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Herein, we demonstrate a method of intravascular catheter-based extrusion of hydrogels with in situ photomodulation to dynamically adjust the hydrogel properties utilizing a custom catheter setup. A novel UV-integrated microcatheter (luminal diameter 0.9 mm) was assembled and a suite of low-viscosity, shear thinning hydrogel precursors were formulated for delivery. We show that by modulating the precursor flow rate (up to 0.2 ml/min) as well as the UV power (0–37.5 mW), we can extrude hydrogels with viscosities dynamically varying from

Bioderived cellulose nanocrystals (CNCs) are used to create light, flexible, biocompatible, and biodegradable electronic devices. Herein, surface modification of cellulose nanocrystals was employed to fabricate cationic and anionic CNCs. Subsequently, we demonstrated rectification behavior from a fixed junction between two agarose hydrogels doped with cationic and anionic cellulose nanocrystals. The current rectification ratio reaches 70 reproducibly, which is significantly higher than that for analogous diodes generated with microfibrillated cellulose (∼15) and the first polyelectrolyte gel diode (∼40). The current-voltage characteristics of the CNC-hydrogel diode are influenced by concentration, gel thickness, scanning frequency, and applied voltage. The high surface area of CNC resulted in high charge density after surface modification, which in turn resulted in good rectification behavior from only small amounts of dopant material.

Flexible and stretchable capacitive pressure sensors have been developed in recent years due to their potential applications in health monitoring, robot skins, body activity measurements and so on. In order to enhance sensor sensitivity, researchers have changed structure of the dielectric of parallel plate capacitive sensor . Here we enhance the sensor sensitivities by changing electrode composition and explore the use of a woven electrode structure sensor with silver coated nylon yarn and EcoflexTM. The woven structure enhanced sensitivity 2.3 times relative to a simple cross-grid geometry (sensitivity was 0.003 kPa-1). Furthermore, it is also observed that the sensor with the woven electrode also had better repeatability and showed less creep than a device using carbon black electrodes. The woven structure of the electrodes enabled the device to be compliant, despite the presence of the stiff nylon fibres – thereby enabling good sensitivity without the creep seen in softer electrodes.

Electronically conducting polymer (ECP) actuators and sensors are ionic EAPs, whose working principle relies on the motion of ions, usually contained in an electrolyte, toward or from the electroactive polymer. We demonstrate here that linear deformation and sensing in open-air are accessible for ionic EAPs if classical trilayer devices are made electromechanically asymmetric by tuning the properties of PEDOT:PSS electrodes according to an electromechanical model. We also present the first results on “dry” ionic conducting membranes based on polymeric ionic liquids. This “dry” electrolyte allows developing ionic EAPs without any liquid component and still presenting large and fast bending deformation

Supercoiled polymer (SCP) actuators have shown promising applicability as artificial muscles due to their low-cost, high strains (10%+), work density that is more than 100 x that of muscle, and non-hysteretic behavior. Here, we present a lightweight, low-cost, SCP-actuated valve that operates by pinching rubber tubing closed. The valve comprises a 3D printable frame and incorporates a pulley system, which functions to reduce the total linear dimensions of the device. The actuator mechanism is compatible with different tubing diameters and materials and, by nature of its design, is isolated from direct contact with the working fluid. Using 1/4”/6.3 mm inside diameter latex tubing, a flow rate of up to 88 L/h and a holding pressure of over 29.4 kPa are demonstrated. The valve is normally open and takes 10 seconds to close by running a current through the coiled, silver-coated nylon actuator. An empirical model of the system is developed and open-loop control incorporated, which effectively reduced valve activation time by 30%. Further developments are suggested to achieve a faster response and pumping action.

International audience; Modelling trilayer conducting polymer is still challenging as it exhibits interrelated coupled multiscale and non-linear characteristics. Therefore, this work proposes to review the underlying electro-chemo-mechanical principles in ultrathin PEDOT trilayer ionic conducting polymers based upon internal ion charge transport, conduction phenomena, redox process and elastic deformation. Microscale governing equations are first analyzed and the choice of appropriate assumptions depending of the used material is discussed. Since exact analytical solutions can be so far given only for some limited conditions, numerical solutions are developed to solve the problem. Then simulations in both sensing and actuating are successfully compared with experiments.

