Crystal structure and thermal properties of the LixNa1–xKZnP2O7 solid solutions and its relation to the MM′ZnP2O7 diphosphate family

Sergey Volkov, Maya Petrova, Olga Sinel'shchikova, Vera Firsova, Valentina Popova, Valery Ugolkov, Maria Krzhizhanovskaya, Rimma Bubnova

Research output

1 Citation (Scopus)

Abstract

New solid solutions of LixNa1–xKZnP2O7 belonging to the MM'ZnP2O7 structural family (M = Li+, Na+, Zn2+; M’ = Na+, K+), were prepared and phase equilibria along the LiKZnP2O7–NaKZnP2O7 section were reported. These solid solutions were investigated single-crystal X-ray diffraction, high-temperature X-ray powder diffraction (HTXRD), differential scanning calorimetry, and impedance spectroscopy. A miscibility gap was found within the range of 0.8 < x < 1.0, and a binodal curve was constructed using HTXRD data. The similarity of the thermal and compositional deformation of LixNa1–xKZnP2O7 solid solutions is revealed: increasing the radius of the metal by 0.01 Å leads to the same deformations of the crystal structure as increasing the temperature by 31 °C. The Li/Na↔Zn cation exchange lead to an increase in conductivity above 300 °C. The alkali mixed effect in activation energy occurs for LixNa1–xKZnP2O7 solid solutions near x = 0.5. The phase with the 2a×2b×c superstructure ordering was observed as a result of the solid solution melting.

Original languageEnglish
Pages (from-to)486-493
Number of pages8
JournalJournal of Solid State Chemistry
Volume269
DOIs
Publication statusPublished - 1 Jan 2019

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diphosphates
Diphosphates
Solid solutions
solid solutions
Thermodynamic properties
thermodynamic properties
Crystal structure
crystal structure
X ray powder diffraction
diffraction
miscibility gap
x rays
Alkalies
Phase equilibria
Temperature
Cations
Differential scanning calorimetry
alkalies
Ion exchange
Melting

Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Volkov, Sergey ; Petrova, Maya ; Sinel'shchikova, Olga ; Firsova, Vera ; Popova, Valentina ; Ugolkov, Valery ; Krzhizhanovskaya, Maria ; Bubnova, Rimma. / Crystal structure and thermal properties of the LixNa1–xKZnP2O7 solid solutions and its relation to the MM′ZnP2O7 diphosphate family. In: Journal of Solid State Chemistry. 2019 ; Vol. 269. pp. 486-493.
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abstract = "New solid solutions of LixNa1–xKZnP2O7 belonging to the MM'ZnP2O7 structural family (M = Li+, Na+, Zn2+; M’ = Na+, K+), were prepared and phase equilibria along the LiKZnP2O7–NaKZnP2O7 section were reported. These solid solutions were investigated single-crystal X-ray diffraction, high-temperature X-ray powder diffraction (HTXRD), differential scanning calorimetry, and impedance spectroscopy. A miscibility gap was found within the range of 0.8 < x < 1.0, and a binodal curve was constructed using HTXRD data. The similarity of the thermal and compositional deformation of LixNa1–xKZnP2O7 solid solutions is revealed: increasing the radius of the metal by 0.01 {\AA} leads to the same deformations of the crystal structure as increasing the temperature by 31 °C. The Li/Na↔Zn cation exchange lead to an increase in conductivity above 300 °C. The alkali mixed effect in activation energy occurs for LixNa1–xKZnP2O7 solid solutions near x = 0.5. The phase with the 2a×2b×c superstructure ordering was observed as a result of the solid solution melting.",
keywords = "Crystal structure, Phase relationships, Solid solutions, Zinc diphosphates",
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Crystal structure and thermal properties of the LixNa1–xKZnP2O7 solid solutions and its relation to the MM′ZnP2O7 diphosphate family. / Volkov, Sergey; Petrova, Maya; Sinel'shchikova, Olga; Firsova, Vera; Popova, Valentina; Ugolkov, Valery; Krzhizhanovskaya, Maria; Bubnova, Rimma.

In: Journal of Solid State Chemistry, Vol. 269, 01.01.2019, p. 486-493.

Research output

TY - JOUR

T1 - Crystal structure and thermal properties of the LixNa1–xKZnP2O7 solid solutions and its relation to the MM′ZnP2O7 diphosphate family

AU - Volkov, Sergey

AU - Petrova, Maya

AU - Sinel'shchikova, Olga

AU - Firsova, Vera

AU - Popova, Valentina

AU - Ugolkov, Valery

AU - Krzhizhanovskaya, Maria

AU - Bubnova, Rimma

PY - 2019/1/1

Y1 - 2019/1/1

N2 - New solid solutions of LixNa1–xKZnP2O7 belonging to the MM'ZnP2O7 structural family (M = Li+, Na+, Zn2+; M’ = Na+, K+), were prepared and phase equilibria along the LiKZnP2O7–NaKZnP2O7 section were reported. These solid solutions were investigated single-crystal X-ray diffraction, high-temperature X-ray powder diffraction (HTXRD), differential scanning calorimetry, and impedance spectroscopy. A miscibility gap was found within the range of 0.8 < x < 1.0, and a binodal curve was constructed using HTXRD data. The similarity of the thermal and compositional deformation of LixNa1–xKZnP2O7 solid solutions is revealed: increasing the radius of the metal by 0.01 Å leads to the same deformations of the crystal structure as increasing the temperature by 31 °C. The Li/Na↔Zn cation exchange lead to an increase in conductivity above 300 °C. The alkali mixed effect in activation energy occurs for LixNa1–xKZnP2O7 solid solutions near x = 0.5. The phase with the 2a×2b×c superstructure ordering was observed as a result of the solid solution melting.

AB - New solid solutions of LixNa1–xKZnP2O7 belonging to the MM'ZnP2O7 structural family (M = Li+, Na+, Zn2+; M’ = Na+, K+), were prepared and phase equilibria along the LiKZnP2O7–NaKZnP2O7 section were reported. These solid solutions were investigated single-crystal X-ray diffraction, high-temperature X-ray powder diffraction (HTXRD), differential scanning calorimetry, and impedance spectroscopy. A miscibility gap was found within the range of 0.8 < x < 1.0, and a binodal curve was constructed using HTXRD data. The similarity of the thermal and compositional deformation of LixNa1–xKZnP2O7 solid solutions is revealed: increasing the radius of the metal by 0.01 Å leads to the same deformations of the crystal structure as increasing the temperature by 31 °C. The Li/Na↔Zn cation exchange lead to an increase in conductivity above 300 °C. The alkali mixed effect in activation energy occurs for LixNa1–xKZnP2O7 solid solutions near x = 0.5. The phase with the 2a×2b×c superstructure ordering was observed as a result of the solid solution melting.

KW - Crystal structure

KW - Phase relationships

KW - Solid solutions

KW - Zinc diphosphates

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JO - Journal of Solid State Chemistry

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