Flexible Thermoelectric Films Research Articles

A Strategy for Fabricating Ultra-Flexible Thermoelectric Films Using Ag2Se-Based Ink.

Flexible thermoelectric materials have drawn significant attention from researchers due to their potential applications in wearable electronics and the Internet of Things. Despite many reports on these materials, it remains a significant challenge to develop cost-effective methods for large-scale, patterned fabrication of materials that exhibit both excellent thermoelectric performance and remarkable flexibility. In this study, we have developed an Ag2Se-based ink with excellent printability that can be used to fabricate flexible thermoelectric films by screen printing and low-temperature sintering. The printed films exhibit a Seebeck coefficient of -161 μV/K and a power factor of 3250.9 μW/m·K2 at 400 K. Moreover, the films demonstrate remarkable flexibility, showing minimal changes in resistance after being bent 5000 times at a radius of 5 mm. Overall, this research offers a new opportunity for the large-scale patterned production of flexible thermoelectric films.

High-Performance Printed Ag2Se/PI Flexible Thermoelectric Film for Powering Wearable Electronics.

We report the magnificent thermoelectric properties of the n-type Ag2Se film printed onto a flexible polyimide (PI) substrate. The orthorhombic β-Ag2Se phase of the processed Ag2Se film is confirmed from the X-ray diffractogram. Remarkably, the resulting Ag2Se/PI film exhibits outstanding thermoelectric properties, boasting maximum power factors of 1.4 and 2.1 mW/mK2 at 300 and 405 K, respectively. Furthermore, the flexibility of the Ag2Se/PI film remains intact even after undergoing 1500 bending cycles with no degradation observed in its thermoelectric performance. To demonstrate the practical application of our findings, a flexible thermoelectric prototype is constructed using the fabricated Ag2Se/PI films, which can harvest an impressive output voltage of 52 mV across a temperature difference of 53 K. Additionally, the prototype generates a maximum power output of 7.2 μW with a 40 K temperature difference and can produce 13 mV output voltage when subjected to around a 10 K temperature gradient when the cold side temperature is maintained at 308 K. Moreover, leveraging body heat with just a 1 K temperature variance between the body and the surrounding environment, the prototype could yield an impressive voltage output of 1.6 mV, marking the highest reported voltage output from human body heat to date. Our study not only introduces a cost-effective method for producing high-performance flexible thermoelectric films but also highlights their potential applications in wearable and implantable electronics.

Screen printing Ag2Se/carbon nanocomposite films for flexible thermoelectric applications

Flexible thermoelectric generators offer the possibility of harvesting waste heat from the human body. However, intrinsic brittleness and the high production cost of bulk thermoelectric materials limit their applications in flexible thermoelectric generators. Herein, flexible Ag2Se/carbon nanocomposite films on polyimide substrates are prepared by scalable screen-printing followed by facial heat treatment. An optimal film shows a maximum power factor of 1617 μW m−1 K−2 at room temperature and good flexibility. The film consists of mainly Ag2Se grains with a preferred (00Ɩ)-orientation and a small amount of carbon. Microstructure observations reveal that the Ag2Se grains with sizes of nano to micrometers have coherent or continuous grain boundaries, and the carbon is mainly amorphous with slight graphitization. A flexible thermoelectric device assembled with the optimal film exhibits a power density of 29.1 W/m2 at a temperature gradient of 35.4 K. This work demonstrates a cost-effective route to high-performance flexible thermoelectric films.

One Stone, Three Birds: Feasible Tuning of Barrier Heights Induced by Hybridized Interface in Free-Standing PEDOT@Bi2Te3 Thermoelectric Films.

Converting low-grade thermal energy into electrical energy is crucial for the development of modern smart wearable energy technologies. The free-standing films of PEDOT@Bi2Te3 prepared by tape-casting hold promise for flexible thermoelectric technology in self-powered sensing applications. Bi2Te3 nanosheets fabricated by the solvothermal method are tightly connected with flat-arranged PEODT molecules, forming an S-Bi bonded interface in the composite materials, and the bandgap is reduced to 1.63 eV. Compared with the PEDOT film, the mobility and carrier concentration of the composite are significantly increased at room temperature, and the conductivity reaches 684 S/cm. Meanwhile, the carrier concentration decreased sharply at 360 K indicating the creation of defect energy levels during the interfacial reaction of the composites, which increased the Seebeck coefficient. The power factor was improved by 68.9% compared to PEDOT. In addition, the introduction of Bi2Te3 nanosheets generated defects and multidimensional interfaces in the composite film, which resulted in weak phonon scattering in the conducting polymer with interfacial scattering. The thermal conductivity of the film is decreased and the ZT value reaches 0.1. The composite film undergoes 1500 bending cycles with a 14% decrease in conductivity and has good flexibility. This self-supporting flexible thermoelectric composite film has provided a research basis for low-grade thermal energy applications.

