Bi3.25La0.75Ti3O12 (BLT) thin films were grown on LaNiO3 (LNO), RuO2 (RuO2) and La0.5Sr0.5CoO3 (LSCO) bottom electrodes by using the polymeric precursor method and microwave furnace. The bottom electrode is found to be an important parameter which affects the crystallization, morphology and leakage current behaviors. The XRD results clearly show that film deposited on LSCO electrode favours the growth of (117) oriented grains whereas in films deposited on LNO and RuO2 the growth of (001) oriented grains dominated. The film deposited on LSCO has a plate-like grain structure, and its leakage current behavior is in agreement with the prediction of the space-charge-limited conduction model. on the other hand, the films deposited on RuO2 and LNO electrodes present a rounded grain shape with some porosity, and its high field conduction is well explained by the Schottky and Poole-Frenkel emission models. The remanent polarization (P-r) and the drive voltage (V-c) were in the range of 11-23 mu C cm(-2) and 0.86-1.56 V, respectively, and are better than the values found in the literature. (c) 2007 Published by Elsevier B.V.
Bismuth titanate (Bi4Ti3O12, BIT) films were evaluated for use as lead-free piezoelectric thin films in micro-electromechanical systems. The films were grown by the polymeric precursor method on LaNiO3/SiO2/Si (1 0 0) (LNO), RuO2/SiO2/Si (1 0 0) (RuO2) and Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 degrees C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefficient, d(33), regardless of bottom electrode is around (similar to 40 pm/V), those over RuO2 and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 mu C/cm(2)), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain films with good qualities for applications in ferroelectric and piezoelectric devices. (c) 2006 Elsevier Ltd. All rights reserved.
Simoes, A. Z.; Ries, A.; Filho, F. M.; Riccardi, C. S.; Varela, José Arana; Longo, Elson
Fonte: American Institute of Physics (AIP)Publicador: American Institute of Physics (AIP)
Tipo: Artigo de Revista CientíficaFormato: 5962-5964
Relevância na Pesquisa
Fatigue-free Bi3.25La0.75Ti3O12 (BLT) thin films were grown on LaNiO3,RuO2, and La0.5Sr0.5CoO3 bottom electrodes in a microwave furnace at 700 degreesC for 10 min. The remanent polarization (P-r) and the drive voltage (V-c) were in the range of 11-23 muC/cm(2) and 0.86-1.56 V, respectively, and are better than the values found in the literature. The BLT capacitors did not show any significant fatigue up to 10(10) read/write switching cycles. (C) 2004 American Institute of Physics.
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); Fatigue-free Bi3.25La0.75Ti3O12 (BLT) thin films were grown on LaNiO3 bottom electrodes grown in a microwave furnace at 700 degrees C for 10 min from the polymeric precursor method. It was found that LaNiO3 (LNO) bottom electrode with pseudocubic structure strongly promote the formation. of (001) texture of BLT films. The remanent polarization (P-r) and the drive voltage (V-c) were 11 mu C/cm(2) and 1.3 V respectively, and are better than the values found in the literature. The polarization of the Au/BLT/LNO/SiO2/Si (100) capacitors with a thickness of 280 nm exhibited no degradation after 1 x 1010 switching cycles at an applied voltage of 5 V with a frequency of 1 MHz. After several tests the capacitors retain 77% of its polarization upon a retention time of 10(4) s. (C) 2008 Elsevier B.V. All rights reserved.
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Pós-graduação em Química - IQ; Nesta tese estudou-se a preparação de filmes finos de PZT não dopados e dopados com Nióbio, depositados sobre substratos de Pt/Ti/SiO2/Si para aplicações em memórias não voláteis de acesso randômico (NVRAM) e memórias ferroelétricas de acesso randômico (FeRAM). A dopagem dos filmes de PZT com Nióbio foi realizada visando obter valores ótimos nas propriedades ferroelétricas para a aplicação destes filmes como memórias ferroelétricas. Todavia, problemas como imprint, corrente de fuga e fadiga na polarização, estão presentes nos dispositivos de memórias contendo filmes de PZT sobre substratos platinizados. Para tentar resolver estes problemas, estudamos a produção de eletrodos de LaNiO3 depositados sobre substratos de SiO2/Si, para substituição dos substratos com eletrodos de Pt na preparação de filmes de PZT. Além disso, a dopagem do PZT com Nb levou a uma melhoria na resistência à fadiga em substratos platinizados. Os filmes foram preparados pelo método das soluções precursoras poliméricas. A influência do tratamento térmico...
