Room-temperature Thermoelectric Performance Research Articles

Robust Room Temperature Thermoelectric Performance of Mg3(Sb, Bi)2‐Based Alloys via Multivalent Mn Doping

Abstractn‐type Mg3(Sb, Bi)2 has excellent room temperature thermoelectric performance, which is, however, severely restricted by the negatively charged Mg vacancies that significantly deteriorate the carrier mobility. Herein, by manipulating the threshold solubility and defect formation energy of Mn, multivalent Mn is selectively introduced that synergistically promotes the carrier conduction according to different Mg chemical potentials; In Mg‐rich areas, interstitial Mn dominates which effectively reduces the migration and accumulation of Mg vacancies, while in Mg poor areas, interstitial Mn switches to substitutional sites that directly compensate for the negative charge. All the Mn centers possess Jahn–Teller inactive positions, leading to an ultra‐stable room temperature thermoelectric performance with a leading ZT up to 0.97. This work reveals the critical effect of multivalent and multifunctional transition metal incorporation in Mg3(Sb, Bi)2‐based alloys toward high room‐temperature thermoelectric performance.

Excellent Room Temperature Thermoelectric Performance in Mg3 Sb2 -Based Alloys via Multi-Functional Doping of Nb.

Mg3 Sb2 -based alloys are attracting increasing attention due to the excellent room temperature thermoelectric properties. However, due to the presence and easy segregation of charged Mg vacancies, the carrier mobility in Mg3 Sb2 -based alloys is always severely compromised that significantly restricts the room temperature performance. General vacancy compensation strategies cannot synergistically optimize the complicated Mg3 Sb2 structures involving both interior and boundary scattering. Herein, due to the multi-functional doping effect of Nb, the electron scattering inside and across grains is significantly suppressed by inhibiting the accumulation of Mg vacancies, and leading to a smooth transmission channel of electrons. The increased Mg vacancies migration barrier and optimized interface potential are also confirmed theoretically and experimentally, respectively. As a result, a leading room temperature zT of 1.02 is achieved. This work reveals the multi-functional doping effect as an efficient approach in improving room temperature thermoelectric performance in complicated defect/interface associated Mg3 Sb2 -based alloys.

Boosting room-temperature thermoelectric performance of Mg3Sb1.5Bi0.5 material through breaking the contradiction between carrier concentration and carrier mobility

Recently, low-cost Mg3Sb2-yBiy-based materials with high performance near room temperatures have been reported, which are considered to be promising candidates for replacing commercial Bi2Te3-based materials. Herein, we report a high power factor of ∼3000 μW m−1 K−1 and a ZT value of 0.82 at room temperature in Ti0.05Mg3.15Sb1.5Bi0.49Te0.01. Ti dopant entering into the Mg1 sublattice slightly increases the carrier concentration by the introduction of impurity states and enhances the carrier mobility by the promotion of grain size growth. The two-donor doping strategy breaks the contradiction between carrier concentration and carrier mobility, thus significantly improving the electrical transport properties near room temperatures. In addition, the introduction of defects by Ti dopant contributes to the decreased lattice thermal conductivity. Consequently, a ZTavg value of 1.19 is obtained at 50–250 ℃, ranking the top among reported n-type thermoelectric materials. Moreover, the as-fabricated single-leg device shows an high engineering efficiency considering the radiation calibration, i.e., 7.2 % and 11.8 % at temperature differences of 250 ℃ and 500 ℃ with Tc = 0 ℃, respectively, demonstrating the great potential of substituting the commercial Bi2Te3-family.

Large Mobility Enables Higher Thermoelectric Cooling and Power Generation Performance in n-type AgPb18+xSbTe20 Crystals.

