Solid-state fabricated carbon nanotube (CNT) sheets have shown promise as thermoacoustic (TA) sound generators, emitting tunable sound waves across a broad frequency spectrum (1-105 Hz) due to their ultralow specific heat capacity. However, their applications as underwater TA sound generators are limited by the reduced mechanical strength of CNT sheets in aqueous environments. In this study, we present a mechanically robust underwater TA device constructed from a three-dimensional (3D) tetrapodal assembly of carbon nanotubes (t-CNTs). These structures feature a high porosity (>99.9%) and a double-hollowed network of well-interconnected CNTs. We systematically explore the impact of different dimensions of t-CNTs and various annealing procedures on sound generation performance. Furnace-annealed t-CNTs, in contrast to directly resistive Joule heating annealing, provide superior, continuous, and homogeneous hydrophobicity across the surface of bulk t-CNTs. As a result, the t-CNTs-based underwater TA device demonstrates stable, smooth, and broad-spectrum sound generation within the frequency range of 1 × 102 to 1 × 104 Hz, along with a weak resonance response. Furthermore, these devices exhibit enhanced and more stable sound generation performance at nonresonance frequencies compared to regular CNT-based devices. This study contributes to advancing the development of underwater TA devices with characteristics such as being nonresonant, high-performing, flexible, elastically compressible, and reliable, enabling operation across a broad frequency range.
Electrochromic smart windows (ESWs) offer an attractive option for regulating indoor lighting conditions. Electrochromic materials based on ion insertion/desertion mechanisms also present the possibility for energy storage, thereby increasing overall energy efficiency and adding value to the system. However, current electrochromic electrodes suffer from performance degradation, long response time, and low coloration efficiency. This work aims to produce defect-engineered brookite titanium dioxide (TiO2 ) nanorods (NRs) with different lengths and investigate their electrochromic performance as potential energy storage materials. The controllable synthesis of TiO2 NRs with inherent defects, along with smaller impedance and higher carrier concentrations, significantly enhances their electrochromic performance, including improved resistance to degradation, shorter response times, and enhanced coloration efficiency. The electrochromic performance of TiO2 NRs, particularly longer ones, is characterized by fast switching speeds (20 s for coloration and 12 s for bleaching), high coloration efficiency (84.96 cm2 C-1 at a 600 nm wavelength), and good stability, highlighting their potential for advanced electrochromic smart window applications based on Li+ ion intercalation.
Circularly polarized (CP) coherent light sources are of great potential for various advanced optical applications spanning displays/imaging to data processing/encryption and quantum communication. Here, the first demonstration of CP amplified spontaneous emission (ASE)/lasing from a free-standing and flexible membrane device is reported. The membrane device consists of perovskite nanocrystals (PNCs) and cholesteric liquid crystals (CLCs) layers sandwiched within a Fabry-Pérot (F-P) cavity architecture. The chiral liquid crystal cavity enables the generation of CP light from the device. The device is completely solution-processable and displays CP ASE with record dissymmetry factor (glum ) as high as 1.4, which is 3 orders of magnitude higher as compared with glum of CP luminescence of chiral ligand-capped colloidal PNCs. The device exhibits ultraflexibility as the ASE intensity remains unchanged after repeated 100 bending cycles and it is stable for more than 3 months with 80% of its original intensity. Furthermore, the ultraflexibility enables the generation of ASE from various objects of different geometric surfaces covered with the flexible perovskite membrane device. This work not only demonstrates the first CP ASE from a PNCs membrane with extremely high glum but also opens the door toward the fabrication of ultraflexible, extremely stable, and all solution-processable perovskite chiral laser devices.
Exploring low-grade waste heat energy harvesting is crucial to address increasing environmental concerns. Thermomagnetic materials are magnetic phase change materials that enable energy harvesting from low-temperature gradients. To achieve a high thermomagnetic conversion efficiency, there are three main material requirements: (i) magnetic phase transition near room temperature, (ii) substantial change in magnetization with temperature, and (iii) high thermal conductivity. Here, we demonstrate a high-performance Gd5Si2.4Ge1.6 thermomagnetic alloy that meets these three requirements. The magnetic phase transition temperature was successfully shifted to 306 K by introducing Ge doping in Gd5Si4, and a sharper and more symmetric magnetization behavior with saturation magnetization of Mmax = 70 emu/g at a 2 T magnetic field was achieved in the ferromagnetic state. The addition of SeS2, as a low-temperature sintering aid, to the Gd-Si-Ge alloy improved the material's density and thermal conductivity by â¼45 and â¼275%, respectively. Our results confirm that the (Gd5Si2.4Ge1.6)0.9(SeS2)0.1 alloy is a suitable composite material for low-grade waste heat recovery in thermomagnetic applications.
