Revisiting Solid-Solid Phase Transitions in Sodium and Potassium Tetrafluoroborate for Thermal Energy Storage

Sumit Konar*, Gertruda Zieniute, Elliot Lascelles, Beth Wild, Andreas Hermann, Yi Wang, Robert J. Quinn, Jan-Willem G. Bos, Andrew Fitch

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

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    Abstract

    In situ synchrotron powder X-ray diffraction (PXRD) study was conducted on sodium and potassium tetrafluoroborate (NaBF4 and KBF4) to elucidate structural changes across solid-solid phase transitions over multiple heating-cooling cycles. The phase transition temperatures from diffraction measurements are consistent with the differential scanning calorimetry data (∼240 °C for NaBF4 and ∼290 °C for KBF4). The crystal structure of the high-temperature (HT) NaBF4 phase was determined from synchrotron PXRD data. The HT disordered phase of NaBF4 crystallizes in the hexagonal, space group P63/mmc (no. 194) with a = 4.98936(2) Å, c = 7.73464(4) Å, V = 166.748(2) Å3, and Z = 2 at 250 °C. Density functional theory molecular dynamics (MD) calculations imply that the P63/mmc is indeed a stable structure for rotational NaBF4. MD simulations reproduce the experimental phase sequence upon heating and indicate that F atoms are markedly more mobile than K and B atoms in the disordered state. Thermal expansion coefficients for both phases were determined from high-precision lattice parameters at elevated temperatures, as obtained from Rietveld refinement of the PXRD data. Interestingly, for the HT-phase of NaBF4, the structure (upon heating) contracts slightly in the a-b plane but expands in the c direction such that overall thermal expansion is positive. Thermal conductivities at room temperature were measured, and the values are 0.8-1.0 W m-1 K-1 for NaBF4 and 0.55-0.65 W m-1 K-1 for KBF4. The thermal conductivity and diffusivity showed a gradual decrease up to the transition temperature and then rose slightly. Both materials show good thermal and structural stabilities over multiple heating/cooling cycles.

    Original languageEnglish
    Pages (from-to)1238-1248
    Number of pages11
    JournalChemistry of Materials
    Volume36
    Issue number3
    Early online date31 Jan 2024
    DOIs
    Publication statusPublished - 13 Feb 2024

    ASJC Scopus subject areas

    • General Chemistry
    • General Chemical Engineering
    • Materials Chemistry

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