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The research on the stable thermoelectric properties and contact interface of high-precision thin-film thermocouples lags far behind the demand. In this study, a zinc-rich Al-doped ZnO (AZO) thin film was fabricated, in which the carriers were mainly donated by the Al dopant, and the oxygen defects migrated together, forming cage defects. Then, an indium tin oxide (ITO)/AZO thin-film thermocouple was prepared. It had a special temperature-dependent voltage curve due to the effects of cage defects on the thermoelectric properties of the AZO thin film and interfacial electron diffusion. When the zinc atoms in the cage defects were excited after annealing, a linear relationship between the temperature and voltage was obtained. The Seebeck coefficient of the thermocouple was constant at 168 µV K-1 over the entire measured temperature range. In addition, the calculated error of the thermocouple was lower than 1% from 50 °C to 500 °C, showing good repeatability. These results showed that defect engineering could effectively be used to improve the temperature range stability of thermoelectric materials and optimize the precision of thin-film thermocouples.
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Silicon is a promising alternative to current thermoelectric materials (Bi(2)Te(3)). Silicon nanoparticle based materials show especially low thermal conductivities due to their high number of interfaces, which increases the observed phonon scattering. The major obstacle with these materials is maintaining high electrical conductivity. Surface functionalization with phenylacetylene shows an electrical conductivity of 18.1 S m(-1) and Seebeck coefficient of 3228.8 µV K(-1) as well as maintaining a thermal conductivity of 0.1 W K(-1) m(-1). This gives a ZT of 0.6 at 300 K which is significant for a bulk silicon based material and is similar to that of other thermoelectric materials such as Mg(2)Si, PbTe and SiGe alloys.
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The engineering of flexible dye sensitized solar cells (DSCs) by mechanical compression is one of the methods that allow low temperature processing of these devices. However, suppressing the high temperature sintering process also significantly reduces the performance of the cells. In our previous work [J. Phys. Chem. C, 2012, 116, 1211], we have attempted to improve flexible DSC performance by coating the porous TiO2 photoanode with an electrodeposited Mg(OH)2 layer. In that work, we have obtained one of the highest photovoltages reported to date in flexible DSCs (847 mV). In order to gain more insights into the reasons for both poorer performance of compressed cells and the origin of the voltage enhancement achieved by the Mg(OH)2 coating, here we present an in-depth study by means of electrochemical impedance spectroscopy, Mott-Schottky plots analysis and open-circuit voltage decays. The existence of a shunt resistance in the mechanically compressed cells is revealed, causing an additional drawback to the poor inter-particle necking. By introducing the Mg(OH)2 coating the recombination in the cell becomes significantly reduced, being the key reason which is responsible for the higher photovoltage. Additionally, the coating and the compression cause modifications in the surface states and in the nature of the interfaces with the electrolyte. This induces TiO2 conduction band displacements and shifts of the relative position of the modified states that influence the performance.
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In recent years, thermoelectric (TE) devices have been used in several refrigeration applications and have gained attention for energy generation. To continue the development of devices with higher efficiency, it is necessary not only to characterize their materials but also to optimize device parameters (e.g., thermal contacts). One attempt to increase the efficiency at the device level consists of the replacement of the typical ceramic layers in TE modules by metallic plates, which have higher thermal conductivity. However, this alternative device design requires the use of a very thin electrical insulating layer between the metallic strips that connect the TE legs and the outer external layers, which introduces an additional thermal resistance. Impedance spectroscopy has been proved to be useful to achieve a detailed characterization of TE modules, being even capable to determine the internal thermal contact resistances of the device. For this reason, we use here the impedance method to analyze the device physics of these TE modules with outer metallic plates. We show for the first time that the impedance technique is able to quantify the thermal contact resistances between the metallic strips and the outer layers, which is very challenging for other techniques. Finally, we discuss from our analysis the prospects of using TE modules with external metallic plates.
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Interactions between the intercalant and the host have been studied in homogeneous amorphous Li(x)WO3 prepared by electron beam evaporation, using electrochemical experiments with films of different thickness (100-400 nm). We have related the intercalation thermodynamics, described previously by us [Solid State Ionics 2005, 176, 1701] with other models that take into account film volume dilatation along the intercalation. A distinct behavior of cell voltage variation with composition and volume change is observed for the thinnest (100 nm) films: cell voltage follows ideal insertion thermodynamics and no deformation was detected using profilometry techniques. In contrast, thicker films exhibited both volume changes and, correspondingly, cell voltage departs from ideality due to contributions to the chemical potential arising from elastic distortions of the host matrix.
