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The nature of mass transport in plants has recently inspired the development of low-cost and sustainable wood-based electronics. Herein, we report a wood electrochemical transistor (WECT) where all three electrodes are fully made of conductive wood (CW). The CW is prepared using a two-step strategy of wood delignification followed by wood amalgamation with a mixed electron-ion conducting polymer, poly(3,4-ethylenedioxythiophene)–polystyrene sulfonate (PEDOT:PSS). The modified wood has an electrical conductivity of up to 69 Sm −1 induced by the formation of PEDOT:PSS microstructures inside the wood 3D scaffold. CW is then used to fabricate the WECT, which is capable of modulating an electrical current in a porous and thick transistor channel (1 mm) with an on/off ratio of 50. The device shows a good response to gate voltage modulation and exhibits dynamic switching properties similar to those of an organic electrochemical transistor. This wood-based device and the proposed working principle demonstrate the possibility to incorporate active electronic functionality into the wood, suggesting different types of bio-based electronic devices.

Osmotic energy generated from the salinity gradient is a kind of clean and renewable energy source, where the ion-exchange membranes play a critical role in its operation. The nanofluidic technique is emerging to overcome the limitations of high resistance and low mass transport of traditional ion-exchange membranes and thus improve osmotic power conversion. However, the currently reported nanofluidic materials suffer from high cost and complicated fabrication processes, which limits their practical application. Here, we report low-cost nanocellulose membranes that can be facilely prepared by a chemical cross-linking approach. The obtained membranes exhibit excellent ion transport characteristics as high-performance nanofluidic osmotic power generators. The control of cross-linker dosage enables the simultaneous tunability of the surface charge density and size of nanofluidic channels created between the interwoven cellulose nanofibrils. The maximum osmotic power generated by the membrane is reached when the cross-linker weight content is 20 wt %. Furthermore, the cross-linked nanocellulose membranes exhibit long-term working stability in osmotic energy harvesting under a wide range of pH values (3.2-9.7). This nanocellulose membrane derived from green and sustainable natural materials demonstrates a promising potential for renewable osmotic energy harvesting. Funding Agencies|Digital Cellulose Center (Swedish Innovation Agency VINNOVA); Wallenberg Wood Science Center (Knut and Alice Wallenberg Foundation); Karl-Erik Onnesjo Foundation

ACS applied materials & interfaces 14(50), 55850 - 55863 (2022). doi:10.1021/acsami.2c15514, Printed paper-based electronics offers solutions to rising energy concerns by supplying flexible, environmentally friendly, low-cost infrastructure for portable and wearable electronics. Herein, we demonstrate a scalable spray-coating approach to fabricate tailored paper poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/cellulose nanofibril (CNF) electrodes for all-printed supercapacitors. Layer-by-layer spray deposition was used to achieve high-quality electrodes with optimized electrode thickness. The morphology of these electrodes was analyzed using advanced X-ray scattering methods, revealing that spray-coated electrodes have smaller agglomerations, resulting in a homogeneous film, ultimately suggesting a better electrode manufacturing method than drop-casting. The printed paper-based supercapacitors exhibit an areal capacitance of 9.1 mF/cm$²$, which provides enough energy to power electrochromic indicators. The measured equivalent series resistance (ESR) is as low as 0.3 Ω, due to improved contact and homogeneous electrodes. In addition, a demonstrator in the form of a self-powered wearable wristband is shown, where a large-area (90 cm$²$) supercapacitor is integrated with a flexible solar cell and charged by ambient indoor light. This demonstration shows the tremendous potential for sequential coating/printing methods in the scaling up of printed wearables and self-sustaining systems., Published by Soc., Washington, DC

Eco-friendly and cost-effective materials and processes to manufacture functional substrates are crucial to further advance the area of printed electronics. One potential key component in the printed electronics platform is an electrically functionalized paper, produced by simply mixing common cellulosic pulp fibers with high-performance electroactive materials. Herein, an electronic paper including nanographite has been prepared using a standardized and scalable papermaking technique. No retention aid was needed to achieve a conducting nanographite loading as high as 50 wt %. The spontaneous retention that provides the integrity and stability of the nanographite paper, likely originates partially from an observed water-stable adhesion of nanographite flakes onto the fiber surfaces. The resulting paper exhibits excellent electrical characteristics, such as an in-plane conductivity of 107 S/cm and an areal capacitance of 9.2 mF/cm(2), and was explored as the back-electrode in printed electrochromic displays. Funding Agencies|Digital Cellulose Centre, a competence center set up by the Swedish Innovation Agency VINNOVA; consortium of Swedish forest industries; Wallenberg Wood Science Center (Knut and Alice Wallenberg Foundation); VINNOVA "EPIC" projectVinnova [2017-05413]; Karl-Erik Onnesjo Foundation

