Proton Conductive BaZr0.8‐xCexY0.2O3‐δ: Influence of NiO Sintering Additive on Crystal Structure, Hydration Behavior, and Conduction Properties

Abstract Y‐doped BaZrO 3 , BaCeO 3 and BaZr 1‐ x Ce x O 3 show high proton conductivity at intermediate temperature and are promising electrolyte candidates in electrochemical devices. However, in most cases, the present cell fabrication process seems to be unavailable to avoid the addition of NiO, which is either added to improve the sinterability of these electrolyte or diffuses from the electrode substrate during co‐sintering. In this work, a systematic investigation was performed to study the effect of NiO on BaZr 0.8‐ x Ce x Y 0.2 O 3‐ δ (BZCY20) covering the full Ce range from 0 to 0.8. The results revealed that regardless of the composition of BZCY20, both the dehydration temperature and proton concentration decreased by adding NiO, which further greatly decreased the ionic conductivity and the transport number. And it is found that the redox cycles in Ce‐rich samples containing Ni makes the grain boundary conductivity worse and the electrolyte brittle. The conclusion is that NiO is detrimental to the performance of the electrochemical cells using these materials as the electrolyte, although compromise might be achieved in certain degree by tuning the Ce content. However, it should be noted that to further improve the cell performance, a new sintering additive or new processing for cell fabrication is essential.