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The addition of an inert ionic compound increases the solubility of a sparingly soluble salt. For example, adding potassium nitrate to a saturated solution of calcium sulfate significantly enhances the solubility of calcium sulfate. Le Châtelier's principle cannot predict this shift in the equilibrium. Instead, this could be explained in terms of changes in the effective concentration of the ions in solution in the presence of added inert salt.
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Multiscale Investigation into Chemically Stable NASICON Solid Electrolyte in Acidic Solutions.

Minjie Hou1, Xiecheng Yang1, Feng Liang1,2

  • 1Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China.

ACS Applied Materials & Interfaces
|July 2, 2021
PubMed
Summary

This study reveals how acidic conditions degrade sodium superionic conductor (NASICON) solid electrolytes. Proton exchange and structural changes, like surface cracks, occur as pH decreases, impacting stability.

Keywords:
NASICONcorrosion mechanismmultiscalesolid electrolytestability

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Chemistry

Background:

  • Sodium superionic conductor (NASICON) solid electrolytes are promising for energy storage due to their conductivity and eco-friendliness.
  • Understanding their chemical stability is crucial for practical applications.

Purpose of the Study:

  • To evaluate the chemical stability of Na3Zr2Si2PO12 NASICON solid electrolyte in acidic solutions.
  • To elucidate the multiscale corrosion mechanism of NASICON under varying pH conditions.

Main Methods:

  • AC impedance spectroscopy to analyze bulk, grain boundary, and surface crack impedance over time.
  • Multiscale characterization using SEM, XPS, XRD, and Raman spectroscopy.
  • Investigation of morphological transformation, degradation depth, chloride penetration, and proton-sodium exchange.

Main Results:

  • Decreasing solution pH accelerates H3O+ and Na+ proton exchange.
  • Loss of Na+ causes shrinkage of phosphorus-oxygen tetrahedra, leading to reduced unit cell volume.
  • Grain refinement and surface crack formation are observed as degradation progresses.

Conclusions:

  • The study provides a multiscale understanding of NASICON degradation mechanisms in acidic media.
  • Findings deepen the physicochemical insights into the stability limits of solid electrolytes.
  • This research is vital for designing more robust NASICON materials for demanding applications.