Ionic Thermal Synthesis and Reversible Heat Storage Performance of Manganese-based Oxides

doi:10.15541/jim20220658

Abstract

Abstract:

Concentrated solar power plant needs to be equipped with large-scale high-temperature heat storage module. Metal oxides can store and release heat through reversible redox reaction. Manganese oxides is non-toxic and cheap, showing great potential for applying in solar power plant, but it displays poor reversibility. Here, a manganese-based oxides with high reversibility by deep eutectic solvent (DES) ionic thermal synthesis was proposed, and effects of synthesis parameters and iron doping on heat storage performance were studied. MnCO₃, as the raw material, was used to produce manganese oxides by ionic thermal decomposition at high temperature and released CO₂, which could also form abundant pore structure, providing great channels for oxygen transmission and diffusionfor redox. Although this Mn₂O₃ synthesis method showed better reactivity than commercial Mn₂O₃, its oxidation rate was low. It is worth noting that oxidation rate of manganese iron oxide doped with 20% Fe, synthesized at 150 ℃, was fast. Its heat storage density reached 300.66 J/g, and reversibility of the reaction was the best, which could realize long-term stable cycle. Our results demonstrated that ionic thermal synthesis can increase the lattice oxygen ratio in manganese oxides, promoting migration of oxygen vacancies, and further improving reversibility and cyclic stability.

Key words: concentrated solar power, heat storage, manganese-based oxide, deep eutectic solvent

CLC Number:

TK513

MENG Bo, XIAO Gang, WANG Xiuli, TU Jiangping, GU Changdong. Ionic Thermal Synthesis and Reversible Heat Storage Performance of Manganese-based Oxides[J]. Journal of Inorganic Materials, 2023, 38(7): 793-799.

Figures/Tables 13

Fig. 1 Redox reaction characteristics of Mn2O3 by ionic thermal synthesis and commercial Mn2O3 Colorful figure is available on website

Fig. 2 (a-d) SEM images of samples before and after cycling, and (e) O1s XPS spectra of Mn2O3 before cycling (a) Commercial Mn2O3 before cycling; (b) Commercial Mn2O3 after cycling; (c) DES Mn2O3 before cycling; (d) DES Mn2O3 after cycling

Fig. 3 Redox reaction of samples with different Fe contents Colorful figure is available on website

Fig. 4 (a) TG curves and (b) oxidation reaction conversion rate-time curves of samples prepared at different ionic thermal synthesis temperatures

Fig. 5 SEM images of samples prepared by ionic thermal synthesis at different temperatures before cycling (a) 120 ℃-4 h; (b) 150 ℃-4 h; (c) 180 ℃-4 h

Fig. 6 (a) Thermochemical heat storage density and (b) thermal cycling curves of 150 ℃-4 h

Fig. 7 O1s XPS spectra of 150 ℃-4h

Fig. 8 Characterization of precursors of manganese-based oxide synthesized by DES (a) XRD pattern; (b) SEM-EDS images; (c) XRD patterns under different heat-treatments; (d) TG curve

Fig. 9 Formation process of heat storage materials induced by

Fig. S1 Photos of DES (a) MnCl2/Urea; (b) (MnCl2, FeCl3)/Urea

Fig. S2 DSC curve of Mn2O3 by ionic thermal synthesis

Fig. S3 TG curves of (Mn0.8Fe0.2)2O3 by solid-phase and ionic thermal synthesis

Fig. S4 XRD patterns of samples after heat treatment under different temperatures prepared by MnCl2/Urea DES

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