Apatite-type lanthanum silicate (LSO) is a material with high oxide-ion conductivity in the low- and intermediate-temperature range (573–873 K) and is, therefore, a promising solid electrolyte for low-temperature applications such as solid oxide fuel cells and oxygen sensors. Herein, the effect of B substitution at the Si site in a c-axis-oriented apatite-type lanthanum silicate (La9.7Si5.3B0.7O26.2, c-LSBO) polycrystal on oxide-ion conduction is investigated. A highly c-axis-oriented LSBO polycrystal is fabricated by a vapor–solid reaction in which a dense La2SiO5 disk is heated in B2O3 vapor at ≥1673 K. The oxide-ion conductivity of c-LSBO reaches 16 mS cm–1 at 678 K with an activation energy of 0.4 eV. The obtained oxide-ion conductivity of c-LSBO is approximately 190 times higher than that of yttria-stabilized zirconia and 5.8 times higher than that of the polycrystalline c-axis-oriented nondoped lanthanum silicate. Based on 11B nuclear magnetic resonance measurements, B is located at the SiO4 site as BO4, suggesting the formation of an oxygen vacancy at the O4 site located along the c-axis due to charge compensation. In addition, molecular dynamics simulations indicate that the oxide-ion diffusion coefficient of the B-doped LSO is higher than that of the nondoped LSO. The high oxide-ion conductivity of c-LSBO is likely attributable to the formation of an oxygen vacancy at the O4 site by B doping, which has a lower valency than Si. Therefore, c-LSBO is a promising candidate as a solid electrolyte in electrochemical devices operating at low and moderately high temperatures.
Nowadays, monitoring and recording CO2 gas has become more and more important in various areas, leading to increasing demand for developing high-sensitive CO2 sensors. In this study, a novel potentiometric CO2 gas sensor is designed based on a new solid electrolyte of Y-doped La9.66Si5.3B0.7O26.14 (Y-LSBO), coated with the Li2CeO3–Au–Li2CO3 composite as a sensing electrode and Pt as a reference electrode. With the optimized composition of a sensing electrode, the electromotive force (EMF) varies linearly with the logarithm of the CO2 concentration in the range of 400–4000 ppm, exhibiting an excellent Nernstian response to CO2 gas in both dry and humid atmospheres. The fabricated CO2 sensor can be well operated at 400 °C in a dry atmosphere and 450 °C in a humid atmosphere. Based on the results, we have proposed that the good CO2 sensing performance may be associated with Li2CeO3 playing a role of “ionic bridge” between the O2– conductor (Y-LSBO) and the Li+ conductor (Li2CO3). This study not only shows the promising potential of a Y-LSBO solid electrolyte utilized in the field of gas sensors but also enriches the research of solid electrolyte–based potentiometric CO2 gas sensors.
A new electrochemical oxygen separation pump was developed by using c-axis-oriented La 9.66 Si 5.3 B 0.7 O 26.14 (c-LSBO), which has high oxide-ionic conductivity (>10 ¹3 S cm ¹1) up to 300°C. Interfacial resistance between the electrode and c-LSBO was investigated to realize the full potential of LSBO as an oxygen separation material. The formation of a Sm-doped CeO 2 (SDC) thin film (thickness: 300 nm) between the electrode and c-LSBO was effective for suppressing the interfacial resistance. Furthermore, a mixed conductive La 0.6 Sr 0.4 Co 0.78 Ni 0.02 Fe 0.2 O 3¹¤ (LSCFN) was applied to the electrode for enhancing the oxygen reduction/evolution activity on the electrode. The LSCFN/SDC/c-LSBO symmetric cell showed an oxygen permeation flux of 3.5 mL cm ¹2 min ¹1 (1.0 A cm ¹2) at 600°C under an applied DC voltage of 1.5 V; this value was 67 times that of Pt/c-LSBO. This oxygen pump based on the LSCFN/SDC/c-LSBO symmetric cell would find promising application in oxygen separation at intermediate temperatures. Further reduction of the interfacial resistance and polarization resistance of the electrode may decrease the operating temperatures to below 400°C.
Apatite-type lanthanum silicate (LSO) exhibits high oxide-ion conductivity and has recently garnered attention as a potential solid electrolyte for high-temperature solid oxide fuel cells and oxygen sensors that operate in the low- and intermediate-temperature ranges (300–500 °C). LSO exhibits anisotropic oxide-ion conduction along with high c-axis-oriented oxide-ion conductivity. To obtain solid electrolytes with high oxide-ion conductivity, a technique for growing crystals oriented along the c-axis is required. For mass production and upscaling, we have thus far focused on the vapor-phase synthesis of c-axis-oriented apatite-type LSO and successfully grew polycrystals of highly c-axis-oriented boron-substituted apatite-type lanthanum silicate (c-LSBO) using B2O3 vapor. Here, we investigated the mechanism of c-LSBO crystal growth to determine why the utilization of B2O3 vapor resulted in such a strong c-axis crystal orientation. The synthesis of c-LSBO by the B2O3 vapor-phase method results in crystal growth accompanied by the diffusion of B2O3 supplied from another new compound that formed on the surface of the La2SiO5 disk, LaBO3. In addition, c-LSBO crystals are formed not only by vapor–solid reactions but also by solid–solid and liquid–solid reactions. The increase in the c-axis orientation degree might be due to the increase in the amount of the liquid-phase interface.
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