Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness

Yejing Li; Xuefeng Wang; Yurui Gao; Qinghua Zhang; Guoqiang Tan; Qingyu Kong; Seongmin Bak; Gang Lu; Xiao Qing Yang; Lin Gu; Jun Lu; Khalil Amine; Zhaoxiang Wang; Liquan Chen

doi:10.1002/aenm.201803087

Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness

Yejing Li, Xuefeng Wang, Yurui Gao, Qinghua Zhang, Guoqiang Tan, Qingyu Kong, Seongmin Bak, Gang Lu, Xiao Qing Yang, Lin Gu, Jun Lu, Khalil Amine, Zhaoxiang Wang, Liquan Chen

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

67 Citations (Scopus)

Abstract

Cathode materials with high energy density, long cycle life, and low cost are of top priority for energy storage systems. The Li-rich transition metal (TM) oxides achieve high specific capacities by redox reactions of both the TM and oxygen ions. However, the poor reversible redox reaction of the anions results in severe fading of the cycling performance. Herein, the vacancy-containing Na_4/7[Mn_6/7(◻_Mn)_1/7]O₂ (◻_Mn for vacancies in the MnO slab) is presented as a novel cathode material for Na-ion batteries. The presence of native vacancies endows this material with attractive properties including high structural flexibility and stability upon Na-ion extraction and insertion and high reversibility of oxygen redox reaction. Synchrotron X-ray absorption near edge structure and X-ray photoelectron spectroscopy studies demonstrate that the charge compensation is dominated by the oxygen redox reaction and Mn³⁺/Mn⁴⁺ redox reaction separately. In situ synchrotron X-ray diffraction exhibits its zero-strain feature during the cycling. Density functional theory calculations further deepen the understanding of the charge compensation by oxygen and manganese redox reactions and the immobility of the Mn ions in the material. These findings provide new ideas on searching for and designing materials with high capacity and high structural stability for novel energy storage systems.

Original language	English
Article number	1803087
Journal	Advanced Energy Materials
Volume	9
Issue number	4
DOIs	https://doi.org/10.1002/aenm.201803087
Publication status	Published - 2019 Jan 24

Bibliographical note

Funding Information:
Y.L., X.W., and Z.W. conceived the idea. Y.L. performed the synthesis, electrochemical test, and characterizations of XRD, SEM, XPS, and Raman. Y.G. performed the DFT calculations. Q.Z. performed the STEM. G.T. carried the in situ synchrotron XRD. Q.K. performed the XAS test. Q.K. and S.B. analyzed the XAS data. All the authors contributed to the analysis and discussion of the paper. This work was financially supported by the National Key Development Program of China (Grant No. 2015CB251100) and the National Natural Science Foundation of China (NSFC Grant No. 51372268). J.L. and K.A. gratefully acknowledge support from the U. S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. The work done at the Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) program, including Battery500 Consortium under contract no. DE-SC0012704. Y.L. appreciates the discussion with Tongchao Liu from Argonne National lab.

Publisher Copyright:
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

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

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/aenm.201803087

Cite this

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title = "Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness",

abstract = "Cathode materials with high energy density, long cycle life, and low cost are of top priority for energy storage systems. The Li-rich transition metal (TM) oxides achieve high specific capacities by redox reactions of both the TM and oxygen ions. However, the poor reversible redox reaction of the anions results in severe fading of the cycling performance. Herein, the vacancy-containing Na4/7[Mn6/7(◻Mn)1/7]O2 (◻Mn for vacancies in the MnO slab) is presented as a novel cathode material for Na-ion batteries. The presence of native vacancies endows this material with attractive properties including high structural flexibility and stability upon Na-ion extraction and insertion and high reversibility of oxygen redox reaction. Synchrotron X-ray absorption near edge structure and X-ray photoelectron spectroscopy studies demonstrate that the charge compensation is dominated by the oxygen redox reaction and Mn3+/Mn4+ redox reaction separately. In situ synchrotron X-ray diffraction exhibits its zero-strain feature during the cycling. Density functional theory calculations further deepen the understanding of the charge compensation by oxygen and manganese redox reactions and the immobility of the Mn ions in the material. These findings provide new ideas on searching for and designing materials with high capacity and high structural stability for novel energy storage systems.",

author = "Yejing Li and Xuefeng Wang and Yurui Gao and Qinghua Zhang and Guoqiang Tan and Qingyu Kong and Seongmin Bak and Gang Lu and Yang, {Xiao Qing} and Lin Gu and Jun Lu and Khalil Amine and Zhaoxiang Wang and Liquan Chen",