International audience

We address a challenge in the engineering of proteins to redirect electron transfer pathways, using the bacterial photosynthetic reaction centre (RC) pigment–protein complex. Direct electron transfer is shown to occur from the QA quinone of the Rhodobacter sphaeroides RC containing a truncated H protein and bound on the quinone side to a gold electrode. In previous reports of binding to the quinone side of the RC, electron transfer has relied on the use of a soluble mediator between the RC and an electrode, in part because the probability of QB quinone reduction is much greater than that of direct electron transfer through the large cytoplasmic domain of the H subunit, presenting a ~ 25 A barrier. A series of C-terminal truncations of the H subunit were created to expose the quinone region of the RC L and M proteins, and all truncated RC H mutants assembled in vivo. The 45M mutant was designed to contain only the N-terminal 45 amino acid residues of the H subunit including the membrane-spanning α-helix; the mutant RC was stable when purified using the detergent N-dodecyl-β-d-maltoside, contained a near-native ratio of bacteriochlorophylls to bacteriopheophytins, and showed a charge-separated state of $${{\text{P}}^{\text{+}}}{{\text{Q}}_{\text{A}}^-}$$ . The 45M-M229 mutant RC had a Cys residue introduced in the vicinity of the QA quinone on the newly exposed protein surface for electrode attachment, decreasing the distance between the quinone and electrode to ~ 12 A. Steady-state photocurrents of up to around 200 nA/cm2 were generated in the presence of 20 mM hydroquinone as the electron donor to the RC. This novel configuration yielded photocurrents orders of magnitude greater than previous reports of electron transfer from the quinone region of RCs bound in this orientation to an electrode.

The electronic and ionic conductivities of conducting polymers can change as a function of oxidation state, and yet, these properties are not generally considered in modeling the electrochemistry and electrochemically driven actuation of these materials. These effects can be significant particularly over large ranges of oxidation state and in long films where electrical contact is made from one end. In this study, a transmission line model is implemented, in which conductivities vary as a function of local oxidation state, with this variation being based on measured values. Our time-domain model is based on a 2-D RC transmission line model implemented using a state-space representation. Voltage drop along the length of the film away from the attachment point and the variation in electronic conductivity with state of charge along this length necessitated the use of a 2-D nonlinear model to obtain effective predictions of response for the film dimension used. The general approach demonstrated may be applied to any situation where properties vary with position and oxidation state, such as in batteries and supercapacitors. The last step showed the successful application of the model to predict actuation of a polypyrrole linear actuator.

Electronic Conducting Polymers (ECP) have been widely studied in a tri-layer configuration as soft, bending actuators. These electroactive materials have also been reported to behave as mechanical strain sensors able to convert mechanical stimulation into electrical signals. This sensing behavior is attributed to the so-called piezoionic effect and is observed and reported in most ionic electroactive polymers (EAPs). However, ambiguities remain on the origin of this effect, being attributed either to stress gradient induced ion motion or to Donnan potentials arising at the ECP/electrolyte interface. In this work, the sensor mechanism of trilayer ECP actuators is studied and discussed as a function of different physical and chemical parameters thanks to the versatile synthesis of conducting interpenetrating polymer networks. Results demonstrate that the main mechanism relies on stress gradient, as in other ionic EAPs, instead of Donnan potential. Moreover, a deep investigation of the electrolyte nature and its concentration is performed. Mobile ions deduced from actuation experiments are correlated with the sign of voltage output during sensing experiments. An interesting inversion point is demonstrated at 2.5 M using 1-ethyl-3-methylimidazolium bis-(trifluoromethyl-sulfonyl)-imide electrolyte in propylene carbonate concentration where simultaneous charge compensation (no sensing) and volume compensation (no actuation) occur for mobile cations and anions, while electrochemical behaviour remains unchanged.

JIF=4.806; International audience; Low cost soft, flexible and stretchable sensors are being explored that can be applied to virtually any surface, and promise to enable tactile sensing on robots, prosthetics, skin and stretchable displays. Previous work has shown that capacitive sensors that are both stretchable and transparent can be created by using ionically conductive hydrogel electrodes. In this study, the electrodes are interpenetrating polymer networks swollen with ionic liquid, enabling high transparency and stretchability, without evaporation. The interpenetrating network is synthesized from poly(ethylene oxide) and nitrile butadiene rubber. Electrodes are patterned using femtosecond laser machining, creating stretchable electrodes. These were encapsulated in a polydimethylsiloxane substrate, producing a 95% transparent sensor (450 nm). A 4x4 tactile array shows the ability to sense proximity and multi-touch, as well as be robust to variations in environmental temperature (from 4 °C to 72 °C). Temperature change has a large effect on the resistance of the electrodes - an effect that could be used to measure device temperature. In addition, the sensor is able to detect proximity and touch while on skin, when covered by a layer of fabric or during stretch.

