Electrical performance tuning in thermoelectric Ca3Co4O9 materials by transition metals additions

This work reports on the effects on high-temperature thermoelectric (TE) properties in bulk, polycrystalline p-type Ca3Co4O9 ceramics, after employing a composite approach consisting of metallic particles additions and two simple sintering schemes. The added Fe, Co and Ni particles are expected to act as porosity fillers upon oxidation in air and provide improved grain connectivity, changing the microstructural features and electrical properties of the resulted materials. The composites have been prepared through a modified Pechini method, followed by one- and two-stage sintering, to produce low-density (one-stage, 1ST) and high-density (two-stage, 2ST) ceramic samples. The electrical conductivity (σ), Seebeck coeffcient (α) and power factor (PF) values have been investigated between 475 and 975 K, in air flow, and related to the sample’s respective phase compositions, morphologies and microstructures. For the Co additions in the 1ST sintering case, the porous samples reached maximum PF values of around 210 μWm-1K2 , being around two times higher than those of the pure Ca3Co4O9 matrix. For the 1STsintered Fe and Ni added samples, the highest PF values of 80 and 90 μWm-1K-2 have been measured for the 3% vol. Ni and 3 and 6% vol. Fe additions, respectively, very close to some of the best reported values from literature. In contrast, 2ST sintering resulted in much denser samples and more complex phase compositions and microstructures, leading to lower electrical performance. The improvements of electrical properties achieved in the present work are promoted by a simultaneous increase in electrical conductivity and Seebeck coefficient values, stemming from pore filling effects and subsequent microstructural modifications.publishe

Enhancement of thermoelectric performance of donor-doped ZnO ceramics by involving an In situ aluminothermic reaction during processing

This work explores the possibility of involving aluminothermy in processing donor-doped zinc oxide-based thermoelectrics by relying on local, strong exothermic effects developed during sintering, with a potential positive impact on the electrical and thermal transport properties. The strategy was exemplified by using aluminium as a dopant, due to its recognized ability to generate additional, available charge carriers in ZnO, and by using two different metallic Al powders and conventional Al2O3 as precursors. Nanosized aluminium powder was involved in order to evaluate the possible desirable effects of the particles size, as compared to aluminium micropowder. A significant enhancement of the electrical and thermoelectric performance of the samples prepared via metallic Al precursors was observed and discussed in terms of the potential impacts provided by the aluminothermic reaction on the microstructure, charge carrier concentration and mobility during sintering. Although the presented results are the first to show evidence of how aluminothermic reactions can be used for boosting the thermoelectric performance of zinc oxide materials, the detailed mechanisms behind the observed enhancements are yet to be understood.publishe

Electrochemical reduction of hematite-based ceramics in alkaline medium: challenges in electrode design

Electrochemical reduction of low-conductive hematite-based ceramics represents a novel approach for iron recovery and waste valorisation. The process itself allows a flexible switching between hydrogen generation and iron reduction, important for the intermittent renewable-energy-powered electrolytic process. The present study focuses on the direct electrochemical reduction of aluminium-containing hematite in strong alkaline media. Within this scope, the reduction mechanisms of porous and dense cathodes, with 60%, 37% and 3% of open porosity, were investigated using different types of electrodes configuration: nickel-foil and Ag-modified nickel-foil supported configuration (cathodes facing or against the counter electrode), and nickel-mesh supported configuration. The efficiency of the iron reduction was compared for different electrode concepts. The results highlight the importance of electrolyte access to the interface between the metallic current collector and ceramic cathode for attaining reasonable electroreduction currents. Both excessively porous and dense ceramic cathodes are hardly suitable for such reduction process, showing a necessity to find a compromise between mechanical strength of the electrode and its open porosity, essential for the electrolyte access.publishe

Unravelling the effects of calcium substitution in BaGd2CoO5 Haldane gap 1D material and its thermoelectric performance

