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  Structural and Electrochemical Properties of Type VIII Ba8Ga16−δSn30+δ Clathrate (δ ≈ 1) during Lithiation

Dopilka, A., Childs, A., Ovchinnikov, A., Zhao, R., Bobev, S., Peng, X., et al. (2021). Structural and Electrochemical Properties of Type VIII Ba8Ga16−δSn30+δ Clathrate (δ ≈ 1) during Lithiation. ACS Applied Materials and Interfaces, 13(36), 42564-42578. doi:10.1021/acsami.1c07240.

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 Creators:
Dopilka, Andrew1, Author
Childs, Amanda2, Author
Ovchinnikov, Alexander2, 3, Author
Zhao, Ran4, Author
Bobev, Svilen2, Author
Peng, Xihong5, Author
Chan, Candace K.1, 6, Author              
Affiliations:
1Materials Science and Engineering, School for Engineering of Matter, Transport and Energy, Arizona State University, P.O. Box 876106, Tempe, Arizona 85827, United States, ou_persistent22              
2Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States, ou_persistent22              
3Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, 10691 Stockholm, Sweden, ou_persistent22              
4School of Molecular Sciences, Arizona State University, P.O. Box 871604, Tempe, Arizona 85287, United States, ou_persistent22              
5College of Integrative Sciences and Arts, Arizona State University Polytechnic Campus, Mesa, Arizona 85212, United States, ou_persistent22              
6Research Group Tüysüz, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1950290              

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 Abstract: 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−δSn30+δ (δ ≈ 1) during lithiation are investigated and compared to those in β-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 β-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 β-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 β-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.

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Language(s): eng - English
 Dates: 2021-04-202021-09-032021-09-15
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acsami.1c07240
 Degree: -

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Title: ACS Applied Materials and Interfaces
  Abbreviation : ACS Appl. Mater. Interfaces
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 13 (36) Sequence Number: - Start / End Page: 42564 - 42578 Identifier: ISSN: 1944-8244
CoNE: https://pure.mpg.de/cone/journals/resource/1944-8244