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Thermoelectric (TE) materials can have a strong benefit to harvest thermal energy if they can be applied to large areas without losing their performance over time. One way of achieving large-area films is through hybrid materials, where a blend of TE materials with polymers can be applied as coating. Here, we present the development of all solution-processed TE ink and hybrid films with varying contents of TE Sb 2 Te 3 and Bi 2 Te 3 nanomaterials, along with their characterization. Using (1-methoxy-2-propyl) acetate (MPA) as the solvent and poly (methyl methacrylate) as the durable polymer, large-area homogeneous hybrid TE films have been fabricated. The conductivity and TE power factor improve with nanoparticle volume fraction, peaking around 60-70% solid material fill factor. For larger fill factors, the conductivity drops, possibly because of an increase in the interface resistance through interface defects and reduced connectivity between the platelets in the medium. The use of dodecanethiol (DDT) as an additive in the ink formulation enabled an improvement in the electrical conductivity through modification of interfaces and the compactness of the resultant films, leading to a 4-5 times increase in the power factor for both p-and n-type hybrid TE films, respectively. The observed trends were captured by combining percolation theory with analytical resistive theory, with the above assumption of increasing interface resistance and connectivity with polymer volume reduction. The results obtained on these hybrid films open a new low-cost route to produce and implement TE coatings on a large scale, which can be ideal for driving flexible, large-area energy scavenging technologies such as personal medical devices and the IoT.
ACS applied materials & interfaces, 2017
In this work, flexible Te films have been synthesized by electrochemical deposition using PEDOT [poly(3,4-ethylenedioxythiophene)] nanofilms as working electrodes. The Te electrodeposition time was varied to find the best thermoelectric properties of the Te/PEDOT double layers. To show the high quality of the Te films grown on PEDOT, the samples were analyzed by Raman spectroscopy, showing the three Raman active modes of Te: E1, A1, and E2. The X-ray diffraction spectra also confirmed the presence of crystalline Te on top of the PEDOT films. The morphology of the Te/PEDOT films was studied using scanning electron microscopy, showing a homogeneous distribution of Te along the film. Also an atomic force microscope was used to analyze the quality of the Te surface. Finally, the electrical conductivity and the Seebeck coefficient of the Te/PEDOT films were measured as a function of the Te deposition time. The films showed an excellent thermoelectric behavior, giving a maximum power fact...
2020
Hybrid thermoelectric flexible films based on poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles and carbon nanotubes were prepared by using layer-by-layer (LbL) assembly. The employed PEDOT nanoparticles were synthesized by oxidative miniemulsion polymerization by using iron(III) p-toluenesulfonate hexahydrate (FeTos) as an oxidant and poly(diallyldimethylammonium chloride) (PDADMAC) as stabilizer. Sodium deoxycholate (DOC) was used as a stabilizer to prepare the aqueous dispersions of the carbon nanotubes. Hybrid thermoelectric films were finally prepared with different monomer/oxidant molar ratios and different types of carbon nanotubes, aiming to maximize the power factor (PF). The use of single-wall (SWCNT), double-wall (DWCNT), and multiwall (MWCNT) carbon nanotubes was compared. The Seebeck coefficient was measured by applying a temperature difference between the ends of the film and the electrical conductivity was measured by the Van der Pauw method. The best hybrid film...
Coatings, 2019
Hybrid thermoelectric flexible films based on poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles and carbon nanotubes were prepared by using layer-by-layer (LbL) assembly. The employed PEDOT nanoparticles were synthesized by oxidative miniemulsion polymerization by using iron(III) p-toluenesulfonate hexahydrate (FeTos) as an oxidant and poly(diallyldimethylammonium chloride) (PDADMAC) as stabilizer. Sodium deoxycholate (DOC) was used as a stabilizer to prepare the aqueous dispersions of the carbon nanotubes. Hybrid thermoelectric films were finally prepared with different monomer/oxidant molar ratios and different types of carbon nanotubes, aiming to maximize the power factor (PF). The use of single-wall (SWCNT), double-wall (DWCNT), and multiwall (MWCNT) carbon nanotubes was compared. The Seebeck coefficient was measured by applying a temperature difference between the ends of the film and the electrical conductivity was measured by the Van der Pauw method. The best hybrid film in this study exhibited a PF of 72 µW m −1 K −2. These films are prepared from aqueous dispersions with relatively low-cost materials and, due to lightweight and flexible properties, they are potentially good candidates to recover waste heat in wearable electronic applications.