To achieve optimal thermoelectric performance, it is crucial to manipulate the scattering processes within materials to decouple the transport of phonons and electrons. In half-Heusler (hH) compounds, selective defect reduction can significantly improve performance due to the weak electron-acoustic phonon interaction. This study utilized Sb-pressure controlled annealing process to modulate the microstructure and point defects of Nb0.55Ta0.40Ti0.05FeSb compound, resulting in a 100% increase in carrier mobility and a maximum power factor of 78 µW cm-1 K-2, approaching the theoretical prediction for NbFeSb single crystal. This approach yielded the highest average zT of ~0.86 among hH in the temperature range of 300-873 K. The use of this material led to a 210% enhancement in cooling power density compared to Bi2Te3-based devices and a conversion efficiency of 12%. These results demonstrate a promising strategy for optimizing hH materials for near-room-temperature thermoelectric applications.
Cu2-xS and Cu2-xSe have recently been reported as promising thermoelectric (TE) materials for medium-temperature applications. In contrast, Cu2-xTe, another member of the copper chalcogenide family, typically exhibits low Seebeck coefficients that limit its potential to achieve a superior thermoelectric figure of merit, zT, particularly in the low-temperature range where this material could be effective. To address this, we investigated the TE performance of Cu1.5-xTe-Cu2Se nanocomposites by consolidating surface-engineered Cu1.5Te nanocrystals. This surface engineering strategy allows for precise adjustment of Cu/Te ratios and results in a reversible phase transition at around 600 K in Cu1.5-xTe-Cu2Se nanocomposites, as systematically confirmed by in situ high-temperature X-ray diffraction combined with differential scanning calorimetry analysis. The phase transition leads to a conversion from metallic-like to semiconducting-like TE properties. Additionally, a layer of Cu2Se generated around Cu1.5-xTe nanoparticles effectively inhibits Cu1.5-xTe grain growth, minimizing thermal conductivity and decreasing hole concentration. These properties indicate that copper telluride based compounds have a promising thermoelectric potential, translated into a high dimensionless zT of 1.3 at 560 K.
Waste-heat electricity generation using high-efficiency solid-state conversion technology can significantly decrease dependence on fossil fuels. Here, a synergistical optimization of layered half-Heusler (hH) materials and module to improve thermoelectric conversion efficiency is reported. This is realized by manufacturing multiple thermoelectric materials with major compositional variations and temperature-gradient-coupled carrier distribution by one-step spark plasma sintering. This strategy provides a solution to overcome the intrinsic concomitants of the conventional segmented architecture that only considers the matching of the figure of merit (zT) with the temperature gradient. The current design is dedicated to temperature-gradient-coupled resistivity and compatibility matching, optimum zT matching, and reducing contact resistance sources. By enhancing the quality factor of the materials by Sb-vapor-pressure-induced annealing, a superior zT of 1.47 at 973 K is achieved for (Nb, Hf)FeSb hH alloys. Along with the low-temperature high-zT hH alloys of (Nb, Ta, Ti, V)FeSb, the single stage layered hH modules are developed with efficiencies of ≈15.2% and ≈13.5% for the single-leg and unicouple thermoelectric modules, respectively, under ΔT of 670 K. Therefore, this work has a transformative impact on the design and development of next-generation thermoelectric generators for any thermoelectric material families.
Thermoelectric (TE) materials have made rapid advancement in the past decade, paving the pathway toward the design of solid-state waste heat recovery systems. The next requirement in the design process is realization of full-scale multistage TE devices in the medium to high temperature range for enhanced power generation. Here, we report the design and manufacturing of full-scale skutterudite (SKD)/half-Heusler (hH) cascaded TE devices with 49-couple TE legs for each stage. The automated pick-and-place tool is employed for module fabrication providing overall high manufacturing process efficiency and repeatability. Optimized Ti/Ni/Au coating layers are developed for metallization as the diffusion barrier and electrode contact layers. The Cu-Sn transient liquid phase sintering technique is utilized for SKD and hH stages, which provides a high strength bonding and very low contact resistance. A remarkably high output power of 38.3 W with a device power density of 2.8 W·cm-2 at a temperature gradient of 513 °C is achieved. These results provide an avenue for widespread utilization of TE technology in waste heat recovery applications.
Thermoelectric (TE) generators enable the direct and reversible conversion between heat and electricity, providing applications in both refrigeration and power generation. In the last decade, several TE materials with relatively high figures of merit (zT) have been reported in the low- and high-temperature regimes. However, there is an urgent demand for high-performance TE materials working in the mid-temperature range (400-700 K). Herein, p-type AgSbTe2 materials stabilized with S and Se co-doping are demonstrated to exhibit an outstanding maximum figure of merit (zTmax ) of 2.3 at 673 K and an average figure of merit (zTave ) of 1.59 over the wide temperature range of 300-673 K. This exceptional performance arises from an enhanced carrier density resulting from a higher concentration of silver vacancies, a vastly improved Seebeck coefficient enabled by the flattening of the valence band maximum and the inhibited formation of n-type Ag2 Te, and ahighly improved stability beyond 673 K. The optimized material is used to fabricate a single-leg device with efficiencies up to 13.3% and a unicouple TE device reaching energy conversion efficiencies up to 12.3% at a temperature difference of 370 K. These results highlight an effective strategy to engineer high-performance TE material in the mid-temperature range.
Halide perovskites show ubiquitous presences in growing fields at both fundamental and applied levels. Discovery, investigation, and application of innovative perovskites are heavily dependent on the synthetic methodology in terms of time-/yield-/effort-/energy- efficiency. Conventional wet chemistry method provides the easiness for growing thin film samples, but represents as an inefficient way for bulk crystal synthesis. To overcome these, here we report a universal solid state-based route for synthesizing high-quality perovskites, by means of simultaneously applying both electric and mechanical stress fields during the synthesis, i.e., the electrical and mechanical field-assisted sintering technique. We employ various perovskite compositions and arbitrary geometric designs for demonstration in this report, and establish such synthetic route with uniqueness of ultrahigh yield, fast processing and solvent-free nature, along with bulk products of exceptional quality approaching to single crystals. We exemplify the applications of the as-synthesized perovskites in photodetection and thermoelectric as well as other potentials to open extra chapters for future technical development.
In order to ensure the health and welfare of livestock, there has been an emphasis on precision farming of ruminant animals. Monitoring the life index of ruminant animals is of importance for intelligent farming. Here, a wearable sensor for monitoring ultraviolet (UV) radiation is demonstrated to understand the effect of primary and secondary photosensitization on dairy animals. Thin films of wide bandgap semiconductor zinc oxide (ZnO) comprising multilevel of nanostructures from microparticles (MP) to nanoparticles (NP), and tetrapod (T-ZnO), were prepared as the UV sensing active materials. The sensitivity was evaluated by exposing the films to various radiation sources, i.e., 365 nm (UV A), 302 nm (UV B), and 254 nm (UV C), and measuring the electrical resistance change. T-ZnO is found to exhibit higher sensitivity and stable response (on/off) upon exposure to UV A and UV B radiation, which is attributed to their higher surface area, aspect ratio, porosity, and interconnective networks inducing a high density of chemical interaction sites and consequently improved photocurrent generation. A wearable sensor using T-ZnO is packaged and attached to a collar for dynamic monitoring of UV response on ruminant animals (e.g., sheep in this study). The excellent performance of T-ZnO wearable sensors for ruminant animals also holds the potential for a wider range of applications such as residential buildings and public spaces.
Nanostructures , Zinc Oxide , Sheep , Animals , Zinc Oxide/chemistry , Livestock , Nanostructures/chemistry , Agriculture , Ruminants
Thermoelectric generators (TEGs) exploiting the Seebeck effect provide a promising solution for waste heat recovery. Among the large number of thermoelectric (TE) materials, half-Heusler (hH) alloys are leading candidates for medium- to high-temperature power generation applications. However, the fundamental challenge in this field has been inhomogeneous material properties at large wafer diameters, insufficient power output from the modules, and rigid form factors of TE modules. This has restricted the transition of TEGs in practical applications for over three decades. Here, we successfully demonstrate large diameter wafers with uniform TE properties, high-power conformal hH TE modules for high-temperature application, and their direct integration on flue gas platforms, such as cylindrical tubes, to form large area flexible TEGs. This new conformal architecture design provides a breakthrough toward medium-/high-temperature TEGs over the conventional BiTe- and polymer-based flexible TEG design. A variable fill factor and greater flexibility due to the conformal design result in higher device performance as compared to conventional rigid TEG devices. Modules with 72-couple hH legs exhibit a device high-power-density of 3.13 W cm-2 and a total output power of 56.6 W under a temperature difference of 570 °C. These results provide a promising pathway toward widespread utilization of thermoelectric technology into the waste heat recovery application and will have a significant impact on the development of practical thermal to electrical converters.
