6 results on '"Mariano Santaya"'
Search Results
2. Ternary Ni−Co−Fe exsolved nanoparticles/perovskite system for energy applications: Nanostructure characterization and electrochemical activity
- Author
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Alberto Caneiro, Liliana Veronica Mogni, H. E. Troiani, and Mariano Santaya
- Subjects
TERNARY ALLOY ,Materials science ,Nanostructure ,PEROVSKITE ,SYMMETRIC-SOFC ,Energy Engineering and Power Technology ,Nanoparticle ,Electrochemistry ,Ternary alloy ,Characterization (materials science) ,Chemical engineering ,purl.org/becyt/ford/2 [https] ,EXSOLUTION ,Electrode ,Materials Chemistry ,Chemical Engineering (miscellaneous) ,Electrical and Electronic Engineering ,Ternary operation ,purl.org/becyt/ford/2.5 [https] ,Perovskite (structure) - Abstract
The exsolution of Ni−Co−Fe from a Sr0.93(Ti0.3Fe0.56Ni0.07Co0.07)O3−δ perovskite (STFNC) is explored as a strategy to produce electrochemically active electrodes for symmetric-SOFC (S-SOFC). It was found that a nanostructured NiCoFe ternary alloy phase, with approximately equal amounts of each metal, can be formed by this method. The STFNC electrode is studied via electrochemical impedance spectroscopy, showing a really interesting potential as S-SOFC electrode: the anode polarization resistance was 1.12 Ω·cm2 in a wet 10%H2 atmosphere at 700 °C (exsolving in situ the NiCoFe phase), and the cathode polarization resistance at 700 °C in air was 0.054 and 0.042 Ω·cm2, before and after exsolution, respectively. Fil: Santaya, Mariano. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro. Archivo Histórico del Centro Atómico Bariloche e Instituto Balseiro | Universidad Nacional de Cuyo. Instituto Balseiro. Archivo Histórico del Centro Atómico Bariloche e Instituto Balseiro; Argentina Fil: Caneiro, Alberto. YPF - Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Mogni, Liliana Verónica. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; Argentina
- Published
- 2020
3. Tracking the Nanoparticle Exsolution/Reoxidation Process in Ni-Doped SrTi0.3Fe0.7O3-δ Electrodes for Intermediate Temperature Symmetric SOFC
- Author
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Raul Garica-Diez, Mauricio Damián Arce, Mariano Santaya, Catalina Jimenez, Horacio Esteban Troiani, Marcus Bär, Emilia A. Carbonio, Liliana Verónica Mogni, Axel Knop-Gericke, and Regan G. Wilks
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chemistry.chemical_compound ,Chemical state ,Materials science ,chemistry ,Chemical engineering ,Reducing atmosphere ,Phase (matter) ,Non-blocking I/O ,Oxide ,Energy-dispersive X-ray spectroscopy ,Dielectric spectroscopy ,Perovskite (structure) - Abstract
Mixed ionic and electronic conductor (MIEC) oxides have been proposed as candidates to replace Ni/YSZ composites as anodes for Solid Oxide Fuel Cells (SOFC) due to their good stability under C-based fuels. Some MIECs have also demonstrated a good electro-catalytic activity both for oxygen reduction and hydrogen oxidation, making them suitable for symmetric configurations (S-SOFC). This approach presents remarkable advantages for reducing manufacturing and operational costs, as well as for extending the cell’s lifetime by reversing gas flows and thus partially reversing the negative effects of sulphur poisoning and carbon deposition that may happen during operation. Also, the catalytic activity of MIEC electrodes can be improved by functionalizing the oxide surface with active nanoparticles. In this work, we study the formation of Ni-Fe alloy nanoparticles by exsolution from a Sr0.93(Ti0.3Fe0.63Ni0.07)O3-δ (STFN) perovskite in reducing atmospheres, and also the process of reoxidation when the exsolved material is exposed to an oxidizing atmosphere. The initial Sr-deficient composition was chosen to alleviate the segregation of Sr [1], which typically can occur in these materials. Exsolution has previously been reported to improve the electrochemical performance of STFN anodes [2], but the mechanisms underlying the exsolution process and the solid/gas interface are still not well understood. The possibility of using S-SOFC materials that undergo exsolution also raises the question of whether the material is regenerated during reoxidation. While oxidation-induced redissolution of exsolved nanoparticles has been observed for Fe-Co exsolution on La0.8Sr1.2Fe0.9Co0.1O4−δ perovskites [3], for the Ni-Fe exsolution in Sr2(Fe1.4Ni0.1Mo0.5)O6− δ, nanoparticles remained at the surface even after reoxidation [4]. The first case is a very interesting result to achieve larger cell lifetimes, and the latter case is interesting as it opens an additional route to increase the cathode performance. In fact, in ref. [5] Ni exsolution in SrTi0.1Fe0.85Ni0.05O3− δ is deliberately employed as design strategy, fully exploiting the non-reversibility of the