Metals and glass are excellent for containing electrolytes and liquids in general, but their rigid mechanics limits their application for mechanically active ionic actuators or flexible/ stretchable electrochemical devices such as batteries and supercapacitors. In this study, we evaluate the performance of spray-coated poly (styrene-block-isobutylene-block-styrene) (SIBS) as a stretchable encapsulant, which suggests that it offers a better combination of compliance and impermeability than any other barrier. We examined the drying time of 360-&micro, m thick encapsulated tri-layer conducting polymer (CP) actuators, comprised of poly(3,4-Ethylenedioxythiophene) (PEDOT) as the CP electrode and an interpenetrated polymer network of polyethylene oxide (PEO) and nitrile butadiene rubber (NBR) as the separator layer, which operates with a 1 M solution of Lithium bis(trifluoromethanesulfonyl)imide (Li+TFSI&minus, ) in propylene carbonate (PC). A 100-&micro, m thick SIBS encapsulation layer is anticipated to help these devices to retain 80% of stored PC for more than 1000 times longer compared to when there is no encapsulation (from less than 0.5 days to over 1.5 years). This low permeability combined with the low Young&rsquo, s modulus of the SIBS film, its biocompatibility, biostability, and FDA approval, as well as ease of fabrication, make this thermoplastic elastomer a promising candidate as an encapsulant for flexible ionic devices such as flexible batteries and supercapacitors, ionic-electrode capacitive sensors, and ionically electroactive actuators. This paves the way for using these devices in implantable and in vivo applications.

The low voltage operation and relatively high strain response of conducting polymer actuators has made their use in tubular actuators such as actively steerable catheter tips of interest. Previous work has shown that bending can be achieved by simply coating a commercial catheter with conducting polymer and patterning. However, these actuators require an external electrolyte to operate. This work presents instead a self-contained tubular actuator in which all ion conduction between active polymer layers occurs internally. The conducting polymer PEDOT provides the active deformation to control its maneuverability and actuation. To form the body of the actuator and an electrolyte medium to enable transfer of ions during the actuation of conducting polymer, a highly ionically conductive interpenetrating polymer network composed of ionically conductive polyethylene oxide and stretchable nitrile butadiene rubber (NBR) is used. This compliant medium also enables a tight radius of curvature. Laser micromachining is used to pattern PEDOT on the surface. A 0.95 mm diameter device is shown to achieve a 22 mm radius of curvatures under activation of 2 V. A closed form beam bending model for tubular trilayer actuators is derived which predicts the radius of curvature as a function of applied voltage and free strain. This model enables easy prediction of deflection, as is demonstrated.

JIF=3.543; International audience; Trilayer conducting polymer actuators are potential alternatives to piezoelectric and electrostatic actuators due to their large strain, and recently demonstrated operation at hundreds of Hertz. However, these actuators exhibit nonlinear electrical and mechanical properties as a function of their oxidation state, when operated over their full strain range, making it more challenging to accurately predict their mechanical behavior. In this paper, an analytical multi-physics model of the conducting polymer actuators is proposed to predict their non-linear dynamic mechanical behavior. To demonstrate the accuracy of the model, a trilayer actuator composed of a solid polymer electrolyte sandwiched between two poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes was fabricated and characterized. This system consists of an electrical subsystem represented by an RC equivalent circuit, an electro-mechanical coupling matrix, and a mechanical subsystem described by using a rigid finite element method. The electrical conductivity and the volumetric capacitance, an empirical strain-to-charge ratio, and Young's modulus of the actuator as a function of the PEDOT electrode charge state were also implemented into the model, using measured values. The proposed model was represented using a Bond Graph formalism. The concordance between the simulations and the measurements confirmed the accuracy of the model in predicting the non-linear dynamic electrical and mechanical response of the actuators. In addition, the information extracted from the model also provided an insight into the critical parameters of the actuators and how they affect the actuator efficiency, as well as the energy distribution including dissipated, stored, and transferred energy. These are the key parameters for designing, optimizing, and controlling the actuation behavior of a trilayer actuator.

Trilayer conducting polymer (CP) actuators are potential alternatives to piezoelectric and electrostatic actuators due to their large strain, and recently demonstrated operation at hundreds of Hertz. However, these actuators exhibit nonlinear electrical and mechanical properties as a function of their oxidation state, when operated over their full strain range, making it more challenging to accurately predict their mechanical behavior. In this paper, an analytical multiphysics model of the CP actuators is proposed to predict their nonlinear dynamic mechanical behavior. To demonstrate the accuracy of the model, a trilayer actuator composed of a solid polymer electrolyte sandwiched between two poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes was fabricated and characterized. This system consists of an electrical subsystem represented by an RC equivalent circuit, an electro-mechanical coupling matrix, and a mechanical subsystem described by using a rigid finite element method. The electrical conductivity and the volumetric capacitance, an empirical strain-to-charge ratio, and Young’s modulus of the actuator as a function of the PEDOT electrode charge state were also implemented into the model, using measured values. The proposed model was represented using a bond graph formalism. The concordance between the simulations and the measurements confirmed the accuracy of the model in predicting the nonlinear dynamic electrical and mechanical response of the actuators. In addition, the information extracted from the model also provided an insight into the critical parameters of the actuators and how they affect the actuator efficiency, as well as the energy distribution including dissipated, stored, and transferred energy. These are the key parameters for designing, optimizing, and controlling the actuation behavior of a trilayer actuator.

An integrated solar energy conversion and storage system is presented using a dye sensitized electrode in a redox battery structure. A stable discharge voltage is shown with high areal energy storage capacity of 180 µW h cm−2 by choosing iodide/polysulfide as the pair of active materials matched with permeable porous electrodes. The solar rechargeable battery system offers a higher round-trip efficiency and potential cost savings on fabrication compared to individual devices.

A novel pressure sensor is proposed exhibiting generative properties from displacement-induced ionic charge separation in gel electrolytes. A mechano-ionic or ‘piezo-ionic’ effect, in analogy to the well-known piezoelectric effect, is hypothesized to originate from a difference in mobilities between cationic and anionic species causing a localized ionic charge gradient upon application of pressure. This gradient can be detected as a voltage or current by using copper electrodes placed at the sides or at regular intervals along a surface of the gel. The voltage generated may be a result of the local concentration gradient induced by the deformation of the gel or perhaps is the result of some ions moving faster through the porous gel than others. In this work, ionic polymer gels based on Poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) co-polymer were synthesized in situ to incorporate an organic electrolyte consisting of bis(trifluoromethane)sulfonimide lithium salt in propylene carbonate. With two electrodes placed under the gel, the samples were subjected to a sinusoidal mechanical force while open circuit voltage was measured to determine the relationship between electrical signal and mechanical input. The voltages generated are 10’s of mV in magnitude at 1 kPa. Results suggest a maximum sensitivity of 25 μV/Pa at 10 mHz, comparable to the voltages expected in piezoelectric polymers such as PVDF (44 μV/Pa for similar dimensions). The non-aqueous, solid-state ionic gels presented in this work provide improved stability and is less prone to evaporation than its aqueous, hydrogel based counterpart. The new mechanism of sensing provides an alternative to the more rigid and less stretchable piezoelectric sensors.

Several studies have been reported on the development of controllable catheters in the biomedical field. Electronic conductive polymers (ECP) actuators appeared to be among the most suitable systems thank to their biocompatibility, low operating potential (± 2V) with a reasonable deformation (2%)[1–3]. Electroactive catheters, especially in neurosurgery, should have two levels of properties: strong deformations tip in order to reach, for example the aneurysms and sweep the total volume of the pouch, and sufficient rigid middle part for getting forward in the tortuous vessels network. We designed an electroactive catheter, constituted of two parts with different deformation ability and modulus. The high deformations tip can be obtained with a weak modulus actuator. On the other hand, the second part needs to possess high modulus where small deformations are sufficient. In this work, interpenetrating polymer networks (IPN) will be used as the structural material of the catheter. The IPN architecture allows the synthesis of actuators containing the ions necessary for the redox process and thus avoiding any interference of the position control due to the exchange with the ions from the physiological medium. In addition, the fact that the catheter can be synthesized in a customized way allows modulating its mechanical properties. By introducing a rigid polystyrene network into a specific part of the actuator, it is possible to locally increase the rigidity of the device while keeping reasonable deformation. First, we will describe the synthesis and the characterization of a beam shape actuators with different local stiffnesses. Then, the first steps for the elaboration of tubular actuator will be presented.

Electrochemical actuators operating in open-air are trilayer electrochemical devices based on an ionically conducting membrane sandwiched between two electrodes of electronic conducting polymers (ECP). Tuning functional properties of the actuator, i.e. the output force, is demonstrated via the modification of the ECP’s surrounding macromolecular architecture. Theoretical models have suggested that the output force of trilayer actuators is related to the Young’s modulus of the electrodes. As a consequence, we designed Interpenetrating Polymer Network (IPN) membranes combining three different polymer networks with a co-continuous morphology to act as a host matrix for ECP electrodes. Each of these polymer networks is chosen for a specific role: (i) poly(ethylene oxide) network providing ionic transport medium within the ECP electrodes, (ii) Nitrile Butadiene Rubber providing endurance, flexibility and robustness to the final device and (iii) polystyrene to increase the Young’s modulus of the ECP electrodes. The synthesized IPNs have been thoroughly characterized. The performances of resulting actuators have been assessed. The output force is almost doubled due to the stiffening effect of the polystyrene phase, as predicted by the beam theory.