High temperature waste heat recovery has gained tremendous interest to generate useful electricity while reducing the harmful impact on the environment. Thermoelectric (TE) solid-state materials enable direct conversion of heat into electricity with high efficiency, thereby offering a practical solution for waste heat recovery. Half-Heusler (hH) alloys are the leading TE materials for medium to high temperature applications, as they exhibit a high figure of merit and mechanical strength at temperatures as high as 973 K. Here we investigate the most promising hH alloys represented as MNiSn, MCoSb, and NbFeSb systems (M = Hf, Zr, and Ti) and provide fundamental understanding of their in-air thermal stability at high temperatures under realistic operating conditions required for energy generation. The understanding of oxidation resistance of TE materials is crucial for their practical deployment in extreme environments without vacuum sealing. The n-type MNiSn and p-type NbFeSb compounds are found to exhibit excellent oxidation resistance at a high temperature of 873 K. The oxidation resistance is enhanced through the presence of an intermetallic Ni-Sn layer for MNiSn and Nb-TiO2 double layer for (Nb,Ti)FeSb. A unicouple thermoelectric generator (TEG) fabricated from thermally stable materials demonstrated consistent performance for more than 150 h at 873 K in air. These results demonstrate the significance of TE materials in waste heat recovery systems.
Thermoelectric generators (TEGs) offer cost-effective and sustainable solid-state energy conversion mechanism from wasted heat into useful electrical power. Thermoelectric (TE) materials based upon bismuth telluride (BiTe) systems are widely utilized in applications ranging from energy generation to sensing to cooling. There is demand for BiTe materials with high figure of merit (zT) and TEG modules with high conversion efficiency over intermediate temperatures (25°C-250°C). Here we provide fundamental breakthrough in design of BiTe-based TE materials and utilize them to demonstrate modules with outstanding conversion efficiency of 8%, which is 40% higher compared with state-of-the-art commercial modules. The average zT of 1.08 for p-type and 0.84 for n-type bismuth telluride alloys is obtained between 25 and 250°C. The significant enhancement in zT is achieved through compositional and defect engineering in both p- and n-type materials. The high conversion efficiency accelerates the transition of TEGs for waste heat recovery.
Thermoelectric power generation is a reliable energy harvesting technique for directly converting heat into electricity. Recent studies have reported the thermal-to-electrical energy conversion efficiency of thermoelectric generators (TEGs) up to 11% under laboratory settings. However, the practical efficiency of TEGs deployed under real environments is still not more than a few percent. In this study, we provide fundamental insight on the operation of TEGs in realistic environments by illustrating the combinatory effect of thermoelectric material properties, device boundary conditions, and environmental thermal resistivity on TEG performance in conjunction with the module parameters. Using numerical and experimental studies, we demonstrate the existence of a critical heat transfer coefficient that dramatically affects the design and performance of TEGs. Results provide a set of concrete design criteria for developing efficient TEGs that meet the metrics for field deployments. High-performance TEGs demonstrated in this study generated up to 28% higher power and 162% higher power per unit mass of thermoelectric materials as compared to the commercial module deployed for low-grade waste heat recovery. This advancement in understanding the TEG operation will have a transformative impact on the development of scalable thermal energy harvesters and in realizing their practical targets for efficiency, power density, and total output power.
Cd doping and metallic Ag additives in Ca3Co4O9+δ polycrystalline materials are shown to result in improved thermoelectric (TE) transport properties. Carrier concentration and mobility were optimized through the combination of doping and compositional modulation approaches. The formation of filiform Ag nanoinclusions between the interlayers and grain boundaries enhances the anisotropic carrier transport, leading to higher carrier mobility. A spin entropy enhancement due to the change of the net valence of Co induced by Cd substitution on the Ca site was confirmed by X-ray photoelectron spectroscopy. High carrier mobility and enhanced spin entropy results in higher electrical conductivity and Seebeck coefficient, leading to the increase of the power factor. In conjunction, mass fluctuation between Cd and Ca on the same crystal site along with the increase of metallic Ag nanoinclusions effectively lowers thermal conductivity. Consequently, the figure-of-merit, zT, has been improved to 0.31 at 950 K for 10 wt % Ag-modified Ca2.9Cd0.1Co4O9+δ specimen, which is a significant improvement compared to the pristine material. This dual-mode control of electron and phonon transport by including Ag additives and Cd doping offers an approach for tuning the correlated TE parameters.
