CaAl 0.2 Mn 0.8 O 3-δ (CAM28) and CaTi 0.2 Mn 0.8 O 3-δ (CTM28) are perovskite metal oxides developed for high-temperature thermochemical energy storage (TCES) applications, e.g., in support of air Brayton power generation. Previous reports for these compounds focus on the equilibrium non-stoichiometry (δ) as a function of temperature and oxygen partial pressure (pO 2 ) and the endotherm (or exotherm) accompanying changes in δ resulting from thermal reduction (or re-oxidation). Herein, we report results for elemental substitution and doping (Al, Co, Fe, La, Sr, Ti, Y, Zn, and Zr) of calcium manganites (CM) that establish the preference for CAM28 and CTM28. Techniques employed include conventional (screening and equilibrium) and ballistically heated multi-cycle thermogravimetric analysis (TGA), conventional and high temperature ( in-situ ) X-ray diffraction (XRD), and differential scanning calorimetry (DSC). Forward-looking results for A-site Y-doped materials, e.g., Ca 0.9 Y 0.1 MnO 3-δ (CYM910), establish a route to increasing the reduction enthalpy relative to CAM28 and CTM28, albeit at the expense of increased reduction temperatures and raw materials costs. A thermodynamic model presented for CAM28, but extendable to related materials, provides values for the reaction enthalpy and extent of reduction as a function of temperature and oxygen partial pressure for use in design efforts. Taken as a whole, the results support the choice of Al-doped CaMnO 3-δ as a low-cost material for TCES in a high temperature air Brayton application, but point the way to achieving higher stored energy densities that could lead to overall cost savings.
Miller, James E., et al. "Modified Calcium Manganites for Thermochemical Energy Storage Applications." Frontiers in Energy Research, vol. 10, Apr. 2022. https://doi.org/10.3389/fenrg.2022.774099
Miller, James E., Babiniec, Sean M., Coker, Eric N., Loutzenhiser, Peter G., Stechel, Ellen B., & Ambrosini, Andrea (2022). Modified Calcium Manganites for Thermochemical Energy Storage Applications. Frontiers in Energy Research, 10. https://doi.org/10.3389/fenrg.2022.774099
Miller, James E., Babiniec, Sean M., Coker, Eric N., et al., "Modified Calcium Manganites for Thermochemical Energy Storage Applications," Frontiers in Energy Research 10 (2022), https://doi.org/10.3389/fenrg.2022.774099
@article{osti_1863143,
author = {Miller, James E. and Babiniec, Sean M. and Coker, Eric N. and Loutzenhiser, Peter G. and Stechel, Ellen B. and Ambrosini, Andrea},
title = {Modified Calcium Manganites for Thermochemical Energy Storage Applications},
annote = { CaAl 0.2 Mn 0.8 O 3-δ (CAM28) and CaTi 0.2 Mn 0.8 O 3-δ (CTM28) are perovskite metal oxides developed for high-temperature thermochemical energy storage (TCES) applications, e.g., in support of air Brayton power generation. Previous reports for these compounds focus on the equilibrium non-stoichiometry (δ) as a function of temperature and oxygen partial pressure (pO 2 ) and the endotherm (or exotherm) accompanying changes in δ resulting from thermal reduction (or re-oxidation). Herein, we report results for elemental substitution and doping (Al, Co, Fe, La, Sr, Ti, Y, Zn, and Zr) of calcium manganites (CM) that establish the preference for CAM28 and CTM28. Techniques employed include conventional (screening and equilibrium) and ballistically heated multi-cycle thermogravimetric analysis (TGA), conventional and high temperature ( in-situ ) X-ray diffraction (XRD), and differential scanning calorimetry (DSC). Forward-looking results for A-site Y-doped materials, e.g., Ca 0.9 Y 0.1 MnO 3-δ (CYM910), establish a route to increasing the reduction enthalpy relative to CAM28 and CTM28, albeit at the expense of increased reduction temperatures and raw materials costs. A thermodynamic model presented for CAM28, but extendable to related materials, provides values for the reaction enthalpy and extent of reduction as a function of temperature and oxygen partial pressure for use in design efforts. Taken as a whole, the results support the choice of Al-doped CaMnO 3-δ as a low-cost material for TCES in a high temperature air Brayton application, but point the way to achieving higher stored energy densities that could lead to overall cost savings. },
doi = {10.3389/fenrg.2022.774099},
url = {https://www.osti.gov/biblio/1863143},
journal = {Frontiers in Energy Research},
issn = {ISSN 2296-598X},
volume = {10},
place = {Switzerland},
publisher = {Frontiers Media SA},
year = {2022},
month = {04}}
Babiniec, Sean M.; Coker, Eric N.; Ambrosini, Andrea
SOLARPACES 2015: International Conference on Concentrating Solar Power and Chemical Energy Systems, AIP Conference Proceedingshttps://doi.org/10.1063/1.4949104
Babiniec, Sean M.; Miller, James E.; Ambrosini, Andrea
ASME 2016 10th International Conference on Energy Sustainability collocated with the ASME 2016 Power Conference and the ASME 2016 14th International Conference on Fuel Cell Science, Engineering and Technology, Volume 1: Biofuels, Hydrogen, Syngas, and Alternate Fuels; CHP and Hybrid Power and Energy Systems; Concentrating Solar Power; Energy Storage; Environmental, Economic, and Policy Considerations of Advanced Energy Systems; Geothermal, Ocean, and Emerging Energy Technologies; Photovoltaics; Posters; Solar Chemistry; Sustainable Building Energy Systems; Sustainable Infrastructure and Transportation; Thermodynamic Analysis of Energy Systems; Wind Energy Systems and Technologieshttps://doi.org/10.1115/ES2016-59646
Miller, James E.; Ambrosini, Andrea; Babiniec, Sean M.
ASME 2016 10th International Conference on Energy Sustainability collocated with the ASME 2016 Power Conference and the ASME 2016 14th International Conference on Fuel Cell Science, Engineering and Technology, Volume 1: Biofuels, Hydrogen, Syngas, and Alternate Fuels; CHP and Hybrid Power and Energy Systems; Concentrating Solar Power; Energy Storage; Environmental, Economic, and Policy Considerations of Advanced Energy Systems; Geothermal, Ocean, and Emerging Energy Technologies; Photovoltaics; Posters; Solar Chemistry; Sustainable Building Energy Systems; Sustainable Infrastructure and Transportation; Thermodynamic Analysis of Energy Systems; Wind Energy Systems and Technologieshttps://doi.org/10.1115/ES2016-59660