Functionally Antagonistic Hybrid Electrode with Hollow Tubular Graphene Mesh and Nitrogen‐Doped Crumpled Graphene for High‐Performance Ionic Soft Actuators

Ionic soft actuators, which exhibit large mechanical deformations under low electrical stimuli, are attracting attention in recent years with the advent of soft and wearable electronics. However, a key challenge for making high‐performance ionic soft actuators with large bending deformation and fast actuation speed is to develop a stretchable and flexible electrode having high electrical conductivity and electrochemical capacitance. Here, a functionally antagonistic hybrid electrode with hollow tubular graphene meshes and nitrogen‐doped crumpled graphene is newly reported for superior ionic soft actuators. Three‐dimensional network of hollow tubular graphene mesh provides high electrical conductivity and mechanically resilient functionality on whole electrode domain. On the contrary, nitrogen‐doped wrinkled graphene supplies ultrahigh capacitance and stretchability, which are indispensably required for improving electrochemical activity in ionic soft actuators. Present results show that the functionally antagonistic hybrid electrode greatly enhances the actuation performances of ionic soft actuators, resulting in much larger bending deformation up to 620%, ten times faster rise time and much lower phase delay in a broad range of input frequencies. This outstanding enhancement mostly attributes to exceptional properties and synergistic effects between hollow tubular graphene mesh and nitrogen‐doped crumpled graphene, which have functionally antagonistic roles in charge transfer and charge injection, respectively.     

Flexible Hybrid Paper Made of Monolayer Co3O4 Microsphere Arrays on rGO/CNTs and Their Application in Electrochemical Capacitors

A facile one‐step hydrothermal method is developed for large‐scale production of well‐designed flexible and free‐standing Co₃O₄/reduced graphene oxide (rGO)/carbon nanotubes (CNTs) hybrid paper as an electrode for electrochemical capacitors. Densely packed unique Co₃O₄ monolayer microsphere arrays uniformly cover the surface of the rGO/CNTs film. The alkaline hydrothermal treatment leads to not only the deposition of Co₃O₄ microspheres array, but also the reduction of the GO sheets at the same time. The unique hybrid paper is evaluated as an electrode for electrochemical capacitors without any ancillary materials. It is found that the obtained hybrid flexible paper, composed of Co₃O₄ microsphere array anchored to the underling conductive rGO/CNTs substrate with robust adhesion, is able to deliver high specific capacitance with excellent electrochemical stability even at high current densities, suggesting its promising application as an efficient electrode material for electrochemical capacitors.     

Fast and High-Strain Electrochemically Driven Yarn Actuators in Twisted and Coiled Configurations

Commercially available yarns are promising precursor for artificial muscles for smart fabric-based textile wearables. Electrochemically driven conductive polymer (CP) coated yarns have already shown their potential to be used in smart fabrics. Unfortunately, the practical application of these yarns is still hindered due to their slow ion exchange properties and low strain. Here, a method is demonstrated to morph poly-3,4-ethylenedioxythiophene:poly-styrenesulfonate (PEDOT:PSS) coated multifilament textile yarns in highly twisted and coiled structures, providing > 1% linear actuation in < 1 s at a potential of + 0.6 V. A potential window of + 0.6 V and –1.2 V triggers the fully reversible actuation of a coiled yarn providing > 1.62% strain. Compared to the untwisted, regular yarns, the twisted and coiled yarns produce > 9 ×  and > 20 ×  higher strain, respectively. The strain and speed are significantly higher than the maximum reported results from other electrochemically operated CP yarns. The yarn's actuation is explained by reversible oxidation/reduction reactions occurring at CPs. However, the helical opening/closing of the twisted or coiled yarns due to the torsional yarn untwisting/retwisting assists the rapid and large linear actuation. These PEDOT:PSS coated yarn actuators are of great interest to drive smart textile exoskeletons.     

Flexible Asymmetric Supercapacitor Based on Structure‐Optimized Mn3O4/Reduced Graphene Oxide Nanohybrid Paper with High Energy and Power Density

A highly flexible Mn₃O₄/reduced graphene oxide (rGO) nanohybrid paper with high electrical conductivity and high mass loading of Mn₃O₄ nanofibers (0.71 g cm^?3) is developed via a facile gel formation and electrochemical reduction process, which is low‐cost, environmental friendly, and easy to scale up. Confined Mn₃O₄ nanofibers are well dispersed within the rGO sheets, which demonstrate to be a promising cathode material for flexible asymmetric supercapacitors (ASCs). When coupled with an electrochemically reduced rGO paper as the anode, a flexible ASC device, based on the Mn₃O₄/rGO nanohybrid paper as the cathode, is assembled; and it demonstrates remarkable electrochemical performance: a high volumetric capacitance of 54.6 F cm^?3 (546.05 mF cm^?2), and remarkable volumetric energy and power density (0.0055 Wh cm^?3 and 10.95 W cm^?3) being achieved with excellent cycling ability. The nanohybrid paper shows great improvement for flexible energy devices in terms of electrochemical properties.     