The room-temperature thermoelectric performance of materials underpins their thermoelectric cooling ability. Carrier mobility plays a significant role in the electronic transport property of materials, especially near room temperature, which can be optimized by proper composition control and growing crystals. Here, we grow Pb-compensated AgPb18+xSbTe20 crystals using a vertical Bridgman method. A large weighted mobility of ∼410 cm2 V-1 s-1 is achieved in the AgPb18.4SbTe20 crystal, which is almost 4 times higher than that of the polycrystalline counterpart due to the elimination of grain boundaries and Ag-rich dislocations verified by atom probe tomography, highlighting the significant benefit of growing crystals for low-temperature thermoelectrics. Due to the largely promoted weighted mobility, we achieve a high power factor of ∼37.8 μW cm-1 K-2 and a large figure of merit ZT of ∼0.6 in AgPb18.4SbTe20 crystal at 303 K. We further designed a 7-pair thermoelectric module using this n-type crystal and a commercial p-type (Bi, Sb)2Te3-based material. As a result, a high cooling temperature difference (ΔT) of ∼42.7 K and a power generation efficiency of ∼3.7% are achieved, revealing promising thermoelectric applications for PbTe-based materials near room temperature.

Enhanced thermoelectric performance of n-type PbTe through introducing PbSe by a fast preparation method

N-type PbTe-based materials exhibit promising thermoelectric performance around 600–900 K, while the near room-temperature thermoelectric performance still needs to be improved due to their high thermal conductivity. Forming solid solutions is an effective strategy to strengthen phonon scatterings and results in lower lattice thermal conductivity. However, the existing preparation methods used in PbTe-based solid solutions are time-consuming and energy-intensive, which limits their further applications. Herein, we report a fast method combined self-propagating high-temperature synthesis (SHS) with spark plasma sintering (SPS) to successfully fabricate PbTe–PbSe solid solutions. Due to the mass and strain fluctuations, a largely reduced room temperature lattice thermal conductivity of 1.27 W m−1 K−1 was achieved in (Pb0.995Bi0.005Te)0.8-(PbSe)0.2, which was 40% lower than that of pristine Pb0.995Bi0.005Te. Besides, carrier mobility increased after PbSe alloying, leading to comparable electrical performance. Consequently, a maximum average thermoelectric figure of merit ZTave reached 0.57 at 300–623 K of (Pb0.995Bi0.005Te)0.8-(PbSe)0.2 and was 21% and 24% higher than those of pristine Pb0.995Bi0.005Te and PbSe, respectively. Such a simple and effective method is expected to be further adopted in other thermoelectric solid solutions.

Optimization of Thermoelectric Property of n‐Type Mg3Sb2 Near Room Temperature via Mn&Se Co‐Doping

AbstractThe Bi2Te3 family has been considered a state‐of‐the‐art thermoelectric material for room‐temperature applications for over half a century. However, scarcity of the material Te has been a persistent issue. Recently, the discovery of n‐type Mg3(Bi, Sb)2‐based materials provides new hope for replacing traditional Bi2Te3, but their thermoelectric properties near room temperature still need improvement for application to practical devices. Herein, a competitive figure of merit of ≈0.8 at 300 K and a high power factor greater than 30 µW cm−1 K−2 at 300 K in n‐type Mg3.14Mn0.06Bi1.4Sb0.59Se0.01 is reported, benefiting from the rationally tuned carrier concentration of 2.29×1019 cm−3 at room temperature. Substituting the Mg site with Mn in Mg3.2Bi1.4Sb0.59Se0.01 changes the dominant carrier scattering mechanism from a mixed scattering of acoustic phonons and ionized impurities to acoustic phonon scattering. Mn doping in Mg3.2Bi1.4Sb0.59Se0.01 also enhances the mobility to 180 cm2 V−1 s−1, reduces the thermal conductivity, and significantly increases the quality factor β of the material. The high room temperature thermoelectric performance of n‐type Mn&Se co‐doped Mg3(Bi, Sb)2‐based materials makes them a highly competitive substitute for commercialized n‐type Bi2Te3.

Strengthened interlayer interaction and improved room-temperature thermoelectric performance of Ag-doped n-type Bi2Te2.7Se0.3

Strengthened interlayer interaction and improved room-temperature thermoelectric performance of Ag-doped n-type Bi2Te2.7Se0.3

Ag2Se Nanorod Arrays with Ultrahigh Room Temperature Thermoelectric Performance and Superior Mechanical Properties.

