A Metal-Organic Framework with Tetrahedral Aluminate Sites as a Single-Ion Li+ Solid Electrolyte

Sabrina Fischer; Jérôme Roeser; Terri C Lin; Ryan H DeBlock; Jonathan Lau; Bruce S Dunn; Frank Hoffmann; Michael Fröba; Arne Thomas; Sarah H Tolbert

doi:10.1002/anie.201808885

A Metal-Organic Framework with Tetrahedral Aluminate Sites as a Single-Ion Li⁺ Solid Electrolyte

Angew Chem Int Ed Engl. 2018 Dec 17;57(51):16683-16687. doi: 10.1002/anie.201808885. Epub 2018 Nov 21.

Authors

Sabrina Fischer^{1

2}, Jérôme Roeser², Terri C Lin¹, Ryan H DeBlock³, Jonathan Lau³, Bruce S Dunn³, Frank Hoffmann⁴, Michael Fröba⁴, Arne Thomas², Sarah H Tolbert^{1

3}

Affiliations

¹ Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, CA, 90095-1569, USA.
² Department of Chemistry, Technische Universität Berlin, BA2, Hardenbergstraße 40, 10623, Berlin, Germany.
³ Department of Materials Science and Engineering, University of California Los Angeles, Los Angeles, CA, 90095-1595, USA.
⁴ Institute of Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King Platz 6, 20146, Hamburg, Germany.

PMID: 30334321
DOI: 10.1002/anie.201808885

Abstract

We demonstrate the synthesis of the first anionic aluminum metal-organic framework (MOFs) constructed from tetrahedral AlO₄ sites. Al-Td-MOF-1 was obtained in a simple two-step synthesis by condensation of 1,4-dihydroxybenzene and lithium aluminum hydride into an amorphous aluminate framework before applying a solvothermal treatment under basic conditions to obtain the crystalline Al-Td-MOF-1 with a chemical composition of Li[Al(C₆ H₄ O₂ )₂ ]. The overall Al-Td-MOF-1 structure consists of one-dimensional chains of alternating edge-sharing AlO₄ and LiO₄ tetrahedral sites describing unidirectional pore channels with a square window aperture of ≈5×5 Å² , best described topologically as a uninodal 6-coordinated snp rod net. Al-Td-MOF-1 features the highest Li⁺ loading reported to date for a MOF (2.50 wt %) and proved to be an effective single-ion solid electrolyte. An ionic conductivity of 5.7×10^-5 S cm^-1 was measured for Al-Td-MOF-1 and the beneficial contribution of crystallinity was evidenced by an 8-fold increase in conductivity between the disordered and crystalline material.

Keywords: lithium ion conduction; metal-organic frameworks; microporous materials; solid electrolyte.

Abstract

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