Scientific reports, 2016
Screen printing allows for direct conversion of thermoelectric nanocrystals into flexible energy harvesters and coolers. However, obtaining flexible thermoelectric materials with high figure of merit ZT through printing is an exacting challenge due to the difficulties to synthesize high-performance thermoelectric inks and the poor density and electrical conductivity of the printed films. Here, we demonstrate high-performance flexible films and devices by screen printing bismuth telluride based nanocrystal inks synthesized using a microwave-stimulated wet-chemical method. Thermoelectric films of several tens of microns thickness were screen printed onto a flexible polyimide substrate followed by cold compaction and sintering. The n-type films demonstrate a peak ZT of 0.43 along with superior flexibility, which is among the highest reported ZT values in flexible thermoelectric materials. A flexible thermoelectric device fabricated using the printed films produces a high power density ...
Advanced Materials Interfaces, 2020
light-emitting diode displays, [7] "green electronics," [8] thermoelectric materials, [9] and chemical sensors. [10] Although ICPs have contributed significantly to recent technological advances, there are limitations associated with their applications. This is partially due to the insolubility of ICPs in various industrial solvents, thereby complicating the methods that can be applied to process the polymers. [11] It is difficult to process these conductive polymers into thin films with the properties required for practical applications. One promising solution in overcoming this dilemma is vapor phase polymerization (VPP), which is a simple method that involves coating a conductive thin film onto substrates of various shapes. [12] Production of several ICP thin films via VPP have been reported since the introduction of PPy thin films in the late 1980s. [13] Compared with conventional liquid-phase polymerization, ICP layers that have been produced using VPP are almost free of agglomerations, and are smooth and are conformably homogenous. [14] Elucidation of the functional film growth mechanism will provide innovative fundamental data to design the aforementioned advanced next-generation devices from a material perspective. To achieve the desired properties for specific applications, a deeper understanding of the mechanisms that cause growth during VPP is required. The major limitations in achieving this include insufficient information and insignificant attention paid to the mechanism by which the oxidant layer interacts with the monomer (as vapor). This has resulted in significant debates to ascertain whether the growth mechanism is a "top-down" or "bottom-up" process. According to the kinetic growth mechanism with respect to the production of conductive thin films, the polymerization rate is determined by the reaction kinetics. [15] There are two recognized growth mechanisms involving the development of ICPs as thin films, namely the top-down process [16-18] and the bottom-up process. [11,19,20] The top-down approach, which was proposed by Nair et al., [17] describes the situation where polymerization occurs either on the surface of the oxidant layer or within the bulk oxidant. In In recent times, there have been debates to ascertain whether the growth mechanism in vapor phase polymerization is a top-down or a bottom-up process. The objective of the present study is to identify the formation mechanisms of the organic-inorganic hybrid film prepared in the gaseous phase on the basis of the practical importance of the hybridization of materials. To this end, poly(3,4-ethylenedioxythiophene)-SiO 2 conductive hybrid films with different layered structures are successfully fabricated. The growth mechanism of the layered organic-inorganic conductive hybrid thin film is elucidated by investigating the variations in the morphological and chemical compositions of its surface. Additionally, a cross-sectional analysis is performed using a scanning electron microscope-energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The results indicate a "bottom-up" growth mechanism, wherein the oxidant diffused through the recently formed layer, generating novel layers; this ultimately leads to formation of the organic-inorganic conductive hybrid film. Moreover, the optoelectronic and mechanical properties of the hybrid conductive films are precisely controlled by adjusting the order of incorporation of monomers in the process and the duration of polymerization of each monomer. Thus, this study achieves the fabrication of a mechanically robust and optically enhanced conductive hybrid film.
RSC Advances, 2015
Conjugated polymers may be used as thermoelectric materials due to their low thermal conductivity and have the advantageous characteristics of conventional polymers, such as low weight, non-toxicity and low cost. Here, a detailed investigation into the thermoelectric properties of PCDTBT films is reported. Moreover, in order to improve the thermoelectric properties of this polymer, FeCl 3 is used as a doping agent. For the most optimally doped film reported in this work, a power factor value of 24 µW m-1 K-2 is obtained at 150 °C. The different films were characterized by Wide-angle X-ray scattering (WAXS) experiments at different temperatures. In order to see the temperature effect, the thermoelectric power factor is measured as a function of temperature from (from RT to 150 °C). Thermal conductivity at room temperature is calculated with two independent methods which give values in agreement within the margin of uncertainty. The results obtained show promise and give insight to motivate future investigation into these types of carbazole derivates.
