2025/08/22 by Christopher L. Rom, Rom, Christopher L., Austin M. Shotwell +10
Chemical Engineering · Engineering · Materials Science · #Advanced Battery Materials and Technologies #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #Molten salt chemistry and electrochemical processes #Thermal Expansion and Ionic Conductivity
paper · pdf · doi:10.48550/arxiv.2508.16066
openalex publication_date 2025/08/22 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Ball milling is a powerful synthetic tool for discovering new inorganic materials. Inspired by the high ionic conductivity in Li2ZrCl6 synthesized via mechanochemistry, we synthesized MgZrCl6 with a similar method. High resolution synchrotron X-ray diffraction shows that MgZrCl6 is poorly crystalline after ball milling, but crystallizes in a layered hexagonal structure (P31c) after heat treatment. In situ synchrotron X-ray diffraction reveals a narrow temperature window around 400 °C in which crystallization occurs. At higher temperatures the phase decomposes. Pair distribution function analysis shows 2D sheets of MgZrCl6 form after milling, with heating driving 3D crystallization. Raman spectroscopy also shows evidence of MgZrCl6 after milling. Electrochemical impedance spectroscopy does not reveal ionic conductivity in MgZrCl6 (limit of detection ca. 1.4 × 10-8 S/cm). In addition to supporting existing design rules for Mg-based solid electrolytes, this work shows the power of ball milling to synthesize temperature-sensitive inorganic compounds with high yield.