Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi2–yMnyO4 (0.4 ≤ y ≤ 1)

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

doi:10.1021/acs.chemmater.5b03360

Title: Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi_2–yMn_yO₄ (0.4 ≤ y ≤ 1)

Journal Article · Wed Oct 28 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b03360· OSTI ID:1261485

Kan, Wang Hay ^[1]; Huq, Ashfia ^[2]; Manthiram, Arumugam ^[1]

Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program. Texas Materials Inst.
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Science Division

The thermal conversion of chemically delithiated layered Li_0.5Ni_1–yMn_yO₂ (0.2 ≤ y ≤ 0.5) into spinel-like LiNi_2–yMn_yO₄ (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.

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Research Organization:: Univ. of Texas, Austin, TX (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Welch Foundation (United States)

Grant/Contract Number:: AC05-00OR22725; AC02-06CH11357; DMR-1122603

OSTI ID:: 1261485

Journal Information:: Chemistry of Materials, Vol. 27, Issue 22; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li _1.3 Ta _0.3 Mn _0.4 O ₂ Cathode Kan, Wang Hay; Wei, Chenxi; Chen, Dongchang Advanced Functional Materials, Vol. 29, Issue 17 https://doi.org/10.1002/adfm.201808294	journal	February 2019
Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries Lee, Boeun; Seo, Hyo Ree; Lee, Hae Ri ChemSusChem, Vol. 9, Issue 20 https://doi.org/10.1002/cssc.201600702	journal	September 2016
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020

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