Multicomponent systems of alkali carbonates indicate high electrical conductivity, high chemical and thermal conductivity, and low viscosity in the medium temperature range around 500°C, and are used as high temperature reaction media, thermocouples, and sensing materials for CO However, in electrochemical reactions, the high reactivity of carbonates is accompanied by the problem of corrosion of electrodes and reaction systems. We have studied ceria-based oxides and zirconia, which have high reactivity through surface treatment of CO2 absorbing media, and have examined the electrical and thermal properties of the composite materials with molten carbonate. Ceria-based oxides have been considered for application in solid oxide fuel cells as solid electrolytes, whereas γ-LiAlO2 has insulating properties and is used as an electrolyte in molten carbonate fuel cells. In this study, lithium carbonate, sodium carbonate, and potassium carbonate are used as the liquid phase, and mono-, binary-, and ternary complex carbonates or carbonates with eutectic compositions are used. The results are summarized on the effect of salt complexation on the improvement of electrical conductivity at low temperature ranges and the lowering of melting points.The solid phase was obtained by drying three types of γ-LiAlO2 (24.0 m2/g, 10.3 m2/g, 5.4 m2/g) and other various oxides such as α-Al2O3, MgO, ZrO2 etc. at 500°C for 2 hours under nitrogen. Li2CO3, Na2CO3, and K2CO3 were used for the carbonate phase and dried at 200°C for 48 hours under a carbon dioxide atmosphere. Eutectic carbonates were prepared by mixing them to form a eutectic composition. Each oxide powder was mixed thoroughly in a mortar to form carbonate at a given volume ratio. The sample was formed by pressurization and sintered at 500°C for 1 hour to obtain a tablet for the measurements of ionic conduction and thermal analysis.As shown in Figure 1, the activation energy of electrical conductivity increased near the solid phase in all cases. The range of influence from the solid phase decreased significantly with increasing carbonate polymorphism: 40 nm for the mono-salt system, 10 nm for the binary system, and about 2 nm for the ternary system. These melting point drops are also affected by the solid phase, but the effect of the distance from the solid phase is not so great. In the vicinity of the solid phase, the effect of the solid phase on ionic conduction is not as strong as that on the phase change, and the more numerous ions move, the less affected by the solid phase the system is. In this presentation, we will discuss the influence of the solid phase from a viewpoint of thermodynamics.Fig.1 Variation of ΔE a with apparent average thickness for various carbonates /inorganic powders coexisting systems. Carbonates: (a)Li2CO3, (b) (Li0.52Na0.48)2CO3, and (c) (Li0.435Na0.315K0.25)2CO3. Figure 1
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