The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials

Xuelong Wang; Xiulin Fan; Xiqian Yu; Seongmin Bak; Zulipiya Shadike; Iradwikanari Waluyo; Adrian Hunt; Sanjaya D. Senanayake; Hong Li; Liquan Chen; Chunsheng Wang; Ruijuan Xiao; Enyuan Hu; Xiao Qing Yang

doi:10.1002/adfm.202001633

The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials

Xuelong Wang, Xiulin Fan, Xiqian Yu, Seongmin Bak, Zulipiya Shadike, Iradwikanari Waluyo, Adrian Hunt, Sanjaya D. Senanayake, Hong Li, Liquan Chen, Chunsheng Wang, Ruijuan Xiao, Enyuan Hu, Xiao Qing Yang

Department of Materials Science and Engineering

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

11 Citations (Scopus)

Abstract

Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X-ray spectroscopy and theoretical calculations is carried out on the Li-Co-Mn-O model system in which the substituting cation Mn⁴⁺, with its 3d³ electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the Co-O bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K-edge X-ray absorption near edge spectroscopy (XANES) spectra show a more “rigid shift” behavior while electron delocalization makes the XANES exhibit a “shape change.” It clearly explains why the K-edge XANES data of some TM oxides show no “rigid shift” while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation.

Original language	English
Article number	2001633
Journal	Advanced Functional Materials
Volume	31
Issue number	2
DOIs	https://doi.org/10.1002/adfm.202001633
Publication status	Published - 2021 Jan 11

Bibliographical note

Funding Information:
X.W. and X.F. contributed equally to this work. The work done at 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 under contract DE‐SC0012704. The work done at Institute of Physics, Chinese Academy of Sciences was supported by the National Natural Science Foundation of China (Grant No. 51772321) and the Youth Innovation Promotion Association (Grant No. 2016005). S.D.S. was supported in part by a DOE Early Career Award. This research used beamlines 7‐BM, 23‐ID‐2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE‐AC02‐98CH10886. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE‐SC0012704. This research also used the Scientific Data and Computing Center, a component of the Computational Science Initiative operated by Brookhaven National Laboratory under Contract No. DE‐SC0012704.

Funding Information:
X.W. and X.F. contributed equally to this work. The work done at 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 under contract DE-SC0012704. The work done at Institute of Physics, Chinese Academy of Sciences was supported by the National Natural Science Foundation of China (Grant No. 51772321) and the Youth Innovation Promotion Association (Grant No. 2016005). S.D.S. was supported in part by a DOE Early Career Award. This research used beamlines 7-BM, 23-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. This research also used the Scientific Data and Computing Center, a component of the Computational Science Initiative operated by Brookhaven National Laboratory under Contract No. DE-SC0012704.

Publisher Copyright:
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

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

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10.1002/adfm.202001633

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title = "The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials",

abstract = "Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X-ray spectroscopy and theoretical calculations is carried out on the Li-Co-Mn-O model system in which the substituting cation Mn4+, with its 3d3 electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the Co-O bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K-edge X-ray absorption near edge spectroscopy (XANES) spectra show a more “rigid shift” behavior while electron delocalization makes the XANES exhibit a “shape change.” It clearly explains why the K-edge XANES data of some TM oxides show no “rigid shift” while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation.",

author = "Xuelong Wang and Xiulin Fan and Xiqian Yu and Seongmin Bak and Zulipiya Shadike and Iradwikanari Waluyo and Adrian Hunt and Senanayake, {Sanjaya D.} and Hong Li and Liquan Chen and Chunsheng Wang and Ruijuan Xiao and Enyuan Hu and Yang, {Xiao Qing}",

note = "Funding Information: X.W. and X.F. contributed equally to this work. The work done at 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 under contract DE‐SC0012704. The work done at Institute of Physics, Chinese Academy of Sciences was supported by the National Natural Science Foundation of China (Grant No. 51772321) and the Youth Innovation Promotion Association (Grant No. 2016005). S.D.S. was supported in part by a DOE Early Career Award. This research used beamlines 7‐BM, 23‐ID‐2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE‐AC02‐98CH10886. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE‐SC0012704. This research also used the Scientific Data and Computing Center, a component of the Computational Science Initiative operated by Brookhaven National Laboratory under Contract No. DE‐SC0012704. Funding Information: X.W. and X.F. contributed equally to this work. The work done at 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 under contract DE-SC0012704. The work done at Institute of Physics, Chinese Academy of Sciences was supported by the National Natural Science Foundation of China (Grant No. 51772321) and the Youth Innovation Promotion Association (Grant No. 2016005). S.D.S. was supported in part by a DOE Early Career Award. This research used beamlines 7-BM, 23-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. This research also used the Scientific Data and Computing Center, a component of the Computational Science Initiative operated by Brookhaven National Laboratory under Contract No. DE-SC0012704. Publisher Copyright: {\textcopyright} 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Bak, Seongmin

AU - Shadike, Zulipiya

AU - Waluyo, Iradwikanari

AU - Hunt, Adrian

AU - Senanayake, Sanjaya D.

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The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials

Abstract

Bibliographical note

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UN SDGs

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