Materiais cerâmicos de inserção aplicados a baterias de íons lítio

Esta revisão visa ser uma introdução à aplicação de materiais cerâmicos em dispositivos de armazenamento de energia, em especial baterias secundárias de íons lítio, dispositivos nos quais os materiais cerâmicos, especialmente óxidos, são muito importantes em todas as partes do dispositivo. A revisão está focada nos materiais cerâmicos para catodos e anodos, partes chaves destes dispositivos. Ela tem por principal finalidade ser uma fonte de informação para aqueles que desejem trabalhar com o desenvolvimento de materiais cerâmicos para tais tipos de dispositivos. Aspectos relacionados à nanotecnologia e materiais óxidos nanoestruturados para esta área são discutidos ao final do artigo.

Thermally activated dynamics in La2CuO4+delta: tilts of the CuO6 octahedra and interstitial O

An intense peak of the elastic energy loss versus temperature is found in La2CuO4 at 150 K (in the LTO phase), at a vibration frequency of similar to 280 Hz. From the dependence of the dissipation curve on frequency it is deduced that the relaxation rate has an activation enthalpy of 0.23 eV. The peak is ascribed to a thermally activated dynamics of the tilts of the CuO6 octahedra which form the La2CuO4 lattice, a fraction of which are supposed to be able to switch between energetically equivalent configurations. The peak is suppressed by interstitial O; this is explained by supposing that each interstitial atom can block several octahedra into a configuration that can accommodate the distortion due to its presence. Increasing the content of excess O, two new thermally activated processes develop, attributed to the hopping of interstitial O atoms which are isolated and which are paired or otherwise aggregated. The activation enthalpy for the diffusion of O at low values of 6 is 0.48 eV.

Oxygen mobility and structural phase transformation in Bi2Sr2CaCu2O8+delta measured by anelastic spectroscopy

One of the most studied ceramic superconductors for application has been, undoubtedly, Bi2Sr2CaCu2O8+delta. Although being a multiphasic material, it has proved to have great advantages compared to other ceramic systems. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature call distinguish among different atomic jumps that occur inside the various phases or at different local ordering. In this paper, mechanical loss spectra of Bi2Sr2CaCu2O8+delta bar shaped samples, made by a conventional method, have been measured between 80 and 600 K, using a torsion pendulum operating in frequencies below 50 Hz, for samples annealed in vacuum up to 600 K. Possible relaxation mechanisms are proposed to explain the origin of the mechanical-loss peaks observed 300 and 500 K. (C) 2004 Elsevier B.V. All rights reserved.

Structure, mobility and clustering of interstitial O in La2CuO4+delta in the limit of small delta

Anelastic spectra (elastic energy absorption as a function of temperature) are reported which provide evidence that excess O in La2CuO4+delta starts forming two different types of defects already at very low concentrations, where no phase separation or changes in the type of O intercalation are believed to occur. The absorption peak with the lowest activation enthalpy, H/k(B) = 5600 K, is visible at lowest values of delta and is attributed to the hopping of single interstitial O2- ions. The second process, with a slightly slower dynamics, appears at higher values of delta and soon becomes preponderant over the former process. The latter process is proposed to be due to stable pairs of O atoms and is put in connection with the formation of partially covalent bonds between interstitial and apical oxygen; such bonds would reduce the doping efficiency of excess O at increasing delta. The geometry of the interstitial O defect is discussed. O 1998 Published by Elsevier B.V. B.V. All rights reserved.

Relaxation and tunnelling of structural units within the LTO phase of La2CuO4

The anelastic relaxation (elastic energy loss and Young modulus) of nearly stoichiometric La2CuO4+delta with LTO structure was measured. Extraordinarily intense effects are present below room temperature in the elastic dynamic susceptibility, indicating relaxational dynamics of a relevant fraction of the lattice. The involved degrees of freedom are identified as rotations of the CuO6 octahedra. Two distinct processes are found at frequencies around 1 kKz: one is observed around 150 K and is characterized by a mean activation energy of 2800 K; the second one occurs below 30 K and is governed by atomic tunnelling. Two explanations are proposed for the faster process: i) formation of fluctuating LTT domains on a scale of few atomic cells; ii) the LTO phase is a dynamical Jahn-Teller phase with all the octahedra tunneling between two LTT-like tilts. In both cases there would be important implications regarding the mechanisms giving rise to charge nanophase separation and strong electron-phonon coupling.

