Carbon Nanotubes: High Electromechanical Response of Ionic Polymer Actuators with Controlled‐Morphology Aligned Carbon Nanotube/Nafion Nanocomposite Electrodes (Adv. Funct. Mater. 19/2010)

Recent advances in fabricating controlled‐morphology vertically aligned carbon nanotubes (VA‐CNTs) with ultrahigh volume fraction create unique opportunities for markedly improving the electromechanical performance of ionic polymer conductor network composite (IPCNC) actuators. Continuous paths through inter‐VA‐CNT channels allow fast ion transport, and high electrical conduction of the aligned CNTs in the composite electrodes lead to fast device actuation speed (>10% strain/second). One critical issue in developing advanced actuator materials is how to suppress the strain that does not contribute to the actuation (unwanted strain) thereby reducing actuation efficiency. Here, experiments demonstrate that the VA‐CNTs give an anisotropic elastic response in the composite electrodes, which suppresses the unwanted strain and markedly enhances the actuation strain (>8% strain under 4 V). The results reported here suggest pathways for optimizing the electrode morphology in IPCNCs using ultrahigh volume fraction VA‐CNTs to further enhanced performance.     

Template Synthesis of Aligned Carbon Nanotube Arrays using Glucose as a Carbon Source: Pt Decoration of Inner and Outer Nanotube Surfaces for Fuel‐Cell Catalysts

A facile method is developed to synthesize aligned arrays of open‐ended carbon nanotubes (CNTs) via in situ glucose polymerization in the inner pores of anodic aluminum oxide templates under hydrothermal conditions, followed by carbonization at high temperature. Pt nanoparticles are decorated on the surfaces of the as‐prepared CNTs using the incipient wet method based on the use of NaBH₄ as a reductant. Characterization of the resulting structures by transmission electron microscopy and field‐emission scanning electron microscopy demonstrates that the Pt nanoparticles are anchored on both the inner and outer walls of CNTs, thus giving rise to a shell–core–shell‐like nanotube composite. The electrocatalytic properties of the Pt–CNT–Pt electrodes are investigated for methanol oxidation by cyclic voltammetry and chronoamperometric measurements. It is found that the hybrid electrodes show superior catalytic performance compared to commercial carbon‐black‐supported Pt. The increased catalytic efficiency of Pt might be a result of the unique morphology of these structures.     

Metal–Organic Framework‐Derived Graphitic Nanoribbons Anchored on Graphene for Electroionic Artificial Muscles

To achieve large bending displacement and fast response time under ultralow input voltages, as well as improved durability, advanced high‐performance ionic actuators still face crucial design challenges that must be resolved. Here, hierarchically porous and unzipped graphitic nanoribbons anchored on graphene as an efficient electrode material for high‐performance electroionic artificial muscles are reported. Using controlled solvothermal and pyrolysis methods, nanoarchitectured carbon is derived from a self‐templated potassium‐based metal–organic frameworks–graphene hybrid. The newly designed ionic actuator demonstrates excellent actuation performance, including large bending displacement (17.4 mm) and a strain difference of 0.51% at 0.5 V AC input, very fast response time (700 ms) at 0.5 V DC input, wide frequency response (0.1–15 Hz), and excellent cycling stability (92%) after 25 000 cycles without any delamination of electrodes under continuous electrical operation. The breakthrough in actuation performance mainly stems from the unzipping of hollow nanorods to hierarchical porous graphitic nanoribbons anchored on graphene with the enlarged surface area, large pore volume, stronger mechanical integrity, and emerging charge storage and transport ability. Further, the electroionic actuator shows promise when applied in the demonstration of a biomimicking Venus flytrap.     

