Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li0.5MnO2

Seymour, Ieuan D.; Chakraborty, Sudip; Middlemiss, Derek S.; Wales, David J.; Grey, Clare P.

doi:10.1021/acs.chemmater.5b01674

Title: Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li_0.5MnO₂

Journal Article · Mon Aug 03 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b01674· OSTI ID:1371076

Seymour, Ieuan D. ^[1]; Chakraborty, Sudip ^[2]; Middlemiss, Derek S. ^[3]; Wales, David J. ^[1]; Grey, Clare P. ^[1]

Univ. of Cambridge (United Kingdom)
Uppsala Univ. (Sweden)
Univ. of Warwick, Coventry (United Kingdom)

The migration mechanism associated with the initial layered-to-spinel transformation of partially delithiated layered LiMnO₂ was studied using hybrid eigenvector-following coupled with density functional theory. The initial part of the transformation mechanism of Li_0.5MnO₂ involves the migration of Li into both octahedral and tetrahedral local minima within the layered structure. The next stage of the transformation process involves the migration of Mn and was found to occur through several local minima, including an intermediate square pyramidal MnO₅ configuration and an independent Mn³⁺ to Mn²⁺ charge-transfer process. The migration pathways were found to be significantly affected by the size of the supercell used and the inclusion of a Hubbard U parameter in the DFT functional. The transition state searching methodology described should be useful for studying the structural rearrangements that can occur in electrode materials during battery cycling, and more generally, ionic and electronic transport phenomena in a wide range of energy materials.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001294

OSTI ID:: 1371076

Journal Information:: Chemistry of Materials, Vol. 27, Issue 16; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Title: Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li_0.5MnO₂