exsolution of nanoparticles. However, it is not clear whether Ni-Fe nanoparticles oxidize to form a (Ni,Fe)Ox phase or if Fe is reincorporated into the lattice leaving only NiO particles at the surface. It is also not clear how Sr segregation is affected by the exsolution/reoxidation treatments, or how the reoxidized STFN perovskite is modified compared to the pristine sample. To address these questions directly, ambient pressure X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy (AP-XPS and NEXAFS) is used to study the chemical structure of STFN in a complete redox cycle in-situ. Based on the measurements, we can provide insights into the chemical states of Fe and Ni and can differentiate the surface and bulk species for Sr and O in each stage of the cycle. We observe that Ni exsolves readily, but we also note that the amount of surface Fe0 increases with increasing H2 content in the reducing atmosphere; Fe0 also increases with the reduction time following an exponential trend until a plateau value is reached within ~1h. Further, we find a significant Sr segregation in reducing atmospheres, which we presume occurs to compensate for the B-site cation exsolution. The amount of Sr segregation remains constant in the nearest surface after reoxidation, but is partially reversed for larger penetration depths; there is also a rapid reversibility in the Fe oxidation state during reoxidation. These observations were complemented with transmission (TEM) and scanning electron microscopy (SEM) studies, with simultaneous energy dispersive spectroscopy (EDS) analysis. In conclusion, we propose a reoxidation-induced reconstruction which forms a Fe- and Sr-rich STF perovskite in the near-surface region, leaving the Ni segregated from the perovskite. Finally, we link the results to the electrochemical impedance spectroscopy (EIS) response of the STFN electrode, observing that this STFN-reoxidized sample shows a significant improvement in its cathode performance compared to the pristine STFN. [1] Fagg, D. P. et al, J. Eur. Ceram. Soc. 21, 1831–1835 (2001). [2] Zhu, T., Troiani, H. E., Mogni, L. V, Han, M. & Barnett, S. A. Joule 2, 478–496 (2018). [3] Zhou, J. et al. Chem. Mater. 28, 2981–2993 (2016). [4] Liu, T. et al. J. Mater. Chem. A 8, 582–591 (2020). [5] Yang, G., Zhou, W., Liu, M. & Shao, Z. ACS Appl. Mater. Interfaces 8, 35308-35314 (2016). Figure 1
- Published
- 2021
4. Study of phase stability of SrTi0.3Fe0.7O3−δ perovskite in reducing atmosphere: Effect of microstructure
- Author
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Mariano Santaya, Liliana Verónica Mogni, Laura Cecilia Baque, Lucía María Toscani, and Horacio Esteban Troiani
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Materials science ,02 engineering and technology ,General Chemistry ,Electrolyte ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,Microstructure ,01 natural sciences ,Cathode ,Grain size ,0104 chemical sciences ,law.invention ,Dielectric spectroscopy ,Chemical engineering ,law ,General Materials Science ,Chemical stability ,Particle size ,0210 nano-technology ,Polarization (electrochemistry) - Abstract
Increasing SOFC electrode's surface area by modification of its microstructure is a well-known technique to reduce electrode polarization resistance. This is because reduced grain size and increased porosity promote diffusion and surface reactions, thus improving the electrode performance. However, a modified microstructure also causes differences in phase stability and in chemical compatibility with other SOFC materials. In this work, we study the effect of particle size in both the electrode performance and the phase stability under different fuel conditions and temperatures. SrTi0.3Fe0.7O3−δ (STF) is both prepared via solid state reaction (STF-SSR) and also by an alternative sol-gel route (STF-SG). The sintering temperature is reduced dramatically with the sol-gel method, hence inducing a higher porosity and a much smaller grain size. As particle size is reduced the stability under fuel conditions is also diminished, so decomposition induced by segregation of metallic Fe and SrO occurs at lower temperatures for the STF-SG sample. The stability under reducing conditions is studied by combined techniques such as TGA, TPR, XRD, SEM and TEM. Performance as anode and cathode is evaluated by Electrochemical Impedance Spectroscopy (EIS) by using electrolyte supported symmetrical cells. Prior to electrochemical experiments, the reactivity between La0.8Sr0.2Ga0.8Mg0.2O3 (LSGM) electrolyte and STF was studied, and also between STF and a Lanthanum Doped Ceria (LDC) buffer layer. It is seen that microstructure also plays a key role in the chemical stability of the STF. The impact of particle size reduction is higher for the anodic polarization resistance, which is reduced twice from STF-SSR to STF-SG.