Collectively Exhaustive Electrodes Based on Covalent Organic Framework and Antagonistic Co‐Doping for Electroactive Ionic Artificial Muscles

In this study, high‐performance ionic soft actuators are developed for the first time using collectively exhaustive boron and sulfur co‐doped porous carbon electrodes (BS‐COF‐Cs), derived from thiophene‐based boronate‐linked covalent organic framework (T‐COF) as a template. The one‐electron deficiency of boron compared to carbon leads to the generation of hole charge carriers, while sulfur, owing to its high electron density, creates electron carriers in BS‐COF‐C electrodes. This antagonistic functionality of BS‐COF‐C electrodes assists the charge‐transfer rate, leading to fast charge separation in the developed ionic soft actuator under alternating current input signals. Furthermore, the hierarchical porosity, high surface area, and synergistic effect of co‐doping of the BS‐COF‐Cs play crucial roles in offering effective interaction of BS‐COF‐Cs with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), leading to the generation of high electro‐chemo‐mechanical performance of the corresponding composite electrodes. Finally, the developed ionic soft actuator based on the BS‐COF‐C electrode exhibits large bending strain (0.62%), excellent durability (90% retention for 6 hours under operation), and 2.7 times higher bending displacement than PEDOT:PSS under extremely low harmonic input of 0.5 V. This study reveals that the antagonistic functionality of heteroatom co‐doped electrodes plays a crucial role in accelerating the actuation performance of ionic artificial muscles.     

A carbon nanotube polymer-based composite with high electromagnetic shielding

A novel, polymer-based carbon nanotube (CNT) composite with high electromagnetic (EM) wave shielding effectiveness (SE) and high mechanical properties was developed. Two types of CNTs with different aspect ratios and morphologies are compared in this study. Amorphous carbon and graphite powder are used as reference materials. The liquid crystal polymer (LCP) and melamine formaldehyde (MF) are used as polymer matrices to study the orientation effect of CNTs in a polymer matrix. The influences of orientation, aspect ratio, mass fraction, and morphology of CNTs upon the shielding effectiveness (SE) of CNT/polymer composites are investigated. The experimental results show that the higher the orientation, the aspect ratio, and the weight percentage of nanomaterials are in the composite, the higher the polymer composites’ SE. The nanomaterials’ morphology, especially CNTs, also affects the SE value of the polymer composite. The highest SE for the CNT/LCP composite obtained is >62 dB. The theoretically calculated SE data are consistent with experimentally obtained data.     

Aligned Carbon Nanotube–Based Flexible Gel Substrates for Engineering Biohybrid Tissue Actuators

Muscle‐based biohybrid actuators have generated significant interest as the future of biorobotics but so far they move without having much control over their actuation behavior. Integration of microelectrodes into the backbone of these systems may enable guidance during their motion and allow precise control over these actuators with specific activation patterns. Here, this challenge is addressed by developing aligned carbon nanotube (CNT) forest microelectrode arrays and incorporating them into scaffolds for cell stimulation. Aligned CNTs are successfully embedded into flexible and biocompatible hydrogels exhibiting excellent anisotropic electrical conductivity. Bioactuators are then engineered by culturing cardiomyocytes on the CNT microelectrode‐integrated hydrogel constructs. The resulting cardiac tissue shows homogeneous cell organization with improved cell‐to‐cell coupling and maturation, which is directly related to the contractile force of muscle tissue. This centimeter‐scale bioactuator has excellent mechanical integrity, embedded microelectrodes, and is capable of spontaneous actuation behavior. Furthermore, it is demonstrated that a biohybrid machine can be controlled by an external electrical field provided by the integrated CNT microelectrode arrays. In addition, due to the anisotropic electrical conductivity of the electrodes provided by aligned CNTs, significantly different excitation thresholds are observed in different configurations such as the ones with electrical fields applied in directions parallel versus perpendicular to the CNT alignment.     

Ultrafast All‐Polymer Electrically Tunable Silicone Lenses

Dielectric elastomer actuators (DEA) are smart lightweight flexible materials integrating actuation, sensing, and structural functions. The field of DEAs has been progressing rapidly, with actuation strains of over 300% reported, and many application concepts demonstrated. However many DEAs are slow, exhibit large viscoelastic drift, and have short lifetimes, due principally to the use of acrylic elastomer membranes and carbon grease electrodes applied by hand. Here a DEA‐driven tunable lens, the world's fastest capable of holding a stable focal length, is presented. By using low‐loss silicone elastomers rather than acrylics, a settling time shorter than 175 μs is obtained for a 20% change in focal length. The silicone‐based lenses show a bandwidth 3 orders of magnitude higher compared to lenses of the same geometry fabricated from the acrylic elastomer. Stretchable electrodes, a carbon black and silicone composite, are precisely patterned by pad‐printing and subsequently cross‐linked, enabling strong adhesion to the elastomer and excellent resistance to abrasion. The lenses operate for over 400 million cycles without degradation, and show no change after more than two years of storage. This lens demonstrates the unmatched combination of strain, speed, and stability that DEAs can achieve, paving the way for complex fast soft machines.     