Electronic conducting polymer based-actuators have attracted lots of interest as alternative materials to traditional piezoelectric and electrostatic actuators. Their specific characteristics such as their low operating voltages and large strains should allow them to adapt better to soft microstructures. Recently, poly (3,4-ethylenedioxythiophene) (PEDOT) e based ionic actuators have overcome some initial stumbling blocks to widespread applications in the microfabricated devices field. These trilayer bending microactuators were fabricated (i) by sequential stacking, using a layer by layer polymerization (LbL) of conducting polymer electrodes and a solid polymer electrolyte and (ii) by micro-patterning, using standard microsystems processes. While microfabrication processing of a trilayer actuator, involving no manual handling has been demonstrated, their bending performances remain limited for practical applications. Moreover, the complete characterization of their electrical, electrochemical, and mechanical properties has never been investigated. This paper describes the optimization of PEDOT electroactive electrodes synthesized with a vapor phase polymerization process. Influence of synthesis parameters on thickness, electronic conductivity and volumetric charge density were studied to determine the guidelines for synthesizing highly efficient electrodes. Afterwards, these parameters are used to guide the LbL synthesis process of ultrathin trilayer actuators. Electrochemical and mechanical properties of the resulting microactuators have been thoroughly characterized. Bending deformation and output force generation have been measured and reached 0.5% and 11 mN respectively. This constitutes the first characterization of ionic PEDOT-based microactuators operating in air of such a thin thickness (11 mm dry and 18.3 mm swelled in 1-Ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMImTFSI)). These actuators and their actuation properties are promising for future soft microsystem devices where the use of polymer actuators should be essential.

At the mention of nylon, you may think of shirts, stockings, fishing line, and sutures. A recent discovery, first reported in February 2014 in Science, is that the strong, tough, and inexpensive threads that make up fabrics and filaments can actively contract and expand?with much greater force than muscle [1]. This newly discovered musclelike action creates opportunities in medical devices?among other areas?that are just beginning to be explored.

Diverse means have been deployed for harvesting electrical energy from mechanical actuation produced by low-grade waste heat, but cycle rate, energy-per-cycle, device size and weight, or cost have limited applications. We report the electromagnetic harvesting of thermal energy as electrical energy using thermally powered torsional and tensile artificial muscles made from inexpensive polymer fibers used for fishing line and sewing thread. We show that a coiled 27 μm-diameter nylon muscle fiber can be driven by 16.7 °C air temperature fluctuations to spin a magnetic rotor to a peak torsional rotation speed of 70 000 rpm for over 300 000 heating–cooling cycles without performance degradation. By employing resonant fluctuations in air temperature of 19.6 °C, an average output electrical power of 124 W per kg of muscle was realized. Using tensile actuation of polyethylene-based coiled muscles and alternating flows of hot and cold water, up to 1.4 J of electrical energy was produced per cycle. The corresponding per cycle electric energy and peak power output, per muscle weight, were 77 J kg−1 and 28 W kg−1, respectively.

Ionic resistance is often a rate limiting factor in electrochemical systems such as batteries, supercapacitors, and ionic polymer actuators. Such cells typically contain laminated and interpenetrated structures consisting of one or two electronically conductive layers and an ionically conductive separator layer. Here we analyze the role of electrodes in determining ionic resistance, and study the effects of interpenetrating ionic and electronically conducting phases. We also show that conducting polymer electrodes that are polymerized on separator layers, as have been applied to create actuators, supercapacitors and electrochromic device, can be widely and unevenly distributed through the device. Swept sine and DC measurements are used with a four-point diffusion cell probe to characterize the phase dependent ionic impedances in 1. polypyrrole (PPy) coated polyvinylidene fluoride (PVDF) and 2. poly(ethylene dioxythiophene) (PEDOT) interpenetrated poly(ethylene oxide) (PEO) − nitrile butadiene rubber (NBR) co-polymer with various PEDOT content levels. A finite Warburg-based model is introduced to explain the frequency dependence, enabling a time constant for ion transport within membrane to be estimated. It is found that the separator layers in the composite membranes are shorted at higher frequencies (10 ∼ 100 Hz). This effect is likely due to interpenetration of the electronic phases into the bulk of the separator layers, providing a means of reducing internal resistance and increase power at short times. Finally, a non-uniform impedance distribution model is introduced to predict the effective composite ionic conductivity in terms of the ionic conductivities of each phase, and their non-uniform volume fractions. Taken together, the approaches presented provide a means of probing the influence of ionic conductivities of various phases on the rate of charging in electrochemical devices.

