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Energies 2020, 13, 5859 11 of 23 thermally stable up to high temperatures, 1150–1400 ◦C), for using this system at lower temperatures (700–1000 ◦C). The material was synthesized from a BaCO3-BaSiO3 mixture and could be reduced at a temperature 350 ◦C lower than pure BaCO3 while retaining about 60% of the energy storage capacity. Furthermore, the material benefited from the addition of a catalytic amount of CaCO3 which improved the reaction kinetics through the formation of Ba2−xCaxSiO4 intermediate compounds. Indeed, this improvement was attributed to the formation of Ba2−xCaxSiO4 facilitating Ba2+ and O2− mobility through induced crystal defects. Due to the part of inactive material, the conversion rate of BaCO3-BaSiO3 mixture with CaCO3 was about 60%, which closely relates to the expected amount of active material. BaO(s) + CO2(g) BaCO3(s) (∆H◦ = −272.5 kJ/mol) BaCO3(s) + BaSiO3(s) Ba2SiO4(s) + CO2(g) (∆H850 ◦C = 126.9 kJ/mol) (4) (5) Application of lithium silicate for TCES at high temperatures was proposed by Takasu et al. [73]. The carbonation/decarbonation of the system (Equation (6)) was tested in TGA under various CO2 pressures and presented a gravimetric energy density of 780 kJ/kg at around 400–700 ◦C, under 100% CO2, with good durability over the course of 5 cycles. Li4SiO4(s) + CO2(g) Li2CO3(s) + Li2SiO3(s) + ∆Hr (∆Hr = −94 kJ/mol) (6) The carbonation of transition metals was also considered to provide new materials for TCES at temperatures below 500 ◦C [74]. The carbonation of CoO, MnO, PbO and ZnO was studied, to obtain CoCO3, MnCO3, PbCO3 and ZnCO3, respectively, under high CO2 pressure (8–50 bar), along with the effect of moisture and temperature (25–500 ◦C). Among these, only ZnCO3 could not be obtained. At temperatures between 50 and 500 ◦C, in the presence of moisture under 8 bar CO2, the corresponding ternary oxides of CoO and MnO were obtained. In the same conditions, PbO reacted to give both PbCO3.PbO and PbCO3.2PbO, and the latter was successfully cycled by varying the pressure between 8 and 2 bar. The carbonation of MnO and PbO was also observed in a reactor, under 50 bar in the presence of water. 4. TCES systems Based on Metal Oxides Metal oxide based TCES systems are especially attractive as they permit working with an open cycle, using air (Equation (7), Figure 5). For this reason, the study of metal oxide systems in similar conditions with control of oxygen partial pressure (pO2) is important. As a common trend, it can be observed that the reduction temperature decreases together with lower partial pressure of the reactive gas (O2). The variation of the temperature as a function of pO2 was illustrated using a Van’t Hoff diagram for several metal oxide pairs (Figure 6). MOred(s) + O2(g) MOox(s) + ∆Hr (7) The potential of CuO/Cu2O, Co3O4/CoO, Mn2O3/Mn3O4 and Pb3O4/PbO was investigated under isotherms while varying pO2 between 0.5 and 0.8 bar [75]. The copper and cobalt oxides showed good reversibility, but manganese oxide showed a beginning of sintering and lead oxide was eliminated as it showed no potential under these operating conditions. The Cu2O/CuO system is also interesting as it possesses high reaction enthalpy and reacts at high temperatures [76]. This system was studied between 800 and 930 ◦C and focused on the effect of partial pressure variation on the reaction kinetics with pO2 = 0.1, 0.2, 0.5 and 1.0 bar. The Avrami-Erofeev’s two-dimensional nucleation model (A2) was determined as the best fitting conversion model and gave an activation energy of 233 kJ/mol, with a frequency factor of 5 × 109 1/s. The potential of liquid multivalent metal oxides was tested inPDF Image | Hi Temp Thermochemical Energy Storage via Solid Gas Reactions
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