Iron–Nitrogen‐Doped Vertically Aligned Carbon Nanotube Electrocatalyst for the Oxygen Reduction Reaction

A highly active iron–nitrogen‐doped carbon nanotube catalyst for the oxygen reduction reaction (ORR) is produced by employing vertically aligned carbon nanotubes (VA‐CNT) with a high specific surface area and iron(II) phthalocyanine (FePc) molecules. Pyrolyzing the composite easily transforms the adsorbed FePc molecules into a large number of iron coordinated nitrogen functionalized nanographene (Fe–N–C) structures, which serve as ORR active sites on the individual VA‐CNT surfaces. The catalyst exhibits a high ORR activity, with onset and half‐wave potentials of 0.97 and 0.79 V, respectively, versus reversible hydrogen electrode, a high selectivity of above 3.92 electron transfer number, and a high electrochemical durability, with a 17 mV negative shift of E _1/2 after 10 000 cycles in an oxygen‐saturated 0.5 m H₂SO₄ solution. The catalyst demonstrates one of the highest ORR performances in previously reported any‐nanotube‐based catalysts in acid media. The excellent ORR performance can be attributed to the formation of a greater number of catalytically active Fe–N–C centers and their dense immobilization on individual tubes, in addition to more efficient mass transport due to the mesoporous nature of the VA‐CNTs.     

Intelligently Actuating Liquid Crystal Elastomer‐Carbon Nanotube Composites

Strategies for obtaining materials that respond to external stimuli by changing shape are of intense interest for the replacement of traditional actuators. Here, a strategy that enables programmable, multiresponsive actuators that use either visible light or electric current to drive shape change in composites comprising carbon nanotubes (CNTs) in liquid crystal elastomers (LCEs) is presented. In the nanocomposites, the CNTs function not only in the traditional roles of mechanical reinforcement and enhancers of thermal and electrical conductivity but also serve as an alignment layer for the LCEs. By controlling the orientation, location, and quantity of layers of CNTs in LCE/CNT composites, programmed, patterned actuators are built that respond to visible light or electrical current. Photothermal LCE/CNT film actuators undergo fast shape change, within 1.2 s using 280 mW cm^?2 light input, and complex, programmed localized deformations. Furthermore, twisting LCE/CNT composite films into a fiber increases uniaxial muscle stroke and work capacity for electrothermal actuation, thereby enabling about 12% actuation strain and 100 kJ m^?3 of work capacity in response to an applied DC voltage of 15.1 V cm^?1.     

Biocompatible Electromechanical Actuators Composed of Silk‐Conducting Polymer Composites

Single‐component, metal‐free, biocompatible, electromechanical actuator devices are fabricated using a composite material composed of silk fibroin and poly(pyrrole) (PPy). Chemical modification techniques are developed to produce free‐standing films with a bilayer‐type structure, with unmodified silk on one side and an interpenetrating network (IPN) of silk and PPy on the other. The IPN formed between the silk and PPy prohibits delamination, resulting in a durable and fully biocompatible device. The electrochemical stability of these materials is investigated through cyclic voltammetry, and redox sensitivity to the presence of different anions is noted. Free‐end bending actuation performance and force generation within silk‐PPy composite films during oxidation and reduction in a biologically relevant environment are investigated in detail. These silk–PPy composites are stable to repeated actuation, and are able to generate forces comparable with natural muscle (>0.1 MPa), making them ideal candidates for interfacing with biological tissues.     