Dry‐Type Artificial Muscles Based on Pendent Sulfonated Chitosan and Functionalized Graphene Oxide for Greatly Enhanced Ionic Interactions and Mechanical Stiffness

Biopolymer‐based artificial muscles are promising candidates for biomedical applications and smart electronic textiles due to their multifaceted advantages like natural abundance, eco‐friendliness, cost‐effectiveness, easy chemical modification and high electical reactivity. However, the biopolymer‐based actuators are showing relatively low actuation performance compared with synthetic electroactive polymers because of inadequate mechanical stiffness, low ionic conductivity and ionic exchange capacity (IEC), and poor durability over long‐term activation. This paper reports a high‐performance electro‐active nano‐biopolymer based on pendent sulfonated chitosan (PSC) and functionalized graphene oxide (GO), exhibiting strong electro‐chemo‐mechanical interations with ionic liquid (IL) in open air environment. The proposed GO‐PSC‐IL nano‐biopolymer membrane shows an icnreased tensile strength and ionic exchange capacity of up to 44.8% and 83.1%, respectively, and increased ionic conductivity of over 18 times, resulting in two times larger bending actuation than the pure chitosan actuator under electrical input signals. Eventually, the GO‐PSC‐IL actuators could show robust and high‐performance actuation even at the very low applied voltages that are required in realistic applications.     

Humidity‐Driven Mechanical and Electrical Response of Graphene/Cloisite Hybrid Films

Humidity‐driven and electrically responsive graphene/cloisite hybrid films are obtained by casting water dispersions of graphene oxide and cloisite Na⁺. Coupling hydrophilicity and a high water vapor barrier in a homogenous film enables to realize humidity‐driven actuators which exploit the water gradient generated across the film section under asymmetric exposure to humidity. The hybrid films are self‐standing, flexible, and exhibit fast humidity‐triggered bidirectional bending up to 75°, which is tuned by varying the relative amount of the two components. Up to 60% of the bending angle can be preserved at the steady state, providing a large and reliable response to humidity. Moreover, thermal treatment results in the reduction of graphene oxide, endowing the films with humidity‐dependent electrical conductivity, which increases from 1.5 × 10^?6 S at 20% relative humidity (RH) up to 2.7 × 10^?5 S at 90% RH. The films are used to realize a humidity‐sensitive electrical switching system in which the reversible actuation is due to water desorption induced by the Joule effect. Due to their ease of preparation and tunable properties, this new class of graphene‐based materials is suitable for the realization of humidity‐driven and electrically responsive actuators and sensors.     

Near‐Infrared Light‐Driven,Highly Efficient Bilayer Actuators Based on Polydopamine‐Modified Reduced Graphene Oxide

Near‐infrared (NIR) light‐driven bilayer actuators capable of fast, highly efficient, and reversible bending/unbending motions toward periodic NIR light irradiation are fabricated by exploiting the photothermal conversion and humidity‐sensitive properties of polydopamine‐modified reduced graphene oxide (PDA‐RGO). The bilayer actuator comprises a PDA‐RGO layer prepared by a filtration method, and this layer is subsequently spin‐coated with a layer of UV‐cured Norland Optical Adhesive (NOA)‐63. Given the hydrophilicity of PDA, the PDA‐RGO layer can absorb water to swell and lose water to shrink. The intrinsic NIR absorbance of RGO sheets convertes NIR light into thermal energy, which transfers the humidity‐responsive PDA‐RGO layer to be NIR light‐responsive. Considering that the shape of the NOA‐63 layer remains unchanged under NIR light, periodic NIR light irradiation leads to asymmetric shrinkage/expansion of the bilayer, which enables fast and reversible bending/unbending motions of the bilayer actuator. We demonstrate that compared with a poly(ethylenimine)‐modified graphene oxide layer, the PDA‐RGO layer is unique in fabricating highly efficient bilayer actuators. A NIR light‐driven walking device capable of performing quick worm‐like motion on a ratchet substrate is built by connecting two polyethylene terephthalate plates as claws on opposite ends of the PDA‐RGO/NOA‐63 bilayer actuator.     

