A Solid Zn-Ion Conductor from an All-Zinc Metal–Organic Framework Replete with Mobile Zn2+ Cations

Iliescu, Andrei; Andrews, Justin L.; Oppenheim, Julius J.; Dincă, Mircea

doi:10.1021/jacs.3c10326

Title: A Solid Zn-Ion Conductor from an All-Zinc Metal–Organic Framework Replete with Mobile Zn²⁺ Cations

Journal Article · 27 November 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c10326 · OSTI ID:2341883

^[1]; Andrews, Justin L. ^[2];

^[2];

^[2]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Massachusetts Institute of Technology
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Here, we describe the synthesis and properties of Zn₃[(Zn₄Cl)₃(BTT)₈]₂ (ZnZnBTT, BTT^3– = 1,3,5-benzenetristetrazolate), a heretofore unknown member of a well-known, extensive family of metal–organic frameworks (MOFs) with the general formula M^II₃[(M^II₄Cl)₃(BTT)₈]₂, which adopts an anionic, sodalite-like structure. As with previous members in this family, ZnZnBTT presents two crystallographically distinct metal cations: a skeletal Zn²⁺ site, fixed within Zn₄Cl(tetrazole)₈ secondary building units (SBUs), and a charge-balancing Zn²⁺ site. Self-assembly of ZnZnBTT from its building blocks has remained elusive; instead, we show that ZnZnBTT is readily accessed by quantitative postsynthetic exchange of all Mn²⁺ ions in MnMnBTT with zinc. We further demonstrate that ZnZnBTT is a promising Zn-ion conductor owing to the mobile charge-balancing extra-framework Zn²⁺ cations. The new material displays a Zn-ion conductivity of σ = 1.15 × 10^–4 S/cm at room temperature and a relatively low activation energy of E_a = 0.317 eV, enabling potential applications in the emerging field of quasi-solid-state zinc-ion batteries.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023288

OSTI ID:: 2341883

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: A Solid Zn-Ion Conductor from an All-Zinc Metal–Organic Framework Replete with Mobile Zn2+ Cations

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Title: A Solid Zn-Ion Conductor from an All-Zinc Metal–Organic Framework Replete with Mobile Zn²⁺ Cations