Sandwich,Vertical‐Channeled Thick Electrodes with High Rate and Cycle Performance

3D thick electrode design is a promising strategy to increase the energy density of lithium‐ion batteries but faces challenges such as poor rate and limited cycle life. Herein, a coassembly method is employed to construct low‐tortuosity, mechanically robust 3D thick electrodes. LiFe_0.7Mn_0.3PO₄ nanoplates (LFMP NPs) and graphene are aligned along the growth direction of ice crystals during freezing and assembled into sandwich frameworks with vertical channels, which prompts fast ion transfer within the entire electrode and reveals a 2.5‐fold increase in ion transfer performance as opposed to that of random structured electrodes. In the sandwich framework, LFMP NPs are entrapped in the graphene wall in a “plate‐on‐sheet” contact mode, which avoids the detachment of NPs during cycling and also constitutes electron transfer highways for the thick electrode. Such vertical‐channel sandwich electrodes with mass loading of 21.2 mg cm^?2 exhibit a superior rate capability (0.2C–20C) and ultralong cycle life (1000 cycles). Even under an ultrahigh mass loading of 72 mg cm^?2, the electrode still delivers an areal capacity up to 9.4 mAh cm^?2, ≈2.4 times higher than that of conventional electrodes. This study provides a novel strategy for designing thick electrodes toward high performance batteries.     

High‐Conductivity Polymer Nanocomposites Obtained by Tailoring the Characteristics of Carbon Nanotube Fillers

We present a detailed study of the influence of carbon nanotube (CNT) characteristics on the electrical conductivity of polystyrene nanocomposites produced using a latex‐based approach. We processed both industrially‐produced multi‐wall CNT (MWCNT) powders and MWCNTs from vertically‐aligned films made in‐house, and demonstrate that while the raw CNTs are individualized and dispersed comparably within the polymer matrix, the electrical conductivity of the final nanocomposites differs significantly due to the intrinsic characteristics of the CNTs. Owing to their longer length after dispersion, the percolation threshold observed using MWCNTs from vertically‐aligned films is five times lower than the value for industrially‐produced MWCNT powders. Further, owing to the high structural quality of the CNTs from vertically‐aligned films, the resulting composite films exhibit electrical conductivity of 10³ S m^?1 at 2 wt% CNTs. On the contrary, composites made using the industrially‐produced CNTs exhibit conductivity of only tens of S m^?1. To our knowledge, the measured electrical conductivity for CNT/PS composites using CNTs from vertically‐aligned films is by far the highest value yet reported for CNT/PS nanocomposites at this loading.     

Rationally Engineered Electrodes for a High‐Performance Solid‐State Cable‐Type Supercapacitor

Wire‐shaped electrodes for solid‐state cable‐type supercapacitors (SSCTS) with high device capacitance and ultrahigh rate capability are prepared by depositing poly(3,4‐ethylenedioxythiophene) onto self‐doped TiO₂ nanotubes (D‐TiO₂) aligned on Ti wire via a well‐controlled electrochemical process. The large surface area, short ion diffusion path, and high electrical conductivity of these rationally engineered electrodes all contribute to the energy storage performance of SSCTS. The cyclic voltammetric studies show the good energy storage ability of the SSCTS even at an ultrahigh scan rate of 1000 V s^?1, which reveals the excellent instantaneous power characteristics of the device. The capacitance of 1.1 V SSCTS obtained from the charge–discharge measurements is 208.36 µF cm^?1 at a discharge current of 100 µA cm^?1 and 152.36 µF cm^?1 at a discharge current of 2000 µA cm^?1, respectively, indicating the ultrahigh rate capability. Furthermore, the SSCTS shows superior cyclic stability during long‐term (20 000 cycles) cycling, and also maintains excellent performance when it is subjected to bending and succeeding straightening process.     

