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Title: High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

Abstract

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co{sub 3}O{sub 4}/CoO, whereas the reaction rate, reversibility and cycling stability of Mn{sub 2}O{sub 3}/Mn{sub 3}O{sub 4} was significantly enhanced with added Fe amounts above ~15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identifymore » other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications. - Highlights: • Solar thermochemical energy storage via reduction/oxidation of mixed metal oxides. • Co-Fe and Mn-Fe mixed oxides are promising candidates for high-temperature energy storage. • Improved cycling of Mn{sub 2}O{sub 3} between bixbyite and cubic spinel by adding 15–50 mol% Fe. • Co{sub 3}O{sub 4} and Mn{sub 2}O{sub 3} reaction temperature and hysteresis gap tuned with Fe addition. • Validation of calculated phase diagram by comparison with experimental results.« less

Authors:
 [1];  [1];  [2]
  1. Processes, Materials, and Solar Energy Laboratory, PROMES-CNRS, 7 Rue du Four Solaire, 66120 Font-Romeu (France)
  2. Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse (France)
Publication Date:
OSTI Identifier:
22742025
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 253; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADDITIVES; CARBON MONOXIDE; COBALT OXIDES; IRON OXIDES; MANGANESE OXIDES; OXIDATION; PHASE DIAGRAMS; REACTION KINETICS; REDOX REACTIONS; SINTERED MATERIALS; SPINELS; TEMPERATURE RANGE 0400-1000 K; THERMAL GRAVIMETRIC ANALYSIS; THERMOCHEMICAL HEAT STORAGE; THERMODYNAMICS; TRANSITION ELEMENTS

Citation Formats

André, Laurie, Abanades, Stéphane, and Cassayre, Laurent. High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.05.015.
André, Laurie, Abanades, Stéphane, & Cassayre, Laurent. High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides. United States. https://doi.org/10.1016/J.JSSC.2017.05.015
André, Laurie, Abanades, Stéphane, and Cassayre, Laurent. 2017. "High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides". United States. https://doi.org/10.1016/J.JSSC.2017.05.015.
@article{osti_22742025,
title = {High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides},
author = {André, Laurie and Abanades, Stéphane and Cassayre, Laurent},
abstractNote = {Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co{sub 3}O{sub 4}/CoO, whereas the reaction rate, reversibility and cycling stability of Mn{sub 2}O{sub 3}/Mn{sub 3}O{sub 4} was significantly enhanced with added Fe amounts above ~15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications. - Highlights: • Solar thermochemical energy storage via reduction/oxidation of mixed metal oxides. • Co-Fe and Mn-Fe mixed oxides are promising candidates for high-temperature energy storage. • Improved cycling of Mn{sub 2}O{sub 3} between bixbyite and cubic spinel by adding 15–50 mol% Fe. • Co{sub 3}O{sub 4} and Mn{sub 2}O{sub 3} reaction temperature and hysteresis gap tuned with Fe addition. • Validation of calculated phase diagram by comparison with experimental results.},
doi = {10.1016/J.JSSC.2017.05.015},
url = {https://www.osti.gov/biblio/22742025}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 253,
place = {United States},
year = {2017},
month = {9}
}