Tubular and fibrous nanostructures of titanates have recently been
synthesized and characterized. Three general approaches (template assisted, anodic oxidation, and alkaline hydrothermal) for the preparation of nanostructured titanate and TiO2 are reviewed. The crystal structures, morphologies, and mechanism of formation
of nanostructured titanates produced by the alkaline hydrothermal method are critically discussed. The physicochemical properties of nanostructured titanates are highlighted and the links between properties and applications are emphasized. Examples of early applications of nanostructured titanates in catalysis, photocatalysis, electrocatalysis, lithium batteries, hydrogen storage, and solar-cell technologies are reviewed. The stability of titanate nanotubes at elevated temperatures and in acid media is considered.

Protonated Titanates and TiO2 Nanostructured Materials: Synthesis, Properties, and Applications

Thermoelectric technology, harvesting electric power directly from heat, is a promising environmentally friendly means of energy savings and power generation. The thermoelectric efficiency is determined by the device dimensionless figure of merit ZT(dev), and optimizing this efficiency requires maximizing ZT values over a broad temperature range. Here, we report a record high ZT(dev) ∼1.34, with ZT ranging from 0.7 to 2.0 at 300 to 773 kelvin, realized in hole-doped tin selenide (SnSe) crystals. The exceptional performance arises from the ultrahigh power factor, which comes from a high electrical conductivity and a strongly enhanced Seebeck coefficient enabled by the contribution of multiple electronic valence bands present in SnSe. SnSe is a robust thermoelectric candidate for energy conversion applications in the low and moderate temperature range.

https://science.sciencemag.org/content/sci/early/2015/11/24/science.aad3749.full.pdf

Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe

There has been a renaissance of interest in exploring highly efficient thermoelectric materials as a possible route to address the worldwide energy generation, utilization, and management. This review describes the recent advances in designing high-performance bulk thermoelectric materials. We begin with the fundamental stratagem of achieving the greatest thermoelectric figure of merit ZT of a given material by carrier concentration engineering, including Fermi level regulation and optimum carrier density stabilization. We proceed to discuss ways of maximizing ZT at a constant doping level, such as increase of band degeneracy (crystal structure symmetry, band convergence), enhancement of band effective mass (resonant levels, band flattening), improvement of carrier mobility (modulation doping, texturing), and decrease of lattice thermal conductivity (synergistic alloying, second-phase nanostructuring, mesostructuring, and all-length-scale hierarchical architectures). We then highlight the decoupling of th...

Rationally Designing High-Performance Bulk Thermoelectric Materials

BACKGROUND Heat and electricity are two forms of energy that are at opposite ends of a spectrum Heat is ubiquitous, but with low quality, whereas electricity is versatile, but its production is demanding Thermoelectrics offers a simple and environmentally friendly solution for direct heat-to-electricity conversion A thermoelectric (TE) device can directly convert heat emanating from the Sun, radioisotopes, automobiles, industrial sectors, or even the human body to electricity Electricity also can drive a TE device to work as a solid-state heat pump for distributed spot-size refrigeration TE devices are free of moving parts and feasible for miniaturization, run quietly, and do not emit greenhouse gasses The full potential of TE devices may be unleashed by working in tandem with other energy-conversion technologies Thermoelectrics found niche applications in the 20th century, especially where efficiency was of a lower priority than energy availability and reliability Broader (beyond niche) application of thermoelectrics in the 21st century requires developing higher-performance materials The figure of merit, ZT, is the primary measure of material performance Enhancing the ZT requires optimizing the adversely interdependent electrical resistivity, Seebeck coefficient, and thermal conductivity, as a group On the microscopic level, high material performance stems from a delicate concert among trade-offs between phase stability and instability, structural order and disorder, bond covalency and ionicity, band convergence and splitting, itinerant and localized electronic states, and carrier mobility and effective mass ADVANCES Innovative transport mechanisms are the fountain of youth of TE materials research In the past two decades, many potentially paradigm-changing mechanisms were identified, eg, resonant levels, modulation doping, band convergence, classical and quantum size effects, anharmonicity, the Rashba effect, the spin Seebeck effect, and topological states These mechanisms embody the current states of understanding and manipulating the interplay among the charge, lattice, orbital, and spin degrees of freedom in TE materials Many strategies were successfully implemented in a wide range of materials, eg, V2VI3 compounds, VVI compounds, filled skutterudites and clathrates, half-Heusler alloys, diamond-like structured compounds, Zintl phases, oxides and mixed-anion oxides, silicides, transition metal chalcogenides, and organic materials In addition, advanced material synthesis and processing techniques, for example, melt spinning, self-sustaining heating synthesis, and field-assisted sintering, helped reach a much broader phase space where traditional metallurgy and melt-growth recipes fell short Given the ubiquity of heat and the modular aspects of TE devices, these advances ensure that thermoelectrics plays an important role as part of a solutions package to address our global energy needs OUTLOOK The emerging roles of spin and orbital states, new breakthroughs in multiscale defect engineering, and controlled anharmonicity may hold the key to developing next generation TE materials To accelerate exploring the broad phase space of higher multinary compounds, we need a synergy of theory, machine learning, three-dimensional printing, and fast experimental characterizations We expect this synergy to help refine current materials selection and make TE materials research more data driven We also expect increasing efforts to develop high-performance materials out of nontoxic and earth-abundant elements The desire to move away from Freon and other refrigerant-based cooling should shift TE materials research from power generation to solid-state refrigeration International round-robin measurements to cross-check the high ZT values of emerging materials will help identify those that hold the most promise We hope the renewable energy landscape will be reshaped if the recent trend of progress continues into the foreseeable future

