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<p>This study investigates the preparation and properties of Ag<sub>7+<i>x</i></sub>(P<sub>1-<i>x</i></sub>Ge<sub><i>x</i></sub>)S<sub>6</sub> solid solutions, specifically comparing the impact of nanopowder dispersion and heterovalent P<sup>+5</sup>→Ge<sup>+4</sup> substitution on the properties of resulting ceramic materials. Nanopowders were prepared via ball milling for 30 and 60 minutes, achieving crystallite sizes of 126–180 nm (30 min) and 98–140 nm (60 min). The ceramics were fabricated by cold pressing (400 MPa) with subsequent annealing. It has been established that the use of nanocrystalline precursors leads to a highly homogeneous ceramic microstructure without distinct intercrystalline boundaries. The subsequent phase transitions during cooling induce microdefects and microcracks that influence mechanical and electrical performance. Microhardness investigation of the ceramics revealed the presence of a normal indentation size effect. The microhardness of ceramics is in the range 0.57–0.94 GPa (<i>P</i> = 1.5 N) and the compositional dependence of microhardness shows nonlinear behavior. The electrical investigations reveal that the ionic conductivity is non-monotonic, reaching a maximum value of 4.96 × 10<sup>-2</sup> S cm<sup>–1</sup> for composition Ag<sub>7.5</sub>P<sub>0.5</sub>Ge<sub>0.5</sub>S<sub>6</sub>. It has been established that reducing the powder grain size to the nanoscale did not significantly increase the maximum ionic conductivity compared to microcrystalline versions, but it lead to a notable decrease in activation energy for compositions Ag<sub>7.25</sub>P<sub>0.75</sub>Ge<sub>0.25</sub>S<sub>6</sub> (0.190 eV) and Ag<sub>7.33</sub>P<sub>0.67</sub>Ge<sub>0.33</sub>S<sub>6</sub> (0.183 eV). These findings demonstrate that Ag<sub>7+<i>x</i></sub>(P<sub>1-<i>x</i></sub>Ge<sub><i>x</i></sub>)S<sub>6</sub> ceramics are promising high-conductivity electrolytes where functional properties can be tuned through both chemical substitution and the control of precursor dispersion.</p>

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Ceramic processing and its effects on the microstructure and electrical properties of Ag7+x(P1-xGex)S6 solid-state ionic conductors

  • 期刊论文

  • 发表日期：

    2026年5月15日

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  • Artem Pogodin,
  • Mykhailo Filep,
  • Tetyana Malakhovska,
  • Vasyl Vakulchak,
  • Vladimir Komanicky,
  • Serhii Vorobiov,
  • Iryna Shender,
  • Vitaliy Bilanych,
  • Oleksandr Kokhan,
  • Ruslan Mariychuk

摘要

This study investigates the preparation and properties of Ag7+x(P1-xGex)S6 solid solutions, specifically comparing the impact of nanopowder dispersion and heterovalent P+5→Ge+4 substitution on the properties of resulting ceramic materials. Nanopowders were prepared via ball milling for 30 and 60 minutes, achieving crystallite sizes of 126–180 nm (30 min) and 98–140 nm (60 min). The ceramics were fabricated by cold pressing (400 MPa) with subsequent annealing. It has been established that the use of nanocrystalline precursors leads to a highly homogeneous ceramic microstructure without distinct intercrystalline boundaries. The subsequent phase transitions during cooling induce microdefects and microcracks that influence mechanical and electrical performance. Microhardness investigation of the ceramics revealed the presence of a normal indentation size effect. The microhardness of ceramics is in the range 0.57–0.94 GPa (P = 1.5 N) and the compositional dependence of microhardness shows nonlinear behavior. The electrical investigations reveal that the ionic conductivity is non-monotonic, reaching a maximum value of 4.96 × 10-2 S cm–1 for composition Ag7.5P0.5Ge0.5S6. It has been established that reducing the powder grain size to the nanoscale did not significantly increase the maximum ionic conductivity compared to microcrystalline versions, but it lead to a notable decrease in activation energy for compositions Ag7.25P0.75Ge0.25S6 (0.190 eV) and Ag7.33P0.67Ge0.33S6 (0.183 eV). These findings demonstrate that Ag7+x(P1-xGex)S6 ceramics are promising high-conductivity electrolytes where functional properties can be tuned through both chemical substitution and the control of precursor dispersion.