Tetragonal tungsten bronzes Nb8−xW9+xO47−δ: optimization strategies and transport properties of a new n-type thermoelectric oxide

Engineering of nanoscaled structures may help controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require the combination of low thermal conductivity and low electrical resistivity. The tetragonal tungsten bronzes Nb8−xW9+xO47 (TTB) allow a continuous variation of the charge carrier concentration while fulfilling at the same time the concept of a “phonon-glass electron-crystal” through a layered nanostructure defined by intrinsic crystallographic shear planes. The thermoelectric properties of the tetragonal tungsten bronzes Nb8−xW9+xO47−δ (0 < x < 2) were studied in the temperature range from 373 to 973 K. Structural defects and the…

Thermal stability and enhanced thermoelectric properties of the tetragonal tungsten bronzes Nb8-xW9+xO47 (0 &lt;x &lt;5)

Thermoelectric materials are believed to play a fundamental role in the energy field over the next years thanks to their ability of directly converting heat into usable electric energy. To increase their integration in the commercial markets, improvements of the efficiencies are needed. At the same time, cheap and non-toxic materials are required along with easily upscalable production cycles. Compounds of the tetragonal tungsten bronze (TTB) series Nb8-xW9+xO47 fulfill all these requirements and are promising materials. Their adaptive structure ensures glass-like values of the thermal conductivity, and the substitution on the cation side allows a controlled manipulation of the electronic p…

Spark Plasma Sintering (SPS)-Assisted Synthesis and Thermoelectric Characterization of Magnéli Phase V6O11

The Magneli phase V6O11 was synthesized in gram amounts from a powder mixture of V6O11/V7O13 and vanadium metal, using the spark plasma sintering (SPS) technique. Its structure was determined with synchrotron X-ray powder diffraction data from a phase-pure sample synthesized by conventional solid-state synthesis. A special feature of Magneli-type oxides is a combination of crystallographic shear and intrinsic disorder that leads to relatively low lattice thermal conductivities. SPS prepared V6O11 has a relatively low thermal conductivity of κ = 2.72 ± 0.06 W (m K)-1 while being a n-type conductor with an electrical conductivity of σ = 0.039 ± 0.005 (μΩ m)-1, a Seebeck coefficient of α = -(3…

Polypropylene-based melt mixed composites with singlewalled carbon nanotubes for thermoelectric applications: Switching from p-type to n-type by the addition of polyethylene glycol

Abstract The thermoelectric properties of melt processed conductive nanocomposites consisting of an insulating polypropylene (PP) matrix filled with singlewalled carbon nanotubes (CNTs) and copper oxide (CuO) were evaluated. An easy and cheap route to switch p-type composites into n-type was developed by adding polyethylene glycol (PEG) during melt mixing. At the investigated CNT concentrations of 0.8 wt% and 2 wt% (each above the electrical percolation threshold of ∼0.1 wt%), and a fixed CuO content of 5 wt%, the PEG addition converted p-type composites (positive Seebeck coefficient (S)) into n-type (negative S). PEG was also found to improve the filler dispersion inside the matrix. Two co…

Solid State Fluorination on the Minute Scale: Synthesis of WO 3− x F x with Photocatalytic Activity

Thermoelectrics: From history, a window to the future

Thermoelectricity offers a sustainable path to recover and convert waste heat into readily available electric energy, and has been studied for more than two centuries. From the controversy between Galvani and Volta on the Animal Electricity, dating back to the end of the XVIII century and anticipating Seebeck’s observations, the understanding of the physical mechanisms evolved along with the development of the technology. In the XIX century Ørsted clarified some of the earliest observations of the thermoelectric phenomenon and proposed the first thermoelectric pile, while it was only after the studies on thermodynamics by Thomson, and Rayleigh’s suggestion to exploit the Seebeck effect for …

Towards higher zT in early transition metal oxides: optimizing the charge carrier concentration of the WO3-x compounds

Abstract Thermoelectric devices are believed to play an important role in the energy research for the next decades. Thanks to their low costs coupled with high stability and sustainability, metal oxides are very promising materials even if their efficiencies still need improvements to ensure a wide applicability. Slightly reduced early transition metal oxides show intrinsic defects in the crystal structure which guarantee very low values of the thermal conductivity. The challenge to fulfil the “phonon-glass electron-crystal” concept is to decouple the optimization of the electronic properties from the thermal transport properties. In this contribution we report the optimization of the charg…