Nanomaterials
Thermoelectric (TE) materials have been considered as a promising energy harvesting technology for sustainably providing power to electronic devices. In particular, organic-based TE materials that consist of conducting polymers and carbon nanofillers make a large variety of applications. In this work, we develop organic TE nanocomposites via successive spraying of intrinsically conductive polymers such as polyaniline (PANi) and poly(3,4-ethylenedioxy- thiophene):poly(styrenesulfonate) (PEDOT:PSS) and carbon nanofillers, and single-walled carbon nanotubes (SWNT). It is found that the growth rate of the layer-by-layer (LbL) thin films, which comprise a PANi/SWNT-PEDOT:PSS repeating sequence, made by the spraying method is greater than that of the same ones assembled by traditional dip coating. The surface structure of multilayer thin films constructed by the spraying approach show excellent coverage of highly networked individual and bundled SWNT, which is similarly to what is observe...
Soft Science, 2023
Thermoelectric materials and devices have garnered significant attention in recent years due to their potential for converting waste heat into usable electricity, opening new avenues for sustainable energy harvesting. As research in the field of thermoelectric materials and devices continues to grow, so does the need for efficient and scalable fabrication methods. Among various fabrication techniques, printing methods have emerged as promising approaches to producing thermoelectric materials and devices, offering advantages such as low cost, high throughput, and design flexibility. Here, we overview the recent advances in printing methods for the fabrication of thermoelectric materials and devices. We discuss the key principles, challenges, and opportunities associated with various printing techniques, including screen printing, inkjet printing, and 3D printing, with a focus on their applications in thermoelectric materials and devices. Furthermore, we highlight the progress made in optimizing the printing parameters, ink formulations, and post-processing methods to enhance the thermoelectric performance of printed materials and devices. Finally, we provide insights into the prospects and potential research directions in the field of printing methods for thermoelectric materials and devices. This review aims to provide a comprehensive overview of the state-of-the-art printing techniques for thermoelectric materials and devices and to serve as a reference for researchers and practitioners working in this rapidly growing field.
Polymer Degradation and Stability, 2008
The thermo-oxidative stability of poly(ethylene terephthalate) (PET) and low-density polyethylene (LDPE) films, coated with organic-inorganic hybrid coatings of various compositions, has been investigated after accelerated ageing tests, in order to ascertain a possible beneficial effect of these coatings on the electrical performances of these insulating materials. The results have shown that the coating affects degradation mechanisms for both LDPE and PET. Thermo-oxidation is slow in LDPE, leading to significantly better insulating characteristics after ageing: a strong reduction of the embrittlement time was also observed. The strong increase of crystallinity upon ageing, observed for both coated and uncoated PET samples, probably dominates the effect of ageing on the electrical properties. As a consequence, only slight beneficial effects on PET electrical performances have been observed (both on conductivity and electrical strength). On the other hand, the coating has a strong effect on molecular weight changes leading to a significant increase of molecular weight for coated PET, while uncoated PET undergoes a significant decrease. This suggests that coated PET should present significantly better properties upon very long times of ageing.
Materials (Basel, Switzerland), 2017
Flexible poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/polypyrrole/paper (PEDOT:PSS/PPy/paper) thermoelectric (TE) nanocomposite films were prepared by a two-step method: first, PPy/paper nanocomposite films were prepared by an in situ chemical polymerization process, and second, PEDOT:PSS/PPy/paper TE composite films were fabricated by coating the as-prepared PPy/paper nanocomposite films using a dimethyl sulfoxide-doped PEDOT:PSS solution. Both the electrical conductivity and the Seebeck coefficient of the PEDOT:PSS/PPy/paper TE nanocomposite films were greatly enhanced from 0.06 S/cm to ~0.365 S/cm, and from 5.44 μV/K to ~16.0 μV/K at ~300 K, respectively, when compared to the PPy/paper TE nanocomposite films. The thermal conductivity of the PEDOT:PSS/PPy/paper composite film (0.1522 Wm(-1)K(-1) at ~300 K) was, however, only slightly higher than that of the PPy/paper composite film (0.1142 Wm(-1)K(-1) at ~300 K). As a result, the ZT value of the PEDOT:PSS/PPy/paper comp...