Ag2Se is an intriguing material for room-temperature energy harvesting. Herein, we report the fabrication of Ag2Se nanorod arrays by glancing angle deposition technique (GLAD) followed by simple selenization in a two-zone furnace. Ag2Se planar films of different thickness were also prepared. The unique tilted Ag2Se nanorod arrays show excellent zT = 1.14 ± 0.09 and a power factor of 3229.21 ± 149.01 μW/m-K2, respectively, at 300 K. The superior thermoelectric performance of Ag2Se nanorod arrays compared to planar Ag2Se films could be ascribed to the unique nanocolumnar architecture that not only facilitates efficient electron transport but also significantly scatters phonons at the interfaces. Furthermore, the nanoindentation measurements were performed to explore mechanical properties of the as-prepared films. The Ag2Se nanorod arrays showed hardness values of 116.51 ± 4.25 MPa and elastic modulus of 10,966.01 ± 529.61 MPa, which are lowered by 51.8 and 45.6%, compared to Ag2Se films, respectively. The synergetic dependence between the tilt structure and thermoelectric properties accompanied with the simultaneous improvement in mechanical properties opens a new avenue for the practical applications of Ag2Se in next-generation flexible thermoelectric devices.

Multi-scale hierarchical microstructure modulation towards high room temperature thermoelectric performance in n-type Bi2Te3-based alloys

Bi2Te3-based thermoelectric materials are widely used in near room temperature refrigeration filed. Although Bi2Te3-based polycrystals prepared by powder metallurgy method exhibit good mechanical properties, the low room temperature dimensionless figure of merit (zT) for n-type alloys restricts their further usage. In this work, the electrical and thermal transport properties are manipulated synergistically by multi-scale hierarchical microstructure modulations in n-type Ag2Te/Bi2Te3 composites, including atomic-scale extrinsic point defects, nano-scale low-angel grain boundaries, mesoscale precipitate, and texturing. The carrier concentration is optimized by extrinsic point defects and the carrier mobility is improved due to the strengthened texture, and thus the power factor reaches a high value of 3.6 × 10−3 Wm−1/K2, which is even higher than the hot deformed counterparts. Simultaneously, the phonon scattering is enhanced by the multi-scale defects and the lattice thermal conductivity is suppressed. A high room temperature zT of ∼1.0 and an average zT of 0.96 in the 300–500 K range with good mechanical properties are obtained without hot deformation. This work puts forward a paradigm of enhancing the thermoelectric properties via multi-scale hierarchical microstructure modulations and is significant to the industrialization of manufacturing Bi2Te3-based alloys and devices.

125Te NMR study of the bulk of topological insulators Bi2Te3 and Sb2Te3

AbstractThe narrow band gap semiconductors Bi2Te3 and Sb2Te3 are well known for their room temperature thermoelectric performance. Recently, they were shown to serve as model systems of three‐dimensional topological insulators with a bulk band gap and very robust, spin‐resolved surface states due to a special band inversion in their periodic bulk. Evidently, it is of interest to investigate the special surface states with a local probe like nuclear magnetic resonance (NMR). However, especially the bulk NMR of these materials shows peculiar and rather unexpected phenomena, e. g., a magnetic field induced deformation of the local charge symmetry and excessive line broadening due to a special internuclear coupling. Here we report a comprehensive account of the room temperature NMR properties of the spin‐1/2 nucleus 125Te of single crystalline Bi2Te3 and Sb2Te3. This includes a very unusual spin‐lattice relaxation that seems not to be reflected in the NMR shift, as well as an exchange enhanced NMR line broadening.

Optimizing Room-Temperature Thermoelectric Performance of n-Type Bi2Te2.7Se0.3.