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A series of processes have been developed to facilitate the rapid discovery of new promising thermoelectric alloys. A novel combinatorial facility where elements are wire-fed and laser-melted was designed and constructed. Different sample compositions can be achieved by feeding different element wires at specific rates. The composition of all the samples prepared was tested by energy dispersive X-ray spectroscopy (EDS). Then, their thermoelectric properties (power factor) at room temperature were screened in a specially designed new high-throughput setup. After the screening, the thermoelectric properties can be mapped with the possibility of identifying compositional trends. As a proof-of-concept, a promising thermoelectric ternary system, Al-Fe-Ti, has been identified, demonstrating the capability of this accelerated approach.
Assuntos
Técnicas de Química Combinatória/métodos , Centrais Elétricas , Ligas , Ensaios de Triagem em Larga Escala , Lasers , Teste de Materiais , Espectrometria por Raios X , Temperatura , Titânio/químicaRESUMO
An apparatus capable of rapid measurement of the Seebeck coefficient and electrical resistivity at room temperature is reported. The novel aspect of this apparatus is the use of 4 multifunctional probes that comprise a junction of two conductors at the tip and serve as both thermocouples and electrical contacts. In addition, one of the probes has a built-in heater that can establish a temperature gradient in the sample for the Seebeck measurement. The technique does not require special sample geometries or preparation of contacts and is suitable for bulk and thin film materials. Together with automated sample stage and data acquisition, the equipment is able to measure both the Seebeck coefficient and electrical resistivity in less than 20 s with good accuracy. Less than 5% and 4% relative errors were found for the measurement of the Seebeck coefficient and electrical resistivity, respectively. This makes the apparatus especially useful for high throughput evaluation of thermoelectric materials.
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Mesoporous p-type NiO films were prepared by aerosol-assisted chemical vapor deposition (AACVD) and characterized by X-ray diffraction (XRD). The nanostructure of the films was investigated by field emission gun scanning electron microscopy (FEG-SEM). The density of states (DOS) in these nanostructured films has been determined by means of electrochemical impedance spectroscopy and cyclic voltammetry. The analysis reveals an exponential distribution of band gap states above the valence band that extends around 1.5 eV. In addition, monoenergetic states were also identified which overlap with the exponential distribution. This distribution of states has an enormous influence in the electronic processes of the devices in which NiO electrodes are employed (electrochromism, water splitting or energy storage). Especially, in p-type dye-sensitized solar cells (p-DSCs), it is thought that intra-band-gap states are responsible for the fast observed recombination processes, whose existence and distribution has not been clearly determined yet and are now confirmed and quantified by our analysis. This provides a better comprehension of the recombination events which represent one of the main losses in p-DSCs.
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The electrochemical behaviour of nanoporous TiO(2) in a room temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide (EMITFSI), was investigated by cyclic voltammetry (CV) and impedance spectroscopy. Exponentially rising currents in voltammetry were attributed to the charging/discharging of electrons in the TiO(2) film and a charge transfer mechanism. The main features of the voltammetry and impedance followed the same trends in the ionic liquid as in other organic solvents and also in aqueous electrolytes. In the presence of lithium ions, the onset potential of the charge accumulation increased due to the change of the initial position of the TiO(2) conduction band. The results show that substitution of organic solvents contained in solar cells, supercapacitors or other electrochemical devices is in general feasible, though requires some adjustment in the electrolyte composition for optimal performance.
Assuntos
Imidazóis/química , Íons , Nanoestruturas/química , Soluções/química , Sulfonamidas/química , Titânio/química , Eletroquímica , Estrutura Molecular , Porosidade , TemperaturaRESUMO
We discuss the interpretation of usually broad oxidation peaks observed in electronically conducting polymers, in terms of the statistical distributions functions of polarons and bipolarons. The analysis is based on examining the chemical capacitance, that relates the change of concentration to a modification of the chemical potential of a given species, for different statistical models. We first review the standard models for single energy species that provide a nernstian dependence, and the limitations of these models are discussed. A new model that assumes a Gaussian distribution of energies related to molecular geometry fluctuations is suggested, and this model shows excellent agreement with the results of electrochemical oxidation of polypyrrole in quasiequilibrium conditions. From a fit of the data, it is found that the density of conjugated chain segments in polypyrrole, Ns approximately 10(21) cm(-3), shows a Gaussian distribution of half width sigma approximately 170 meV, tentatively attributed to bipolaron formation energies.