Metastable Li1+δMn2O4 (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

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

doi:10.1021/acs.chemmater.8b03199

Title: Metastable Li_1+δMn₂O₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

Journal Article · 04 December 2018 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.8b03199 · OSTI ID:1490608

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here, we examine the reaction mechanisms driven by the lithiation of Li_1+δMn₂O₄ (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 LiMn₂O₄ and Li₂Mn₂O₄ experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn–Teller distorted Mn³⁺. 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. In conclusion, these findings redefine the conventional understandings on two-phase reactions of this spinel material.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Nuclear Physics (NP) (SC-26)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1490608

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 1 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Metastable Li1+δMn2O4 (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

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Title: Metastable Li_1+δMn₂O₄ (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations