A polymer-based textile thermoelectric generator for wearable energy harvesting

Conducting polymers offer new opportunities to design soft, conformable and light-weight thermoelectric textile generators that can be unobtrusively integrated into garments or upholstery. Using the widely available conducting polymer:polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as the p-type material, we have prepared an electrically conducting sewing thread, which we then embroidered into thick wool fabrics to form out-of-plane thermoelectric textile generators. The influence of device design is discussed in detail, and we show that the performance of e-textile devices can be accurately predicted and optimized using modeling developed for conventional thermoelectric systems, provided that the electrical and thermal contact resistances are included in the model. Finally, we demonstrate a thermoelectric textile device that can generate a, for polymer-based devices, unprecedented power of 1.2 μW at a temperature gradient ΔT of 65 K, and over 0.2 μW at a more modest ΔT of 30 K

Machine-Washable Conductive Silk Yarns with a Composite Coating of Ag Nanowires and PEDOT:PSS

Electrically conducting fibers and yarns are critical components of future wearable electronic textile (e-textile) devices such as sensors, antennae, information processors, and energy harvesters. To achieve reliable wearable devices, the development of robust yarns with a high conductivity and excellent washability is urgently needed. In the present study, highly conductive and machine-washable silk yarns were developed utilizing a Ag nanowire and PEDOT:PSS composite coating. Ag nanowires were coated on the silk yarn via a dip-coating process followed by coating with the conjugated polymer:polyelectrolyte complex PEDOT:PSS. The PEDOT:PSS covered the Ag nanowire layers while electrostatically binding to the silk, which significantly improved the robustness of the yarn as compared with the Ag nanowire-coated reference yarns. The fabricated conductive silk yarns had an excellent bulk conductivity of up to ∼320 S/cm, which is largely retained even after several cycles of machine washing. To demonstrate that these yarns can be incorporated into e-textiles, the conductive yarns were used to construct an all-textile out-of-plane thermoelectric device and a Joule heating element in a woven heating fabric

Thermally Activated in Situ Doping Enables Solid-State Processing of Conducting Polymers

Free-standing bulk structures encompassing highly doped conjugated polymers are currently heavily explored for wearable electronics as thermoelectric elements, conducting fibers, and a plethora of sensory devices. One-step manufacturing of such bulk structures is challenging because the interaction of dopants with conjugated polymers results in poor solution and solid-state processability, whereas doping of thick conjugated polymer structures after processing suffers from diffusion-limited transport of the dopant. Here, we introduce the concept of thermally activated latent dopants for in situ bulk doping of conjugated polymers. Latent dopants allow for noninteractive coprocessing of dopants and polymers, while thermal activation eliminates any thickness-dependent diffusion and activation limitations. Two latent acid dopants were synthesized in the form of thermal acid generators based on aryl sulfonic acids and an o-nitrobenzyl capping moiety. First, we show that these acid dopant precursors can be coprocessed noninteractively with three different polythiophenes. Second, the polymer films were doped in situ through thermal activation of the dopants. Ultimately, we demonstrate that solid-state processing with a latent acid dopant can be readily carried out and that it is possible to dope more than 100 μm-thick polymer films through thermal activation of the latent dopant

Sequential doping of solid chunks of a conjugated polymer for body-heat-powered thermoelectric modules

Sequential doping of 1 mm3 sized cubes of regio-regular poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-tetracyanoquinodimethane is found to result in a doping gradient. The dopant ingresses into the solid material and after two weeks of sequential doping yields a 250 μm thick doped surface layer, while the interior of the cubes remains undoped. The doping gradient is mapped with energy dispersive x-ray spectroscopy (EDX), which is used to estimate a diffusion coefficient of 1 7 10-10 cm2 s-1 at room temperature. The cubes, prepared by pressing at 150 \ub0C, feature alignment of polymer chains along the flow direction, which yields an electrical conductivity of 2.2 S cm-1 in the same direction. A 4-leg thermoelectric module was fabricated with slabs of pressed and doped P3HT, which generated a power of 0.22 μW for a temperature gradient of 10.2 \ub0C generated by body heat

Energy harvesting textiles for a rainy day: woven piezoelectrics based on melt-spun PVDF microfibres with a conducting core

