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Energies 2020, 13, 5859 13 of 23 Energies 2020, 13, x FOR PEER REVIEW 12 of 24 Figure 6. Transition temperature variation (1/T) as a function of pO2 for a selection of metal oxides Figure 6. Transition temperature variation (1/T) as a function of pO2 for a selection of metal oxides represented through Van’t Hoff diagram. represented through Van’t Hoff diagram. Mn2O3/Mn3O4 is a largely studied redox system for TCES application (MnO2 was eliminated The potential of CuO/Cu2O, Co3O4/CoO, Mn2O3/Mn3O4 and Pb3O4/PbO was investigated under because of no reversibility [8]), due to the relatively high gravimetric energy storage density of the isotherms while varying pO2 between 0.5 and 0.8 bar [75]. The copper and cobalt oxides showed good material and its availability, low toxicity and cost. However, the stability of this system decreases greatly reversibility, but manganese oxide showed a beginning of sintering and lead oxide was eliminated over several oxidation/reduction cycles due to sintering and to the formation of the hausmannite phase as it showed no potential under these operating conditions. The Cu2O/CuO system is also interesting which decreases the reversibility [84]. The doping of Mn2O3 with silicon oxides is a recently investigated as it possesses high reaction enthalpy and reacts at high temperatures [76]. This system was studied option to answer the reversibility issues of manganese oxide-based TCES systems. The reactivity between 800 and 930 °C and focused on the effect of partial pressure variation on the reaction kinetics and stability of Mn/Si particles were studied in a packed-bed reactor using 2 to 10 wt% added silica, with pO2 = 0.1, 0.2, 0.5 and 1.0 bar. The Avrami-Erofeev’s two-dimensional nucleation model (A2) with an interest for Si-doping potential to help spontaneous O2 release and increase the stability was determined as the best fitting conversion model and gave an activation energy of 233 kJ/mol, of the material over several reduction/oxidation cycles [89]. In both TGA and packed-bed reactor, with a frequency factor of 5 × 109 1/s. The potential of liquid multivalent metal oxides was tested in the sample composed of 6 wt% SiO2 and 94 wt% Mn3O4 presented the highest amount of oxygen liquid chemical looping thermal energy storage (LCL-TES) [77]. The free Gibbs energy of PbO/Pb, release. In addition, MnSiO3 particles demonstrated a good physical stability under air at high MnO2/Mn and BaO2/Ba, were determined using the Ellingham diagram, and these oxides were temperatures. The effect of Si4+ doping to Mn2O3 on the reactivity and stability of the Mn2O3/Mn3O4 eliminated for TES application as their ΔG° were found to be positive. Conversely, the negative ΔG° system was also studied, over 40 reduction/oxidation cycles [90]. The re-oxidation of Mn3O4 was of PbO2/PbO, PbO2/Pb3O4, Pb3O4/PbO, CuO/Cu2O and Sb2O5/Sb2O3 validated them as potential improved with the introduction of Si cations, especially for a sample synthesized via a sol-gel method candidates. CuO/Cu2O presented the highest total enthalpy of 404.67 kJ/mol, but formation of the using 1 mol% Si-doping. The segregation of Si4+ on Mn2O3 grain surfaces was observed and proved to molten phase occurred at very high temperatures (~1200 °C), and the corrosiveness of the system help control and reduce the diffusivity at the grain boundaries. A method based on a combination of when molten would make the implementation difficult. Pb oxides were noted as easier to implement drop calorimetry and acid-solution calorimetry was used to measure the total enthalpy and standard since lead’s melting temperature is below 1000 °C even though the associated total reaction enthalpy enthalpy of materials forming at high temperatures, Mn-Mg oxides, involving tin (II) chloride as a is lower (250.09 kJ/mol) and toxicity may be a barrier. The integration of CuO/Cu2O to TCES processes reducing agent to increase their dissolution rate [91,92]. With this method, the chemical energy storage was considered, and the reaction kinetics and stability of the material was studied in a fixed-bed found for Mn-Mg-O systems (1000–1500 ◦C, pO2 = 0.2 atm) with different molar ratios of Mn/Mg reactor [78]. Kinetic models were derived for the charging and discharging steps using isokinetic and (2/1, 1/1, and 2/3) was 565.3 ± 54.8, 586.3 ± 55.0 and 590.9 ± 62.5 kJ/kg, respectively. The volumetric isothermal measurement. The cycling of Fe2O3/Fe3O4 was studied using pressure-swing by energy density of the 1/1 composition under pO2 = 0.2 atm was measured at 1813 ± 175 MJ/m3 during performing the reduction under vacuum and the re-oxidation using compressed air stream [79]. The the reduction [93]. The study concludes that the manganese ratio should not be raised above 2/1. study of BaO2/BaO revealed its capacity to undergo several redox cycles without deactivation The study also investigated further doping of the manganese-magnesium oxide system with cobalt, (Equation (8)), using a thermal pre-treatment at high temperatures to enhance the oxidation iron, zinc or nickel oxides, which did not improve the reactivity, energy density nor stability of the conversion of the material [80]. Since the high temperature pre-treatment eliminated impurities in system. Among the investigated metal doping for the enhancement of manganese oxide cycling the sample, it is speculated that a high purity of BaO2 would show better redox performances. performances, the addition of iron was demonstrated to yield especially good results. A study focusing 2BaO(s) + O2(g) ⇄ 2BaO2(s) on the mixed oxide (Mn0.7Fe0.3)2O3 investigated the improvement of the particle stability via the (ΔH° = −86.3 kJ/mol BaO) (8)PDF Image | Hi Temp Thermochemical Energy Storage via Solid Gas Reactions
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