Organic Electronics, 2019
Flexible and lightweight printed thermoelectric devices are becoming increasingly attractive with the advent of ubiquitous sensing and within the context of an increasing energy demand and the associated environmental issues. In this study, flexible thermoelectric devices based on efficient solution-processed organic/hybrid thermoelectric materials have been successfully patterned. The ntype component hexylammonium titanium disulfide (TiS2(HA)x) nanocomposite reaches a ZT of 0.08 ± 0.06 at room temperature and was successfully printed on a flexible substrate using inkjet technology which yielded a functional device. The device operates in a near-ambient temperature range and retains its performance under mechanical bending, demonstrating thus the flexible properties of the device.
Progress in Organic Coatings, 2015
This work contributes to the development of a new generation of protective coatings composed of organic-inorganic materials. A silica based hybrid film was used in this work as high performance materials. The silica sol-gel film reveals enhanced thermo-mechanical properties in comparison with the pure polymer film. Herein, we demonstrate the possibility of employing cheap SiO 2 as prospective nanofillers for hybrid coatings with active thermo-mechanical properties. Organic-inorganic hybrid coatings based on polyimide and silica were synthesized through a simple physical mixing technique. 3,3 ,4,4-Biphenyltetracarboxylic dianhydride (BPDA), benzene-1,3-diamine (BDA), 3,3-oxydianiline (ODA) and SiO 2 , were used as precursors for the hybrid coatings. These hybrid coatings were deposited via spin coating onto a galvanized iron, aluminum and copper in order to study the adhesive strength. The effects induced by the silica content on the mechanical properties of the coated samples were investigated. The mechanical properties of hybrid composite were found to be enhanced compared to polyimide coating. The main objective was to observe potential improvements in the mechanical and thermal properties of PI-silica hybrid films. Morphology, and structural changes in the composite films were studied as well as adhesion and impact strength and these characteristics were compared with those of unreinforced polyimide films.
Materials Advances, 2021
Hybrid nanocomposite materials are widely being investigated due to their superior thermoelectric and mechanical properties. Due to their eco-friendly behaviour, and low cost processing, these can be utilized in flexible thermoelectric devices.
Chemical Engineering and Processing: Process Intensification, 2013
Polymer based solar cells (PSC) can be manufactured in a continuous roll to roll process as a low cost regenerative energy source. Coating ink properties and film thicknesses of 30-200 nm are challenging with respect to the manufacturing process, which itself has an important impact on film properties and cell efficiencies. In this paper we compare the large area coating methods: knife coating, slot-die coating, and spray coating with laboratory spin coating. Properties of coating inks and a viscosity model for commercial PEDOT:PSS types are discussed. The significantly smaller viscosity to surface tension ratio, of typical coating inks for PSC compared to conventional coating inks, causes a different behavior during the coating process. Wet film thickness, homogeneity, and process stability and their dependence on process parameters are addressed for each coating method. Hole-conductive and photoactive layers, consisting of polymer-fullerene and polymer-nanoparticle blends, are then compared with respect to homogeneity, AFM topography and absorption spectra. First results indicate that the coating method itself has an impact on polymer-fullerene film morphology and opto-electric properties.
Journal of Alloys and Compounds, 2019
Efficient protection against degradation process of tetrahedrite-based thermoelectric materials was obtained employing AlTiN based thin films. The coatings were deposited via reactive direct current physical vapour deposition magnetron sputtering. The composition, thermal and electrical behaviour of thin films were investigated by X-ray diffraction, energy dispersive spectroscopy associated to field emission scanning electron microscopy, thermogravimetric analyses and electrical conductivity measurements. The barrier features for oxygen protection during thermal treatment in air at 500 C were qualitatively evaluated, studying the coating behaviour over the higher operating temperature of tetrahedrite based thermoelectric devices.
