Anhydrous Superprotonic Conductivity in the Zirconium Acid Triphosphate ZrH5(PO4)3**

Sacha Fop; Riccardo Vivani; Silvia Masci; Mario Casciola; Anna Donnadio

doi:10.26434/chemrxiv-2022-2h4g1

Anhydrous Superprotonic Conductivity in the Zirconium Acid Triphosphate ZrH₅(PO₄)₃**

Sacha Fop^*, Riccardo Vivani, Silvia Masci, Mario Casciola, Anna Donnadio^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

2 Downloads (Pure)

Abstract

The development of solid-state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen-based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH₅(PO₄)₃ (ZP3), which exhibits record-high proton conductivity of 0.5–3.1×10⁻² S cm⁻¹ in the range 25–110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25–110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer.

Original language	English
Article number	e202218421
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	18
Early online date	23 Mar 2023
DOIs	https://doi.org/10.26434/chemrxiv-2022-2h4g1 https://doi.org/10.1002/anie.202218421
Publication status	Published - 24 Apr 2023

Bibliographical note

Funding Information:
S.F. gratefully acknowledges the Ramsay Memorial Trust and the University of Aberdeen's School of Natural and Computing Sciences for the provision of a Ramsay Memorial Fellowship. This paper benefited from the insights of Professor Giulio Alberti who was a pioneer and one of the most authoritative scientists of the chemistry of M phosphates and phosphonates. IV

A previous version of this manuscript has been deposited on a preprint server (https://doi.org/10.26434/chemrxiv-2022-2h4g1).

Keywords

Conducting Materials
Fuel Cells
Proton Conductivity
Solid Acids
Zirconium Phosphates

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© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. https://creativecommons.org/licenses/by-nc/4.0/
Final published version, 2.8 MBLicence: CC BY-NC

Cite this

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abstract = "The development of solid-state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen-based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH5(PO4)3 (ZP3), which exhibits record-high proton conductivity of 0.5–3.1×10−2 S cm−1 in the range 25–110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25–110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer.",

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