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Structural and Electrochemical Properties of Type VIII Ba8Ga16−δSn30+δClathrate (δ≈1) during Lithiation
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). University of Delaware, United States.ORCID iD: 0000-0002-0537-4234
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Number of Authors: 72021 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 13, no 36, p. 42564-42578Article in journal (Refereed) Published
Abstract [en]

Clathrates of the tetrel (Tt = Si, Ge, Sn) elements are host-guest structures that can undergo Li alloying reactions with high capacities. However, little is known about how the cage structure affects the phase transformations that take place during lithiation. To further this understanding, the structural changes of the type VIII clathrate Ba8Ga16-delta Sn30+delta (delta approximate to 1) during lithiation are investigated and compared to those in beta-Sn with ex situ X-ray total scattering measurements and pair distribution function (PDF) analysis. The results show that the type VIII clathrate undergoes an alloying reaction to form Li-rich amorphous phases (LixBa0.17Ga0.33Sn0.67, x = 2-3) with local structures similar to those in the crystalline binary Li-Sn phases that form during the lithiation of beta-Sn. As a result of the amorphous phase transition, the type VIII clathrate reacts at a lower voltage (0.25 V vs Li/Li+) compared to beta-Sn (0.45 V) and goes through a solid-solution reaction after the initial conversion of the crystalline clathrate phase. Cycling experiments suggest that the amorphous phase persists after the first lithiation and results in considerably better cycling than in beta-Sn. Density functional theory (DFT) calculations suggest that topotactic Li insertion into the clathrate lattice is not favorable due to the high energy of the Li sites, which is consistent with the experimentally observed amorphous phase transformation. The local structure in the clathrate featuring Ba atoms surrounded by a cage of Ga and Sn atoms is hypothesized to kinetically circumvent the formation of Li-Sn or Li-Ga crystalline phases, which results in better cycling and a lower reaction voltage. Based on the improved electrochemical performance, clathrates could act as tunable precursors to form amorphous Li alloying phases with novel electrochemical properties.

Place, publisher, year, edition, pages
2021. Vol. 13, no 36, p. 42564-42578
Keywords [en]
clathrate, amorphous, pair distribution function, density functional theory, lithium, energy storage
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-197869DOI: 10.1021/acsami.1c07240ISI: 000697282300021PubMedID: 34477361OAI: oai:DiVA.org:su-197869DiVA, id: diva2:1604343
Available from: 2021-10-19 Created: 2021-10-19 Last updated: 2022-02-25Bibliographically approved

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Ovchinnikov, Alexander

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