Transport properties of mechanochemically synthesized copper (I) selenide for potential applications in energy conversion and storage.

This work studied the thermal stability, electrical, and thermoelectrical properties of copper(I) selenide, Cu2Se synthesized by high-energy milling in a planetary ball mill. The phase composition was investigated by X-ray powder diffraction analysis and scanning electron microscopy. The conversion of the precursors during mechanochemical synthesis and the stability of the product was monitored by thermal analysis. The dependence of electrical properties on the product porosity was observed. For the densification of Cu2Se, the method of spark plasma sintering was applied to prepare suitable samples for thermoelectric characterization. High-temperature thermoelectric properties of synthetic Cu2Se were compared to its natural analogue-mineral berzelianite in terms of its potential application in energy conversion. Based on the results a relatively high figure-of-merit, ZT parameter (~ 1.15, T = 770 K) was obtained for undoped Cu2Se, prepared by rapid mechanochemical reaction (5 min). Cyclic voltammetry measurements of Na/NaClO4/Cu2Se cell implied that mechanochemically synthesized Cu2Se could be used as a promising intercalation electrode for sodium-ion batteries.

Anderson Localization of Phonons in Thermally Superinsulating Graphene Aerogels with Metal-Like Electrical Conductivity.

In the quest to improve energy efficiency and design better thermal insulators, various engineering strategies have been extensively investigated to minimize heat transfer through a material. Yet, the suppression of thermal transport in a material remains elusive because heat can be transferred by multiple energy carriers. Here, the realization of Anderson localization of phonons in a random 3D elastic network of graphene is reported. It is shown that thermal conductivity in a cellular graphene aerogel can be drastically reduced to 0.9 mW m-1 K-1 by the application of compressive strain while keeping a high metal-like electrical conductivity of 120 S m-1 and ampacity of 0.9 A. The experiments reveal that the strain can cause phonon localization over a broad compression range. The remaining heat flow in the material is dominated by charge transport. Conversely, electrical conductivity exhibits a gradual increase with increasing compressive strain, opposite to the thermal conductivity. These results imply that strain engineering provides the ability to independently tune charge and heat transport, establishing a new paradigm for controlling phonon and charge conduction in solids. This approach will enable the development of a new type of high-performance insulation solutions and thermally superinsulating materials with metal-like electrical conductivity.

The manipulation of natural mineral chalcopyrite CuFeS2via mechanochemistry: properties and thermoelectric potential.

In this study, the properties of the natural mineral chalcopyrite CuFeS2 after mechanical activation in a planetary mill were studied. The intensity of mechanical activation was controlled by changing the revolutions of the mill in the range 100-600 min-1. A series of characterization techniques, such as XRD, SEM, TEM, TA (DTA, TG, and DTG), particle size analysis, and UV-vis spectroscopy was applied and reactivity studies were also performed. Several new features were revealed for the mechanically activated chalcopyrite, e.g. the poly-modal distribution of produced nanoparticles on the micrometer scale, agglomeration effects by prolonged milling, possibility to modify the shape of the particles, X-ray amorphization and a shift from a non-cubic (tetragonal) structure to pseudo-cubic structure. The thermoelectric response was evaluated on the "softly" compacted powder via the spark plasma sintering method (very short holding time, low sintering temperature, and moderate pressure) by measuring the Seebeck coefficient and electrical and thermal conductivity above room temperature. The milling process produced samples with lower resistivity compared to the original non-activated sample. The Seebeck data close to zero confirmed the "compensated" character of natural chalcopyrite, reflecting its close-to stoichiometric composition with low concentration of both n- and p-type charge carriers. Alternatively, an evident correlation between thermal conductivity and energy supply by milling was observed with the possibility of band gap manipulation, which is associated with the energy delivered by the milling procedure.

Black Phosphorus: Fundamental Properties and Influence of Impurities Induced by Its Synthesis.

Black phosphorus (BP) has been among the most widely explored materials in recent years because of its exceptional properties. A vapor transport method using tin and iodide as mineralizers was used to synthesize large crystals which can be used for fundamental physical characterization including electrical and heat transport and heat capacity. This method is compared to other reported procedures (high-pressure crystal growth and mercury catalysis) which are broadly used and the most dominant procedures for the obtainment of bulk layered BP. In addition, we have investigated any possible impurities which could have been introduced by synthesis and their possible incorporation into BP and their influence on the physical properties of BP.

InSe:Ge-doped InSe van der Waals heterostructure to enhance photogenerated carrier separation for self-powered photoelectrochemical-type photodetectors.