Disordered distribution of defects in polythiophene

In this work we study the electronic structure associated to a disordered distribution of bipolarons in polythiophene. The polymer chain is modelled by a tight-binding Hamiltonian with explicit treatment of electron-phonon coupling and the elastic energy of the sigma framework. The model also includes the electrostatic interaction due to the counterions. The density of states of the disordered system is obtained by the use of the Negative Factor Counting technique. Our results show that ion-induced conformational disorder can account for the closure of the gap and that the states around the Fermi level are extended. © 1993.

Thermally activated dynamics of the tilts of the CuO6 octahedra, hopping of interstitial O, and possible instability towards the LTT phase in La2CuO4+δ

The anelastic spectrum (dynamic Young's modulus and elastic energy absorption) of La2CuO4+δ has been measured between 1 and 700 K with 0<δ<0.02. The spectrum of stoichiometric La2CuO4 in the low-temperature orthorhombic (LTO) phase is dominated by two intense relaxation processes which cause softenings of 16% around 150 K and 9% below 30 K at f∼1 kHz. The relaxation at 150 K is attributed to the presence of a fraction of the CuO6 octahedra which are able to change their tilted configuration by thermal activation between orientations which are nearly energetically equivalent, possibly within the twin boundaries. The relaxation below 30 K is governed by tunneling, and involves a considerable fraction of the lattice atoms. It is proposed that the double-well potentials for the low-temperature relaxation are created by the tendency of the LTO phase to form low-temperature tetragonal (LTT) domains, which however are not stabilized like when La is partially substituted with Ba. On doping with excess O, the relaxation rates of these processes are initially enhanced by hole doping, while their intensities are depressed by lattice disorder; an explanation of this behavior is provided. Excess O also causes two additional relaxation processes. The one appearing at lower values of δ is attributed to the hopping of single interstitial O2- ions, with a hopping rate equal to τ-1=2×10-14exp(-5600/T) s. The second process is slower and can be due to O pairs or other complexes containing excess O.

Anelastic spectroscopy in TiO2

Titanium dioxide (rutile) has a lot of interesting and useful features and hence is widely utilized for application. It has been used as white pigment, photocatalyst, biocompatible material and semiconductor material used in solar battery. In semiconducting TiO2 oxygen vacancies are said to play an important role in the electrical conduction. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature can distinguish among the different atomic jumps, which occur in the various phases or at different local ordering. In this paper, it is reported anelastic relaxation measurements in TiO2 samples using a torsion pendulum operating in frequencies around 40Hz, in the temperature range between -173°C to 330°C with heating rate of 1°C/min. The results shown a reduction in the elasticity modulus with the increase in the corn starch content used for this consolidation.

Anelastic spectroscopy in Al2O3

Engineering ceramics have found use in many applications, such as engine parts, ball bearings, artificial bone and hip replacements and gyroscopes, because of their good chemical inertness, hardness, high temperature stability and excellent wear resistance. Oxide ceramic may meet these demands. Alumina (Al2O3) ceramics offer a high potential for many engineering applications, such as wear- and/or corrosion-resistant components, and as material for substrates or housings in microelectronic devices. Alumina is used among other things for seal ring, draw-cones, guides, water mixing tapes, bearing parts, medical prostheses and cutting tools. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature can distinguish among the different atomic jumps, which occurs in the various phases or at different local ordering. In this paper, it is reported anelastic relaxation measurements in Al2O3 samples using commercial starch. These measurements were carried out in a torsion pendulum operating in frequencies around 40 Hz. The results shown strongly influence of the type of forming in the elastic modulus obtained by anelastic relaxation measurements.