3D Printing of Interdigitated Dielectric Elastomer Actuators

Dielectric elastomer actuators (DEAs) are soft electromechanical devices that exhibit large energy densities and fast actuation rates. They are typically produced by planar methods and, thus, expand in‐plane when actuated. Here, reported is a method for fabricating 3D interdigitated DEAs that exhibit in‐plane contractile actuation modes. First, a conductive elastomer ink is created with the desired rheology needed for printing high‐fidelity, interdigitated electrodes. Upon curing, the electrodes are then encapsulated in a self‐healing dielectric matrix composed of a plasticized, chemically crosslinked polyurethane acrylate. 3D DEA devices are fabricated with tunable mechanical properties that exhibit breakdown fields of 25 V µm^?1 and actuation strains of up to 9%. As exemplars, printed are prestrain‐free rotational actuators and multi‐voxel DEAs with orthogonal actuation directions in large‐area, out‐of‐plane motifs.     

Flexible Thermoelectric Polymer Composites Based on a Carbon Nanotubes Forest

Polymer‐based composites are of high interest in the field of thermoelectric (TE) materials because of their properties: abundance, low thermal conductivity, and nontoxicity. In applications, like TE for wearable energy harvesting, where low operating temperatures are required, polymer composites demonstrate compatible with the targeted specifications. The main challenge is reaching high TE efficiency. Fillers and chemical treatments can be used to enhance TE performance of the polymer matrix. The combined application of vertically aligned carbon nanotubes forest (VA‐CNTF) is demonstrated as fillers and chemical post‐treatment to obtain high‐efficiency TE composites, by dispersing VA‐CNTF into a poly (3,4‐ethylenedioxythiophene) polystyrene sulfonate matrix. The VA‐CNTF keeps the functional properties even in flexible substrates. The morphology, structure, composition, and functional features of the composites are thoroughly investigated. A dramatic increase of power factor is observed at the lowest operating temperature difference ever reported. The highest Seebeck coefficient and electrical conductivity are 58.7 µV K^?1 and 1131 S cm^?1, respectively. The highest power factor after treatment is twice as high in untreated samples. The results demonstrate the potential for the combined application of VA‐CNTF and chemical post‐treatment, in boosting the TE properties of composite polymers toward the development of high efficiency, low‐temperature, flexible TEs.     

Piezoresistive Properties of Ag/Silica Nano‐Composite Thin Films Close to the Percolation Threshold

The effect of mechanical stress on the electrical properties of Ag/silica nano‐composite sol–gel films, fabricated using an ultra‐violet (UV) photo‐reduction process, is studied over a large range of Ag volume fractions, φ. The ability to finely tune φ in situ by varying the UV exposure time enables the direct identification of the critical volume fraction, φ* ≈ 13.1%, around which the resistance changes by 6 orders of magnitude and the average piezoresistive gage factor, <G>, peaks at 4330. <G> is orders of magnitude larger than that of bulk silicon and φ* is close to the value expected for percolation in 3 dimensions. It is shown experimentally that this giant piezoresistance is the result of a stress‐induced change in the average Ag cluster size that significantly modifies the sample resistance when φ ～ φ*. In terms of the potential use of any composite material as a sensitive strain sensor, a sensor figure‐of‐merit (F) that accounts for both <G> and for the measured, expected divergence in resistance fluctuations close to φ* is defined. It is shown that maximum F is achieved in composites slightly to the metallic side of the percolation transition. In the case studied here, the maximum value of F, which is 5–10 times larger than that measured on commercial strain gages under the same conditions, is obtained for φ ≈ 13.4%. The ability to finely tune φ in‐situ therefore suggests that Ag/silica nano‐composites could be the basis for a highly sensitive, low power, strain sensing technology.     

Under‐Water Superaerophobic Pine‐Shaped Pt Nanoarray Electrode for Ultrahigh‐Performance Hydrogen Evolution