Two-dimensional (2D) van der Waals (vdW) materials with tunable heterostructures and superior optoelectronic properties have opened a new platform for various applications, e.g., field-effect transistors, ultrasensitive photodetectors and photocatalysts. In this work, an InSe/InSe(Ge) (germanium doped InSe) vdW heterostructure is designed to improve the photoresponse performance of sole InSe in a photoelectrochemical (PEC)-type photodetector. Photoelectrochemical measurements demonstrated that this heterostructure has excellent photoresponse characteristics, including a photocurrent density of 9.8 µA cm-2, a photo-responsivity of 64 µA W-1, and a response time/recovery time of 0.128 s/0.1 s. Moreover, the measurements also revealed the self-powering capability and long-term cycling stability of this heterostructure. The electronic properties of the prepared pure and Ge-doped single crystals unveiled a negative and temperature-independent thermoelectric power and temperature-activated resistivity. The negative character of dominating charge carriers was confirmed by Hall measurements, which corroborated by electrical resistivity revealed a carrier concentration below ∼1015 cm-3 and an electron mobility of ∼500 cm2 V-1 s-1 in Ge-doped crystals. Additionally, the Mott-Schottky model explored the mechanism of charge transfer and enhanced PEC performance. Band bending at the InSe/InSe(Ge)-electrolyte interface benefits the separation and transformation of photogenerated carriers from the heterostructure to electrolyte due to the tunable energy band alignment. These results indicate that the InSe/InSe(Ge) vdW heterostructure is promising for PEC-type photodetectors, which provide a novel way to utilize 2D vdW heterostructures in optoelectronics.

Mechanochemistry for Energy Materials: Impact of High-Energy Milling on Chemical, Electric and Thermal Transport Properties of Chalcopyrite CuFeS2 Nanoparticles.

Chalcopyrite CuFeS2 , a semiconductor with applications in chemical sector and energy conversion engineering, was synthetized in a planetary mill from elemental precursors. The synthesis is environmentally friendly, waste-free and inexpensive. The synthesized nano-powders were characterized by XRD, SEM, EDX, BET and UV/Vis techniques, tests of chemical reactivity and, namely, thermoelectric performance of sintered ceramics followed. The crystallite size of ∼13 nm and the strain of ∼17 were calculated for CuFeS2 powders milled for 60, 120, 180 and 240 min, respectively. The evolution of characteristic band gaps, Eg, and the rate constant of leaching, k, of nano-powders are corroborated by the universal evolution of the parameter SBET /X (SBET -specific surface area, X-crystallinity) introduced for complex characterization of mechanochemically activated solids in various fields such as chemical engineering and/or energy conversion. The focus on non-doped semiconducting CuFeS2 enabled to assess the role of impurities, which critically and often negatively influence the thermoelectric properties.

Broadband dielectric spectroscopy of La0.65Sr0.35MnO3@TiO2 core-shell nanocomposites.

Core-shell composites of ferromagnetic conducting nanoparticles La0.65Sr0.35MnO3 (LSMO) embedded in an insulating matrix of TiO2 (LSMO@TiO2) have been processed, structurally and magnetically characterized, and their DC magnetoresistivity and complex dielectric response measured and fitted from Hz up to the infrared (IR) range (1014 Hz). XRD indicates that the TiO2 shells are amorphous. Modelling of the IR spectra using standard models based on the effective medium approximation has it confirmed and has characterized the effective phonon modes of the LSMO nanoceramics and LSMO@TiO2 composite. Modelling of the lower-frequency spectra has shown that TiO2 shell thicknesses are rather non-uniform down to thin nm values, which leads to giant low-frequency permittivity values and non-negligible free-carrier tunnelling among the LSMO cores. Two main dielectric dispersion regions were observed and shown to be due to the inhomogeneous conductivity-the one occuring in the 1011-1012 Hz range relates to nonmagnetic less-conducting dead layers on the surface of LSMO nanocrystallites and the broad second one below the 1010 Hz range is due to the non-uniform thicknesses of the dielectric TiO2 shells. In the IR range, effective phonon modes of the LSMO nanoceramics and LSMO@TiO2 composite were characterized from the reflectivity spectra.

Thermoelectric properties of the tetrahedrite-tennantite solid solutions Cu12Sb4-xAsxS13 and Cu10Co2Sb4-yAsyS13 (0 ≤ x, y ≤ 4).

Tetrahedrites, a class of copper- and sulfur-rich minerals, exhibit inherently very low lattice thermal conductivity and adjustable electronic properties that make them interesting candidates for thermoelectric applications. Here, we investigate the influence of isovalent As substitution on the Sb site on the structural and transport properties (5-700 K) of the two solid solutions Cu12Sb4-xAsxS13 and Cu10Co2Sb4-yAsyS13 (0 ≤ x, y ≤ 4). Electronic band structure calculations predict that As has only a weak influence on the valence bands and hence, on the p-type metallic character of Cu12Sb4S13. In agreement with these predictions, all the samples of the series Cu12Sb4-xAsxS13 exhibit p-type metallic behavior with relatively low electrical resistivity and moderate thermopower values that only slightly evolve with the As content. In contrast, the substitution of Co for Cu in As-rich samples seems less favorable as suggested by a decrease in the Co concentration with increasing the As content. This trend leads to a concomitant increase in the electrical resistivity and thermopower leaving the ZT values practically unchanged with respect to purely Cu-based samples. As a result, peak ZT values ranging between 0.60 and 0.75 are achieved at 700 K for both series. The lack of significant variations in the ZT values confirms the robustness of the thermoelectric performances of tetrahedrites with respect to variations in the Sb-to-As ratio.