Bi2Te3-based compounds are exclusive commercial thermoelectric materials around room temperature. For n-type compounds, optimal thermoelectric properties are normally obtained at temperatures higher than room temperature to suppress the bipolar effect through increased carrier concentration. We find that doping with trace amounts of Cd and the addition of excess Bi are effective ways to optimize carrier concentration and achieve enhanced room-temperature thermoelectric performance for the Bi2Te2.7Se0.3 alloy in this work. For the Cd-doped samples, the replacement of Cd with Bi leads to not only a significant decrease in electron concentration but also apparently reduces the total thermal conductivity. The addition of excess Bi in the samples creates a Bi-rich synthetic atmosphere during the synthesis process, leading to increased BiTe antisite defects, decreased electron concentration, and reduced total thermal conductivity. Doping a small amount of Cd or adding excess Bi causes optimal thermoelectric performance of the n-type Bi2Te2.7Se0.3 sample shifts obviously toward low temperatures, and the samples with 0.4 atom % Cd and 0.8 atom % excess Bi achieve maximum zT of ∼0.97 at 448 K and ∼0.88 at 348 K, respectively.

Enhancing the room temperature thermoelectric performance of n-type Bismuth-telluride-based polycrystalline materials by low-angle grain boundaries

Bi2Te3-based thermoelectric materials are widely used in solid-state refrigeration near room temperature. However, the room temperature figure of merit (zT) of n-type Bi2Te3-based polycrystals produced by once sintering is always lower than 0.8. Herein, low-angle grain boundaries (LAGBs) are introduced in n-type Bi2Te2.7+xSe0.3 by a simple step-hot-pressing procedure (once sintering) and well characterized by scanning transmission electron microscopy. LAGBs consist of dislocation arrays that can effectively scatter the medium-frequency phonons and thus suppress the lattice thermal conductivity. Although LAGBs also serve as scattering centers of low-energy electrons and deteriorate the carrier mobility, they could contribute to the enhanced Seebeck coefficient owing to the increased scattering factor. Overall, the samples with LAGBs own lower electronic thermal conductivity at the same power factor level. Finally, a high room temperature zT of 0.94 is obtained in n-type Bi2Te2.7Se0.3, which is comparable to those produced by multiple-time sintering. Moreover, step-hot-pressing is also found to be effective in promoting the room temperature zT of p-type Bi2Te3-based polycrystals. This work puts forward a new and simple method to construct LAGBs in Bi2Te3-based alloys that enhances their zTs, and sheds light on the underlying mechanisms about how the LAGB affects the electrical and thermal transport properties.

Weak-ferromagnetism for room temperature thermoelectric performance enhancement in p-type (Bi,Sb)2Te3

Unceasing efforts have been devoted to performance enhancement of thermoelectric (TE) materials, and recently reports suggested a new approach by utilizing magnetism to increase power factor. This work investigated the doping effect of Fe on the TE properties of Bi2Te3-based materials. A series of Fex(Bi,Sb)2-xTe3 bulk samples were synthesized via mechanical alloying combined with spark plasma sintering. XRD results and DFT calculations indicate that Fe2+ and Fe3+ would coexist and substitute Bi3+ site firstly and shrink lattice. The co-doped Fe2+/Fe3+ in (Bi,Sb)2Te3 is helpful to reduce carrier concentration (nH), band gap (Eg) and increase effective mass (m∗). With further increase of x, ferromagnetic FeTe2 second phase was precipitated from (Bi,Sb)2Te3 matrix. A weak-ferromagnetism was observed in all Fe-doped samples via M-H curve, which could scatter low energy carriers along with little effect on high-energy carriers, whereby the mobility was enhanced effectively. Owing to the synergistic effect of weak-ferromagnetism and optimized band structure, the maximum power factor reaches up to 45 μWcm−1K−2 as x = 0.05, which is 28.5% higher than that at x = 0. The peak ZT value reaches up to 1.2 at 323 K along with a theoretical ηmax of 7.6% in the range of 303–473 K were achieved in x = 0.05 sample. The results suggest that introducing weak-ferromagnetism is an effective way to enhance room temperature TE performance of Bi–Sb–Te based materials.