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); Processo FAPESP: 08/57150-6; Processo FAPESP: 11/20536-7; Processo FAPESP: 13/07296-2; Ferroelectric thin films and LaNiO3 (LNO) metallic conductive oxide thin films were prepared by a chemical solution deposition (CSD) method. PBCT60, PBST60 and PCST60 ferroelectric thin films were grown on different structures such as LNO/Si and single-crystalline quartz SiO2 (X-cut) substrates. The LNO layer acts as the bottom electrode for the electrical measurements. X-ray diffraction (XRD) analysis shows that LNO thin films on Si substrates and PBCT60, PBST60 and PCST60 thin films on LNO/Si structures are poly-crystalline with a moderate (110)-texture and a complete perovskite phase. LNO, PBCT60, PBST60 and PCST60 thin films have a continuous, dense and homogenous microstructure with a grain size on the order of 50-80 nm. Electrical resistivity-dependence temperature data confirm that LNO thin films display a good metallic character over a wide large range of temperatures. Optical characteristics of PBCT60, PBST60 and PCST60 thin films have also been investigated using ultraviolet-visible (UV-vis) spectroscopy in the wavelength range of 200-1100 nm. Ferroelectric thin films show a direct allowed optical transition with optical band gap values on the of order of 3.54...
Tese de mestrado em Química Tecnológica, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2012; No desenvolvimento deste trabalho foram caracterizados eléctrodos, utilizando como electrocatalisador o óxido do tipo perovskite LaNiO3, sintetizado através de uma técnica de autocombustão. Também foi testada, como electrocatalisador, uma mistura do óxido LaNiO3 e 5% em massa de nanopartículas de Pt-Ru dispersas em carbono. Como substrato utilizou-se espuma de níquel e papel de carbono.
O pó foi caracterizado por DRX de pós, SEM e BET. A fase cristalina LaNiO3 foi sintetizada com sucesso. As imagens de SEM mostraram que o pó preparado apresenta-se compacto e aglomerado sendo visíveis partículas esféricas e placas. Os estudos de BET para o LaNiO3, LaNiO3 + Pt-Ru e LaNiO3 + C revelaram que as áreas superficiais são 10,7; 6,9 e 11,6 m2 g-1.
Os eléctrodos foram preparados através da técnica de brush painting e foram caracterizados morfologicamente através de técnicas de microscopia: MO, SEM e AFM. As imagens mostraram que filme fino do catalisador possui uma superfície homogénea e compacta apresentando alguma rugosidade.
A caracterização electroquímica foi feita através de medidas de potencial em circuito aberto e voltametria cíclica. Foi possível determinar que o par redox envolvido nos processos que ocorrem na interface eléctrodo/KOH 1M é Ni2+/Ni3+. A determinação dos factores de rugosidade e de morfologia mostrou que os eléctrodos possuem elevada rugosidade e baixa porosidade...
The electrodes were obtained by coating a nickel foam support with the oxide suspension. Optical microscopy and cyclic voltammetry were used on the electrodes characterization. The evaluation of the electrodes electrocatalytic activity, towards the oxygen evolution reaction in alkaline medium, was performed by means of steady state measurements. The reaction follows a first order kinetics, with respect to OH- concentration, with Tafel slopes close to 40 mV, for low overpotentials. Based on the apparent and real current densities it was possible to conclude that the increase on the electrode activity, when compared with the published data, is mostly related to geometric factors. This fact has been associated with the high electrode/electrolyte contact area provided by the foam nickel substrate. Synergetic effects between the Ni foam and the perovskite oxide cannot be discarded.
