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We study the electrode polarization behaviour of differentNa-Ca-phosphosilicate glasses by measuring the differential capacitance betweenblocking Pt electrodes. At low applied dc bias voltages, we detect a linearcapacitance regime with interfacial capacitance values considerably larger thanexpected from double layer theories and also considerably larger than found forionic liquids with similar ion concentrations. With increasing bias voltages,the differential capacitance of interfacial layer exhibits a maximum around 1 Vand a strong drop at higher voltages. We suggest that these features are causedby pseudocapacitive processes, namely by the adsorption of mobile Na+ ions atthe electrodes followed by electronic charge transfer. While pseudocapacitiveprocesses are well known in liquid electrochemistry, more detailed studies onsolid electrolytes should offer perspectives for improved energy storage insolid-state supercapacitors

Electrode Polarization in Glassy Electrolytes: Large Interfacial Capacitance Values and Indication for Pseudocapacitive Charge Storage