Ion selective membranes are at the heart of energy conversion and harvesting, water treatment, and biotechnologies. The currently available membranes are mostly based on expensive and non-biodegradable polymers. Here, we report a cation-selective and low-cost membrane prepared from renewable nanocellulose and 1,2,3,4-butanetetracarboxylic acid which simultaneously serves as crosslinker and source of anionic surface groups. Charge density and structure of the membranes are studied. By using different degrees of crosslinking, simultaneous control over both the nanochannel structure and surface charge concentration is achieved, which in turn determines the resulting ion transport properties. Increasing negative charge concentration via higher crosslinker content, the obtained ion conductivity reaches up to 8 mS/cm (0.1 M KCl). Optimal ion selectivity, also influenced by the solution pH, is achieved at 20 wt% crosslinker addition (with ion conductivity of 1.6 mS/cm). As regular similar to 1.4 nm nanochannels were formed at this composition, nanofluidic contribution to ion transport is likely. Funding Agencies|Digital Cellulose Centre; Wallenberg Wood Science Center (Knut and Alice Wallenberg Foundation); Karl-Erik Onnesjo Foundation; Treesearch, a collaboration platform for Swedish forest industrial research

The global efforts in electrifying our society drive the demand for low-cost and sustainable energy storage solutions. In the present work, a novel material concept was investigated to enable fabrication of several 10 meter-long rolls of supercapacitor paper electrodes on a pilot-scale paper machine. The material concept was based on cationized, cellulose-rich wood-derived fibres, conducting polymer PEDOT:PSS, and activated carbon filler particles. Cationic fibres saturated with anionic PEDOT:PSS provide a conducting scaffold hosting the activated carbon, which functions as the active charge-storage material. The response from further additives was systematically investigated for several critical paper properties. Cellulose nanofibrils were found to improve mechanical properties, while carbon black enhanced both the conductivity and the storage capacity of the activated carbon, reaching a specific capacitance of 67 F g(-1). This pilot trial shows that "classical" papermaking methods are fit for the purpose and provides valuable insights on how to further advance bio-based energy storage solutions for large-scale applications. Funding Agencies|Swedish Innovation Agency VINNOVA [2016-05193]; Swedish Foundation for Strategic Research [GMT14-0058]

Low weight, small footprint, and high performances are essential requisites for the implementation of energy storage devices within consumer electronics. One way to achieve these goals is to increase the thickness of the active material layer. In this work, carbonized and graphitized rayon felt, a cellulose-derived material, is used as a three-dimensional current collector scaffold to enable the incorporation of large amount of active energy storage materials and ionic liquid-based gel electrolyte in the supercapacitor devices. PEDOT:PSS, alone or in combination with active carbon, has been used as the active material. Three-dimensional supercapacitors with high per unit area capacitance (more than 1.1 F/cm(2)) have been achieved owing to the loading of large amount of active material in the felt matrix. Areal energy density of more than 101 mu Wh/cm(2) and areal power density of more than 5.9 mW/cm(2) have been achieved for 0.8 V operating voltage at a current density of 1 mA/cm(2). A nanographite material was found to be beneficial in reducing the internal serial resistance of the supercapacitor to lower than 1.7 omega. Furthermore, it was shown that even after 2000 times cycling test, the devices could still retain its performance with at least 88% coulombic efficiency for all the devices. All the materials are readily available commercially, environmentally sustainable and the process can potentially be upscaled with industrial process. Funding Agencies|Knut och Alice Wallenbergs Stiftelse; Onnesjo foundation; Stiftelsenfor Strategisk Forskning; VINNOVA

Nanostructured wood veneer with added electroactive functionality combines structural and functional properties into eco-friendly, low-cost nanocomposites for electronics and energy technologies. Here, we report novel conducting polymer-impregnated wood veneer electrodes where the native lignin is preserved, but functionalized for redox activity and used as an active component. The resulting electrodes display a well-preserved structure, redox activity, and high conductivity. Wood samples were sodium sulfite-treated under neutral conditions at 165 degrees C, followed by the tailored distribution of PEDOT:PSS, not previously used for this purpose. The mild sulfite process introduces sulfonic acid groups inside the nanostructured cell wall, facilitating electrostatic interaction on a molecular level between the residual lignin and PEDOT. The electrodes exhibit a conductivity of up to 203 S m(-1) and a specific pseudo-capacitance of up to 38 mF cm(-2), with a capacitive contribution from PEDOT:PSS and a faradaic component originating from lignin. We also demonstrate an asymmetric wood pseudo-capacitor reaching a specific capacitance of 22.9 mF cm(-2) at 1.2 mA cm(-2) current density. This new wood composite design and preparation scheme will support the development of wood-based materials for use in electronics and energy storage. Funding Agencies|Wallenberg Wood Science Center (Knut and Alice Wallenberg Foundation); Karl-Erik Onnesjo Foundation; Treesearch, a collaboration platform for Swedish forest industrial research

To address the rising need of sustainable solutions in electronic devices, the development of electronically conductive composites based on lightweight but mechanically strong wood structures is highly desirable. Here, a facile approach for the fabrication of highly conductive wood/polypyrrole composites through top-down modification of native lignin followed by polymerization of pyrrole in wood cell wall. By sodium sulfite treatment under neutral condition, sulfonated wood veneers with increased porosity but well-preserved cell wall structure containing native lignin and lignosulfonates are obtained. The wood structure has a content of sulfonic groups up to 343 mu mol g(-1) owing to in situ sulfonated lignin which facilitates subsequent oxidative polymerization of pyrrole, achieving a weight gain of polypyrrole as high as 35 wt%. The lignosulfonates in the wood structure act as dopant and stabilizer for the synthesized polypyrrole. The composite reaches a high conductivity of 186 S m(-1) and a specific pseudocapacitance of 1.71 F cm(-2) at the current density of 8.0 mA cm(-2). These results indicate that tailoring the wood/polymer interface in the cell wall and activating the redox activity of native lignin by sulfonation are important strategies for the fabrication of porous and lightweight wood/conductive polymer composites with potential for sustainable energy applications. Funding Agencies|Wallenberg Wood Science Center - Knut and Alice Wallenberg Foundation

The global electrification of our society requires an enormous capacity of electrical energy storage. This drives the demand for low-cost and sustainable solutions, where the electrode materials are key components. In the present work, all-organic supercapacitor electrodes have successfully been demonstrated to be produced on a pilot-scale paper machine, thereby showing the feasibility of large-scale production of “paper-based energy storage”. The material concept was based on activated charcoal from pyrolyzed coconut and cationized cellulose pulp, the latter having small amounts of electrostatically adsorbed PEDOT:PSS in order to create a conducting, percolating network. In a pre-trial lab experiment, it was evident that even small addition of 1 wt% PEDOT:PSS gave a large increase in capacitance compared to samples with only activated charcoal. In the pilot trials, the addition of carboxymethylated nanocellulose and/or carbon black was further investigated. The different additions significantly affected several paper properties such as tensile strength and conductivity, but the specific capacitance of the activated charcoal was not affected and was found to be around 65-70 F/g. As more than half of the electrodes mass consisted of pulp fibers, the specific capacitance of the paper electrodes was about 25-30 F/g, which is in the same order of commercial supercapacitor electrodes. The successful production of several 10-meter-long rolls of supercapacitor electrode paper shows the feasibility of producing energy storage devices with papermaking methods, and the work as a whole provides valuable insights on how to further advance bio-based energy storage solutions.

The dimensions of the material serving as the channel in organic electrochemical transistors (OECTs) are important for the overall switching performance. Here, a laser ablation step is included in the OECT manufacturing process, in an attempt to shorten the channel length of the OECT. The source and drain electrodes are formed by laser ablation of a previously screen printed carbon-based rectangle, which in this study resulted in an average channel length equal to 25 mu m. All other processing steps rely on screen printing, allowing for large-area manufacturing of OECTs and OECT-based circuits on flexible substrates. This approach results in a manufacturing yield of 89%; 178 out of a total of 200 OECTs exhibited an ON/OFF ratio exceeding 1000 with a statistical mean value of 28 000 and reproducible switching performance. OECT-based circuits, here demonstrated by a logic inverter, provide a reasonably high voltage gain of 12. The results thus demonstrate another reliable OECT manufacturing process, based on the combination of laser ablation and screen printing. Funding Agencies|Swedish foundation for Strategic Research (Silicon-Organic Hybrid Autarkic Systems) [SE13-0045]; Knut and Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University; European Union [825339, 964677]; onnesjo Foundation

The ongoing electrification of many energy systems has created a large demand for low-cost and scalable electrical energy storage solutions. Conducting polymer supercapacitors have received significant attention for this purpose due to the abundance of their constituent materials. Although there exists a large body of experimental work on conducting polymer supercapacitors, a detailed understanding of the mixed electronic-ionic transport processes within these devices and the included materials, is still lacking. Modelling, in combination with experimental data, is a powerful tool to facilitate a detailed understanding of the transport processes within the materials and devices. However, to date, there has been a shortage of physical models which account for the non-ideal capacitances typically found in conducting polymer-based supercapacitors. Here, we report a novel model which reproduces experimental data and provides insights into the cyclic voltammograms, galvanostatic charge-discharge curves, self-discharge characteristics, and impedance spectroscopy results of supercapacitors based on the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and cellulose nanofibrils. We find that the non-ideal capacitive characteristics of the supercapacitors can be reproduced by the incorporation of heterogeneous ion transport features within the electrodes, comprising low ion diffusivity regions. The difference in charging rates of the high and low ion diffusivity regions accounts for the experimentally observed trends in cyclic voltammograms and self-discharge characteristics. The developed model demonstrates how complex transport processes, which govern the specifications of organic energy devices, can be analysed beyond the scope of conventional equivalent circuit models. It also provides an insight into how various transport and polarization processes are manifested in real measurement data and thus defines the limiting processes of conducting polymer energy storage devices. Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Linkoping University; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research; Wallenberg Wood Science Centre

Low-voltage operating organic electronic circuits with long-term stability characteristics are receiving increasing attention because of the growing demands for power efficient electronics in Internet of Things applications. To realize such circuits, inverters, the fundamental constituents of many circuits, with stable transfer characteristics should be designed to provide low-power consumption. Here, a rational inverter design, based on fully screen printed p-type organic electrochemical transistors with a channel size of 150 x 80 mu m(2), is explored for driving conditions with input voltage levels that differs of about 1 V. Further, three different inverter circuits are explored, including resistor ladders with resistor values ranging from tens of k ohm to a few M ohm. The performance of single inverters, 3-stage cascaded inverters and 3-stage ring oscillators are characterized with respect to output voltage levels, propagation delay, static power consumption, voltage gain, and operational frequency window. Depending on the application, the key performance parameters of the inverter can be optimized by the specific combination of the input voltage levels and the resistor ladder values. A few of the inverters are in fact fully functional up to 30 Hz, even when using input voltage levels as low as (0 V, 1 V). Funding Agencies|Swedish foundation for Strategic Research (Silicon-Organic Hybrid Autarkic Systems)Swedish Foundation for Strategic Research [SE13-0045]; Knut and Alice Wallenberg Foundation (Wallenberg Wood Science Center); European UnionEuropean Commission [825339]; onnesjo Foundation

Ultrathin devices are rapidly developing for skin-compatible medical applications and wearable electronics. Powering skin-interfaced electronics requires thin and lightweight energy storage devices, where solution-processing enables scalable fabrication. To attain such devices, a sequential deposition is employed to achieve all spray-coated symmetric microsupercapacitors (mu SCs) on ultrathin parylene C substrates, where both electrode and gel electrolyte are based on the cheap and abundant biopolymer, cellulose. The optimized spraying procedure allows an overall device thickness of approximate to 11 mu m to be obtained with a 40% active material volume fraction and a resulting volumetric capacitance of 7 F cm(-3). Long-term operation capability (90% of capacitance retention after 10(4) cycles) and mechanical robustness are achieved (1000 cycles, capacitance retention of 98%) under extreme bending (rolling) conditions. Finite element analysis is utilized to simulate stresses and strains in real-sized mu SCs under different bending conditions. Moreover, an organic electrochromic display is printed and powered with two serially connected mu-SCs as an example of a wearable, skin-integrated, fully organic electronic application. Funding Agencies|European Research Council (ERC) under the European Unions Horizon 2020 research and innovation programEuropean Research Council (ERC) [949191]; city council of Brno, Czech Republic

The potential of the screen printing method for large-scale production of organic electrochemical transistors (OECTs), combining high production yield with low cost, is here demonstrated. Fully screen-printed OECTs of 1mm(2) area, based on poly(3,4-ethylenedioxythiophene) doped with poly(styrensulfonate) (PEDOT:PSS), have been manufactured on flexible polyethylene terephthalate (PET) substrates. The goal of this project effort has been to explore and develop the printing processing to enable high yield and stable transistor parameters, targeting miniaturized digital OECT circuits for large-scale integration (LSI). Of the 760 OECTs manufactured in one batch on a PET sheet, only two devices were found malfunctioning, thus achieving an overall manufacturing yield of 99.7%. A drain current ON/OFF ratio at least equal to 400 was applied as the strict exclusion principle for the yield, motivated by proper operation in LSI circuits. This consistent performance of low-footprint OECTs allows for the integration of PEDOT:PSS-based OECTs into complex logic circuits operating at high stability and accuracy. Funding Agencies|Swedish foundation for Strategic Research (Silicon-Organic Hybrid Autarkic Systems)Swedish Foundation for Strategic Research [SE13-0045]; Knut and Alice Wallenberg Foundation (Wallenberg Wood Science Center); Linkoping University; Knut and Alice Wallenberg Foundation (Wallenberg Scholars)

The increasing demands to further electrify and digitalize our society set demands for a green electrical energy storage technology that can be scaled between very small, and heavily distributed electrical energy sources, to very large volumes. Such technology must be compatible with fast-throughput, large-volume and low-cost fabrication processes, such as using printing and coating techniques. Here, we demonstrate a sequential production protocol to fabricate supercapacitors including electrodes based on cellulose nanofibrils (CNF) and the conducting polymer PEDOT:PSS. Thin and lightweight paper electrodes, carbon adhesion layers and the gel electrolyte are fabricated using spray coating, screen printing, and bar coating, respectively. These all solid-state supercapacitors are flexible, mechanically robust and exhibit a low equivalent series resistance (0.22 ohm), thus resulting in a high power density (similar to 10(4)W/kg) energy technology. The supercapacitors are combined and connected to a power management circuit to demonstrate a smart packaging application. This work shows that operational and embedded supercapacitors can be manufactured in a manner to allow for the integration with, for instance smart packaging solutions, thus enabling powered, active internet-of-things (IoT) devices in a highly distributed application. Funding Agencies|Swedish foundation for strategic researchSwedish Foundation for Strategic Research; Knut and Alice Wallenberg Foundation (Wallenberg Wood Science Center); Onnesjo foundation; Linkoping University

Precise manipulation of light-matter interactions has enabled a wide variety of approaches to create bright and vivid structural colors. Techniques utilizing photonic crystals, Fabry-Perot cavities, plasmonics, or high-refractive-index dielectric metasurfaces have been studied for applications ranging from optical coatings to reflective displays. However, complicated fabrication procedures for sub-wavelength nanostructures, limited active areas, and inherent absence of tunability of these approaches impede their further development toward flexible, large-scale, and switchable devices compatible with facile and cost-effective production. Here, a novel method is presented to generate structural color images based on monochromic conducting polymer films prepared on metallic surfaces via vapor phase polymerization and ultraviolet (UV) light patterning. Varying the UV dose enables synergistic control of both nanoscale film thickness and polymer permittivity, which generates controllable structural colors from violet to red. Together with grayscale photomasks this enables facile fabrication of high-resolution structural color images. Dynamic tuning of colored surfaces and images via electrochemical modulation of the polymer redox state is further demonstrated. The simple structure, facile fabrication, wide color gamut, and dynamic color tuning make this concept competitive for applications like multifunctional displays. Funding Agencies|Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Swedish Research Council (VR)Swedish Research Council; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Composites of biopolymers and conducting polymers are emerging as promising candidates for a green technological future and are actively being explored in various applications, such as in energy storage, bioelectronics, and thermoelectrics. While the device characteristics of these composites have been actively investigated, there is limited knowledge concerning the fundamental intracomponent interactions and the modes of molecular structuring. Here, by use of cellulose and poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), it is shown that the chemical and structural makeup of the surfaces of the composite components are critical factors that determine the materials organization at relevant dimensions. AFM, TEM, and GIVVAXS measurements show that when mixed with cellulose nanofibrils, PEDOT:PSS organizes into continuous nanosized beadlike structures with an average diameter of 13 nm on the nanofibrils. In contrast, when PEDOT:PSS is blended with molecular cellulose, a phase-segregated conducting network morphology is reached, with a distinctly relatively lower electric conductivity. These results provide insight into the mechanisms of PEDOT:PSS crystallization and may have significant implications for the design of conducting biopolymer composites for a vast array of applications. Funding Agencies|Energimyndigheten [P43561-1]; Stiftelsen far Strategisk Forskning

Demands on the storage of energy have increased for many reasons, in part driven by household photovoltaics, electric grid balancing, along with portable and wearable electronics. These are fast-growing and differentiated applications that need large volume and/or highly distributed electrical energy storage, which then requires environmentally friendly, scalable and flexible materials and manufacturing techniques. However, the limitations on current inorganic technologies have driven research efforts to explore organic and carbon-based alternatives. Here, we report a conducting polymer:cellulose composite that serves as the active material in supercapacitors which has been incorporated into all-printed energy storage devices. These devices exhibit a specific capacitance of approximate to 90 F g(-1) and an excellent cyclability (amp;gt;10 000 cycles). Further, a design concept coined supercapacitors on demand is presented, which is based on a printing-cutting-folding procedure, that provides us with a flexible production protocol to manufacture supercapacitors with adaptable configuration and electrical characteristics. Funding Agencies|Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [GMT14-0058]

The conducive polymer poly(3,4-ethylenedioxythiphene):poly(styrenesulfonate) (PEDOT:PSS) is widely used in organic electronics and printed electronics due to its excellent electronic and ionic conductivity. PEDOT:PSS films exhibit anisotropic conductivities originating from the interplay of film deposition processes and chemical structure. The previous studies found that high boiling point solvent treated PEDOT:PSS exhibits an anisotropy of 3-4 orders magnitude. Even though both the in-plane and out-of-plane conductivities are important for the device performance, the out-of-plane conductivity is rarely studied due to the complexity with the experiment procedure. Cellulose-based paper or films can also exhibit anisotropic behavior due to the combination of their intrinsic fibric structure and film formation process. We have previously developed a conducive paper based on PEDOT:PSS and cellulose which could be used as the electrodes in energy storage devices. In this work we developed a novel measurement set-up for studying the anisotropy of the charge transport in such composite materials. A tool with two parallel plates mounted with spring loaded probes was constructed enabling probing both lateral and vertical directions and resistances from in-plane and out-of-plane directions to be obtained. The measurement results were then input and analyzed with a model based on a transformation method developed by Montgomery, and thus the in-plane and out-of-plane conductivities could be detangled and derived. We also investigated how the conductivity anisotropy depends on the microstructure of the cellulose template onto which the conducive polymer self-organizes. We show that there is a relatively small difference between the in-plane and out-of-plane conductivities which is attributed to the unique 3D-structure of the composites. This new knowledge gives a better understanding of the possibilities and limitations for using the material in electronic and electrochemical devices. Funding Agencies|Swedish Foundation for Strategic Research [GMT14-0058]

