Unconventional and Powerful Ion Sources for Solid-State Ion Exchange, Cu2SO4 and Cu3PO4: Exemplified by Synthesis of Metastable \beta-CuGaO2 from Stable \beta-LiGaO2

Abstract

This study introduces a new method for synthesizing Cu+-containing metastable phases through ion exchange. Traditionally, CuCl has been used as a Cu+ ion source for solid-state ion exchanges; however, its thermodynamic driving force is often insufficient for complete ion exchange with Li+-containing precursors. First-principles calculations have identified Cu2SO4 and Cu3PO4 as more powerful alternatives, providing a higher driving force than CuCl. It has been experimentally demon-strated that these ion sources can open up new reaction pathways through experimental ion exchanges, such as from \beta-LiGaO2 to \beta-CuGaO2, which were previously unattainable. An important perspective provided by this study is that the poten-tial of such basic compounds to act as powerful ion sources has been overlooked, and that they were identified through straightforward first-principles calculations. This work presents the initial strategic design of an ion exchange reaction by exploring suitable ion sources, thereby expanding the potential for synthesizing metastable materials.