Fast actuation of conducting polymer trilayers has been achieved by reducing the thickness of the device to as little as 6 μm. Reducing size also reduces force and displacement. Here the tradeoffs between speed of response, force and deformation angle are explored, and related to an example application – a tactile feedback interface that aims to make use of the very high sensitivity of our fingertip skin to vibrations of about 150 Hz. In general, the actuation rate in these devices is limited by the speed of charging, and by inertia. Here we use an established transmission line model to simulate charging speed. By making use of the empirical relationship between strain and charge, and using beam bending theory, the extent of charging enables estimation of the degree of actuator deformation and the forces that can be generated. In seeking to achieve non-resonant actuation at frequencies of 150 Hz or more, while also generating the forces and displacements needed for tactile stimulation, it is found that electronic and ionic conductivities of the conducting polymer electrodes needs to be on the order of 24,000 S/m and 0.04 S/m, respectively. These values along with the required dimensions appear to be feasible.

The purpose of this study is to find an optimal mixture ratio of the platinum-loaded carbon catalyst and the electrolyte in a membrane electrode assembly (MEA) of a proton exchange membrane fuel cell for reducing the activation resistance, which influences the electrochemical surface area, activation polarization, and maximum power density of the MEA. First, mixture ratios of 10, 20, 40, and 60 wt% platinum-loaded carbon catalysts and electrolyte were examined. The results indicated that the fuel cell performance improved for mixing weight ratios of 1.0:2.0 in 10 wt% Pt/C, 1.0:1.8 in 20 wt% Pt/C, 1.0:1.1 in 40 wt% Pt/C, and 1.0:0.5 in 60 wt% Pt/C. Next, we evaluated the activation resistances of the MEA from the AC impedance characteristics using the optimal mixing weight ratio of the platinum-loaded carbon catalyst and the electrolyte. It was found that the activation resistances of the anode and cathode decrease with an increase in the weight ratio of platinum-loaded carbon in the catalyst layer.

Electrochemical double-layer capacitors (EDLCs) are devices that store enormous amounts of charge electrostatically when a potential is applied between electrodes of very high surface area (typically made of porous carbon) and an electrolyte. Wider commercialization of this technology has been held back by the lack of ultralow-cost electrode materials. We demonstrate that used coffee grounds can be processed to form low-cost electrodes. The surface and electrochemical characteristics of microporous activated carbons from used coffee grounds (CGCs) were measured. First, optimal times and temperatures for carbonization and activation were identified on the basis of Brunauer–Emmett–Teller (BET) surface area, pore volume, and pore size distribution. Second, CGCs were used as polarized electrodes in EDLCs, whose capacitances were evaluated using cyclic voltammetry. The results show that carbonization for 1 h at 600 °C with a heating rate of 300 °C/h, followed by CO2 activation for 2 h at 1000 °C, affords the highest BET surface area (1867 m2/g) compared to other works. The produced CGCs have many micropores of less than 2 nm across, which contribute to the formation of an electric double layer. Capacitors made using these CGCs show the highest capacitance (103 F/g) in 0.8 M (C2H5)4NBF4/PC as an organic electrolyte, which is much higher than the ∼80 F/g typically used in organic-electrolyte-based commercial EDLCs, suggesting that coffee grounds are a useful electrode material. © 2014 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.

Highly efficient light absorption and charge separation within the photosystem and reaction center (RC) complexes of photosynthetic plants and bacteria are of great interest for solar cell and photo detector applications, since they offer almost unity quantum yield and expected ultimate power conversion efficiencies of more than 18% and 12%, respectively. In addition, the charge separated states created by these protein complexes are very long lived compared to conventional semiconductor solar cells. In this work, a novel technique is presented for the deposition of photosynthetic protein complexes, by electrospraying RCs of Rhodobacter sphaeroides onto highly ordered pyrolytic graphite (HOPG) electrodes. Remarkably, it is shown that the RCs not only survive exposure to the high electric fields but also yield peak photocurrent densities of up to 7 μA cm−2, which is equal to the highest value reported to date.

The rate of charging of supercapacitor and battery electrodes is often limited by the transport of ions through the active electrode material. One way to accelerate this transport is to increase the porosity of the electrode, at the cost of electrode capacity. This tradeoff is studied through the fabrication and characterization of porous carbon nanofibre/polypyrrole films used as storage electrodes. Electrospun poly (acrylonitrile-co-acrylamide) fibres were carbonized and then electrochemically coated with variable amounts of polypyrrole. The resulting hybrid materials were characterized using both conventional methods such as cyclic voltammetry, electron microscopy and conductivity, as well as ionic conductivity and pulsed-field-gradient nuclear magnetic resonance which directly probe ion transport. It is found that with modest porosity, these materials retain much of the capacitance (∼50%) of bulk polypyrrole with dramatically increased (∼300 times) charge and discharge rates, suggesting the potential of the approach for increasing the useful frequency range of polypyrrole-based supercapacitors, as well as other storage materials whose porosity can be varied. Simple transport models based on series or parallel arrangements of electrolyte and active electrode are developed to explain the results and identify the factors limiting charge/discharge rates.