Harmonic, reactive and unbalance compensation by means of CPT framework

This paper presents possible selective current compensation strategies based on the Conservative Power Theory (CPT). This recently proposed theory, introduces the concept of complex power conservation under non-sinusoidal conditions. Moreover, the related current decompositions results in several current terms, which are associated with a specific physical phenomena (power absorption P, energy storage Q, voltage and current distortion D). Such current components are used in this work for the definition of different current compensators, which can be selective in terms of minimizing particular disturbing effects. The choice of one or other current component for compensation directly affects the sizing and cost of active and/or passive devices and it will be demonstrated that it can be done to attend predefined limits for harmonic distortion, unbalances and/or power factor. Single and three-phase compensation strategies will be discussed by means of the CPT Framework. Simulation and experimental results will be demonstrated in order to validate their performance. © 2009 IEEE.

Selective current compensators based on the conservative power theory

This paper presents possible selective current compensation strategies based on the Conservative Power Theory (CPT). This recently proposed theory, introduces the concept of complex power conservation under non-sinusoidal conditions. Moreover, the related current decompositions results in several current terms, which are associated with a specific physical phenomena (power absorption P, energy storage Q, voltage and current distortion D). Such current components are used in this work for the definition of different current compensators, which can be selective in terms of minimizing particular disturbing effects. The choice of one or other current component for compensation directly affects the sizing and cost of active and/or passive devices and it will be demonstrated that it can be done to attend predefined limits for harmonic distortion, unbalances and/or power factor. Single-phase compensation strategies will be discussed by means of the CPT and simulation results will demonstrate their performance. © 2009 IEEE.

Possible shunt compensation strategies based on conservative power theory

Considering the Conservative Power Theory (CPT), this paper proposes some novel compensation strategies for shunt passive or active devices. The CPT current decompositions result in several current terms, which are associated with specific physical phenomena (average power consumption P, energy storage Q, load and source distortion D, unbalances N). These current components were used in this work for the definition of different current compensators, which can be selective in terms of minimizing particular disturbing effects. Compensation strategies for single and three-phase four-wire circuits have also been considered. Simulation results have been demonstrated in order to validate the possibilities and performance of the proposed strategies. © 2010 IEEE.

Reference generator for voltage controlled power conditioners

Voltage reference generation is an important issue on electronic power conditioners or voltage compensators connected to the electric grid. Several equipments, such as Dynamic Voltage Restorers (DVR), Uninterruptable Power Supplies (UPS) and Unified Power Quality Conditioners (UPQC) need a proper voltage reference to be able to compensate electric network disturbances. This work presents a new reference generator's algorithm, based on vector algebra and digital filtering techniques. It is particularly suited for the development of voltage compensators with energy storage, which would be able to mitigate steady state disturbances, such as waveform distortions and unbalances, and also transient disturbances, like voltage sags and swells. Simulation and experimental results are presented for the validation of the proposed algorithm. © 2011 IEEE.

Shunt active compensation based on the Conservative Power Theory current's decomposition

Considering the operation of shunt active compensators, such as active power filters, this paper proposes possible compensation strategies by means of the recent formulation of the Conservative Power Theory (CPT). The CPT current's decomposition results in several current components, which are associated with specific load characteristics (power transfer, energy storage, unbalances and/or non linearities). These current components are used for the definition of different compensation strategies, which can be selective in terms of minimizing particular disturbing effects. In order to validate the applicability of these new compensation strategies, simulation and experimental results for three-phase four-wire systems are presented. © 2011 IEEE.

Tri-state single-phase integrated inverters with input to output power decoupling control

Researches on control for power electronics have looked for original solutions in order to advance renewable resources feasibility, specially the photovoltaic (PV). In this context, for PV renewable energy source the usage of compact, high efficiency, low cost and reliable converters are very attractive. In this context, two improved simplified converters, namely Tri-state Boost and Tri-state Buck-Boost integrated single-phase inverters, are achieved with the presented Tri-state modulation and control schemes, which guarantees the input to output power decoupling control. This feature enhances the field of single-phase PV inverters once the energy storage is mainly inductive. The main features of the proposal are confirmed with some simulations and experimental results. © 2012 IEEE.