Acid-base chemistry and proton conductivity of CsHSO4, CsH2PO4 and their mixtures with N-heterocycles  

David Aili, Ying Gao, Junyoung Han, Qingfeng Li

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Caesium hydrogen sulfate (CsHSO4) and caesium dihydrogen phosphate (CsH2PO4) are solid acids that undergo superprotonic phase-transitions at about 140 and 230 °C, respectively. As a result, the proton conductivity is increased by several orders of magnitude. However, the practical operational temperature range is narrow due to decomposition of the high-conductivity phases. For CsHSO4, it is known that this window can be extended to lower temperatures by addition of carefully selected N-heterocycles. The present work investigates if the same approach can be used to extend the practical operating temperature range of CsH2PO4 as well. Binary mixtures of CsH2PO4 with 1,2,4-triazole, benzimidazole or imidazole were prepared by means of mechanochemical synthesis. Mixtures based on CsHSO4 were prepared as a basis for a comparative discussion. It was found that CsHSO4 formed organic-inorganic salts, while CsH2PO4 formed heterogeneous mixtures with the N-heterocycles due to its weaker acidity. At a N-heterocycle content of 30 mol%, enhanced proton conductivity was observed for both solid acids at temperatures below their superprotonic phase transitions.
Original languageEnglish
JournalSolid State Ionics
Pages (from-to)13-19
Publication statusPublished - 2017


  • Solid acid
  • Caesium dihydrogen phosphate
  • Composite
  • Electrolyte
  • Conductivity


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