The LaNiO3 perovskite-type oxide is one of the most tested anode for the oxygen evolution reaction in alkaline solutions. It is well established that the oxide preparation conditions and the electrode fabrication are key factors to control the electrochemical behaviour of oxide coatings. In a previous work the authors studied the influence of preparation conditions of the oxide and support type on the electrochemical behaviour of Ni foam coated LaNiO3 electrodes. Ni foam was selected as support due to its unique characteristics namely low contact resistance between the oxide and support, possibility of high metal oxide loadings and dimensional stability . No studies were performed, concerning the influence of the oxide loading. Studies performed by Singh et al. on LaNiO3 coatings on Ni foil supports have shown that the electrode roughness factor increased with increase in oxide loading at the beginning and finally attained a constant value around 0.03 g cm-2 . The present work reports on the study of the dependence of roughness factor (Rf) and morphology factor (φ) on the oxide loading for Ni foam coated LaNiO3 electrodes with loadings varying between 0.02 and 0.14 g cm-2. Cyclic voltammetry and electrochemical impedance spectroscopy were used to evaluate the Rf and φ values...
LaNiO3 film electrodes were prepared by brush painting using nickel-foam supports in order to increase its surface area available for electrochemical
reactions. Loadings varying between 20 and 140 mg cm-2 were tested. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to evaluate
the coatings roughness (Rf) and morphology (f) factors, complemented by optical microscopy observations. The values obtained from the two methods are in excellent agreement. The Rf values, ranging from 848 ± 50 to 4260 ± 60, are within the highest in the open literature. A simulation, of the effect of the oxide loading on the coatings Rf values, was performed using just the experimental values of the roughness factors for oxide free foam and pelleted electrodes. It was found that the increase of oxide loading causes a quasi linear increase of the electrodes active surface area. Simulated values were in excellent agreement with the experimental roughness factors and pore resistances obtained by CV and EIS. The electrodes were tested for oxygen evolution.
Perovskite-type oxides are potential catalysts for next generation of regenerative fuel cells. In particular, LaNiO3 has been recognised as one of the most promising oxygen electrodes. In this work LaNiO3 perovskite-type oxides, prepared by a self-combustion method [1, 2], have been used for the preparation of porous gas-diffusion electrodes (GDE). Electrodes were prepared on Toray carbon paper (CP) substrates, consisting of a diffusion layer, a catalyst layer and a Nafion® layer. The
gas diffusion layers were prepared using Vulcan XC-72R. The catalyst ink was prepared by suspending the material in isopropanol, stirring the mixture in an ultrasonic bath to thoroughly disperse it. Ink slurries were also pasted onto glassy carbon discs and used as working electrodes for full kinetic studies at potential domains for the oxygen reduction (ORR) and oxygen evolution (OER) reactions. A systematic study on the effect of the oxide loading (OL) on the electrodes surface area was done by cyclic voltammetry. It was found a quasi linear variation between the electrodes surface area and the oxide loading. Roughness values varying from 106±3 to 307±6 were obtained for OL between 1 and 5 mg cm-2 respectively. The results show that the peak current density increases with the increasing on oxide loading as shown in Fig. 1. Higher current densities for ORR were obtained for the electrodes prepared using LaNiO3-based perovskite with partial substitution of Ni by Cu. Stability studies of the GDEs...
In this work LaNiO3 perovskite-type oxide, prepared by a self-combustion method, was optimized for activity and stability as an anode material for water electrolysis. A full electrochemical study was conducted in order to kinetically characterize electrodes prepared using carbon paper as a base for porous gas-diffusion electrodes in alkaline media, regarding water oxidation and oxygen reduction reactions at room temperature. An electrode stability study was performed by potential cycling and at constant current density, using cyclic voltammetry and electrochemical impedance spectroscopy to check on stability after cycling with complementary scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDS) analysis of fresh and degraded electrodes. Comparison was made using nickel foam as a support for LaNiO3 deposition. Carbon instability in the potential region of interest contrasted with the lower contact resistance between the oxide and support of the Ni foam. Higher metal oxide loadings and dimensional stability were also possible.
