X-ray scattering reveals ion clustering of dilute chromium species in molten chloride medium

Enhancing the solar energy storage and power delivery afforded by emerging molten salt-based technologies requires a fundamental understanding of the complex interplay between structure and dynamics of the ions in the high-temperature media. Here we report results from a comprehensive study integrating synchrotron X-ray scattering experiments, ab initio molecular dynamics simulations and rate theory concepts to investigate the behavior of dilute Cr3+ metal ions in a molten KCl-MgCl2 salt. Our analysis of experimental results assisted by a hybrid transition state-Marcus theory model reveals unexpected clustering of chromium species leading to the formation of persistent octahedral Cr-Cr dimers in the high-temperature low Cr3+ concentration melt. Furthermore, our integrated approach shows that dynamical processes in the molten salt system are primarily governed by the charge density of the constituent ions, with Cr3+ exhibiting the slowest short-time dynamics. These findings challenge several assumptions regarding specific ionic interactions and transport in molten salts, where aggregation of dilute species is not statistically expected, particularly at high temperature.

Automated summary

This study reveals the clustering behavior of dilute Cr3+ metal ions in molten salt and demonstrates that the dynamical processes are primarily controlled by the charge density of the constituent ions. These findings challenge assumptions about specific ionic interactions and transport in molten salts.