Optimization of Power Factor for a Screen-Printed Silver Selenide-Based Flexible Thermoelectric Film by Hot Pressing

Optimization of Power Factor for a Screen-Printed Silver Selenide-Based Flexible Thermoelectric Film by Hot Pressing

The synergistic effect of hole co-doping on carrier transports and phonon tuning in Sb2Te3 flexible thermoelectric thin film

Sb2Te3 thermoelectric thin film is one of the best competitive candidates for preparing self-powered wearable micro-electronic devices. However, the interdependent relationship between Seebeck coefficient, electrical conductivity and thermal conductivity limits the improvement of thermoelectric properties. In this work, we demonstrate maximum power factor of 21.06 μWcm−1K−2 and a high average power factor of 18.77 μWcm−1K−2 in (Bi, In) co-doped Sb2Te3 flexible thin film. The high power factor is ascribed to the increase in effective mass and state density after Bi doping proved by first-principles calculations and experiments, which leads to an increase in the Seebeck coefficient. Further In co-doping can increase the carrier concentration, which not only improve the electrical conductivity, but also suppress the bipolar excitation and inhibit carrier migration in the opposite direction. Moreover, the estimated thermal conductivity for the prepared thin films is low due to the enhancement of phonon scattering caused by the introduction of interfaces and defects, resulting in high ZT. A flexible device prepared by co-doped thin film represents the competitive power density of ∼ 5.47 × 102 μWcm−2 at temperature difference of 36 K. All the results confirm that hole co-doping strategy can efficiently enhance the collaborative regulations of the carrier and phonon transportation to realize high thermoelectric performance in Sb2Te3 flexible thin film.

High-Performance W-Doped Bi0.5Sb1.5Te3 Flexible Thermoelectric Films and Generators.

Bi-Sb-Te-based thermoelectric materials have the best room-temperature thermoelectric properties, but their inherent brittleness and rigidity limit their application in the wearable field. In this study, W-doped p-type Bi0.5Sb1.5Te3 (W-BST) thin films were prepared using magnetron sputtering on polyimide substrates to create thermoelectric generators (TEGs). Bending tests showed that the thin film has excellent flexibility and mechanical durability, meeting the flexible requirements of wearable devices. W doping can significantly increase the carrier concentration, Seebeck coefficient, and electrical conductivity of BST thin films. At 300 K, the power factor of the W-BST film is 2.25 times higher than that of the undoped film, reaching 13.75 μW cm-1 K-2. First-principles calculations showed that W doping introduces significant impurity peaks in the bandgap, in which W d electrons remarkably hybridize with the Sb and Te p electrons, leading to an improved electrical conductivity of BST films. Furthermore, W doping significantly reduces the work function of BST films, thereby improving the carrier mobility. A TEG module fabricated from four layers of W-BST thin films achieved a maximum output power density of 6.91 mW cm-2 at a temperature difference of 60 K. Application tests showed that the flexible TEG module could power a portable clock using the temperature difference between body temperature and room temperature. At a medium temperature of 439 K, the assembled TEG module can provide a stable output voltage of 1.51 V to power a LED. This study demonstrates the feasibility of combining inorganic thermoelectric materials with flexible substrates to create high-performance flexible TEGs.

Effects of working pressure during magnetron sputtering on thermoelectric performance of flexible p-type Bi0.5Sb1.5Te3 thin films

The influence of argon working pressure during magnetron sputtering on thermoelectric properties has been investigated on p-type Bi0.5Sb1.5Te3 flexible films deposited at various working pressures in the range from 2 to 5 Pa. The microstructure and orientations, atomic compositions, and carrier concentration could be regulated by adjusting the working pressure, due to the size-dependent inhibition of the deposition of the sputtered Bi, Sb, and Te atoms from argon ions. Profiting from the occurrence of the (006) orientation, the nearest stoichiometric ratio, the highest carrier concentration and mobility, and the quantum confinement effect, the film deposited at 4 Pa displays the maximum power factor of 1095 μW m−1 K−2 at 360 K. These results suggest that the electrical transport properties of the sputtered flexible thermoelectric thin films can be synergistically optimized by selecting an appropriate working pressure.