The growth of renewable energy production has sparked a huge demand for cheap and large-scale electrical storage solutions. Organic supercapacitors and batteries are envisioned as one, among several, candidates for this task due to the great abundance of their constituent materials. In particular, the class of supercapacitors based on conjugated polymer-redox biopolymer composites are of great interest, since they combine the benefit of high electrical conductivity of the conducting polymers with the low cost and high specific capacitance of redox biopolymers. The optimization of such complex systems is a grand challenge and until now there have been a lack of models available to ease that task. Here, we present a novel model that combines the charge transport and impedance properties of conducting polymers with the electrochemical characteristics of redox polymers. The model reproduces a wide range of experimental data and elucidates the coupling of several critical processes within these supercapacitors, such as the double-layer capacitance, redox kinetics and dissolution/release of the redox polymer to the electrolyte. Further, the model also predicts the dependencies of the power and energy densities on the electrode composition. The developed model shows how organic supercapacitors can be analyzed beyond archetypical equivalent circuit models and thus constitutes a promising tool for further advancements and optimization within the field of research of green energy storage technology. Funding Agencies|Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation; Linkoping University; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research

Printed and flexible organic electronics is a steadily expanding field of research and applications. One of the most attractive features of this technology is the possibility of large area and high throughput production to form low-cost electronics on different flexible substrates. With an increasing demand for sustainable energy production, low-cost and large volume technologies to store high-quality energy become equally important. These devices should be environmentally friendly with respect to their entire life cycle. Supercapacitors and batteries based on paper hold great promise for such applications due to the low cost and abundance of cellulose and other forest-derived components. We report a thick-film paper-supercapacitor system based on cellulose nanofibrils, the mixed ion-electron conducting polymer PEDOT: PSS and sulfonated lignin. We demonstrate that the introduction of sulfonated lignin into the cellulose-conducting polymer system increases the specific capacitance from 110 to 230 F g(-1) and the areal capacitance from 160 mF cm(-2) to 1 F cm(-2). By introducing lignosulfonate also into the electrolyte solution, equilibrium, with respect to the concentration of the redox molecule, was established between the electrode and the electrolyte, thus allowing us to perform beyond 700 charge/discharge cycles with no observed decrease in performance. Funding Agencies|Knut and Alice Wallenberg foundation [KAW 2011.0050]; Swedish Foundation for Strategic Research [GMT14-0058]; Onnesjo Foundation; Swedish Energy Agency; Advanced Functional Materials Center at Linkoping University

State-of-the-art solar energy harvesting systems based on photovoltaic technology require constant illumination for optimal operation. However, weather conditions and solar illumination tend to fluctuate. Here, a device is presented that extracts electrical energy from such light fluctuations. The concept combines light-induced heating of gold nanodisks (acting as plasmonic optical nanoantennas), and an organic pyroelectric copolymer film (poly(vinylidenefluoride-co-trifluoroethylene)), that converts temperature changes into electrical signals. This hybrid device can repeatedly generate current pulses, not only upon the onset of illumination, but also when illumination is blocked. Detailed characterization highlights the key role of the polarization state of the copolymer, while the copolymer thickness has minor influence on performance. The results are fully consistent with plasmon-assisted pyroelectric effects, as corroborated by combined optical and thermal simulations that match the experimental results. Owing to the tunability of plasmonic resonances, the presented concept is compatible with harvesting near infrared light while concurrently maintaining visible transparency. Funding agencies: Wenner-Gren Foundations; Swedish Research Council [2015-05070]; Swedish Foundation for Strategic Research; AForsk Foundation; Royal Swedish Academy of Sciences; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Lin

Ferroelectric-coated counter electrodes control the electrochemistry of conducting polymers., Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is an organic mixed ion-electron conducting polymer. The PEDOT phase transports holes and is redox-active, whereas the PSS phase transports ions. When PEDOT is redox-switched between its semiconducting and conducting state, the electronic and optical properties of its bulk are controlled. Therefore, it is appealing to use this transition in electrochemical devices and to integrate those into large-scale circuits, such as display or memory matrices. Addressability and memory functionality of individual devices, within these matrices, are typically achieved by nonlinear current-voltage characteristics and bistability—functions that can potentially be offered by the semiconductor-conductor transition of redox polymers. However, low conductivity of the semiconducting state and poor bistability, due to self-discharge, make fast operation and memory retention impossible. We report that a ferroelectric polymer layer, coated along the counter electrode, can control the redox state of PEDOT. The polarization switching characteristics of the ferroelectric polymer, which take place as the coercive field is overcome, introduce desired nonlinearity and bistability in devices that maintain PEDOT in its highly conducting and fast-operating regime. Memory functionality and addressability are demonstrated in ferro-electrochromic display pixels and ferro-electrochemical transistors.

An understanding of the doping and ion distributions in light-emitting electrochemical cells (LECs) is required to approach a realistic conduction model which can precisely explain the electrochemical reactions, p-n junction formation, and ion dynamics in the active layer and to provide relevant information about LECs for systematic improvement of function and manufacture. Here, Fourier-transform infrared (FTIR) microscopy is used to monitor anion density profile and polymer structure in situ and for time-resolved mapping of electrochemical doping in an LEC under bias. The results are in very good agreement with the electrochemical doping model with respect to ion redistribution and formation of a dynamic p-n junction in the active layer. We also physically slow ions by decreasing the working temperature and study frozen-junction formation and immobilization of ions in a fixed-junction LEC device by FTIR imaging. The obtained results show irreversibility of the ion redistribution and polymer doping in a fixed-junction device. In addition, we demonstrate that infrared microscopy is a useful tool for in situ characterization of electroactive organic materials. Funding Agencies|Power Papers project from the Knut and Alice Wallenberg Foundation [2011-0050]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]

A supercapacitor made from organic and nature-based materials, such as conductive polymers (PEDOT:PSS), nanocellulose, and an the organic dye molecule (alizarin), is demonstrated. The dye molecule, ...

In conventional light-emitting electrochemical cells (LECs), an off-centered p-n junction is one of the major drawbacks, as it leads to exciton quenching at one of the charge-injecting electrodes and results in performance instability. To combat this problem, we have developed a new device configuration, the double-gate light-emitting electrochemical transistor (DG-LECT), in which the location of the light-emitting p-n junction can be precisely defined via the position of the two gate terminals. Based on a planar LEC structure, two gate electrodes made from an electrochemically active conducting polymer are employed to predefine the p- and n-doped area of the light-emitting polymer. Thus, a p-n junction is formed in between the p-doped and n-doped regions. We demonstrate a homogeneous and centered p-n junction as well as other predefined junction patterns in these DG-LECT devices. Additionally, we report an electrical model that explains the operation of the DG-LECTs. The DG-LECT device provides a new tool to study the fundamental physics of LECs, as it dissects the key working process of LEC into decoupled p-doping, n-doping, and electroluminescence.

Polyelectrolytes are promising electronically insulating layers for low-voltage organic field effect transistors. However, the polyelectrolyte–semiconductor interface is difficult to manufacture due to challenges in wettability. We introduce an amphiphilic semiconducting copolymer which, when spread as a thin film, can change its surface from hydrophobic to hydrophilic upon exposure to water. This peculiar wettability is exploited in the fabrication of polyelectrolyte-gated field-effect transistors operating below 0.5 V. The prepared amphiphilic semiconducting copolymer is based on a hydrophobic regioregular poly(3-hexylthiophene) (P3HT) covalently linked to a hydrophilic poly(sulfonated)-based random block. Such a copolymer is obtained in a three-step strategy combining Grignard metathesis (GRIM), atom transfer radical polymerization (ATRP) processes, and a postmodification method. The structure of the diblock copolymer was characterized using FT-IR, 1H NMR spectroscopy, and gel permeation chromatography...

Low cost and flexible devices such as wearable electronics, e-labels and distributed sensors will make the future "internet of things" viable. To power and communicate with such systems, high frequency rectifiers are crucial components. We present a simple method to manufacture flexible diodes, operating at GHz frequencies, based on self-adhesive composite films of silicon micro-particles (Si-mu Ps) and glycerol dispersed in nanofibrillated cellulose (NFC). NFC, Si-mu Ps and glycerol are mixed in a water suspension, forming a self-supporting nanocellulose-silicon composite film after drying. This film is cut and laminated between a flexible pre-patterned Al bottom electrode and a conductive Ni-coated carbon tape top contact. A Schottky junction is established between the Al electrode and the Si-mu Ps. The resulting flexible diodes show current levels on the order of mA for an area of 2 mm(2), a current rectification ratio up to 4 x 10(3) between 1 and 2 V bias and a cut-off frequency of 1.8 GHz. Energy harvesting experiments have been demonstrated using resistors as the load at 900 MHz and 1.8 GHz. The diode stack can be delaminated away from the Al electrode and then later on be transferred and reconfigured to another substrate. This provides us with reconfigurable GHz-operating diode circuits. Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Foundation for Strategic Research; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

Because solar and wind power produce electricity intermittently, electricity needs to be stored in large batteries composed of materials of high abundancy. X. Crispin and co‐workers demonstrate, in article number 1500305, that paper functionalized with a conducting polymer constitutes a promising electrode for supercapacitors, and potentially batteries. Atomic force microscopy reveals cellulose nanofibers with a conducting polymer coating, as demonstrated in the paper battery of the cover image.

