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Research Papers

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

[+] Author and Article Information
Christos Agrafiotis

Deutsches Zentrum für Luft- und Raumfahrt/
German Aerospace Center—DLR,
Institute of Solar Research,
Linder Höhe,
Cologne 51147, Germany
e-mail: Christos.Agrafiotis@dlr.de

Mathias Pein

Deutsches Zentrum für Luft- und Raumfahrt/
German Aerospace Center—DLR,
Institute of Solar Research,
Linder Höhe,
Cologne 51147, Germany;
Faculty of Mechanical Science and Engineering,
Institute of Power Engineering,
TU Dresden,
Dresden 01062, Germany
e-mail: Mathias.Pein@dlr.de

Dimitra Giasafaki

National Centre for Scientific
Research “Demokritos,”
Institute of Nanoscience and Nanotechnology,
Aghia Paraskevi,
Attica 15341, Greece
e-mail: d.giasafaki@inn.demokritos.gr

Stefania Tescari

Deutsches Zentrum für Luft- und Raumfahrt/
German Aerospace Center—DLR,
Institute of Solar Research,
Linder Höhe,
Cologne 51147, Germany
e-mail: Stefania.Tescari@dlr.de

Martin Roeb

Deutsches Zentrum für Luft- und Raumfahrt/
German Aerospace Center—DLR,
Institute of Solar Research,
Linder Höhe,
Cologne 51147, Germany
e-mail: Martin.Roeb@dlr.de

Christian Sattler

Deutsches Zentrum für Luft- und Raumfahrt/
German Aerospace Center—DLR,
Institute of Solar Research,
Linder Höhe,
Cologne 51147, Germany
e-mail: Christian.Sattler@dlr.de

1Corresponding author.

Contributed by the Solar Energy Division of ASME for publication in the JOURNAL OF SOLAR ENERGY ENGINEERING: INCLUDING WIND ENERGY AND BUILDING ENERGY CONSERVATION. Manuscript received September 7, 2018; final manuscript received November 23, 2018; published online January 8, 2019. Guest Editors: Tatsuya Kodama, Christian Sattler, Nathan Siegel, Ellen Stechel.

J. Sol. Energy Eng 141(2), 021010 (Jan 08, 2019) (11 pages) Paper No: SOL-18-1420; doi: 10.1115/1.4042226 History: Received September 07, 2018; Revised November 23, 2018

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.

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Figures

Grahic Jump Location
Fig. 1

(a) Schematic of potential applications of redox oxides in the form of structured porous bodies (e.g., oxide-coated or oxide-made honeycombs and foams) in solar tower concentrating facilities (perovskites are shown as an exemplary oxide composition). If the temperatures required are not that high to require direct solar irradiation, the targeted applications can be implemented downstream of the solar receiver and (b) perovskites as tunable redox materials: rational cation doping in the A and B sites enables tuning the redox thermodynamics to suit a given application (a) adapted and (b) reproduced from [1] with permission of The Royal Society of Chemistry.

Grahic Jump Location
Fig. 2

Effect of Mn source on weight change (TGAs) of CaMnO3–δ and CaMn0.9Ti0.1O3–δ powders from Mn2O3 and Mn3O4, during redox cycling between 1000 °C and 300 °C, ramp rate 5 °C/min, 15 cycles, no dwell

Grahic Jump Location
Fig. 3

Effect of Mn source on phase composition (XRDs) of CaMnO3–δ and CaMn0.9Ti0.1O3–δ powders from Mn2O3 and Mn3O4, (a), (b) CaMnO3–δ and (c), (d) CaMn0.9Ti0.1O3–δ powders from Mn3O4, before and after TGA; (a), (c) entire diffraction angle range and (b), (d) magnification on the range containing the major peak

Grahic Jump Location
Fig. 4

TGA comparison of A-site and B-site doped perovskite compositions tested: (a) five cycles, all samples and (b) magnification of the third cycle

Grahic Jump Location
Fig. 5

Effect of B-site doping of Ca-Mn perovskites on weight change and redox reaction enthalpies: (a) the DSC curves of only the third reduction–oxidation cycle is shown for reasons of clarity and (b) magnification of only the reduction step of the third cycle to delineate the DSC peaks shape and their correspondence to the TGA curves

Grahic Jump Location
Fig. 6

Effect of A- and B-site doping of perovskite compositions tested on weight change and on redox reaction enthalpies; only the third reduction–oxidation cycle is shown for reasons of clarity: (a) Ca-Mn perovskites, effect of A-site doping of Ca with Sr and (b) Sr-Mn perovskites (Ca-free); effect of B-site doping of Mn with Fe

Grahic Jump Location
Fig. 7

TGA/DSC comparison of A-site and B-site doped perovskite compositions tested versus Co3O4 and (0.75)(Mn2O3)*(0.25)(Fe2O3): (a) Co3O4 and (0.75)(Mn2O3)*(0.25)(Fe2O3) and (b) perovskites, respectively, TGA, five cycles, under the same x–y, scales for direct visual comparison, and (c) TGA and DSC comparison among Co3O4, (0.75)(Mn2O3)*(0.25)(Fe2O3) and the perovskites with the higher reaction enthalpies, magnification of the third cycle

Grahic Jump Location
Fig. 8

Thermochemical oxygen pumping comparison among three representative A-site and B-site doped perovskite compositions, Co3O4 and (0.75)(Mn2O3)*(0.25)(Fe2O3): (a) response in oxygen concentration at the outlet of the setup without any and with various pumping materials and (b) total oxygen absorbed from the splitting material during its oxidation with and without the presence of pumping materials

Grahic Jump Location
Fig. 9

(a) Typical perovskite sintered bar specimen for the dilatometry experiments, (b)–(d) dilatometry curves (ΔL (%) versus temperature) during heating and cooling of the same three representative A-site and B-site doped perovskite compositions: (a) Ca0.90Sr0.10MnO3–δ, (b) SrFeO3–δ, and (c) SrMnO3–δ

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