Identifying the distribution of Al3+ in LiNi0.8Co0.15Al0.05O2

Nicole M. Trease; Ieuan D. Seymour; Maxwell D. Radin; Hao Liu; Haodong Liu; Sunny Hy; Natalya Chernova; Pritesh Parikh; Arun Devaraj; Kamila M. Wiaderek; Peter J. Chupas; Karena W. Chapman; M. Stanley Whittingham; Ying Shirley Meng; Anton Van Der Van; Clare P. Grey

doi:10.1021/acs.chemmater.6b02797

Identifying the distribution of Al³⁺ in LiNi_0.8Co_0.15Al_0.05O₂

Nicole M. Trease, Ieuan D. Seymour, Maxwell D. Radin, Hao Liu, Haodong Liu, Sunny Hy, Natalya Chernova, Pritesh Parikh, Arun Devaraj, Kamila M. Wiaderek, Peter J. Chupas, Karena W. Chapman, M. Stanley Whittingham, Ying Shirley Meng^*, Anton Van Der Van, Clare P. Grey

^*Corresponding author for this work

Chemistry

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

78 Citations (Scopus)

Abstract

The doping of Al into layered Li transition metal (TM) oxide cathode materials, LiTMO₂, is known to improve the structural and thermal stability, although the origin of the enhanced properties is not well understood. The effect of aluminum doping on layer stabilization has been investigated using a combination of techniques to measure the aluminum distribution in layered LiNi_0.8Co_0.15Al_0.05O₂ (NCA) over multiple length scales with ²⁷Al and ⁷Li MAS NMR, local electrode atom probe (APT) tomography, X-ray and neutron diffraction, DFT, and SQUID magnetic susceptibility measurements. APT ion maps show a homogeneous distribution of Ni, Co, Al, and O₂ throughout the structure at the single particle level in agreement with the high-temperature phase diagram. ⁷Li and ²⁷Al NMR indicates that the Ni³⁺ ions undergo a dynamic Jahn-Teller (JT) distortion. ²⁷Al NMR spectra indicate that the Al reduces the strain associated with the JT distortion, by preferential electronic ordering of the JT lengthened bonds directed toward the Al³⁺ ion. The ability to understand the complex atomic and orbital ordering around Al³⁺ demonstrated in the current method will be useful for studying the local environment of Al³⁺ in a range of transition metal oxide battery materials.

Original language	English
Pages (from-to)	8170-8180
Number of pages	11
Journal	Chemistry of Materials
Volume	28
Issue number	22
Early online date	31 Oct 2016
DOIs	https://doi.org/10.1021/acs.chemmater.6b02797
Publication status	Published - 22 Nov 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

Data Availability Statement

Acknowledgement:
This work was supported as part of the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, under Award # DE-SC0012583. The neutron diffraction was conducted at Oak Ridge National Laboratory on POWGEN beamline by mail-in program. Sample preparation and analysis for APT were performed at William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) under Science theme proposal #49095. EMSL is a national scientific user facility sponsored by DOE's Office of Biological and Environmental Research (Contract No. DE-AC05-76RLO1830) and located at Pacific Northwest National Laboratory (PNNL).

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10.1021/acs.chemmater.6b02797

Cite this

Trease, N. M., Seymour, I. D., Radin, M. D., Liu, H., Liu, H., Hy, S., Chernova, N., Parikh, P., Devaraj, A., Wiaderek, K. M., Chupas, P. J., Chapman, K. W., Whittingham, M. S., Meng, Y. S., Van Der Van, A., & Grey, C. P. (2016). Identifying the distribution of Al³⁺ in LiNi_0.8Co_0.15Al_0.05O₂. Chemistry of Materials, 28(22), 8170-8180. https://doi.org/10.1021/acs.chemmater.6b02797

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abstract = "The doping of Al into layered Li transition metal (TM) oxide cathode materials, LiTMO2, is known to improve the structural and thermal stability, although the origin of the enhanced properties is not well understood. The effect of aluminum doping on layer stabilization has been investigated using a combination of techniques to measure the aluminum distribution in layered LiNi0.8Co0.15Al0.05O2 (NCA) over multiple length scales with 27Al and 7Li MAS NMR, local electrode atom probe (APT) tomography, X-ray and neutron diffraction, DFT, and SQUID magnetic susceptibility measurements. APT ion maps show a homogeneous distribution of Ni, Co, Al, and O2 throughout the structure at the single particle level in agreement with the high-temperature phase diagram. 7Li and 27Al NMR indicates that the Ni3+ ions undergo a dynamic Jahn-Teller (JT) distortion. 27Al NMR spectra indicate that the Al reduces the strain associated with the JT distortion, by preferential electronic ordering of the JT lengthened bonds directed toward the Al3+ ion. The ability to understand the complex atomic and orbital ordering around Al3+ demonstrated in the current method will be useful for studying the local environment of Al3+ in a range of transition metal oxide battery materials.",

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