Transparent and flexible thermoelectric thin films based on copper sulfides

As a promising thermoelectric material, CuS has attracted significant attention due to its high conductivity, abundance of elements, and eco-friendliness. However, the study on CuS-based thermoelectric thin films is still lacking, impeding the advancement of CuS-based thermoelectric devices. Herein, high-quality CuS thin films have been fabricated through a facile vulcanization process. The effects of vulcanization temperature and film thickness on the thermoelectric properties of CuS thin films have been investigated. An optimal high power factor of 73.25 μW/m−1 K−2 is found at 400 K for a 20 nm-thick sample, and the optical transmittance is over 80% in the visible light spectrum. Meanwhile, excellent flexibility of the CuS thin films has been demonstrated. These results demonstrate the high promise of CuS thin films for transparent and flexible thermoelectric device applications.

Largely enhanced performance of Cu2Se film by doping sulfur for flexible thermoelectric generators

Herein, a facile method to prepare flexible S-doped Cu2Se thermoelectric films on porous nylon membranes is developed. First, S-doped Cu2Se powders with nominal compositions of Cu2Se1-xSx (x = 0, 0.02, 0.04, or 0.06) are synthesized by a hydrothermal method. Then, the as-prepared powders are deposited onto nylon substrates by vacuum-assisted filtration and hot-pressing. By adjusting the amount of S doping, the carrier concentration and mobility of the films are tuned, and the thermoelectric properties of the films are effectively optimized. As a result, the Cu2Se0.96S0.04 film displays a highest power factor of ∼662.2 μW m−1 K−2 at 300 K, representing one of the highest values reported for Cu2Se-based flexible films. The film also exhibits excellent flexibility (after 1500 bending cycles around a 4 mm radius rod, 90.8% of the initial electrical conductivity is retained). Additionally, a six-leg flexible thermoelectric generator is assembled with the Cu2Se0.96S0.04 film and outputs a peak power of 1.89 μW at a temperature difference of 23.1 K. This work presents a new method for preparing cost-effective and high-performance Cu2Se flexible thermoelectric films.

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu3SbSe4-Based Flexible Hybrid Films.

Fabrication of large-sized inorganic nanosheets is an efficient strategy to promote carrier transportation in flexible thermoelectric (TE) films. Herein, we report the self-assembly of large-sized Cu3SbSe4 nanosheets by using a Se nanowire template via wet chemical synthesis and then vacuum-assisted filter these plate-like microcrystals on nylon to prepare Cu3SbSe4 flexible thermoelectric (TE) hybrid films. SEM reveals that the as-synthesized Cu3SbSe4 powders by using Se nanowires as selenium sources presented 2D plate-like micron structures uniformly and tightly self-assembled by acute triangle-like nanoparticles. Furthermore, XPS evidences that extra Sb vacancies are generated in the unit cell of Cu3SbSe4 crystals synthesized by using the Se NW template, resulting in the shrinkage of the unit cell and the narrowing interplanar spacing, which are characterized by XRD and TEM. As a result, both carrier concentration and carrier mobility have been significantly improved. The high carrier concentration is proved to originate from the extra carriers induced by Sb vacancies, and the high carrier mobility of the film is mainly ascribed to its continuous grain boundaries in the plate-like microcrystal morphology. The large-sized nanosheet Cu3SbSe4/nylon hybrid film (CSS MPs) exhibits a high power factor (PF) of 235.45 μW m-1 K-2 at 400 K, which is 4.23 times higher than that of the Cu3SbSe4/nylon hybrid film (CSS NPs) where Cu3SbSe4 crystals are synthesized by using raw Se particles. This work reveals a novel approach to prepare plate-like Se-based semiconductors, which requires both high carrier concentration and high carrier mobility.

Flexible Ag2Se Thermoelectric Films Enable the Multifunctional Thermal Perception in Electronic Skins.

Skin is critical for shaping our interactions with the environment. The electronic skin (E-skin) has emerged as a promising interface for medical devices to replicate the functions of damaged skin. However, exploration of thermal perception, which is crucial for physiological sensing, has been limited. In this work, a multifunctional E-skin based on flexible thermoelectric Ag2Se films is proposed, which utilizes the Seebeck effect to replicate the sensory functions of natural skin. The E-skin can enable capabilities including temperature perception, tactile perception, contactless perception, and material recognition by analyzing the thermal conduction behaviors of various materials. To further validate the capabilities of constructed E-skins, a wearable device with multiple sensory channels was fabricated and tested for gesture recognition. This work highlights the potential for using flexible thermoelectric materials in advanced biomedical applications including health monitoring and smart prosthetics.

