Temperature dependent electrochemical characterization of an optimized molecular weight polymeric LiFePO4 cathode all-solid-state battery

Recent advances in PEO-based polymer all-solid-state batteries (ASSBs), including optimized composite cathode formulations, are bringing this technology closer to practical deployment. However, temperature remains a limiting factor, as PEO-based SPEs typically require around 70 ° C to ensure adequate ionic transport, while operation at higher temperatures may introduce mechanical, interfacial and long-term stability limitations. Since real applications involve dynamic temperature profiles differing from nominal conditions, quantifying the cell response beyond thermal activation becomes essential for the design of any application from an engineering perspective. With this aim, three lab-scale monolayer pouch cells incorporating a previously optimized 700 kg mol −1 PEO-based LiFePO 4 composite cathode are characterized through galvanostatic discharge experiments at different temperatures and currents. The analysis provides engineering-relevant parameters, including storage capacity, limiting discharge current, open-circuit voltage (OCV), and area-specific effective full-cell conductance ( Y ). The thermal dependence of equilibrium and charge-transport properties is interpreted through Seebeck-type and Vogel–Tammann–Fulcher (VTF) relationships, enabling an experimental estimation of the OCV temperature coefficient (dOCV/dT) and temperature-dependent charge transport response. In addition, the cathode electronic conductivity is also measured as a function of temperature. These results provide electro–physical parameters for electrochemical modelling, thermal management design, and operating strategy assessment of PEO-based ASSBs under non-isothermal operating conditions.