Thermoelectric materials with crystal-amorphicity duality induced by large atomic size mismatch

Summary Discovering novel materials and attaining higher performance are the eternal pursuit of thermoelectric materials research. Here, we report a material series, (Cu1−xAgx)2(Te1−ySy) (0.16 ≤ x ≤ 0.24, 0.16 ≤ y ≤ 0.24), which adopts a complex orthorhombic structure differing from any known crystal structure of (Cu/Ag)2(S/Te). This material series is featured by the crystal-amorphicity duality induced by the large anionic size mismatch: a crystalline sublattice of highly size-mismatched anions Te/S coexists with an amorphous-like sublattice of cations Cu/Ag. In the context of structure-property correlation, the crystal-amorphicity duality gave rise to not only interesting electrical properties but also exceptionally low lattice thermal conductivities from 300 to 1,000 K. A state-of-the-art figure of merit zT of 2.0 is obtained in the x = y = 0.22 sample at 1,000 K. These results give insights into crystal-amorphicity duality as a paradigm-shifting materials design approach to develop high-performance thermoelectric materials.

Improved room-temperature thermoelectric characteristics in F4TCNQ-doped CNT yarn/P3HT composite by controlled doping

Abstract High room-temperature thermoelectric performance is important for low-grade waste heat power generation as there are plenty of heat thrown away uselessly in our daily life, most of which are below 100 °C. However, most of the thermoelectric materials are limited to high temperature application. In this work, room-temperature thermoelectric power factor of carbon nanotube (CNT) yarn is improved by controlled doping, which is achieved by making composite with poly 3-hexylthiophene −2, 5-diyl (P3HT) followed by doping with 2, 3, 5, 6-tetrafluo-7, 7, 8, 8-tetracyanoquinodimethane (F4TCNQ). The temperature-dependent Seebeck coefficient based on power–law model suggests that P3HT shifts the Fermi energy of CNT yarn towards the valence band edge, and reduces the ionic scattering and carrier relaxation time. As a result, the Seebeck coefficient is increased while the variation of Seebeck coefficient with temperature is reduced, and hence, the room-temperature thermoelectric power factor is improved. With controlled doping, the power factor of CNT yarn/P3HT composite reaches to 1640–2160 μW m−1K−2 at the temperature range of 25–100 °C, which is higher than that of CNT yarn alone.

Enhancing room-temperature thermoelectric performance of n-type Bi2Te3-based alloys via sulfur alloying

Bismuth-telluride-based alloys are the best thermoelectric materials used in commercial solid-state refrigeration near room temperature. Nevertheless, for n-type polycrystalline alloys, their thermoelectric figure of merit (zT) values at room temperature are often less than 1.0, due to the high electron concentration originating from the donor-like effect induced by the mechanical deformation process. Herein, carrier concentration for better performance near room temperature was optimized through manipulating intrinsic point defects by sulfur alloying. Sulfur alloying significantly decreases antisite defects concentration and suppresses donor-like effect, resulting in optimized carrier concentration and reduced electronic thermal conductivity. The hot deformation process was also applied to improve carrier mobility due to the enhanced texture. As a result, a high zT value of 1 at 300 K and peak zT value of 1.1 at 350 K were obtained for the twice hot-deformed Bi2Te2.7Se0.21S0.09 sample, which verifies sulfur alloying is an effective method to improve thermoelectric performance of n-type polycrystalline Bi2Te3-based alloys near room temperature.

Room temperature thermoelectric performance of Methyl Ammonium Lead Iodide Perovskite and their MWCNT-PANI composites

The excellent properties of Methyl Ammonium Lead Iodide (MAPI) have already created an extensive research interest in photovoltaic applications. However, their utility in thermoelectric application is still not realized thoroughly by researchers. By continuing this interest, we have explored the formation of low dimensional CH3NH3PbI3 (MAPI) perovskite in presence of Polyaniline (PANI) and Multi-Walled Carbon Nanotubes (MWCNT) and its thermoelectric performance. For this purpose, a two stage, in-situ synthesis method was developed to prepare various composites such as MAPI-PANI, MWCNT-MAPI and MWCNT-PANI-MAPI. The as-formed MWCNT-PANI-MAPI composite revealed p-type conductivity with enhanced ZT (up to ~20,000 times) and power factor (3000 times) at room temperature as compared to pristine MAPI sample. Finally, we have demonstrated a proto-type thermoelectric power generator (TE device) fabricated using the best performing composite sample and measured its power output and efficiency at varied δT.

