noting increased stability upon doping with 4d elements Mo and Ru. Driven by these findings, Mo is co-doped with Co into Li[Li0.2Ni0.2Mn0.6]O2, showing notably reduced voltage decay and capacity fade without sacrificing energy density and cycle life, and the evidence of Mo incorporation is presented. Calculations suggest that this is due to a modified charge density distribution around anions upon incorporation of Mo, altering the local band structure and impeding oxygen vacancy formation, while maintaining the anionic activity available for redox.",
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Wynn, TA, Fang, C, Zhang, M, Liu, H, Davies, DM, Wang, X, Lau, D, Lee, JZ, Huang, BY, Fung, KZ, Ni, CT & Meng, YS 2018, 'Mitigating oxygen release in anionic-redox-active cathode materials by cationic substitution through rational design', Journal of Materials Chemistry A, 卷 6, 編號 47, 頁 24651-24659. https://doi.org/10.1039/c8ta06296j

Mitigating oxygen release in anionic-redox-active cathode materials by cationic substitution through rational design. / Wynn, Thomas A.; Fang, Chengcheng; Zhang, Minghao; Liu, Haodong; Davies, Daniel M.; Wang, Xuefeng; Lau, Derek; Lee, Jungwoo Z.; Huang, Bo Yuan; Fung, Kuan Zong; Ni, Chung Ta; Meng, Ying Shirley.

於: Journal of Materials Chemistry A, 卷 6, 編號 47, 01.01.2018, p. 24651-24659.

研究成果: Article

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AU - Fang, Chengcheng

AU - Zhang, Minghao

AU - Liu, Haodong

AU - Davies, Daniel M.

AU - Wang, Xuefeng

AU - Lau, Derek

AU - Lee, Jungwoo Z.

AU - Huang, Bo Yuan

AU - Fung, Kuan Zong

AU - Ni, Chung Ta

AU - Meng, Ying Shirley

PY - 2018/1/1

Y1 - 2018/1/1

N2 - When substituting excess lithium in the transition metal layer, oxygen extends its role as a framework in classical layered oxide cathodes, exhibiting electrochemical activity and enhancing the reversible capacities of layered oxides through anionic redox mechanisms. However, oxygen activity comes with instability in the form of oxygen loss, which is associated with irreversible voltage decay and capacity fade. To understand this irreversible loss and to increase the stability of lattice oxygen, density functional theory is applied to calculate oxygen vacancy formation energies in lithium rich transition metal layered oxides for a variety of dopants, noting increased stability upon doping with 4d elements Mo and Ru. Driven by these findings, Mo is co-doped with Co into Li[Li0.2Ni0.2Mn0.6]O2, showing notably reduced voltage decay and capacity fade without sacrificing energy density and cycle life, and the evidence of Mo incorporation is presented. Calculations suggest that this is due to a modified charge density distribution around anions upon incorporation of Mo, altering the local band structure and impeding oxygen vacancy formation, while maintaining the anionic activity available for redox.

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