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<p>The effect of the cation in pure salts (n-C<sub>y</sub>H<sub>2y+1</sub>)<sub>4</sub>ClO<sub>4</sub> (y = 3, 4) and in composites based on them with highly dispersed nanodiamonds (specific surface area 300 ± 20 m<sup>2</sup>/g) has been studied using X-ray diffraction analysis (including high-temperature X-ray diffraction analysis), differential scanning calorimetry and impedance spectroscopy. Pure salts undergo 2 (n-C<sub>3</sub>H<sub>7</sub>)<sub>4</sub>ClO<sub>4</sub> at 173 ºC and 178 ºC) or 1 (n-C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>ClO<sub>4</sub> at 60 ºC) solid–solid phase transitions. Both salts undergo polymorphic transformations to a disordered weakly conducting cubic phase with the space group <i>P</i> <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11581_2025_6243_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="10" /> </InlineMediaObject> <EquationSource Format="TEX">\(\overline{4 }\)</EquationSource> <EquationSource Format="MATHML"><math> <mover> <mn>4</mn> <mo>¯</mo> </mover> </math></EquationSource> </InlineEquation> <i>3n</i>. The addition of nanodiamonds leads to a significant decrease in the enthalpies of phase transformations and intensities of reflections, which is associated with the formation of amorphous phases with a thickness of about 2&#xa0;nm. The introduction of nanodiamonds leads to a significant increase in conductivity compared to the original compounds. The maximum conductivity values were achieved for the compositions 0.02(n-C<sub>3</sub>H<sub>7</sub>)<sub>4</sub>NClO<sub>4</sub>–0.98C<sub>ND</sub> (4.9 × 10<sup>–4</sup> S/cm at 165 ⁰C) and 0.015(n-C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>NClO<sub>4</sub>–0.985C<sub>ND</sub> (7.1 × 10<sup>–4</sup> S/cm at 165 ⁰C), which is associated with the formation of a highly conductive amorphous phase, whose conductivity is 3–4 orders of magnitude higher than that of the original salts.</p>

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Comparative study of physico-chemical properties of tetraalkylammonium perchlorates and composites on their basis

  • 期刊论文

  • 发表日期：

    2025年3月22日

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  • Ivan Stebnitskii,
  • Yulia Mateyshina,
  • Nikolai Uvarov

摘要

The effect of the cation in pure salts (n-CyH2y+1)4ClO4 (y = 3, 4) and in composites based on them with highly dispersed nanodiamonds (specific surface area 300 ± 20 m2/g) has been studied using X-ray diffraction analysis (including high-temperature X-ray diffraction analysis), differential scanning calorimetry and impedance spectroscopy. Pure salts undergo 2 (n-C3H7)4ClO4 at 173 ºC and 178 ºC) or 1 (n-C4H9)4ClO4 at 60 ºC) solid–solid phase transitions. Both salts undergo polymorphic transformations to a disordered weakly conducting cubic phase with the space group P \(\overline{4 }\) 4 ¯ 3n. The addition of nanodiamonds leads to a significant decrease in the enthalpies of phase transformations and intensities of reflections, which is associated with the formation of amorphous phases with a thickness of about 2 nm. The introduction of nanodiamonds leads to a significant increase in conductivity compared to the original compounds. The maximum conductivity values were achieved for the compositions 0.02(n-C3H7)4NClO4–0.98CND (4.9 × 10–4 S/cm at 165 ⁰C) and 0.015(n-C4H9)4NClO4–0.985CND (7.1 × 10–4 S/cm at 165 ⁰C), which is associated with the formation of a highly conductive amorphous phase, whose conductivity is 3–4 orders of magnitude higher than that of the original salts.