Semiconductor glass with superior flexibility and high room temperature thermoelectric performance.

Most crystalline inorganic materials, except for metals and some layer materials, exhibit bad flexibility because of strong ionic or covalent bonds, while amorphous materials usually display poor electrical properties due to structural disorders. Here, we report the simultaneous realization of extraordinary room temperature flexibility and thermoelectric performance in Ag2Te1-x S x -based materials through amorphization. The coexistence of amorphous main phase and crystallites results in exceptional flexibility and ultralow lattice thermal conductivity. Furthermore, the flexible Ag2Te0.6S0.4 glass exhibits a degenerate semiconductor behavior with a room temperature Hall mobility of ~750 cm2 V-1 s-1 at a carrier concentration of 8.6 × 1018 cm-3, which is at least an order of magnitude higher than other amorphous materials, leading to a thermoelectric power factor also an order of magnitude higher than the best amorphous thermoelectric materials known. The in-plane prototype uni-leg thermoelectric generator made from this material demonstrates its potential for flexible thermoelectric device.

High-Performance Ag-Modified Bi0.5Sb1.5Te3 Films for the Flexible Thermoelectric Generator.

Bi-Sb-Te-based semiconductors possess the best room-temperature thermoelectric performance, but are restricted for application in the wearable field because of their inherent brittleness, rigidity, and nonscalable manufacturing techniques. Therefore, how to obtain thermoelectric materials with excellent thermoelectric properties and flexibility through the batch production process is a serious challenge. Here, we report the fabrication of flexible p-type thermoelectric Ag-modified Bi0.5Sb1.5Te3 films on flexible substrates using a facile approach. Their optimized power factors are ∼12.4 and ∼14.0 μW cm-1 K-2 at 300 and 420 K, respectively. These high-power factors mainly originate from the optimized carrier transport of the composite system, through which a high level of electrical conductivity is achieved, whereas a remarkably improved Seebeck coefficient is simultaneously obtained. Bending tests demonstrate the excellent flexibility and mechanical durability of the composite films, and their power factors decrease by only about 10% after bending for 650 cycles with a bending radius of 5 mm. A flexible thermoelectric module is designed and constructed using the optimized composite films and displays a power density of ∼1.4 mW cm-2 at a relatively small ΔT of 60 K. This work demonstrates the potential of inorganic thermoelectric materials to be made on flexible/wearable substrates for energy harvesting and management devices.

Bi2Te3 single crystals with high room-temperature thermoelectric performance enhanced by manipulating point defects based on first-principles calculation.

Intrinsic Bi2Te3 is a representative thermoelectric (TE) material with high performance at low temperature, which enables applications for electronic cooling. However, antisite defects easily form in p-type Bi2Te3, resulting in the difficulty of further property enhancement. In this work, the formation energy of native point defects in Bi2Te3 supercells and the electronic structure of Bi2Te3 primitive unit cell were calculated using first-principles. The antisite defect Bi_Te1 has a lower formation energy (0.68 eV) under the Te-lack condition for p-type Bi2Te3. The effects of point defects on TE properties were investigated via a series of p-type Bi2Te3−x (x = 0, 0.02, 0.04, 0.06, 0.08) single crystals prepared by the temperature gradient growth method (TGGM). Apart from the increased power factor (PF∥) which originates from the increased carrier concentration (n∥) and m*, the thermal conductivity (κ∥) was also cut down by the increased point defects. Benefitting from the high PF∥ of 4.09 mW m−1 K−2 and the low κ∥ of 1.77 W m−1 K−1, the highest ZT∥ of 0.70 was obtained for x = 0.06 composition at 300 K, which is 30% higher than that (0.54) of the intrinsic Bi2Te3.