Perovskites are of great interest when searching replacements for precious metals as catalyst for bifunctional oxygen electrodes involving the oxygen evolution(OER) and oxygen reduction reaction (ORR) as is the case of regenerative fuel cells. In this work a full electrochemical study on the electrochemical properties of gas diffusion electrodes (GDEs) using LaNiO3-based catalysts, conducted in alkaline media, led to a study of cyclability and durability. The incorporation of GDEs in a low power electrolyzer/fuel cell prototype was also attempted. The stability of the electrodes was assessed by potential cycling and at constant current density with good
Catalytic processing of fuels was explored in this thesis for both low-temperature polymer electrolyte membrane (PEM) fuel cell as well as high-temperature solid oxide fuel cell (SOFC) applications. Novel catalysts were developed to generate hydrogen for PEM applications from the oxidative steam reforming of methanol. The activity of lanthanum nickel perovskite (LaNiO3) was examined in both dilute fuel and full fuel conditions. Autothermal operation was successfully achieved with higher hydrogen selectivity than conventional Pd-based catalysts. The selected complex oxide catalyst was applied as a thin film onto a 0.2 [mu]m-thick Pd membrane. Pure hydrogen effluent was obtained from the resulting microreactor as desired for PEM applications. SOFC systems would be of interest for portable power generation if the thermal cycling and slow start-up issues could be addressed. One potential solution is the development of Si-supported ultrathin electrolyte structures (~100 nm-thick) of low thermal mass. Due to the low maximum fabrication temperature (< 600°C), electrodes cannot be applied by traditional ceramic processing techniques. Alternative wet-chemical approaches were explored for the electrode deposition. In particular, ceria sol-gel and yttria-stabilized zirconia (YSZ) colloid were developed as inorganic binders for cathode application at temperatures below 600°C. The YSZ sol provided adhesion strength for La0.8Sr0.2Fe0.8Co0.2O3 (LSCF) in excess of 1000 psi. However...
ABSTRACT: Regenerative fuel cells (RFCs) can provide very high energy storage at minimal weight in a dual mode system, by combining an electrolyzer and a fuel cell. Although RFCs are an appealing technology their development is still at an early stage. One key issue is the search for highly active electrocatalysts for both oxygen reduction and water oxidation. Presently, platinum is the best electrocatalyst for the oxygen reduction reaction (ORR), but has a poor oxygen evolution (OER) performance while metal oxides catalyze the OER but not the ORR. Yet, the search for the development of bi-functional oxygen electrodes is also associated to structurally stable gas diffusion layers - they must be capable of withstanding high potentials when cells are operated in the electrolyzer mode and in addition, mass transport limitations when used as a cathode in fuel cell mode. A novel approach is used in this work to tackle the issue, focussing on the development of stable gas diffusion electrodes for the oxygen reactions, having as a base high surface area LaNiO3. Previous work by the authors has optimised the synthesis of the mentioned perovskite-type oxide, prepared by a self-combustion method. The high electrochemical surface area and low porosity of the oxide has been indicated by electrochemical impedance spectroscopy (EIS) and BET measurements. A full characterization has been the subject of recent publications [1...
One key issue in the development of Regenerative fuel cells (RFCs) is the availability of cheap, highly active electrocatalysts for both oxygen reduction and water oxidation. Perovskite-type oxides, with the general formula ABO3, are potential catalysts for next generation of regenerative fuel cells. In particular, LaNiO3 has been recognised as one of the most promising oxygen electrodes. In this work LaNiO3 perovskite-type oxides, prepared by a self-combustion method [1, 2], have been simultaneously optimized for activity and stability as an anode and cathode material for water oxidation and oxygen reduction reaction (ORR), respectively. Extremely high surface area has been measured by BET analysis with matching electrochemical activity estimated by cyclic voltammetry and electrochemical impedance spectroscopy. A full electrochemical study has been conducted in order to kinetically characterize the prepared electrodes in alkaline media, using a Ni foam and carbon paper as support material for the electrodes. For LaNiO3 deposits on Ni foam, low contact resistance between the oxide and support, possibility of high metal oxide loadings and dimensional stability were accomplished with remarkable stability in the region of oxygen evolution. For LaNiO3 deposits on carbon paper...
In this work LaNiO3 oxide was prepared by a self-combustion method using citric acid. The electrodes were obtained by coating a nickel foam support with the oxide suspension. Optical microscopy and cyclic voltammetry were used on the electrodes characterization. The evaluation of the electrodes electrocatalytic activity, towards the oxygen evolution reaction in alkaline medium, was performed by means of steady state measurements. The reaction follows a first order kinetics, with respect to OH- concentration, with Tafel slopes close to 40 mV, for low overpotentials. Based on the apparent and real current densities it was possible to conclude that the increase on the electrode activity, when compared with the published data, is mostly related to geometric factors. This fact has been associated with the high electrode/electrolyte contact area provided by the foam nickel substrate. Synergetic effects between the Ni foam and the perovskite oxide cannot be discarded.