Recent advances in ubiquitous low-power electronics call for the development of light-weight and flexible energy sources. The textile format is highly attractive for unobtrusive harvesting of energy from e.g., biomechanical movements. Here, we report the manufacture and characterisation of fully textile piezoelectric generators that can operate under wet conditions. We use a weaving loom to realise textile bands with yarns of melt-spun piezoelectric microfibres, that consist of a conducting core surrounded by β-phase poly(vinylidene fluoride) (PVDF), in the warp direction. The core-sheath constitution of the piezoelectric microfibres results in a—for electronic textiles—unique architecture. The inner electrode is fully shielded from the outer electrode (made up of conducting yarns that are integrated in the weft direction) which prevents shorting under wet conditions. As a result, and in contrast to other energy harvesting textiles, we are able to demonstrate piezoelectric fabrics that do not only continue to function when in contact with water, but show enhanced performance. The piezoelectric bands generate an output of several volts at strains below one percent. We show that integration into the shoulder strap of a laptop case permits the continuous generation of four microwatts of power during a brisk walk. This promising performance, combined with the fact that our solution uses scalable materials and well-established industrial manufacturing methods, opens up the possibility to develop wearable electronics that are powered by piezoelectric textiles

Roll-to-Roll Dyed Conducting Silk Yarns: A Versatile Material for E-Textile Devices

KGaA, Weinheim Textiles are a promising base material for flexible and wearable electronic applications such as sensors, actuators, and energy harvesters. An essential component in such electronic textiles (e-textiles) is electrically conducting yarns. Here, a continuous dyeing process is presented to convert an off-the-shelf silk sewing thread into a wash and wear resistant functional thread with a conductivity of about 70 S cm−1; a record high value for coated yarns. An aqueous ink based on the conducting polymer:polyelectrolyte complex poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is modified, to produce more than 100 m of dyed conducting threads, which are subsequently converted into e-textiles by both hand weaving and machine embroidery. The yarns are resistant to abrasion and wear, and can be machine washed at least 15 times with retained electronic properties. The woven fabric is used to design a capacitive touch sensor which functions as an e-textile keyboard

Bulk-Processed Plasmonic Plastic Nanocomposite Materials for Optical Hydrogen Detection

Conspectus Sensors are ubiquitous, andtheir importanceis only going to increaseacross many areas of modern technology. In this respect, hydrogengas (H-2) sensors are no exception since they allow mitigationof the inherent safety risks associated with mixtures of H-2 and air. The deployment of H-2 technologies is rapidlyaccelerating in emerging energy, transport, and green steel-makingsectors, where not only safety but also process monitoring sensorsare in high demand. To meet this demand, cost-effective and scalableroutes for mass production of sensing materials are required. Here,the state-of-the-art often resorts to processes derived from the microelectronicsindustry where surface-based micro- and nanofabrication are the methodsof choice and where (H-2) sensor manufacturing is no exception. In this Account, we discuss how our recent efforts to develop sensorsbased on plasmonic plastics may complement the current state-of-the-art.We explore a new H-2 sensor paradigm, established througha series of recent publications, that combines (i) the plasmonic opticalH(2) detection principle and (ii) bulk-processed nanocompositematerials. In particular, plasmonic plastic nanocomposite sensingmaterials are described that comprise plasmonic H-2-sensitivecolloidally synthesized nanoparticles dispersed in a polymer matrixand enable the additive manufacturing of H-2 sensors ina cost-effective and scalable way. We first discuss the concept ofplasmonic plastic nanocomposite materials for the additive manufacturingof an active plasmonic sensing material on the basis of the threekey components that require individual and concerted optimization:(i) the plasmonic sensing metal nanoparticles, (ii) the surfactant/stabilizermolecules on the nanoparticle surface from colloidal synthesis, and(iii) the polymer matrix. We then introduce the working principleof plasmonic H-2 detection, which relies on the selectiveabsorption of H species into hydride-forming metal nanoparticles that,in turn, induces distinct changes in their optical plasmonic signaturein proportion to the H-2 concentration in the local atmosphere.Subsequently, we assess the roles of the key components of a plasmonicplastic for H-2 sensing, where we have established that(i) alloying Pd with Au and Cu eliminates hysteresis and introducesintrinsic deactivation resistance at ambient conditions, (ii) surfactant/stabilizermolecules can significantly accelerate and decelerate H-2 sorption and thus sensor response, and (iii) polymer coatings acceleratesensor response, reduce the limit of detection (LoD), and enable molecularfiltering for sensor operation in chemically challenging environments.Based on these insights, we discuss the rational development and detailedcharacterization of bulk-processed plasmonic plastics based on glassyand fluorinated matrix polymers and on tailored flow-chemistry-basedsynthesis of Pd and PdAu alloy colloidal nanoparticles with optimizedstabilizer molecules. In their champion implementation, they enablehighly stable H-2 sensors with response times in the 2 srange and an LoD of few 10 ppm of H-2. To put plasmonicplastics in a wider perspective, we also report their implementationusing different polymer matrix materials that can be used for 3D printingand (an)isotropic Au nanoparticles that enable the manufacturing ofmacroscopic plasmonic objects with, if required, dichroic opticalproperties and in amounts that can be readily upscaled. We advertisethat melt processing of plasmonic plastic nanocomposites is a viableroute toward the realization of plasmonic objects and sensors, producedby scalable colloidal synthesis and additive manufacturing techniques