A pine‐shaped Pt nanostructured electrode with under‐water superaerophobicity for ultrahigh and steady hydrogen evolution reaction (HER) performance is successfully fabricated by a facile and easily scalable electrodeposition technique. Due to the lower bubble adhesive force (11.5 ± 1.2 μN), the higher bubble contact angle (161.3° ± 3.4°) in aqueous solution, and the smaller size of bubbles release for pine‐shaped Pt nanostructured electrode, the incomparable under‐water superaerophobicity for final repellence of bubbles from submerged surface with ease, is successfully achieved, compared to that for nanosphere electrode and for Pt flat electrode. With the merits of superior under‐water superaerophobicity and excellent nanoarray morphology, pine‐shaped Pt nanostructured electrode with the ultrahigh electrocatalytic HER performance, excellent durability, no obvious current fluctuation, and dramatically fast current density increase at overpotential range (3.85 mA mV^?1, 2.55 and 13.75 times higher than that for nanosphere electrode and for Pt flat electrode, respectively), is obtained, much superior to Pt nanosphere and flat electrodes. The successful introduction of under‐water superaerophobicity to in‐time repel as‐formed H₂ bubbles may open up a new pathway for designing more efficient electrocatalysts with potentially practical utilization in the near future.     

Flexible Low‐Power Operative Organic Source‐Gated Transistors

Low‐voltage operation and fast switching ability are necessary for wearable electronic devices. Recently, electrolyte dielectric materials have been widely used to decrease driving voltages; however, they often exhibit unwanted doping effects and power dissipation problems. Here, a method for dramatically lowering driving voltages is reported in organic electronics via source‐gated transistor (SGT) structures. SGTs are fabricated by evaporating asymmetric metals with different work functions for the source and drain electrodes. Versatile organic semiconductor‐based SGTs demonstrate a significantly lower drain voltage (<10 V) for the saturation regime compared to that of typical field‐effect transistors with the same dielectric layer (>80 V). Furthermore, coating reduced Pyronin B (rPyB) onto n‐type SGTs decreases the threshold voltage from 51.2 to 0.1 eV and improves air‐stability, exhibiting a maintained electron mobility (>90%) for 40 d. The air‐stability is due to both the energetic and kinetic factors, including a decreased lowest unoccupied molecular orbital level of the n‐type semiconductor after doping and covering the active layer with rPyB. Finally, flexible SGTs are fabricated on a Parylene‐C substrate that shows highly stable operation in a bending test. The results demonstrate a promising technology for low‐power, flexible electronic devices via electrode engineering.     

Ultrahigh Electrical Resistance of Poly(cyclohexyl methacrylate)/Carbon Nanotube Composites Prepared Using Surface‐Initiated Polymerization

Multiwalled carbon nanotubes on which poly(cyclohexyl methacrylate)s are densely grafted (PCHMA‐CNTs), are synthesized using a modified surface‐initiated atom transfer radical polymerization technique. The electrical resistance of PCHMA‐CNT is systematically characterized under direct current (DC) and alternating current and compared to that of conventional nanocomposites prepared by blending PCHMA with the CNT (PCHMA/CNT). At a comparable volume fraction of CNT, DC volume resistivity of PCHMA‐CNT is 14 orders of magnitude higher than that of PCHMA/CNT. This is because the grafted polymer with a combination of the high molecular weight and the high grafting density isolates individual CNTs at a long distance in the PCHMA‐CNT system. In addition, impedance analysis reveals that the highly insulated PCHMA‐CNT has the same electrical nature as neat PCHMA, i.e., it is a dielectric. Furthermore, dynamic mechanical analysis shows PCHMA‐CNT has a good mechanical properties as well as ultrahigh electrical resistance.     

Photothermal Bimorph Actuators with In‐Built Cooler for Light Mills,Frequency Switches,and Soft Robots

Photothermal bimorph actuators are widely used for smart devices, which are generally operated in a room temperature environment, therefore a low temperature difference for actuation without deteriorating the performance is preferred. The strategy for the actuator is assembling a broadband‐light absorption layer for volume expansion and an additional water evaporation layer for cooling and volume shrinkage on a passive layer. The response time and temperature‐change‐normalized bending speed under NIR, white, and blue light illumination are at the same level of high performance, fast photothermal actuators based on polymer or polymer composites. The classical beam theory and finite element simulations are also conducted to understand the actuation mechanism of the actuator. A new type of light mill is designed based on a wing‐flapping mechanism and a light‐modulated frequency switch. A fast‐walking robot (with a speed of 26 mm s^?1) and a fast‐and‐strong mechanical gripper with a large weight‐lifting ratio (≈2142), respectively, are also demonstrated.