Flexible Thermoelectric Films with Different Ag2Se Dimensions: Performance Optimization and Device Integration

Flexible Thermoelectric Films with Different Ag₂Se Dimensions: Performance Optimization and Device Integration

Vacuum filtration method towards flexible thermoelectric films

Thermoelectric (TE) conversion technology can directly exploit the temperature difference of several Kelvin between the human body and the environment to generate electricity, which provides a self-powered solution for wearable electronics. Flexible TE materials are increasingly being developed through various methods, among which the vacuum filtration method stands out for its unique advantages, attracting the favor of researchers. It has been proven to construct flexible TE thin films with excellent performance effectively. This paper presents a comprehensive overview and survey of the advances of the vacuum filtration method in producing flexible TE thin films. The materials covered in this study include conducting polymer-based materials, carbon nanoparticle-based materials, inorganic materials, two-dimensional materials, and ternary composites. Finally, we explore potential research outlooks and the significance of flexible films, which are at the forefront of research in TE materials science.

Two-step surface treatment of femtosecond laser irradiation and ionic liquid to enhance thermoelectric properties of PEDOT:PSS films

Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has garnered significant considerable interest in the field of flexible thermoelectric films owing to its very low thermal conductivity, highly adjustable electrical conductivity (σ) and Seebeck coefficient (S). However, improving the σ and S of PEDOT:PSS simultaneously remains challenging for achieving efficient thermoelectrics. In this paper, we proposed a two-step process involving femtosecond laser irradiation and ionic liquid (IL) 1-Ethyl-3-MethylImidazolium DiCyAmide treatment to enhance the thermoelectric properties of PEDOT: PSS thin films. This finding revealed that the increase in PEDOT: PSS conductivity was attributed to both laser irradiation and the post-treatment with IL, in which the former enabled the efficient elimination of insulating PSS from the surface of the conductive polymer, the latter further contributed to the decoupling of PEDOT and PSS. The enhanced Seebeck coefficient was due to the ion exchange resulting from IL post-processing, which regulated the PEDOT doping level. By employing laser irradiation and surface treatment with IL, the modified PEDOT:PSS films showed a S of 20.63 μV·K−1, a σ of 960.7 S·cm−1, and a power factor (PF) of 40.89 μW·m−1·K−2. Furthermore, a thermoelectric device was developed which can generate a voltage of 0.8 mV at a temperature difference of 11.7 K.

Magnetic ordering boost excellent thermoelectric performance of flexible films

The poor electrical transport performance of flexible thermoelectric (TE) films is a major bottleneck for the development of in-plane heat dissipation technology based on Peltier effect. Herein, ordered Fe nanoparticles (Fe-NPs) and in-situ Fe3O4 nanoparticles (Fe3O4-NPs) as magnetic functional elements (MFEs) were embedded into Bi0·5Sb1·5Te3 (BST)/epoxy flexible films in order to enhance the TE performance. The remarkable increases in electrical conductivity of BST/MFEs/BST/epoxy flexible films have been confirmed to originate from the carrier mobility increases. The retention of large Seebeck coefficient is attributed to the negative magnetoresistance (MR−) induced by spin-dependent scattering and weak localization effect from MFEs. As a result, the maximum power factor of BST/MFEs/BST/epoxy flexible films increased by 45%, and the maximum cooling temperature difference enhanced by 1.6 times. This work reveals that the ordered MFEs can significantly boost the electro-thermal conversion performance of flexible TE films and the magnetoresistance theory can reveal the scattering mechanism of charge carriers in thermo-electromagnetic flexible films.

Preparation, morphology and thermoelectric performance of PEDOT/CuI nanocomposites

Incorporating inorganic nanomaterials into a polymer matrix is one of the most effective ways to create thermoelectric performance for applications where physical flexibility is essential. In this study, flexible thermoelectric nanocomposite films were synthesized by incorporating inorganic copper iodide (CuI) nanosheets as the filler into poly (3,4-ethylene dioxythiophene): poly (styrene sulfonate) (PEDOT: PSS). The process involved the preparation of bulk CuI from precursors and, subsequently, the nanosheet synthesis by dissolving the bulk CuI in dimethyl sulfoxide (DMSO). The morphology of the nanosheets and the nanocomposite films was thoroughly examined, and the film’s thermoelectric performance was evaluated using a standard thermoelectric measurement system, ZEM-3. The morphological observation revealed a triangular nanosheet geometry for CuI, with an average lateral dimension of ~33 nm. The PEDOT/CuI nanocomposite films were prepared by mixing CuI nanosheets with PEDOT: PSS through ultrasonication and filtration on a PVDF membrane. The film with 6.9 vol% of CuI nanosheets exhibited an electrical conductivity and Seebeck coefficient of 852.07 S·cm-1 and 14.95 µV·K-1, respectively. This resulted in an enhanced power factor of 19.04 µW·m-1·K-2, much higher than the individual composite components. It demonstrated a trend of increasing power factor with the nanosheets up to 6.9 vol% due to improved electrical conductivity. The increase in electrical conductivity can be attributed to the screening effect induced by DMSO, which leads to a conformational change in the PEDOT chains. Furthermore, an optimal fraction of CuI nanosheets also contributes to this conformational change, further enhancing the electrical conductivity.Graphical