Electrodes that selectively exchange charge with only certain redox couples in a mixture could improve the performance of photogalvanic and bio-photovoltaic cells described in the literature. One avenue to achieve selectivity is through the use of semiconducting rather than metallic electrodes to exploit the presence of the bandgap to control reaction rates. In this paper, Fluorine doped Tin oxide (F:SnO2), Copper(II) oxide (CuO) and Nickel oxide (NiO) electrodes are investigated as a means to achieving selective redox reactions. The reactions of methyl viologen, ferricyanide/ferrocyanide and ferric/ferrous couples on the three semiconducting electrodes were studied using cyclic voltammetry and sampled current voltammetry. The rate of electron transfer between the electrodes and the redox couples depended on the difference between the semiconductor majority carrier band edge and the standard redox potential of the redox couple. Most noticeably, the rate constant of methyl viologen on F:SnO2 was two orders of magnitude higher than that for the ferric/ferrous ion. Similar results were obtained with the NiO electrode while electrochemical instability hampered the tests of the CuO electrode.

In this work, use of the galvanostatic intermittent titration technique to extract lithium ion diffusion coefficients in tin thin films is studied. The measured results are first analyzed under the traditional solid solution assumptions. The change of phase in the electrode is then modeled using a moving boundary model, which more accurately predicts the potential transients during the galvanostatic pulse.

Polypyrrole and other conducting polymers are of interest in actuators, sensors, energy storage devices and organic electronics. The patterning of these polymers can be challenging, particularly polypyrrole due to its insolubility. This paper reports the first micropatterning of polypyrrole using high-frequency pulses of extremely miniaturized electrical discharge. Microstructures with surface roughness of 70 nm are produced in the polymer with sub-micron depth control. Patterning of polypyrrole film deposited on a commercial medical catheter is demonstrated toward enabling smart catheters that use the patterned film as integrated actuators. This novel micropatterning capability opens up new possibilities for polypyrrole and likely other polymers, promoting micro-device applications for them.

A new gene expression system was developed in Rhodobacter sphaeroides, replacing a pRK415-based system used previously. The broad host-range IPTG-inducible plasmid pIND4 was used to create the plasmid pIND4-RC1 for expression of the puhA and pufQBALMX genes, encoding the reaction centre (RC) and light-harvesting complex 1 (LH1) proteins. The strain R. sphaeroides ΔRCLH was used to make a knockout of the rshI restriction endonuclease gene, enabling electroporation of DNA into the bacterium; a subsequent knockout of ppsR was made, creating the strain R. sphaeroides RCx lacking this oxygen-sensing repressor of the photosynthesis gene cluster. Using pIND4-RC1, LH1 levels were increased by a factor of about 8 over pRS1 per cell in cultures grown semi-aerobically. In addition, the ppsR knockout allowed for photosynthetic pigment-protein complex synthesis in the presence of high concentrations of molecular oxygen; here, LH1 levels per cell increased by 20 % when grown under high aeration conditions. A new medium (called RLB) is the E. coli medium LB supplemented with MgCl2 and CaCl2, which was found to increase growth rates and final cell culture densities, with an increase of 30 % of LH1 per cell detected in R. sphaeroides RCx(pIND4-RC1) grown in RLB versus LB medium. Furthermore, cell density was about three times greater in RLB compared to semi-aerobic conditions. The combination of all the modifications resulted in an increase of LH1 and RC per mL of culture volume by approximately 35-fold, and a decrease in the length of culture incubation time from about 5 days to ~36 h.

Metal nanowires are twisted to form yarns that are strong (0.4 to 1.1 GPa), pliable, and more conductive (3 × 106 S m−1) than carbon nanotube yarns. Niobium nanowire fibers are extracted by etching a copper-niobium nano-composite material fabricated using the severe plastic deformation process. When impregnated with paraffin wax, the niobium (Nb) nanowire yarns produce fast rotational actuation as the wax is heated. The heated wax expands, untwisting the yarn, which then re-twists upon cooling. Normalized to yarn length, 12 deg mm−1 of torsional rotation was achieved along with twist rates in excess of 1800 rpm. Tensile modulus of 19 ± 5 GPa was measured for the Nb yarns, which is very similar to those of carbon multiwalled nanotubes.