Ecobenign and high-temperature-stable oxides are considered a promising alternative to traditional Bi2Te3-, Bi2Se3-, and PbTe-based thermoelectric materials. The quest for high-performing thermoelectric oxides is still open and, among other challenges, includes the screening of various materials systems for potentially promising electrical and thermal transport properties. In this work, a new family of acceptor-substituted Haldane gap 1D BaGd2CoO5 dense ceramic materials was characterized in this respect. The substitution of this material with calcium results in a general improvement of the electrical performance, contributed by an interplay between the charge carrier concentration and their mobility. Nevertheless, a relatively low electrical conductivity was measured, reaching ∼5 S/cm at 1175 K, resulting in a maximum power factor of ∼25 μW/(K × m2) at 1173 K for BaGd1.80Ca0.20CoO5. On the other hand, the unique anisotropic 1D structure of the prepared materials promotes efficient phonon scattering, leading to low thermal conductivities, rarely observed in oxide electroceramics. While the BaGd2–xCaxCoO5 materials show attractive Seebeck coefficient values in the range 210–440 μV/K, the resulting dimensionless figure of merit is still relatively low, reaching ∼0.02 at 1173 K. The substituted BaGd2–xCaxCoO5 ceramics show comparable thermoelectric performance in both inert and air atmospheres. These features highlight the potential relevance of this structure type for thermoelectric applications, with future emphasis placed on methods to improve conductivity.publishe

Redox-promoted tailoring of the high-temperature electrical performance in Ca3Co4O9 thermoelectric materials by metallic cobalt addition

This paper reports a novel composite-based processing route for improving the electrical performance of Ca3Co4O9 thermoelectric (TE) ceramics. The approach involves the addition of metallic Co, acting as a pore filler on oxidation, and considers two simple sintering schemes. The (1-x)Ca3Co4O9/xCo composites (x = 0%, 3%, 6% and 9% vol.) have been prepared through a modified Pechini method, followed by one- and two-stage sintering, to produce low-density (one-stage, 1ST) and high-density (two-stage, 2ST) ceramic samples. Their high-temperature TE properties, namely the electrical conductivity (σ), Seebeck coefficient (α) and power factor (PF), were investigated between 475 and 975 K, in air flow, and related to their respective phase composition, morphology and microstructure. For the 1ST case, the porous samples (56%-61% of ρth) reached maximum PF values of around 210 and 140 μWm-1·K-2 for the 3% and 6% vol. Co-added samples, respectively, being around two and 1.3 times higher than those of the pure Ca3Co4O9 matrix. Although 2ST sintering resulted in rather dense samples (80% of ρth), the efficiency of the proposed approach, in this case, was limited by the complex phase composition of the corresponding ceramics, impeding the electronic transport and resulting in an electrical performance below that measured for the Ca3Co4O9 matrix (224 μWm-1·K-2 at 975K).publishe

Design of alumina monoliths by emulsion-gel casting: understanding the monolith structure from a rheological approach

Multimodal porous cellular alumina structures (monoliths) were prepared by an emulsion-gel casting technique using eco-friendly and inexpensive lipids such as corn oil, castor oil, margarine and their mixtures as the dispersed phase. The monoliths obtained showed good mechanical stability, exhibiting compressive strengths in the range of 8–50 N·mm−2. Mercury intrusion porosimetry analysis showed that the monoliths produced presented porosities ranging from 28% to 60% and average pore sizes within 0.2–3.2 μm. The formation of the porous networks was interpreted based on combined droplet coalescence, flocculation and Ostwald ripening effects. The presence of such effects along the emulsion storage time led to changes in their viscoelastic and morphological properties, which were found to correlate with structural descriptors of monoliths after sintering (e.g. average pore sizes and porosity). These correlations open up the possibility to anticipate the final structure of the monoliths and adjust emulsion-gel conditions to produce customized cellular structures with fine-tuned porosities and pore sizes, envisaging their application in membrane processes or chromatography.publishe

