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Energies 2020, 13, 5859 15 of 23 Energies 2020, 13, x FOR PEER REVIEW 15 of 24 Figure 7. (a) Redox activity of Co3 O4 /CoO foam made from commercial Co3 O4 , (b) variation of Figure 7. (a) Redox activity of Co3O4/CoO foam made from commercial Co3O4, (b) variation of the the tempetreamtuperreatguraepgabpebtwetweeen theererdeudcutiocntioand aonxidatoioxnidstaetpionf Csot 4/CoofOCdoepOend/iCngooOn tdhepdoepnidnging on the composition. doping composition. 5. TCES Systems Based on Perovskites 5. TCES Systems Based on Perovskites Perovskites have also been considered as an innovative option for TCES application. Taking Perovskites have also been considered as an innovative option for TCES application. Taking advantage advantage of oxygen vacancies in perovskites structures and their oxygen ion conducting properties, ofoxygenvacanciesinperovskitesstructuresandtheiroxygenionconductingproperties,ABO perovskites ABO3 perovskites can be used to store energy via O2 exchange (Equation (9)). Some perovskites of3fer canbeusedthteoinsteorreesteingearbgiylitvyiatoOstoreexacnhdanreglea(sEeqouxyagteionnin(9a))c.oSntoinmueoupsewroavysfkoliltoewsiongffethrethvearinatieorneisntingability 2 temperature [103] (Figure 8). Different perovskites with Fe, Co or Mn on the B site were studied, and to store and release oxygen in a continuous way following the variation in temperature [103] (Figure 8). Co-based perovskites showed the highest O2 exchange capacity together with high reaction Different perovskites with Fe, Co or Mn on the B site were studied, and Co-based perovskites showed enthalpies [103]. The enhancement of O2 exchange capacity in these systems was achieved with the thehighestO exchangecapacitytogetherwithhighreactionenthalpies[103].Theenhancementof pres2ence of Ba on the A site (BaCoO3, BaFeO3 and Ba0.5Sr0.5CoO3), as compared to the presence of Sr. O exchanHgoewceavpera,cointylyiBnaCthoOesecosuyldstbeemres-owxidaiszeadchcoimevpeledtelwyiutnhdethr2e0p%rOeseatnmcoespohfeBrea.ontheAsite(BaCoO, 2323 BaFeO and Ba Sr CoO ), as compaAreBdO3to⇄thAeBOprese+n1c/2eΔoδfOSr. However, only BaCoO(9) could be 3 0.50.53 3 re-oxidized completely under 20% O2 atmosphere. ABO3−δ ABO3-δ-∆δ + 1/2 ∆δO2 −δ 3 -δ The BaySr1−yCoO3−δ system was also studied, along with LaxSr1−x (Mn, Fe, Co)O3−δ, by Gokon et al. [104]. The study concluded on the suitability of Ba0.3Sr0.7CoO3−δ and Ba0.7Sr0.3CoO3−δ for TCES above 600 ◦C in air stream. It was noted that no direct correlation was observed between the oxygen storage capacity and the tendency of the heat storage capacity for these systems. For comparison, it is mentioned that the charging/discharging capacity of Ba0.3Sr0.7CoO3−δ is higher than that of Fe-doped manganese oxides, which have been shown to be a promising system for TCES. The LaxSr1−x(Mn, Fe, Co)O3−δ system was studied further with focus on the LaxSr1−xCoyMn1−yO3−δ (LSCM) and LaxSr1-xCoyFe1−yO3−δ (LSCF) series [105,106]. TGA and structural investigation revealed that the systems with low La content presented the highest redox activity, with an optimum reached for x = 0.3, while the perovskites adopted a cubic structure, or tetragonal structure for LSCM. Higher La content led to a higher distortion in the perovskite structure, related to a decrease in redox activity. Among all the systems studied, the LSCM3791 composition presented the highest gravimetric energy density (250 kJ/kg-ABO3). Very recently, dual-phase La0.65Sr0.35MnO3−xCeO2 composites (with x = 0, 5, 10, 20, 50, and 100%) were investigated for oxygen exchange and CO2 splitting, via thermochemical redox reactions, for the purpose of fuel production [107]. This work demonstrated the enhancement in -Δ δ 2 3eOp 34 (9)PDF Image | Hi Temp Thermochemical Energy Storage via Solid Gas Reactions
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