International audience; Conducting polymer actuators have long been of interest as an alternative to piezoelectric and electrostatic actuators due to their large strains and low operating voltages. Recently, poly (3,4-ethylenedioxythiophene) (PEDOT) - based ionic actuators have been shown to overcome many of the initial obstacles to widespread application in micro-fabricated devices by demonstrating stable operation in air and at high frequencies, along with microfabrication compatible processing using a layer by layer method that does not require any handling. However, there is still a need for characterization, prediction, and control of the actuator behavior. This paper describes the fabrication and characterization of thin trilayers composed of a 7 mu m thick solid polymer electrolyte (SPE) sandwiched between two 2.1 mu m thick PEDOT-containing layers. Beam properties including capacitance, elastic moduli of the layers, and the extent of charge driven strain, are applied to predict curvature, frequency response and force generation. The actuator is represented by an electrical circuit, a mechanical system described via dynamic beam theory, and a strain-to-charge ratio for the electro-mechanical coupling matrix, which together predict the actuator curvature and the resonant response. The success of this physical model promises to enable design and control of micro-fabricated devices.

There is increasing interest in creating bendable and stretchable electronic interfaces that can be worn or applied to virtually any surface. The electroactive polymer community is well placed to add value by incorporating sensors and actuators. Recent work has demonstrated transparent dielectric elastomer actuation as well as pressure, stretch or touch sensing. Here we present two alternative forms of sensing. The first uses ionically conductive and stretchable gels as electrodes in capacitive sensors that detect finger proximity. In this case the finger acts as a third electrode, reducing capacitance between the two gel electrodes as it approaches, which can be detected even during bending and stretching. Very light finger touch is readily detected even during deformation of the substrate. Lateral resolution is achieved by creating a sensor array. In the second approach, electrodes placed beneath a salt containing gel are able to detect ion currents generated by the deformation of the gel. In this approach, applied pressure results in ion currents that create a potential difference around the point of contact, leading to a voltage and current in the electrodes without any need for input electrical energy. The mechanism may be related to effects seen in ionomeric polymer metal composites (IPMCs), but with the response in plane rather than through the thickness of the film. Ultimately, these ionically conductive materials that can also be transparent and actuate, have the potential to be used in wearable devices.

JIF=2.963; International audience; With the recent growing interest for soft actuation, many new types of ionic polymers working in air have been developed. Due to the interrelated mechanical, electrical, and chemical properties which greatly influence the characteristics of such actuators, their behavior is complex and difficult to understand, predict and optimize. In light of this challenge, an original linear multiphysics finite difference bond graph model was derived to characterize this ionic actuation. This finite difference scheme was divided into two coupled subparts, each related to a specific physical, electrochemical or mechanical domain, and then converted into a bond graph model as this language is particularly suited for systems from multiple energy domains. Simulations were then conducted and a good agreement with the experimental results was obtained. Furthermore, an analysis of the power efficiency of such actuators as a function of space and time was proposed and allowed to evaluate their performance.

A stretchable, transparent touch pad and proximity sensor made using silicone and gel operates while being bent and stretched., The development of bendable, stretchable, and transparent touch sensors is an emerging technological goal in a variety of fields, including electronic skin, wearables, and flexible handheld devices. Although transparent tactile sensors based on metal mesh, carbon nanotubes, and silver nanowires demonstrate operation in bent configurations, we present a technology that extends the operation modes to the sensing of finger proximity including light touch during active bending and even stretching. This is accomplished using stretchable and ionically conductive hydrogel electrodes, which project electric field above the sensor to couple with and sense a finger. The polyacrylamide electrodes are embedded in silicone. These two widely available, low-cost, transparent materials are combined in a three-step manufacturing technique that is amenable to large-area fabrication. The approach is demonstrated using a proof-of-concept 4 × 4 cross-grid sensor array with a 5-mm pitch. The approach of a finger hovering a few centimeters above the array is readily detectable. Light touch produces a localized decrease in capacitance of 15%. The movement of a finger can be followed across the array, and the location of multiple fingers can be detected. Touch is detectable during bending and stretch, an important feature of any wearable device. The capacitive sensor design can be made more or less sensitive to bending by shifting it relative to the neutral axis. Ultimately, the approach is adaptable to the detection of proximity, touch, pressure, and even the conformation of the sensor surface.

Poly(3,4-ethylenedioxythiophene) (PEDOT) is formed inside a metal–organic framework (MOF). MOF removal leads to sub-millimetre structures of the nanostructured conducting polymer., Reactions inside the pores of metal–organic frameworks (MOFs) offer potential for controlling polymer structures with regularity to sub-nanometre scales. We report a wet-chemistry route to poly-3,4-ethylenedioxythiophene (PEDOT)–MOF composites. After a two-step removal of the MOF template we obtain unique and stable macroscale structures of this conductive polymer with some nanoscale regularity.