Probing Ion-Blocking Electrode Rigs for Ionic Conductivity in Hybrid Solid Polymer Electrolytes

Solid electrolytes are critical for structural batteries, combining energy storage with structural strength for applications like electric vehicles and aerospace. However, achieving high ionic conductivity remains challenging, compounded by a lack of standardized testing methodologies. This study examines the impact of experimental setups and data interpretation methods on the measured ionic conductivities of solid polymer electrolytes (SPEs). SPEs were prepared using a polymer-induced phase separation process, resulting in a bi-continuous microstructure for improved ionic transport. Eight experimental rigs were evaluated, including two- and four-electrode setups with materials like stainless steel, copper, and aluminum. Ionic conductivity was assessed using electrochemical impedance spectroscopy, with analysis methods comparing cross-sectional and surface-area-based approaches. Results showed that the four-electrode stainless steel setup yielded the highest ionic conductivity using the cross-sectional method. However, surface-area-based methods provided more consistent results across rigs. Copper setups produced lower conductivities but exhibited less data variability, indicating their potential for reproducible measurements. These findings highlight the critical influence of experimental design on conductivity measurements and emphasize the need for standardized testing protocols. Advancing reliable characterization methods will support the development of high-performance solid electrolytes for multifunctional energy storage applications.