Wider Potential Windows of Cellulose Multiwall Carbon Nanotube Fibers Leading to Qualitative Multifunctional Changes in an Organic Electrolyte.

The trend across the whole of society is to focus on natural and/or biodegradable materials such as cellulose (Cell) over synthetic polymers. Among other usage scenarios, Cell can be combined with electroactive components such as multiwall carbon nanotubes (CNT) to form composites, such as Cell-CNT fibers, for applications in actuators, sensors, and energy storage devices. In this work, we aim to show that by changing the potential window, qualitative multifunctionality of the composites can be invoked, in both electromechanical response as well as energy storage capability. Cell-CNT fibers were investigated in different potential ranges (0.8 V to -0.3 V, 0.55 V to -0.8 V, 1 V to -0.8 V, and 1.5 V to -0.8 V), revealing the transfer from cation-active to anion-active as the potential window shifted towards more positive potentials. Moreover, increasing the driving frequency also shifts the mode from cation- to anion-active. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy were conducted to determine the ion species participating in charge compensation under different conditions.

Solvent Effect in Imidazole-Based Poly(Ionic liquid) Membranes: Energy Storage and Sensing.

Polymerized ionic liquids (PILs) are interesting new materials in sustainable technologies for energy storage and for gas sensor devices, and they provide high ion conductivity as solid polymer electrolytes in batteries. We introduce here the effect of polar protic (aqueous) and polar aprotic (propylene carbonate, PC) electrolytes, with the same concentration of lithium bis(trifluoromethane) sulfonimide (LiTFSI) on hydrophobic PIL films. Cyclic voltammetry, scanning ionic conductance microscopy and square wave voltammetry were performed, revealing that the PIL films had better electroactivity in the aqueous electrolyte and three times higher ion conductivity was obtained from electrochemical impedance spectroscopy measurements. Their energy storage capability was investigated with chronopotentiometric measurements, and it revealed 1.6 times higher specific capacitance in the aqueous electrolyte as well as novel sensor properties regarding the applied solvents. The PIL films were characterized with scanning electron microscopy, energy dispersive X-ray, FTIR and solid state nuclear magnetic resonance spectroscopy.

Multifunctionality of Polypyrrole Polyethyleneoxide Composites: Concurrent Sensing, Actuation and Energy Storage.

In films of conducting polymers, the electrochemical reaction(s) drive the simultaneous variation of different material properties (reaction multifunctionality). Here, we present a parallel study of actuation-sensing-energy storage triple functionality of polypyrrole (PPy) blends with dodecylbenzenesulfonate (DBS-), PPy/DBS, without and with inclusion of polyethyleneoxide, PPy-PEO/DBS. The characterization of the response of both materials in aqueous solutions of four different salts indicated that all of the actuating, sensing and charge storage responses were, independent of the electrolyte, present for both materials, but stronger for the PPy-PEO/DBS films: 1.4× higher strains, 1.3× higher specific charge densities, 2.5× higher specific capacitances and increased ion-sensitivity towards the studied counterions. For both materials, the reaction energy, the material potential and the strain variations adapt to and sense the electrical and chemical (exchanged cation) conditions. The driving and the response of actuation, sensing and charge can be controlled/read, simultaneously, via just two connecting wires. Only the cooperative actuation of chemical macromolecular motors from functional cells has such chemical multifunctionality.

Cellulose-Multiwall Carbon Nanotube Fiber Actuator Behavior in Aqueous and Organic Electrolyte.

As both consumers and producers are shifting from fossil-derived materials to other, more sustainable approaches, there is a growing interest in bio-origin and biodegradable polymers. In search of bio-degradable electro-mechanically active materials, cellulose-multi wall carbon nanotube (Cell-CNT) composites are a focus for the development of actuators and sensors. In the current study, our aim was to fabricate Cell-CNT composite fibers and study their electro-mechanical response as linear actuators in aqueous and propylene carbonate-based electrolyte solutions. While the response was (expectedly) strongly solvent dependent, the different solvents also revealed unexpected phenomena. Cell-CNT fibers in propylene carbonate revealed a strong back-relaxation process at low frequencies, and also a frequency dependent response direction change (change of actuation direction). Cell-CNT fibers operated in aqueous electrolyte showed response typical to electrochemical capacitors including expansion at discharging with controllable actuation dependence on charge density. While the response was similarly stable in both electrolyte solution systems, the aqueous electrolytes were clearly favorable for Cell-CNT with 3.4 times higher conductivities, 4.3 times higher charge densities and 11 times higher strain.

