Improvement of Energy Efficiency in Anode-Supported Proton Ceramic Fuel Cells By Lanthanum Tungstate Hole Blocking Layer

Abstract

For efficient operation of proton ceramic fuel cell (PCFC), transport properties of hole and electron are important factors to be controlled as well as that of protons. Ba-based perovskite-type proton conductors have been used as typical electrolytes for the PCFCs because of their high proton conductivity. However, they also exhibit apparent hole conduction under oxidative atmospheres which causes leakage current through the electrolyte. The leakage current leads to not only a decrease in cell voltages but also a reduction of the energy efficiency since the leakage current cannot be utilized as electric power while hydrogen is consumed to generate protons and electrons. Therefore, a novel approach to suppress the leakage current has been required.Lanthanum tungstate (La28−x W4+x O54+3/2x ; LWO) with a high La/W ratio of 6.7 is one of the attractive proton conductors with a quite low hole conductivity. Though its proton conductivity is lower than the typical perovskite-type electrolytes, a high protonic transport number is attractive as a hole blocking layer for the PCFCs. An introduction of a thin LWO hole blocking layer on the Ba-based proton conductors with the high proton conductivity will suppress the leakage current by changing a profile of oxygen chemical potential in the electrolytes as we have proposed previously (Y. Matsuzaki et al., ECS Trans. 91, 1009-1018 (2019)).In this study, we explored the influence of the LWO hole blocking layer on the cell performances of PCFCs by theoretical calculations and experiments. In the theoretical calculations, a BZY|LWO bilayer cell model in which the LWO layer was located at the cathode side was employed. The calculations suggested that the bilayer structure not only improves efficiency but also gives flexibility to control the cell performance as required. Moreover, we experimentally investigated the performance of anode-supported cells with a BZY monolayer electrolyte and with a BZY|LWO bilayer electrolyte to elucidate the effect of the LWO layer.An LWO layer thickness (L LWO) dependence of the OCV in the BZY|LWO bilayer model was calculated based on the transport properties of BZY and LWO. Dependences of the energy efficiency and the power density with respect to a ratio of to a total electrolyte thickness (L total) of 10 μm were calculated for the model at a fixed external current density (I ext) of 250 mA/cm2 and at a fixed terminal voltage (V T) of 1.05 V, respectively. ε was defined by ε = V T I ext/V th I ion, where V th and I ion are a Nernst voltage and an ionic current density. We assumed the following operation conditions; operation temperature of 600 °C, 3% H2O + 97% H2 for anode gas, and 3% H2O + 19.4% O2 + 77.6 % Ar for cathode gas. In the experiments, a BZY monolayer electrolyte and a BZY|LWO bilayer electrolyte were prepared on NiO-BZY cermet substrates by the pulsed-laser deposition (PLD). La0.6Sr0.4Co0.2Fe0.8O3− d (LSCF) cathode was applied for both the cells. To suppress chemical reactions of LWO with BZY and LSCF, thin La-doped ceria (LDC) layers were introduced. The resulted structure of the monolayer cell and the bilayer cell were Ni-BZY|BZY(3.5 μm)|LSCF and Ni-BZY|BZY(3.5 μm)|LDC(40 nm)|LWO(1 μm)|LDC(40 nm)|LSCF, respectively. Cell performance tests were performed at 600 °C supplying 3% humidified H2 + Ar gas for the anode and 3% humidified 20% O2 + Ar gas for the cathode.The calculated OCV of the BZY monolayer model was 1.08 V and steeply increased up to 1.13 V by employing the thin LWO layer with L LWO/L total of 0.017 owing to suppression of the leakage current. Calculated dependences of ε and the power density for the model are shown in Fig.1. The efficiency and the power density showed a steep increase with increasing L LWO/L total. They showed the maximum values at certain L LWO/L total values, and then gradually decreased as L LWO/L total approached 1. This calculation result indicates that the cells exhibiting both the high ε and the high power density can be developed by employing the bilayer structure with the thin LWO hole blocking layer. Moreover, It is notable that, as the performance of the bilayer cell can be tuned by changing as presented in Fig. 1, the bilayer structure increases a degree of freedom for the design of the cells to satisfy various performance requirements. In the experiments, an enhancement of the OCV from 0.95 V for the BZY monolayer cell to 1.01 V for the bilayer cell was actually observed as suggested by the calculation. We consider that these theoretical calculations and experimental results present the effectiveness of the LWO hole blocking layer for the development of the high-performance PCFCs with high-design flexibility. Figure 1