Soft Science, 2022
Sticky thermoelectric (TE) materials have been inversely designed to enable the mass production of flexible TE sheets through lamination or roll-to-roll processes without using electrically conductive adhesives. They have also been demonstrated as inorganic/organic hybrid materials consisting of TE inorganic particles and low-volatilizable organic solvents to exhibit Seebeck coefficients based on the TE particles and low thermal conductivities based on the organic matrix. To achieve energy harvesting of 250 µW for driving various electric devices using voltage boosters, herein, we employ p- and n-type Bi2Te3 particles due to their high Seebeck coefficients, and cover the Bi2Te3 bodies with Au skins because the interfacial electrical resistance depends on the electrical resistance of opposing substances at the interface. After controlling the plating amount to cover the Bi2Te3 particles with Au skins, we achieve a TE power generation two orders of magnitude greater than the previous study, i.e., 255 µW on a hot plate of 110 °C with a 6 × 6 module. Overall, with input from other organic devices, like organic light-emitting diodes and dye-sensitized solar cells, this study presents a hierarchical design for TE hybrid materials that suppresses the thermal conduction by hybridizing TE particles with the organic matrix at the microscale. This reduces the electrical resistance by modifying the interfaces of the TE particles at the nanoscale and optimizes the Seebeck coefficient of TE particles at the atomic scale. To compete with solid-state TE modules with regards to power generation capacity, the hierarchical design towards a possible further two orders of magnitude improvement is also discussed.
Renewable and Sustainable Energy Reviews, 2017
These days, climate change as a motivating force for most of the researches focuses on the development of more environmentally-friendly and energy-efficient devices. In this field, thermoelectric (TE) technology has important properties rather than the other types of renewable technologies in which it requires no sunlight, moving parts, and also is freely scalable. Among using of TE materials, crystalline semiconductors attract a lot of attention (e.g.: bismuth chalcogenides and lead telluride (PbTe)); however, their usage has been restricted due to concerns regarding toxicity. Consequently, the application of low dimensional polymer-nanocomposite materials (e.g.: thin films) has been studied regarding to their low cost, non-toxic, manufacturability, and favorable thermoelectric characteristics. In this research the effects of silane products on fabrication of polymerbased TE thin films are evaluated. The results demonstrated the silane layers can ameliorate the final TE performance via the surface chemical treatment and dispersion of nanoparticles, increasing the interfaces and boundaries for phonon scattering and structural stabilities against the mechanical and thermal stresses for the fragile low-dimensional nanoparticles.
Organic Electronics, 2016
While the majority of research on organic thermoelectric generators has focused on individual devices with organic films having thicknesses of several hundred nanometers (nano-films), films with micrometer-scale thicknesses (micro-films) provide a longer thermal conduction path that results in a larger temperature gradient and higher thermoelectric voltages in modules. In this study, the properties of solution-processed nano-and microfilms of the p-type semiconductor P3HT doped with two different dopants, F 4-TCNQ and Fe 3þ-tos 3 $6H 2 O, were investigated. While doping with F 4-TCNQ resulted in high electrical conductivity only in nano-films, doping with Fe 3þ-tos 3 $6H 2 O from a 25 mM solution yielded power factors of up to~30 mWm À1 K À2 with a conductivity of 55.4 Scm À1 in microfilms. Changes in the molecular packing were compared based on X-ray diffraction, and the best operational stability in air was found for the Fe 3þ-tos 3 $6H 2 O-doped microfilms. Using Fe 3þ-tos 3 $6H 2 O as dopant, flexible thermoelectric modules with solution-processed microfilms patterned by a photo-etching technique that does not require alignment and assembly of individual devices were demonstrated, exhibiting a maximum power output of 1.94 nWK À2 for a uni-leg module with 48 elements. Analysis of the flexible module performance showed that the performance is limited by the contact resistance, which must be taken into consideration when optimizing module structure.
J. Mater. Chem. C, 2015
PEDOT-Tos is one of the conducting polymers that displays the most promising thermoelectric properties.
IEEE Sensors Journal, 2014
Energy harvesting devices based on piezoelectric, pyroelectric and thermoelectric materials offer an attractive solution for battery-and wireless sensor nodes for a range of sensor applications. Current devices are typically fabricated using semi-manual approaches leading to higher costs and reduced yields as well as significant material wastage. Powder-based thick film devices have been shown to be capable of harvesting mW-levels of power while the associated printing technologies offer commercially attractive fabrication solutions. This article provides a review of examples of recent piezoelectric, pyroelectric and thermoelectric powder-based thick film energy harvester devices and outlines potential fabrication techniques, ink compositions, and ways to reduce processing temperatures that can be used to create integrated thick film energy harvesting devices. The key to the creation of such devices is the management of thermal budgets and processing environments to ensure the functional properties of the thick films are maximised. Index Terms-Energy harvesting, environmentally friendly manufacturing techniques, materials processing, piezoelectric devices, thermoelectric devices, thick film devices.
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