Electrochemical lithium intercalation chemistry of condensed molybdenum metal cluster oxide: LiMo4O6

Sung Chul Lim, Munseok S. Chae, Jongwook W. Heo, Seung Tae Hong

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The electrochemical lithium-ion intercalation properties of molybdenum metal-cluster oxide LixMo4O6 (0.33 ≤ x ≤ 1.0) in an organic electrolyte of 1.0 M LiPF6 in ethylene carbonate/dimethyl carbonate (1:2 v/v) were characterized for the first time. Li0.66Mo4O6 (tetragonal, P4/mbm, a = 9.5914(3) Å, c = 2.8798(1) Å, V = 264.927(15) Å3, Z = 2) was prepared via ion-exchange of indium and lithium ions from InMo4O6 (tetragonal, P4/mbm, a = 9.66610(4) Å, c = 2.86507(2) Å, V = 267.694(2) Å3, Z = 2), which was first synthesized from a stoichiometric mixture of In, Mo, and MoO3 via a solid-state reaction for 11 h at 1100 °C. Then, Li0.33Mo4O6 was obtained via electrochemical charge of the electrode at 3.4 V vs. Li. The electrochemical lithium-ion insertion into Li0.33Mo4O6 occurs stepwise: three separate peaks were observed in the cyclic voltammogram and three quasi-plateaus in the galvanostatic profile, indicating a complicated intercalation mechanism. However, examination of the structural evolution of LixMo4O6 during the electrochemical cycle indicated a reversible reaction over the measured voltage range (2.0–3.2 V) and x range (0.33 ≤ x ≤ 1.00). Despite the excellent electrochemical reversibility, LixMo4O6 showed poor rate performance with a low capacity of 36.3 mAh g−1 at a rate of 0.05 C. Nonetheless, this work demonstrates a new structural class of lithium cathode materials with condensed metal clusters and 1D tunnels, and provides a host material candidate for multivalent-ion batteries.

Original languageEnglish
Pages (from-to)90-95
Number of pages6
JournalJournal of Solid State Chemistry
Volume254
DOIs
StatePublished - Oct 2017
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2017 Elsevier Inc.

Funding

This research was supported by Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) and funded by the Ministry of Science, ICT and Future Planning (2015M3D1A1069707).

FundersFunder number
Ministry of Science, ICT and Future Planning2015M3D1A1069707
National Research Foundation of Korea

    Keywords

    • Crystal structure
    • InMoO
    • Li intercalation
    • LiMoO
    • Lithium ion battery
    • Molybdenum metal cluster

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