Fabrication of Carbon-Based Ionic Electromechanically Active Soft Actuators.

Ionic electromechanically active capacitive laminates are a type of smart material that move in response to electrical stimulation. Due to the soft, compliant and biomimetic nature of this deformation, actuators made of the laminate have received increasing interest in soft robotics and (bio)medical applications. However, methods to easily fabricate the active material in large (even industrial) quantities and with a high batch-to-batch and within-batch repeatability are needed to transfer the knowledge from laboratory to industry. This protocol describes a simple, industrially scalable and reproducible method for the fabrication of ionic carbon-based electromechanically active capacitive laminates and the preparation of actuators made thereof. The inclusion of a passive and chemically inert (insoluble) middle layer (e.g., a textile-reinforced polymer network or microporous Teflon) distinguishes the method from others. The protocol is divided into five steps: membrane preparation, electrode preparation, current collector attachment, cutting and shaping, and actuation. Following the protocol results in an active material that can, for example, compliantly grasp and hold a randomly shaped object as demonstrated in the article.

Improving the Electrochemical Performance and Stability of Polypyrrole by Polymerizing Ionic Liquids.

Polypyrrole (PPy) based electroactive materials are important building blocks for the development of flexible electronics, bio-sensors and actuator devices. As the properties and behavior of PPy depends strongly on the operating environment-electrolyte, solvent, etc., it is desirable to plant immobile ionic species into PPy films to ensure stable response. A premade ionic polymer is not optimal in many cases, as it enforces its own structure on the conducting polymer, therefore, polymerization during fabrication is preferred. Pyrrole (Py) was electropolymerized at low temperature together with a polymerizable ionic liquid (PIL) monomer in a one-step polymerization, to form a stable film on the working electrode. The structure and morphology of the PPyPIL films were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared (FTIR) spectroscopy and solid-state NMR (ssNMR) spectroscopy. The spectroscopy results confirmed the successful polymerization of Py to PPy and PIL monomer to PIL. The presence of (TFSI-) anions that balance the charge in PPyPIL was confirmed by EDX analysis. The electrical properties of PPyPIL in lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) aqueous and propylene carbonate solutions were examined with cyclic voltammetry (CV), chronoamperometry, and chronopotentiometry. The blend of PPyPIL had mixed electronic/ionic conductive properties that were strongly influenced by the solvent. In aqueous electrolyte, the electrical conductivity was 30 times lower and the diffusion coefficient 1.5 times higher than in the organic electrolyte. Importantly, the capacity, current density, and charge density were found to stay consistent, independent of the choice of solvent.

Printed PEDOT:PSS Trilayer: Mechanism Evaluation and Application in Energy Storage.

Combining ink-jet printing and one of the most stable electroactive materials, PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)), is envisaged to pave the way for the mass production of soft electroactive materials. Despite its being a well-known electroactive material, widespread application of PEDOT:PSS also requires good understanding of its response. However, agreement on the interpretation of the material's activities, notably regarding actuation, is not unanimous. Our goal in this work is to study the behavior of trilayers with PEDOT:PSS electrodes printed on either side of a semi-interpenetrated polymer network membrane in propylene carbonate solutions of three different electrolytes, and to compare their electroactive, actuation, and energy storage behavior. The balance of apparent faradaic and non-faradaic processes in each case is discussed. The results show that the primarily cation-dominated response of the trilayers in the three electrolytes is actually remarkably different, with some rather uncommon outcomes. The different balance of the apparent charging mechanisms makes it possible to clearly select one electrolyte for potential actuation and another for energy storage application scenarios.

Ionic electroactive polymer artificial muscles in space applications.

A large-scale effort was carried out to test the performance of seven types of ionic electroactive polymer (IEAP) actuators in space-hazardous environmental factors in laboratory conditions. The results substantiate that the IEAP materials are tolerant to long-term freezing and vacuum environments as well as ionizing Gamma-, X-ray, and UV radiation at the levels corresponding to low Earth orbit (LEO) conditions. The main aim of this material behaviour investigation is to understand and predict device service time for prolonged exposure to space environment.