A novel patterning technique of conductive polymers produced by vapor phase polymerization is demonstrated. The method involves exposing an oxidant film to UV light which changes the local chemical environment of the oxidant and subsequently the polymerization kinetics. This procedure is used to control the conductivity in the conjugated polymer poly(3,4-ethylenedioxythiophene): tosylate by more than six orders of magnitude in addition to producing high-resolution patterns and optical gradients. The mechanism behind the modulation in the polymerization kinetics by UV light irradiation as well as the properties of the resulting polymer are investigated. Funding Agencies|Knut and Alice Wallenberg Foundation [KAW 2011.0050, KAW 2014.0041, KAW 2012.0302]

Electronically conducting polymers constitute an emerging class of materials for novel electronics, such as printed electronics and flexible electronics. Their properties have been further diversified to introduce elasticity, which has opened new possibility for "stretchable" electronics. Recent discoveries demonstrate that conducting polymers have thermoelectric properties with a low thermal conductivity, as well as tunable Seebeck coefficients - which is achieved by modulating their electrical conductivity via simple redox reactions. Using these thermoelectric properties, all-organic flexible thermoelectric devices, such as temperature sensors, heat flux sensors, and thermoelectric generators, are being developed. In this article we discuss the combination of the two emerging fields: stretchable electronics and polymer thermoelectrics. The combination of elastic and thermoelectric properties seems to be unique for conducting polymers, and difficult to achieve with inorganic thermoelectric materials. We introduce the basic concepts, and state of the art knowledge, about the thermoelectric properties of conducting polymers, and illustrate the use of elastic thermoelectric conducting polymer aerogels that could be employed as temperature and pressure sensors in an electronic-skin. Funding Agencies|European Research Council (ERC) [307596]; Swedish Foundation for Strategic Research; Knut and Alice Wallenberg Foundation; Swedish Energy Agency; Advanced Functional Materials Center at Linkoping University; Research Institute of Sweden (RISE)

Poly(3,4-ethylenedioxythiophene) chemically doped with poly(styrene sulfonic acid) (PEDOT:PSS) is a material system commonly used as a conductive and transparent coating in several important electronic applications. The material is also electrochemically active and exhibits electrochromic (EC) properties making it suitable as the active element in EC display applications. In this work uniformly coated PEDOT:PSS layers were used both as the pixel electrode and as the counter electrode in EC display components. The pixel and counter electrodes were separated by a whitish opaque and water-based polyelectrolyte and the thicknesses of the two EC layers were varied independently in order to optimize the color contrast of the display element. A color contrast (ΔE∗, CIE L∗a∗b∗ color space) exceeding 40 was obtained with maintained relatively short switching time at an operational voltage less than 2 V. funding agencies|VINNOVA (research and innovation for sustainable growth in Sweden)

An electrochemical circuit to record time-temperature history has been realized by using the propagation of over-oxidation fronts in stripes of poly(3,4-ethylenedioxythiopehene) blended with poly(styrenesulfonate) (PEDOT:PSS). The over-oxidation front propagation has been characterized and related to the phase change of polyethylene glycol (PEG) electrolytes. The electrolytes were chosen to have a phase transition in the temperature interval to be monitored, resulting in large conductivity variations and thereby an easily interpreted output. A demonstrator has been fabricated and shown to detect a temperature increase and a following temperature decrease. This very simple device is cheap to produce and could be used to monitor the temperature of packages.

Solar photovoltaic technologies could fully deploy and impact the energy conversion systems in our society if mass-produced energy-storage solutions exist. A supercapacitor can regulate the fluctua ...

We report a flexible self-standing adhesive composite made from PEDOT:PSS and nanofibrillated cellulose. The material exhibits good combined mechanical and electrical characteristics(an elastic modulus of 4.4 MPa, and an electrical conductivity of 30 S cm−1 ). The inherent self-adhesiveness of the material enables it to be laminated and delaminated repeatedly to form and reconfigure devices and circuits. This modular property opens the door for a plethora of applications where reconfigurability and ease-of-manufacturing are of prime importance. We also demonstrate a paper composite with ionic conductivity and combine the two materials to construct electrochemical devices, namely transistors, capacitors and diodes with high values of transconductance, charge storage capacity and current rectification. We have further used these devices to construct digital circuits such as NOT, NAND and NOR logic.

Monolithic integration of an electrolyte-gated organic field-effect transistor (OFET) and an organic electrochromic pixel is reported. Thanks to its versatility, the polyanionic proton conductor po ...