First-Principles Study of Spinel MgTiS2 as a Cathode Material

Kolli, Sanjeev Krishna; Van der Ven, Anton

doi:10.1021/acs.chemmater.8b00552

First-Principles Study of Spinel MgTiS₂ as a Cathode Material

Journal Article · Tue Mar 20 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b00552· OSTI ID:1480081

^[1]; Van der Ven, Anton ^[1]

Univ. of California, Santa Barbara, CA (United States)

Spinel intercalation hosts are well known to to facilitate high rate capability and high voltage Li-ion batteries. A recent experimental study has shown that Mg can reversibly intercalate in spinel TiS₂, demonstrating the viability of Li intercalation host crystal structures for Mg-ion batteries. We report on a first-principles statistical mechanics study of Mg insertion into spinel TiS₂, accounting for occupancy on both octahedrally and tetrahedrally coordinated interstitial sites. In contrast to Li-containing spinels, we predict mixed octahedral and tetrahedral site occupancy at nondilute Mg concentrations consistent with the recent experimental study of Sun et al. The onset of mixed occupancy is correlated with an increase in the spinel volume upon Mg insertion, which is more pronounced in MgxTiS₂ than in its Li counterpart. Lastly, the results in this study suggest that the degree of mixed occupancy could be controlled through the volume of the host with addition of electrochemically inactive species.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1480081

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 7 Vol. 30; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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