Proton-conductive coordination polymer glass for solid-state anhydrous proton batteries

Nattapol Ma; Soracha Kosasang; Atsushi Yoshida; Satoshi Horike

doi:10.1039/d1sc00392e

Proton-conductive coordination polymer glass for solid-state anhydrous proton batteries

Chem Sci. 2021 Mar 12;12(16):5818-5824. doi: 10.1039/d1sc00392e.

Authors

Nattapol Ma¹, Soracha Kosasang², Atsushi Yoshida¹, Satoshi Horike^{1

3

4

5}

Affiliations

¹ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University Katsura, Nishikyo-ku Kyoto 615-8510 Japan horike@icems.kyoto-u.ac.jp.
² Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology Rayong 21210 Thailand.
³ AIST-Kyoto University Chemical Energy Materials Open Innovation Laboratory (ChEM-OIL), National Institute of Advanced Industrial Science and Technology (AIST) Yoshida-Honmachi, Sakyo-ku Kyoto 606-8501 Japan.
⁴ Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University Yoshida-Honmachi, Sakyo-ku Kyoto 606-8501 Japan.
⁵ Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology Rayong 21210 Thailand.

Abstract

Designing solid-state electrolytes for proton batteries at moderate temperatures is challenging as most solid-state proton conductors suffer from poor moldability and thermal stability. Crystal-glass transformation of coordination polymers (CPs) and metal-organic frameworks (MOFs) via melt-quenching offers diverse accessibility to unique properties as well as processing abilities. Here, we synthesized a glassy-state CP, [Zn₃(H₂PO₄)₆(H₂O)₃](1,2,3-benzotriazole), that exhibited a low melting temperature (114 °C) and a high anhydrous single-ion proton conductivity (8.0 × 10^-3 S cm^-1 at 120 °C). Converting crystalline CPs to their glassy-state counterparts via melt-quenching not only initiated an isotropic disordered domain that enhanced H⁺ dynamics, but also generated an immersive interface that was beneficial for solid electrolyte applications. Finally, we demonstrated the first example of a rechargeable all-solid-state H⁺ battery utilizing the new glassy-state CP, which exhibited a wide operating-temperature range of 25 to 110 °C.