Deconvolution of Water-Splitting on the Triple-Conducting Ruddlesden–Popper-Phase Anode for Protonic Ceramic Electrolysis Cells

Triple-conducting materials have been proved to improve the performance of popular protonic ceramic electrolysis cells. However, partially because of the complexity of the water-splitting reaction involving three charge carriers, that is, oxygen (O2–), proton (H+), and electron (e–), the triple-conducting reaction mechanism was not clear, and the reaction conducting pathways have seldom been addressed. In this study, the triple-conducting Ruddlesden–Popper phase Pr1.75Ba0.25NiO4+δ as an anode on the BaCe0.7Zr0.1Y0.1Yb0.1O3−δ electrolyte was fabricated and its electroresponses were characterized by electrochemical impedance spectroscopy with various atmospheres and temperatures. The impedance spectra are deconvoluted by means of the distribution of the relaxation time method. The surface exchange rate and chemical diffusivity of H+ and O2– are characterized by electrical conductivity relaxation. The physical locations of electrochemical processes are also identified by atomic layer deposition with a surface inhibitor. A microkinetics model is proposed toward conductivities, triple-conducting pathways, reactant dependency, surface exchange and bulk diffusion capabilities, and other relevant properties. Finally, the rate-limiting steps and suggestions for further improvement of electrode performance are presented.