Highly Conductive Few‐Layer Graphene/Al2O3 Nanocomposites with Tunable Charge Carrier Type

An ex situ strategy for fabrication of graphene oxide (GO)/metal oxide hybrids without assistance of surfactant is introduced. Guided by this strategy, GO/Al₂O₃ hybrids are fabricated by two kinds of titration methods in which GO and Al₂O₃ colloids are utilized as titrant for hybrids of low and high GO content respectively. After sintered by spark plasma sintering, few‐layer graphene (FG)/Al₂O₃ nanocomposites are obtained and GO is well reduced to FG simultaneously. A percolation threshold as low as 0.38 vol.% is achieved and the electrical conductivity surpasses 10³ Sm^?1 when FG content is only 2.35 vol.% in FG/Al₂O₃ composite, revealing the homogeneous dispersion and high quality of as‐prepared FG. Furthermore, it is found that the charge carrier type changes from p‐ to n‐type as graphene content becomes higher. It is deduced that this conversion is related to the doping effect induced by Al₂O₃ matrix and is thickness‐dependent with respect to FG.     

Facile Synthesis of Graphene Quantum Dots from 3D Graphene and their Application for Fe3+ Sensing

Owing to their small size, biocompatibility, unique and tunable photoluminescence, and physicochemical properties, graphene quantum dots (GQDs) are an emerging class of zero‐dimensional materials promising a wide spectrum of novel applications in bio‐imaging, optical, and electrochemical sensors, energy devices, and so forth. Their widespread use, however, is largely limited by the current lack of high yield synthesis methods of high‐quality GQDs. In this contribution, a facile method to electrochemically exfoliate GQDs from three‐dimensional graphene grown by chemical vapor deposition (CVD) is reported. Furthermore, the use of such GQDs for sensitive and specific detection of ferric ions is demonstrated.     

Ultrahigh Conductive Graphene Paper Based on Ball‐Milling Exfoliated Graphene

Due to low density, extremely high electrical and thermal conductivities, graphene has great potential to construct lightweight thermal conductive paper for high‐power electric devices. However, the remarkable properties of graphene are on a molecular level and difficult to achieve when processed into macroscopic paper. Here, an effective route to construct ultrahigh conductive graphene paper is developed. First, large‐volume, high‐concentration, plane‐defect‐free, few‐layer graphene dispersion is fast produced from graphite at high yield through ball milling. The exfoliated graphene dispersion is further processed into graphene paper through fast filtration, thermal treatment, and mechanical compression. The electrical and thermal conductivities of the resultant graphene paper are as high as 2231 S cm^?1 and 1529 W m^?1 K^?1, superior to previously reported graphene papers. Structural analyses confirm that the ultrahigh conductivities are attributed to high quality of graphene sheets, their compact ordered stacking, and large graphitic crystalline domain size, which improve electron and phonon transport within basal plane of graphene sheet and between graphene sheets.     

Asymmetric Supercapacitors Based on Graphene/MnO2 Nanospheres and Graphene/MoO3 Nanosheets with High Energy Density

Asymmetric supercapacitors with high energy density are fabricated using a self‐assembled reduced graphene oxide (RGO)/MnO₂ (GrMnO₂) composite as a positive electrode and a RGO/MoO₃ (GrMoO₃) composite as a negative electrode in safe aqueous Na₂SO₄ electrolyte. The operation voltage is maximized by choosing two metal oxides with the largest work function difference. Because of the synergistic effects of highly conductive graphene and highly pseudocapacitive metal oxides, the hybrid nanostructure electrodes exhibit better charge transport and cycling stability. The operation voltage is expanded to 2.0 V in spite of the use of aqueous electrolyte, revealing a high energy density of 42.6 Wh kg^?1 at a power density of 276 W kg^?1 and a maximum specific capacitance of 307 F g^?1, consequently giving rise to an excellent Ragone plot. In addition, the GrMnO₂//GrMoO₃ supercapacitor exhibits improved capacitance with cycling up to 1000 cycles, which is explained by the development of micropore structures during the repetition of ion transfer. This strategy for the choice of metal oxides provides a promising route for next‐generation supercapacitors with high energy and high power densities.     

