In this study, the efficiency of proton-conducting ceramic fuel cells was improved by designing bilayer electrolytes with high ion conductivity and low hole conduction. The designs were carried out by finding the thicknesses of anode and cathode-side electrolytes that optimizes efficiency using integral equations based on Wagner theory. Results obtained for bilayer electrolytes were compared with those of single-layer electrolytes. Best performances were found when thin layers of lanthanum tungstate (La28-x W4+x O54+3x/2v2-3x/2) with an La/W ratio of 6.7 (LWO67) were used as cathode-side electrolytes attached to commonly used perovskite materials like BaCe0.9Y0.1O3- δ (BCY10), BaZr0.8Y0.2O3- δ (BZY20), and BaZr0.1Ce0.7Y0.1Yb0.1O3- δ (BZCYYb1711). In addition, the transport properties of a single-layer LWO67 electrolyte were further analyzed by using the Nernst-Planck-Poisson (NPP) model for which parameters were fitted. Finally, a bilayer NPP formulation was explored to obtained the charged defect fluxes and other useful information to enhance the efficiency of a bilayer BZY20|BZCYYb1711 electrolyte.

A highly efficient power generation system was designed by minimizing leakage current in protonic ceramic fuel cells (PCFCs) using bilayer electrolytes. The best electrolyte designs are achieved by optimizing the cell efficiency based on the transport properties of electrolyte materials assuming hydrogen as fuel. In parallel, the effect of the electrodes on the overall cell performance was also considered. Additionally, a PCFC system was modeled using the designed cells. Two PCFC systems were investigated. One based on hydrogen as a fuel, and another based on methane as fuel. It was found that a bilayer electrolyte consisting of BaZr0.8Y0.2O3−δ (BZY) with a thin layer of lanthanum tungstate (La28-xW4+xO54+3x/2v2-3x/2) is the most effective at reducing leakage current at 600°C. For this cell, a system efficiency of 69% (LHV, DC) and 65% (LHV, AC) were obtained under the cell voltage of 0.93 V, with a leakage current ratio of less than 1%, and fuel utilization of 95% when using hydrogen as fuel. On the other hand, when methane was used as fuel, the efficiency increased up to 78% (LHV, DC) and 74% (LHV, AC).

Proton-conducting oxides have attracted much attention in recent years due to their good ion conductivity at intermediate temperatures (500-700°C), as opposed to conventional oxide ion-conducting oxides that require high temperatures (usually, >900°C). Lowering the operating temperature of reversible protonic ceramic electrochemical cells (RePCECs) is desirable as it reduces material, heating, and insulation costs, while also increasing the operating life of the cell. Nevertheless, along with the desired proton conductivity, typical proton-conducting solid electrolytes also allow the transport of other charged defects like oxygen-vacancies, electrons, and electron holes. The presence of these other defects, especially the electron holes, causes leakage current that significantly reduces the cell’s electrical efficiency. Therefore, an electrolyte capable of reducing leakage current is necessary. Unfortunately, there is usually a trade-off between high ionic conductivity and low hole conduction. For example, while lanthanum tungstate (LWO) has a low electron conductivity and is capable of suppressing hole conduction below 800°C, its proton conductivity is lower than that of commonly used perovskite materials like yttria-doped barium cerate (BCY) or yttria-doped barium zirconate (BZY). Nonetheless, previous studies showed that LWO67 can act as a leakage current-blocking layer when deposited on a BZY82 base electrolyte and the estimated leakage current was almost 200 times lower than that of a BZY82 single layer electrolyte under open-circuit conditions. This suggests that under certain operating conditions, bilayer electrolytes can achieve better performance when compared to their corresponding single-layer electrolytes. Therefore, in this study, we design proton-conducting bilayer electrolytes by investigating the incorporation and transport of charged defects using a steady-state Nernst-Planck-Poisson (NPP) model. The main goals of this work are twofold. Firstly, to find the combination of electrolytes that better suppresses leakage current. For this purpose, we calculate the defect concentration, flux, and electrostatic profiles inside common materials like BCY, BZY, BZCYYb, BZCY, LWO, and different combinations of bilayer electrolytes to better understand how the addition of a leakage current-blocking layer affects proton conduction and overall efficiency. We consider three mobile defects when solving the NPP equation, protons (OHO •), oxygen vacancies (vO ••), and electron holes that are treated as small polarons localized at oxygen sites (OO •). Afterward, the I-V curve and relevant theoretical efficiency are predicted within and A cm-2 (fuel cell and electrolyzer operation) at 500, 600 and 700°C, in order to identify the most promising one. Secondly, to design a cell by finding the optimal thickness of the better performing bilayer electrolyte that maximizes efficiency.