Metastable Li                         1+δ                         Mn                         2                         O                         4                          (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

Bohang Song; Gabriel M. Veith; Jinseon Park; Mina Yoon; Pamela S. Whitfield; Melanie J. Kirkham; Jue Liu; Ashfia Huq

doi:10.1021/acs.chemmater.8b03199

Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

Bohang Song, Gabriel M. Veith, Jinseon Park, Mina Yoon, Pamela S. Whitfield, Melanie J. Kirkham, Jue Liu, Ashfia Huq

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

30 Scopus citations

Abstract

In this work, we examine the reaction mechanisms driven by the lithiation of Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) spinels via in operando neutron powder diffraction (NPD). New reaction mechanisms are proposed involving solid-solution regions within both cubic and tetragonal spinel phases in addition to a continuous phase transition between them. In operando NPD is an ideal tool to follow the light elements such as lithium and oxygen in cathode materials which are often the key to fully understand their structural evolutions. Here, we report a novel methodology to prepare an extremely thick electrode with ∼378 mg·cm ^-2 loading density suitable for the in operando NPD studies. Enabled by such thick electrode, we find that the metal oxygen M-O (M = Li and Mn) bond lengths in both end members LiMn ₂ O ₄ and Li ₂ Mn ₂ O ₄ experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn-Teller distorted Mn ³⁺ . First-principles density functional theory calculations confirm these metastable intermediates and further propose atomistic reaction pathways for the phase transition by coupling a global structure search algorithm. These findings redefine the conventional understandings on two-phase reactions of this spinel material.

Original language	English
Pages (from-to)	124-134
Number of pages	11
Journal	Chemistry of Materials
Volume	31
Issue number	1
DOIs	https://doi.org/10.1021/acs.chemmater.8b03199
State	Published - Jan 8 2019

Funding

The authors thank Dr. Robert Schmidt for his assistance with the neutron experiment. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (B.S., P.S.W., M.J.K., J.L., and A.H.). Electrochemistry and synthesis was supported by US Department of Energy, Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division (G.M.V.). The 7Li used in this research was supplied by the United States Department of Energy Office of Science by the Isotope Program in the Office of Nuclear Physics. First-principles calculations were performed at the Center for Nanophase Materials Sciences (M.Y.), which is a DOE Office of Science User Facility, supported by the US Department of Energy, Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division, and by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2016M3D1A1919181) (J.P.). Computing resources were provided by the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under contract no. DE-AC02-05CH11231.

Funders	Funder number
Center for Nanophase Materials Sciences
DOE Office of Science
National Energy Research Scientific Computing Center
US Department of Energy
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering
Ministry of Science, ICT and Future Planning	NRF-2016M3D1A1919181
National Research Foundation of Korea

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Song, B., Veith, G. M., Park, J., Yoon, M., Whitfield, P. S., Kirkham, M. J., Liu, J., & Huq, A. (2019). Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations Chemistry of Materials, 31(1), 124-134. https://doi.org/10.1021/acs.chemmater.8b03199

Song, Bohang ; Veith, Gabriel M. ; Park, Jinseon et al. / Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations In: Chemistry of Materials. 2019 ; Vol. 31, No. 1. pp. 124-134.

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title = " Metastable Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations ",

abstract = " In this work, we examine the reaction mechanisms driven by the lithiation of Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) spinels via in operando neutron powder diffraction (NPD). New reaction mechanisms are proposed involving solid-solution regions within both cubic and tetragonal spinel phases in addition to a continuous phase transition between them. In operando NPD is an ideal tool to follow the light elements such as lithium and oxygen in cathode materials which are often the key to fully understand their structural evolutions. Here, we report a novel methodology to prepare an extremely thick electrode with ∼378 mg·cm -2 loading density suitable for the in operando NPD studies. Enabled by such thick electrode, we find that the metal oxygen M-O (M = Li and Mn) bond lengths in both end members LiMn 2 O 4 and Li 2 Mn 2 O 4 experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn-Teller distorted Mn 3+ . First-principles density functional theory calculations confirm these metastable intermediates and further propose atomistic reaction pathways for the phase transition by coupling a global structure search algorithm. These findings redefine the conventional understandings on two-phase reactions of this spinel material.",

author = "Bohang Song and Veith, {Gabriel M.} and Jinseon Park and Mina Yoon and Whitfield, {Pamela S.} and Kirkham, {Melanie J.} and Jue Liu and Ashfia Huq",

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Song, B, Veith, GM, Park, J, Yoon, M, Whitfield, PS, Kirkham, MJ , Liu, J & Huq, A 2019, ' Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations ', Chemistry of Materials, vol. 31, no. 1, pp. 124-134. https://doi.org/10.1021/acs.chemmater.8b03199

Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations . / Song, Bohang; Veith, Gabriel M.; Park, Jinseon et al.
In: Chemistry of Materials, Vol. 31, No. 1, 08.01.2019, p. 124-134.

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

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AU - Liu, Jue

AU - Huq, Ashfia

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N2 - In this work, we examine the reaction mechanisms driven by the lithiation of Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) spinels via in operando neutron powder diffraction (NPD). New reaction mechanisms are proposed involving solid-solution regions within both cubic and tetragonal spinel phases in addition to a continuous phase transition between them. In operando NPD is an ideal tool to follow the light elements such as lithium and oxygen in cathode materials which are often the key to fully understand their structural evolutions. Here, we report a novel methodology to prepare an extremely thick electrode with ∼378 mg·cm -2 loading density suitable for the in operando NPD studies. Enabled by such thick electrode, we find that the metal oxygen M-O (M = Li and Mn) bond lengths in both end members LiMn 2 O 4 and Li 2 Mn 2 O 4 experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn-Teller distorted Mn 3+ . First-principles density functional theory calculations confirm these metastable intermediates and further propose atomistic reaction pathways for the phase transition by coupling a global structure search algorithm. These findings redefine the conventional understandings on two-phase reactions of this spinel material.

AB - In this work, we examine the reaction mechanisms driven by the lithiation of Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) spinels via in operando neutron powder diffraction (NPD). New reaction mechanisms are proposed involving solid-solution regions within both cubic and tetragonal spinel phases in addition to a continuous phase transition between them. In operando NPD is an ideal tool to follow the light elements such as lithium and oxygen in cathode materials which are often the key to fully understand their structural evolutions. Here, we report a novel methodology to prepare an extremely thick electrode with ∼378 mg·cm -2 loading density suitable for the in operando NPD studies. Enabled by such thick electrode, we find that the metal oxygen M-O (M = Li and Mn) bond lengths in both end members LiMn 2 O 4 and Li 2 Mn 2 O 4 experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn-Teller distorted Mn 3+ . First-principles density functional theory calculations confirm these metastable intermediates and further propose atomistic reaction pathways for the phase transition by coupling a global structure search algorithm. These findings redefine the conventional understandings on two-phase reactions of this spinel material.

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Song B, Veith GM, Park J, Yoon M, Whitfield PS, Kirkham MJ et al. Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations Chemistry of Materials. 2019 Jan 8;31(1):124-134. doi: 10.1021/acs.chemmater.8b03199

Metastable Li _1+δ Mn ₂ O ₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

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