- Published
- 2019
5. Exsolution and electrochemistry in perovskite solid oxide fuel cell anodes: Role of stoichiometry in Sr(Ti,Fe,Ni)O3
- Author
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Liliana Verónica Mogni, Scott A. Barnett, Mariano Santaya, Minfang Han, Tenglong Zhu, and Horacio Esteban Troiani
- Subjects
Materials science ,Alloy ,Oxide ,Energy Engineering and Power Technology ,02 engineering and technology ,engineering.material ,010402 general chemistry ,Electrochemistry ,01 natural sciences ,Metal ,chemistry.chemical_compound ,Phase (matter) ,Electrical and Electronic Engineering ,Physical and Theoretical Chemistry ,Perovskite (structure) ,Renewable Energy, Sustainability and the Environment ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Chemical engineering ,chemistry ,visual_art ,visual_art.visual_art_medium ,engineering ,Solid oxide fuel cell ,0210 nano-technology ,Stoichiometry - Abstract
The exsolution of metal cations from oxides under reducing fuel conditions results in the formation of surface metallic nanoparticles, which can reduce Solid Oxide Fuel Cell anode polarization resistance. However, the loss of the B-site cations shifts the stoichiometry of the perovskite oxide. Depending on the amount exsolved and the initial stoichiometry, the exsolution can presumably shift the oxide away from its single-phase perovskite region. Herein, the direct comparison of initially stoichiometric composition Sr(Ti0.3Fe0.63Ni0.07)O3-δ (STFN0) with initially A-site deficient Sr0.95(Ti0.3Fe0.63Ni0.07)O3-δ (STFN5) is conducted and reported. X-ray diffraction along with scanning and transmission electron microscopy analysis of the oxides, which are both reduced at 850 °C in H2/H2O/Ar, shows a similar size and density of exsolved Fe–Ni alloy nanoparticles, albeit with slightly different alloy compositions. Whereas the oxide phase in reduced STFN5 shows a well-ordered perovskite structure, the greater B-site deficiency in reduced STFN0 results in a highly disordered and strained structure. The electrochemical performance of STFN0 anodes is inferior to that of STFN5 anodes, and even worse than SrTi0.3Fe0.7O3-δ (Ni-free) anodes. It appears that an initial Sr deficiency is important to avoid a too-high B-site deficiency after exsolution, which distorts the perovskite structure and impairs electrochemical processes.
- Published
- 2019
6. Tracking the Nanoparticle Exsolution/Reoxidation Process in Ni-Doped SrTi0.3Fe0.7O3-δ Electrodes for Intermediate Temperature Symmetric SOFC.
- Author
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Mariano, Santaya, Catalina Elena, Jiménez, Mauricio D., Arce, Horacio Esteban, Troiani, Emilia A., Carbonio, Raul, Garica-Diez, Regan George, Wilks, Axel, Knop-Gericke, Marcus, Bär, and Liliana, Mogni
- Published
- 2021
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