http://science.sciencemag.org/content/sci/357/6358/eaak9997.full.pdf

Advances in thermoelectric materials research: Looking back and moving forward

Lead chalcogenides have long been used for space-based and thermoelectric remote power generation applications, but recent discoveries have revealed a much greater potential for these materials. This renaissance of interest combined with the need for increased energy efficiency has led to active consideration of thermoelectrics for practical waste heat recovery systems—such as the conversion of car exhaust heat into electricity. The simple high symmetry NaCl-type cubic structure, leads to several properties desirable for thermoelectricity, such as high valley degeneracy for high electrical conductivity and phonon anharmonicity for low thermal conductivity. The rich capabilities for both band structure and microstructure engineering enable a variety of approaches for achieving high thermoelectric performance in lead chalcogenides. This Review focuses on manipulation of the electronic and atomic structural features which makes up the thermoelectric quality factor. While these strategies are well demonstrated in lead chalcogenides, the principles used are equally applicable to most good thermoelectric materials that could enable improvement of thermoelectric devices from niche applications into the mainstream of energy technologies.

Band Engineering of Thermoelectric Materials

From an environmental perspective, lead-free SnTe would be preferable for solid-state waste heat recovery if its thermoelectric figure-of-merit could be brought close to that of the lead-containing chalcogenides. In this work, we studied the thermoelectric properties of nanostructured SnTe with different dopants, and found indium-doped SnTe showed extraordinarily large Seebeck coefficients that cannot be explained properly by the conventional two-valence band model. We attributed this enhancement of Seebeck coefficients to resonant levels created by the indium impurities inside the valence band, supported by the first-principles simulations. This, together with the lower thermal conductivity resulting from the decreased grain size by ball milling and hot pressing, improved both the peak and average nondimensional figure-of-merit (ZT) significantly. A peak ZT of ∼1.1 was obtained in 0.25 atom % In-doped SnTe at about 873 K.

https://www.pnas.org/content/pnas/110/33/13261.full.pdf

High thermoelectric performance by resonant dopant indium in nanostructured SnTe

Modulation-doping was theoretically proposed and experimentally proved to be effective in increasing the power factor of nanocomposites (Si80Ge20)70(Si100B5)30 by increasing the carrier mobility but not the figure-of-merit (ZT) due to the increased thermal conductivity. Here we report an alternative materials design, using alloy Si70Ge30 instead of Si as the nanoparticles and Si95Ge5 as the matrix, to increase the power factor but not the thermal conductivity, leading to a ZT of 1.3 ± 0.1 at 900 °C.

/pdf/enhancement-of-thermoelectric-properties-by-modulation-3b6n32y24g.pdf

Enhancement of Thermoelectric Properties by Modulation-Doping in Silicon Germanium Alloy Nanocomposites

We present detailed studies of potassium doping in PbTe1–ySey (y = 0, 0.15, 0.25, 0.75, 0.85, 0.95, and 1). It was found that Se increases the doping concentration of K in PbTe as a result of the balance of electronegativity and also lowers the lattice thermal conductivity because of the increased number of point defects. Tuning the composition and carrier concentration to increase the density of states around the Fermi level results in higher Seebeck coefficients for the two valence bands of PbTe1–ySey. Peak thermoelectric figure of merit (ZT) values of ∼1.6 and ∼1.7 were obtained for Te-rich K0.02Pb0.98Te0.75Se0.25 at 773 K and Se-rich K0.02Pb0.98Te0.15Se0.85 at 873 K, respectively. However, the average ZT was higher in Te-rich compositions than in Se-rich compositions, with the best found in K0.02Pb0.98Te0.75Se0.25. Such a result is due to the improved electron transport afforded by heavy K doping with the assistance of Se.

/pdf/heavy-doping-and-band-engineering-by-potassium-to-improve-4ra4hnshhc.pdf

Heavy doping and band engineering by potassium to improve the thermoelectric figure of merit in p-type PbTe, PbSe, and PbTe(1-y)Se(y).

Bismuth telluride (Bi2Te3) and its alloys have been widely investigated as thermoelectric materials for cooling applications at around room temperature. We report a systematic study on many compounds in the Bi2Te3–Bi2Se3–Bi2S3 system. All the samples were fabricated by high energy ball milling followed by hot pressing. Among the investigated compounds, Bi2Te2S1 shows a peak ZT ∼0.8 at 300 °C and Bi2Se1S2 ∼0.8 at 500 °C. The results show that these compounds can be used for mid-temperature power generation applications. The leg efficiency of thermoelectric conversion for segmented elements based on these n-type materials could potentially reach 12.5% with a cold side at 25 °C and a hot side at 500 °C if appropriate p-type legs are paired, which could compete well with the state-of-the-art n-type materials within the same temperature range, including lead tellurides, lead selenides, lead sulfides, filled-skutterudites, and half Heuslers.

/pdf/studies-on-the-bi2te3-bi2se3-bi2s3-system-for-mid-2cxbtq00rc.pdf

Cyril Opeil

Papers

High thermoelectric performance by resonant dopant indium in nanostructured SnTe

Enhancement of Thermoelectric Properties by Modulation-Doping in Silicon Germanium Alloy Nanocomposites

Heavy doping and band engineering by potassium to improve the thermoelectric figure of merit in p-type PbTe, PbSe, and PbTe(1-y)Se(y).

Studies on the Bi2Te3–Bi2Se3–Bi2S3 system for mid-temperature thermoelectric energy conversion

Effect of Hf Concentration on Thermoelectric Properties of Nanostructured N‐Type Half‐Heusler Materials HfxZr1–xNiSn0.99Sb0.01