Thermoelectric generators (TEGs) can convert body heat into electricity, thereby providing a continuous power source for wearable and implantable devices. For wearables, the low fill factor (area occupied by legs over the TEG base area) TEG modules are relevant as they provide large thermal gradient across the legs and require less material, which reduces the cost and weight. However, TEGs with a fill factor below 15% suffer from reduced mechanical robustness; consequently, commercial modules are usually fabricated with a fill factor in the range of 25-50%. In this study, TEG modules with a low and high fill factor are demonstrated and their performance is compared in harvesting body heat. Fabricated modules demonstrate â¼80% output power enhancement as compared to commercially available designs, resulting in high power density of up to 35 µW/cm2 in a steady state. This enhanced power is achieved by using two-third less thermoelectric materials in comparison to commercial modules. These results will advance the ongoing development of wearable devices by providing a consistent high specific power density source.
Thermoelectric coolers are attracting significant attention for replacing age-old cooling and refrigeration devices. Localized cooling by wearable thermoelectric coolers will decrease the usage of traditional systems, thereby reducing global warming and providing savings on energy costs. Since human skin as well as ambient air is a poor conductor of heat, wearable thermoelectric coolers operate under huge thermally resistive environment. The external thermal resistances greatly influence thermoelectric material behavior, device design, and device performance, which presents a fundamental challenge in achieving high efficiency for on-body applications. Here, we examine the combined effect of heat source/sink thermal resistances and thermoelectric material properties on thermoelectric cooler performance. Efficient thermoelectric coolers demonstrated here can cool the human skin up to 8.2 °C below the ambient temperature (170% higher cooling than commercial modules). Cost-benefit analysis shows that cooling over material volume for our optimized thermoelectric cooler is 500% higher than that of the commercial modules.
Oxide thermoelectric materials are nontoxic, chemically and thermally stable in oxidizing environments, cost-effective, and comparatively simpler to synthesize. However, thermoelectric oxides exhibit comparatively lower figure of merit (ZT) than that of metallic alloy counterparts. In this study, nanoscale texturing and interface engineering were utilized for enhancing the thermoelectric performance of oxide polycrystalline Ca3Co4O9 materials, which were synthesized using conventional sintering and spark plasma sintering (SPS) techniques. Results demonstrated that nanoscale platelets (having layered structure with nanoscale spacing) and metallic inclusions provide effective scattering of phonons, resulting in lower thermal conductivity and higher ZT. Thermoelectric measurement direction was found to have a significant effect on the magnitude of ZT because of the strong anisotropy in the transport properties induced by the layered nanostructure. The peak ZT value for the Ca2.85Lu0.15Co3.95Ga0.05O9 specimen measured along both perpendicular and parallel directions with respect to the SPS pressure axis is found be 0.16 at 630 °C and 0.04 at 580 °C, respectively. The peak ZT of 0.25 at 670 °C was observed for the spark plasma-sintered Ca2.95Ag0.05Co4O9 sample. The estimated output power of 2.15 W was obtained for the full size model, showing high-temperature thermoelectric applicability of this nanostructured material without significant oxidation.
Nano- and mesostructuring is widely used in thermoelectric (TE) materials. It introduces numerous interfaces and grain boundaries that scatter phonons and decrease thermal conductivity. A new approach has been developed for the rational design of the interfaces in TE materials by using all-inorganic nanocrystals (NCs) that serve as a "glue" for mesoscopic grains. For example, circa 10â nm Biâ NCs capped with (N2H5)4Sb2Te7 chalcogenidometallate ligands can be used as an additive to BiSbTe particles. During heat treatment, NCs fill up the voids between particles and act as a "glue", joining grains in hot-pressed pellets or solution-processed films. The chemical design of NC glue allowed the selective enhancement or decrease of the majority-carrier concentration near the grain boundaries, and thus resulted in doped or de-doped interfaces in granular TE material. Chemically engineered interfaces can be used as to optimize power factor and thermal conductivity.
