Redox Oxides-Based Solar Thermochemistry and Its Materialization to Reactor/Heat Exchanger Concepts for Efficient Solar Energy Harvesting, Transformation and Storage

Ca-Mn-based perovskites doped in their A- and B-site were synthesized and comparatively tested versus the Co3O4/CoO and (Mn,Fe)2O3/(Mn,Fe)3O4 redox pairs with respect to thermochemical storage and oxygen pumping capability, as a function of the kind and extent of dopant. The perovskites' induced heat effects measured via differential scanning calorimetry are substantially lower: the highest reaction enthalpy recorded by the CaMnO3–δ composition was only 14.84 kJ/kg compared to 461.1 kJ/kg for Co3O4/CoO and 161.0 kJ/kg for (Mn,Fe)2O3/(Mn,Fe)3O4. Doping of Ca with increasing content of Sr decreased these heat effects; more than 20 at % Sr eventually eliminated them. Perovskites with Sr instead of Ca in the A-site exhibited also negligible heat effects, irrespective of the kind of B site cation. On the contrary, perovskite compositions characterized by high oxygen release/uptake can operate as thermochemical oxygen pumps enhancing the performance of water/carbon dioxide splitting materials. Oxygen pumping via Ca0.9Sr0.1MnO3–δ and SrFeO3–δ doubled and tripled, respectively, the total oxygen absorbed by ceria during its re-oxidation versus that absorbed without their presence. Such effective pumping compositions exhibited practically no shrinkage during one heat-up/cool-down cycle. However, they demonstrated an increase of the coefficient of linear expansion due to the superposition of “chemical expansion” to thermal-only one, the effect of which on the long-term dimensional stability has to be further quantified through extended cyclic operation.

[1]  C. Sattler,et al.  Redox Behavior of Solid Solutions in the SrFe1-x Cux O3-δ System for Application in Thermochemical Oxygen Storage and Air Separation , 2018, Energy Technology.

[2]  G. Jackson,et al.  Redox cycles with doped calcium manganites for thermochemical energy storage to 1000 °C , 2018, Applied Energy.

[3]  Henrik Leion,et al.  Stabilizing Particles of Manganese-Iron Oxide with Additives for Thermochemical Energy Storage , 2018, Energy Technology.

[4]  S. Brendelberger,et al.  Demonstration of thermochemical oxygen pumping for atmosphere control in reduction reactions , 2018, Solar Energy.

[5]  C. Sattler,et al.  Redox thermodynamics and phase composition in the system SrFeO3 − δ — SrMnO3 − δ , 2017 .

[6]  C. Sattler,et al.  Applications and limitations of two step metal oxide thermochemical redox cycles; a review , 2017 .

[7]  G. Jackson,et al.  Thermochemical energy storage in strontium-doped calcium manganites for concentrating solar power applications , 2017 .

[8]  J. Rupp,et al.  Perovskite oxides – a review on a versatile material class for solar-to-fuel conversion processes , 2017 .

[9]  C. Sattler,et al.  Exploitation of thermochemical cycles based on solid oxide redox systems for thermochemical storage of solar heat. Part 6: Testing of Mn-based combined oxides and porous structures , 2017 .

[10]  A. McDaniel.  Renewable energy carriers derived from concentrating solar power and nonstoichiometric oxides , 2017 .

[11]  N. Knoblauch,et al.  Chemically induced volume change of CeO2−δ and nonstoichiometric phases , 2017 .

[12]  C. Sattler,et al.  Experimental evaluation of a pilot-scale thermochemical storage system for a concentrated solar power plant , 2017 .

[13]  S. Brendelberger,et al.  Vacuum pumping options for application in solar thermochemical redox cycles – Assessment of mechanical-, jet- and thermochemical pumping systems , 2017 .

[14]  D. Serrano,et al.  Understanding Redox Kinetics of Iron-Doped Manganese Oxides for High Temperature Thermochemical Energy Storage , 2016 .

[15]  S. Abanades,et al.  Experimental assessment of oxygen exchange capacity and thermochemical redox cycle behavior of Ba and Sr series perovskites for solar energy storage , 2016 .

[16]  M. Lange,et al.  Perovskite oxides for application in thermochemical air separation and oxygen storage , 2016 .

[17]  G. Karagiannakis,et al.  Cobalt/cobaltous oxide based honeycombs for thermochemical heat storage in future concentrated solar power installations: Multi-cyclic assessment and semi-quantitative heat effects estimations , 2016 .

[18]  A. Ambrosini,et al.  High performance reduction/oxidation metal oxides for thermochemical energy storage (PROMOTES) , 2016 .

[19]  A. Ambrosini,et al.  ABO3 (A = La, Ba, Sr, K; B = Co, Mn, Fe) perovskites for thermochemical energy storage , 2016 .

[20]  A. Ambrosini,et al.  Investigation of LaxSr1−xCoyM1−yO3−δ (M = Mn, Fe) perovskite materials as thermochemical energy storage media , 2015 .

[21]  David P Serrano,et al.  Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron. , 2015, ChemSusChem.

[22]  Kyle M. Allen,et al.  Design Principles of Perovskites for Thermochemical Oxygen Separation , 2015, ChemSusChem.

[23]  C. Sattler,et al.  A review on solar thermal syngas production via redox pair-based water/carbon dioxide splitting thermochemical cycles , 2015 .

[24]  Souzana Lorentzou,et al.  Cobalt oxide based structured bodies as redox thermochemical heat storage medium for future CSP plants , 2014 .

[25]  Can Li,et al.  Thermochemical CO2 splitting reaction with supported LaxA1−xFeyB1−yO3 (A = Sr, Ce, B = Co, Mn; 0 ⩽ x, y ⩽ 1) perovskite oxides , 2014 .

[26]  Christian Sattler,et al.  Exploitation of thermochemical cycles based on solid oxide redox systems for thermochemical storage of solar heat. Part 1: Testing of cobalt oxide-based powders , 2014 .

[27]  M. Allendorf,et al.  Considerations in the Design of Materials for Solar‐Driven Fuel Production Using Metal‐Oxide Thermochemical Cycles , 2014 .

[28]  W. Chueh,et al.  Sr- and Mn-doped LaAlO3-δ for solar thermochemical H2 and CO production , 2013 .

[29]  A. Steinfeld,et al.  Lanthanum–Strontium–Manganese Perovskites as Redox Materials for Solar Thermochemical Splitting of H2O and CO2 , 2013 .

[30]  THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER , 2012 .

[31]  Matthias Hänel,et al.  Jülich Solar Power Tower—Experimental Evaluation of the Storage Subsystem and Performance Calculation , 2011 .

[32]  V. Zaspalis,et al.  Perovskite membrane reactor for continuous and isothermal redox hydrogen production from the dissociation of water , 2008 .

[33]  Alan Atkinson,et al.  Chemically-induced stresses in ceramic oxygen ion-conducting membranes , 2000 .