Fernando Manuel Bico Marques

This work provides an overview on established achievements and debatable findings involving Ca, Gd or Sm-doped ceria-based electrolytes, using Li₂CO₃, LiNO₃ and Na₂CO₃ as sintering aid or as second phase. The performance of these materials is discussed considering the characteristics of the oxides and of the salts or derived second(ary) phases (e.g., alkali metal oxides and hydroxides, eutectic mixtures), extensively surveyed to identify influential parameters with respect to processing and electrical performance (e.g., melting and boiling points, thermal decomposition, hydrolysis). The analysis of published data highlights the possible contribution of additional charge carriers to the total conductivity, besides oxide-ion vacancies. Claimed bulk and grain boundary conductivity enhancements are deeply discussed, as well as advantages and limitations of impedance spectroscopy as characterization tool. Irrespective of controversial reasons, reports on unusual improvements of grain boundary conductivity sustain the possibility of advanced grain boundary engineering to enhance the performance of these materials.

Pure NiO or lithiated NiO with distinct Li/Ni atomic proportions (50/50—LN55 and 30/70—LN37) were tested as protective barrier layers (PBLs) to enhance the stability of LaCoO₃ (LC) electrodes in cells with composite electrolytes (CEs) consisting of Gd‐doped ceria (CGO) and a eutectic mixture of Na and Li carbonates (NLCs). PBLs and LC layers were sequentially deposited by screen printing before firing at 700°C and 550°C, respectively, to yield symmetrical cells (LC|PBL|CE|PBL|LC). Electrochemical testing involved impedance spectroscopy measurements in air in the 500°C to 650°C range. Scanning electron microscopy combined with energy‐dispersive X‐ray spectroscopy (SEM/EDS) revealed that distinct PBLs possess uneven wetting tendency, with impact on the role of LC layers. The best electrode performance (0.55 Ω cm² electrode area specific resistance at 550°C in air) was observed using the LN37 PBL, stable throughout endurance tests up to 200 hours. Possible electrode mechanisms consistent with experimental evidence suggest an active role of the molten phase as an intermediate provider of O²⁻ transport between the electrode and CGO.