High-temperature creep resistant ternary blends based on polyethylene and polypropylene for thermoplastic power cable insulation

The impact of a small amount of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) on the thermomechanical and electrical properties of blends comprising low-density polyethylene (LDPE) and isotactic polypropylene (PP) is investigated. SEBS is found to assemble at the PP:LDPE interface as well as within isolated PP domains. The addition of 10\ua0wt% SEBS significantly increases the storage modulus between the melting temperatures of the two polyolefins, 110 and 160\ub0C, and results in improved resistance to creep during both tensile deformation as well as compression. Furthermore, the ternary blends display a very low direct-current (DC) conductivity as low as 3.4 7 10 \ua0S m at 70\ub0C and 30 kV mm , which is considerably lower than values measured for neat LDPE. The here presented type of ternary blend shows potential as an insulation material for high-voltage direct current power cables

All-Polymer Conducting Fibers and 3D Prints via Melt Processing and Templated Polymerization

Because of their attractive mechanical properties, conducting polymers are widely perceived as materials of choice for wearable electronics and electronic textiles. However, most state-of-the-art conducting polymers contain harmful dopants and are only processable from solution but not in bulk, restricting the design possibilities for applications that require conducting micro-to-millimeter scale structures, such as textile fibers or thermoelectric modules. In this work, we present a strategy based on melt processing that enables the fabrication of nonhazardous, all-polymer conducting bulk structures composed of poly(3,4-ethylenedioxythiophene) (PEDOT) polymerized within a Nafion template. Importantly, we employ classical polymer processing techniques including melt extrusion followed by fiber spinning or fused filament 3D printing, which cannot be implemented with the majority of doped polymers. To demonstrate the versatility of our approach, we fabricated melt-spun PEDOT:Nafion fibers, which are highly flexible, retain their conductivity of about 3 S cm(-1) upon stretching to 100% elongation, and can be used to construct organic electrochemical transistors (OECTs). Furthermore, we demonstrate the precise 3D printing of complex conducting structures from OECTs to centimeter-sized PEDOT:Nafion figurines and millimeter-thick 100-leg thermoelectric modules on textile substrates. Thus, our strategy opens up new possibilities for the design of conducting, all-polymer bulk structures and the development of wearable electronics and electronic textiles

Electrically Conducting Elastomeric Fibers with High Stretchability and Stability

Stretchable conducting materials are appealing for the design of unobtrusive wearable electronic devices. Conjugated polymers with oligoethylene glycol side chains are excellent candidate materials owing to their low elastic modulus and good compatibility with polar stretchable polymers. Here, electrically conducting elastomeric blend fibers with high stretchability, wet spun from a blend of a doped polar polythiophene with tetraethylene glycol side chains and a polyurethane are reported. The wet-spinning process is versatile, reproducible, scalable, and produces continuous filaments with a diameter ranging from 30 to 70\ua0\ub5m. The fibers are stretchable up to 480% even after chemical doping with iron(III) p-toluenesulfonate hexahydrate and exhibit an electrical conductivity of up to 7.4 S cm−1, which represents a record combination of properties for conjugated polymer-based fibers. The fibers remain conductive during elongation until fiber fracture and display excellent long-term stability at ambient conditions. Cyclic stretching up to 50% strain for at least 400 strain cycles reveals that the doped fibers exhibit high cyclic stability and retain their electrical conductivity. Finally, a directional strain sensing device, which makes use of the linear increase in resistance of the fibers up to 120% strain is demonstrated