Direct processing of cellular ceramics from a single red mud precursor

The feasibility of recycling red mud waste by its direct transformation into highly-porous cellular ceramics was successfully demonstrated. Ceramic materials with designed cellular porosity were processed by emulsification of red mud suspensions with liquid paraffin. Taguchi method was used to study the effects provided by varying the red mud load in the suspension, gelatine content and emulsion stirring time on the micro structural features of the cellular ceramics. Additional experiments analysed the effects of the organic to suspension ratio and firing temperature. Emulsification of paraffin followed by gelatine consolidation, drying, elimination of the droplets of the discontinuous organic phase and firing, allowed one to design cellular ceramic pieces with open porosity up to 75%, consisting in interconnected cells with adjustable cell size and low resistance to percolation. These results allow one to consider prospective applications of red mud-based cellular ceramics with designed microstructures as highly-porous membranes for the capture of pollutants.publishe

Alkaline electrochemical reduction of a magnesium ferrospinel into metallic iron for the valorisation of magnetite-based metallurgical waste

The electrochemical reduction of iron oxides in alkaline media arises as a novel approach for ironmaking and iron-rich waste valorisation. Strong advantages and attractive aspects of alkaline electroreduction include lower electric energy consumption, absence of CO2 emissions, and non-polluting valuable by-products such as H2 and O2. Another potential advantage originates from the compatibility of this concept with intermittent renewable energies. However, to bring this technology to a competitive level, especially compared to the traditional steelmaking, innovative approaches and developments in materials processing and their appropriate integration into the electrolysis process are required. This research work explores the prospects for electrochemical reduction of a magnesium-containing ferrospinel, as a potential component in iron-containing wastes. The experimental approach considers bulk cathode- and suspension-based electrolysis concepts, which allow reaching 55% and 20% Faradaic efficiencies of the reduction to metallic iron, respectively. The effects imposed by the magnesium presence on the electroreduction kinetics, phase composition and morphology of the electroreduction products are evaluated and discussed. The obtained results open new perspectives for the recovery of metallurgical residues with low magnesium impurities content.publishe

Synergistic effects of zirconium- and aluminum co-doping on the thermoelectric performance of zinc oxide

This work aims to explore zirconium as a possible dopant to promote thermoelectric performance in bulk ZnO-based materials, both within the single-doping concept and on simultaneous co-doping with aluminum. At 1100–1223 K mixed-doped samples demonstrated around ∼2.3 times increase in ZT as compared to single-doped materials, reaching ∼0.12. The simultaneous presence of aluminum and zirconium imposes a synergistic effect on electrical properties provided by their mutual effects on the solubility in ZnO crystal lattice, while also allowing a moderate decrease of the thermal conductivity due to phonon scattering effects. At 1173 K the power factor of mixed-doped Zn0.994Al0.003Zr0.003O was 2.2–2.5 times higher than for single-doped materials. Stability tests of the prepared materials under prospective operation conditions indicated that the gradual increase in both resistivity and Seebeck coefficient in mixed-doped compositions with time may partially compensate each other to maintain a relatively high power factorpublishe

Environmentally friendly synthesis methods to obtain the misfit [Ca2CoO3-δ]0.62[CoO2] thermoelectric material

This work reports the microstructural and thermoelectric characterization of the misfit [Ca2CoO3-δ]0.62[CoO2] compound obtained by a solid-state synthesis using mollusk shells and a proteic sol-gel method, which uses gelatin as a polymerizing agent. The results clearly demonstrate the capability of these routes to produce pure Ca3Co4O9 with plate-like morphology. Sintered ceramic samples show randomly oriented grains and relative densities in the range of 63–67%. The obtained microstructures provide reasonable electrical properties and result in competitive thermoelectric performance for the material prepared by the proteic sol-gel synthesis (P.F. of 205 μW/K2 m at 700 °C).publishe