note = "Funding Information: Y.L., X.W., and Z.W. conceived the idea. Y.L. performed the synthesis, electrochemical test, and characterizations of XRD, SEM, XPS, and Raman. Y.G. performed the DFT calculations. Q.Z. performed the STEM. G.T. carried the in situ synchrotron XRD. Q.K. performed the XAS test. Q.K. and S.B. analyzed the XAS data. All the authors contributed to the analysis and discussion of the paper. This work was financially supported by the National Key Development Program of China (Grant No. 2015CB251100) and the National Natural Science Foundation of China (NSFC Grant No. 51372268). J.L. and K.A. gratefully acknowledge support from the U. S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. The work done at the Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) program, including Battery500 Consortium under contract no. DE-SC0012704. Y.L. appreciates the discussion with Tongchao Liu from Argonne National lab. Publisher Copyright: {\textcopyright} 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

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doi = "10.1002/aenm.201803087",

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AU - Li, Yejing

AU - Wang, Xuefeng

AU - Gao, Yurui

AU - Zhang, Qinghua

AU - Tan, Guoqiang

AU - Kong, Qingyu

AU - Bak, Seongmin

AU - Lu, Gang

AU - Yang, Xiao Qing

AU - Gu, Lin

AU - Lu, Jun

AU - Amine, Khalil

AU - Wang, Zhaoxiang

AU - Chen, Liquan

N1 - Funding Information: Y.L., X.W., and Z.W. conceived the idea. Y.L. performed the synthesis, electrochemical test, and characterizations of XRD, SEM, XPS, and Raman. Y.G. performed the DFT calculations. Q.Z. performed the STEM. G.T. carried the in situ synchrotron XRD. Q.K. performed the XAS test. Q.K. and S.B. analyzed the XAS data. All the authors contributed to the analysis and discussion of the paper. This work was financially supported by the National Key Development Program of China (Grant No. 2015CB251100) and the National Natural Science Foundation of China (NSFC Grant No. 51372268). J.L. and K.A. gratefully acknowledge support from the U. S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. The work done at the Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) program, including Battery500 Consortium under contract no. DE-SC0012704. Y.L. appreciates the discussion with Tongchao Liu from Argonne National lab. Publisher Copyright: © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/1/24

Y1 - 2019/1/24

N2 - Cathode materials with high energy density, long cycle life, and low cost are of top priority for energy storage systems. The Li-rich transition metal (TM) oxides achieve high specific capacities by redox reactions of both the TM and oxygen ions. However, the poor reversible redox reaction of the anions results in severe fading of the cycling performance. Herein, the vacancy-containing Na4/7[Mn6/7(◻Mn)1/7]O2 (◻Mn for vacancies in the MnO slab) is presented as a novel cathode material for Na-ion batteries. The presence of native vacancies endows this material with attractive properties including high structural flexibility and stability upon Na-ion extraction and insertion and high reversibility of oxygen redox reaction. Synchrotron X-ray absorption near edge structure and X-ray photoelectron spectroscopy studies demonstrate that the charge compensation is dominated by the oxygen redox reaction and Mn3+/Mn4+ redox reaction separately. In situ synchrotron X-ray diffraction exhibits its zero-strain feature during the cycling. Density functional theory calculations further deepen the understanding of the charge compensation by oxygen and manganese redox reactions and the immobility of the Mn ions in the material. These findings provide new ideas on searching for and designing materials with high capacity and high structural stability for novel energy storage systems.

AB - Cathode materials with high energy density, long cycle life, and low cost are of top priority for energy storage systems. The Li-rich transition metal (TM) oxides achieve high specific capacities by redox reactions of both the TM and oxygen ions. However, the poor reversible redox reaction of the anions results in severe fading of the cycling performance. Herein, the vacancy-containing Na4/7[Mn6/7(◻Mn)1/7]O2 (◻Mn for vacancies in the MnO slab) is presented as a novel cathode material for Na-ion batteries. The presence of native vacancies endows this material with attractive properties including high structural flexibility and stability upon Na-ion extraction and insertion and high reversibility of oxygen redox reaction. Synchrotron X-ray absorption near edge structure and X-ray photoelectron spectroscopy studies demonstrate that the charge compensation is dominated by the oxygen redox reaction and Mn3+/Mn4+ redox reaction separately. In situ synchrotron X-ray diffraction exhibits its zero-strain feature during the cycling. Density functional theory calculations further deepen the understanding of the charge compensation by oxygen and manganese redox reactions and the immobility of the Mn ions in the material. These findings provide new ideas on searching for and designing materials with high capacity and high structural stability for novel energy storage systems.

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Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness

Abstract

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UN SDGs

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