High-Performance Ag2Se Film by a Microwave-Assisted Synthesis Method for Flexible Thermoelectric Generators.

Flexible Ag2Se thermoelectric (TE) films are promising for wearable applications near room temperature (RT). Herein, a Ag2Se film on a nylon membrane with high TE performance was fabricated by a facile method. First, Ag2Se powders were prepared by a microwave-assisted synthesis method using Ag nanowires as a template. Second, the Ag2Se powders were deposited onto nylon via vacuum filtration followed by hot pressing. Through modulating the Ag/Se molar ratio for synthesizing the Ag2Se powders, an optimized Ag2Se film demonstrates a high power factor of 1577.1 μW m-1 K-2 and good flexibility at RT. The flexibility of the Ag2Se film is mainly attributed to the flexible nylon membrane. In addition, a six-leg flexible TE generator (f-TEG) fabricated with the optimized Ag2Se film exhibits a maximum power density of 18.4 W m-2 at a temperature difference of 29 K near RT. This work provides a new solution to prepare high-TE-performance flexible Ag2Se films for f-TEGs.

Enhanced thermoelectric performance of Bi2Te3 by carbon nanotubes and silicate aerogel co-doping toward ocean energy harvesting

In this work, we propose a doped-modified thermoelectric generator (TEG) film and apply it to an ocean energy harvesting prototype that primarily utilizes ocean thermal energy. Firstly, A new Bi2Te3-based thermoelectric material with improved performance was synthesized by doping Bi2Te3 with Carbon nanotubes (CNTs) for their high electrical conductivity and Silica aerogel for their low thermal conductivity. Subsequently, a performance-optimized, flexible thermoelectric film was fabricated using electron printing technology. By combining the flexible thermoelectric film with a Triboelectric nanogenerator (TENG) and Electromagnetic generator (EMG), a hybrid energy harvesting prototype was developed that can harvest marine renewable energy. The prototype demonstrates a relatively high output voltage of 61 V and an output power of 81.2 μW, corresponding to a power density of 8.1 W/m3 in simulated marine environmental experiments. This ocean-oriented hybrid energy prototype based on co-doped thermoelectric materials unveils new possibilities for self-powered devices in the field of ocean energy harvesting.

Flexible Thermoelectric Films Based on Bi2Te3 Nanowires and Boron Nitride Nanotube Networks with Carbon Doping.

Energy recovery and reuse, industrial waste heat, and thermal energy recovery and conversion in emerging electronic devices are topics of widespread interest. Flexible composite thermoelectric (TE) films have become the key to TE conversion, and many studies and synthesis methods related to them have made great progress. However, little research has been performed on the corresponding composites of typical TE materials with low-dimensional nanotubular materials, particularly modulation of the overall TE properties using doped low-dimensional nanotubular materials. In this work, high-quality bismuth telluride (Bi2Te3) nanowires and boron nitride nanotubes (BNNTs) were prepared using electrolytic deposition and high-temperature catalytic deposition, respectively. Bi2Te3-BNNTs composite films were prepared using a solvent hot pressing method. The Bi2Te3-BNNTs composite film conductivity reached 179.6 S/cm at room temperature (300 K), the corresponding Seebeck coefficient was 171.4 μV/K, and the power factor (PF) was 52.8 nW/mK2. Carbon doping of BNNTs resulted in carbon-boron nitride nanotubes (BCNNTs), and Bi2Te3-BNNTs composite films were prepared. The Bi2Te3-BCNNTs composite films obtained a conductivity of 4629.6 S/cm, at room temperature (300 K), a corresponding Seebeck coefficient of 181.2 μV/K, and a PF of 1520.0 nW/mK2. This study has important reference value for the application of TE conversion. Moreover, the electrical conductivity decreased by no more than 10% after 400 cycles of bending tests, and the electrical conductivity showed signs of recovery after repressing thermally, which undoubtedly proves that Bi2Te3-BCNNTs composite films have good flexibility and thermal stability, and this has contributed to the application and promotion of flexible thermoelectric materials.