Bio‐Inspired All‐Organic Soft Actuator Based on a π–π Stacked 3D Ionic Network Membrane and Ultra‐Fast Solution Processing

Next generation electronic products, such as wearable electronics, flexible displays, and smart mobile phones, will require the use of unprecedented electroactive soft actuators for haptic and stimuli‐responsive devices and space‐saving bio‐mimetic actuation. Here, a bio‐inspired all‐organic soft actuator with a π–π stacked and 3D ionic networked membrane based on naphthalene‐tetracarboxylic dianhydride (Ntda) and sulfonated polyimide block copolymers (SPI) is presented, utilizing an ultra‐fast solution process. The π–π stacked and self‐assembled 3D ionic networked membrane with continuous and interconnected ion transport nanochannels is synthesized by introducing simple and strong atomic level regio‐specific interactions of hydrophilic and hydrophobic SPI co‐blocks with cations and anions in the ionic liquid. Furthermore, a facile and ultrafast all‐solution process involving solvent blending, dry casting, and solvent dropping is developed to produce electro‐active soft actuators with highly conductive polyethylenedioxythiophene (PEDOT):polystyrenesulfonate (PSS) electrodes. Ionic conductivity and ion exchange capacity of the π–π stacked Ntda‐SPI membrane can be increased up to 3.1 times and 3.4 times of conventional SPI, respectively, resulting in a 3.2 times larger bending actuation. The developed bio‐inspired soft actuator is a good candidate for satisfying the tight requirements of next generation soft electronic devices due to its key benefits such as low operating voltage and comparatively large strains, as well as quick response and facile processability.     

Three Dimensional Graphene Foam/Polymer Hybrid as a High Strength Biocompatible Scaffold

Graphene foam (GrF)/polylactic acid–poly‐ε‐caprolactone copolymer (PLC) hybrid (GrF‐PLC) scaffold is synthesized in order to utilize both the desirable properties of graphene and that of foams such as excellent structural characteristics and a networked 3‐D structure for cells to proliferate in. The hybrid scaffold is synthesized by a dip‐coating method that enables retention of the porous 3D structure. The excellent wettability of PLC with graphene foam along with the formation of PLC bridges leads to a ≈3700% enhancement in strength and a ≈3100% increase in ductility in the GrF‐PLC scaffold. Biocompatibility of both graphene foam and GrF‐PLC scaffold is demonstrated by culturing of human mesenchymal stem cells (hMSCs) for 28 days, a period over which cell proliferation is robust. The hMSCs are differentiated in chondrogenic media and supported chondrogenesis in both scaffolds. The demand for aggrecan extracellular matrix protein synthesis is reduced in hybrids due to improved bearing of cell‐induced loads, this may be critical for ensuring adequate cellular distribution and layering of extracellular matrix. Hence, the unique mechanical and biotolerant properties of the GrF‐PLC scaffold are suited for musculoskeletal tissue engineering applications, such as the growth of de novo cartilage to replace cartilage lost due to injury or osteoarthritis.     

石墨烯/硅基异质集成光电子器件

石墨烯/硅基异质集成的光子器件研究在近年来取得了巨大进展,因石墨烯所具有的诸多独特的物理性质如超高载流子迁移率、超高非线性系数等,石墨烯/硅基异质集成器件展现出了诸如超大带宽、超低功耗等优异性能。文章介绍了近年来报道的典型石墨烯/硅基异质集成器件,包括石墨烯/硅基电光调制器、石墨烯/硅基热光调制器和石墨烯/硅基光电探测器,简要阐述了其原理与性能,并对其未来的应用与发展做出了展望。     

Bidirectional All‐Optical Synapses Based on a 2D Bi2O2Se/Graphene Hybrid Structure for Multifunctional Optoelectronics

Neuromorphic computing has been extensively studied to mimic the brain functions of perception, learning, and memory because it may overcome the von Neumann bottleneck. Here, with the light‐induced bidirectional photoresponse of the proposed Bi₂O₂Se/graphene hybrid structure, its potential use in next‐generation neuromorphic hardware is examined with three distinct optoelectronic applications. First, a photodetector based on a Bi₂O₂Se/graphene hybrid structure presents positive and negative photoresponsibility of 88 and ?110 A W^?1 achieved by the excitation of visible wavelength and ultraviolet wavelength light at intensities of 1.2 and 0.3 mW cm^?2, respectively. Second, this unique photoresponse contributes to the realization of all optically stimulated long‐term potentiation or long‐term depression to mimic synaptic short‐term plasticity and long‐term plasticity, which are attributed to the combined effect of photoconductivity, bolometric, and photoinduced desorption. Third, the devices are applied to perform digital logic functions, such as “AND” and “OR,” using full light modulation. The proposed Bi₂O₂Se/graphene‐based optoelectronic device represents an innovative and efficient building block for the development of future multifunctional artificial neuromorphic systems.