One‐Step Ionic‐Liquid‐Assisted Electrochemical Synthesis of Ionic‐Liquid‐Functionalized Graphene Sheets Directly from Graphite

Graphite, inexpensive and available in large quantities, unfortunately does not readily exfoliate to yield individual graphene sheets. Here a mild, one‐step electrochemical approach for the preparation of ionic‐liquid‐functionalized graphite sheets with the assistance of an ionic liquid and water is presented. These ionic‐liquid‐treated graphite sheets can be exfoliated into functionalized graphene nanosheets that can not only be individuated and homogeneously distributed into polar aprotic solvents, but also need not be further deoxidized. Different types of ionic liquids and different ratios of the ionic liquid to water can influence the properties of the graphene nanosheets. Graphene nanosheet/polystyrene composites synthesized by a liquid‐phase blend route exhibit a percolation threshold of 0.1 vol % for room temperature electrical conductivity, and, at only 4.19 vol %, this composite has a conductivity of 13.84 S m⁻¹, which is 3–15 times that of polystyrene composites filled with single‐walled carbon nanotubes.     

Microsphere Structure Composite Phase Change Material with Anti-Leakage,Self-Sensing,and Photothermal Conversion Properties for Thermal Energy Harvesting and Multi-Functional Sensor

The low thermal conductivity and liquid melt leakage of phase change materials are long-standing bottlenecks for efficient and safe thermal energy harvesting. Although high thermal conductivity materials combined with phase change materials can address the thermal conductivity problem, ensuring no leakage and no reduction in latent heat in the meantime remains challenging. Here, a strategy to synthesize microsphere-structured phase change composites by encapsulating phase change materials in graphene via emulsion polymerization (no additional emulsifier) and chemical reduction is proposed. Multiple graphene sheets are connected to construct an efficient thermally conductive (increase 58.5 times in thermal conductivity) and electrically conductive network. The composite microspheres exhibit no leakage (<0.5%) and superior phase transition behavior after 1500 heating-cooling cycles, and sense external environments such as temperature changes and water drops falling, allowing them to be engineered into devices for temperature monitoring. In addition, it converts electrical energy into thermal energy to achieve rapid temperature increases. The incorporation of polydopamine improves the photothermal efficiency of the phase change microspheres and senses light irradiation, offering a promising route to extend the single source of thermal energy. This method provides new insight into the photothermal integration and intelligent sensing of phase-change materials.     

Highly Conductive Nanocomposites with Three‐Dimensional,Compactly Interconnected Graphene Networks via a Self‐Assembly Process

Polymer‐based materials with high electrical conductivity are of considerable interest because of their wide range of applications. The construction of a 3D, compactly interconnected graphene network can offer a huge increase in the electrical conductivity of polymer composites. However, it is still a great challenge to achieve desirable 3D architectures in the polymer matrix. Here, highly conductive polymer nanocomposites with 3D compactly interconnected graphene networks are obtained using a self‐assembly process. Polystyrene (PS) and ethylene vinyl acetate (EVA) are used as polymer matrixes. The obtained PS composite film with 4.8 vol% graphene shows a high electrical conductivity of 1083.3 S/m, which is superior to that of the graphene composite prepared by a solvent mixing method. The electrical conductivity of the composites is closely related to the compact contact between graphene sheets in the 3D structures and the high reduction level of graphene sheets. The obtained EVA composite films with the 3D graphene structure not only show high electrical conductivity but also exhibit high flexibility. Importantly, the method to fabricate 3D graphene structures in polymer matrix is facile, green, low‐cost, and scalable, providing a universal route for the rational design and engineering of highly conductive polymer composites.     

Robust Fabrication of Nonstick,Noncorrosive, Conductive Graphene‐Coated Liquid Metal Droplets for Droplet‐Based,Floating Electrodes

Nontoxic liquid metals (conductive materials in a liquid state at room temperature) are an emerging class of materials for applications ranging from soft electronics and robotics to medical therapy and energy devices. Their sticky and corrosive properties, however, are becoming more of a critical concern for circuits and devices containing other metals as these are easily destroyed or contaminated by the liquid metals. Herein, a feasible method for fabricating highly conductive graphene‐coated liquid metal (GLM) droplets is reported and their application as nonstick, noncorrosive, movable, soft contacts for electrical circuits is demonstrated. The as‐prepared GLM droplets consist of a liquid‐phase soft core of liquid metal and a slippery outer layer of graphene sheets. These structures address the issue of simultaneous control of the wettability and conductivity of a soft electronic contact by combining extraordinary properties, i.e., nonstick, noncorrosive, yet exhibiting high electronic conductivity while in contact with metal substrates, e.g., Au, Cu, Ag, and Ni. As proof‐of‐concept, the as‐prepared GLM droplets are demonstrated as floating electrodes for movable, recyclable electronic soft contacts in electrical circuits.     

Hydrophilic Nanotube Supported Graphene–Water Dispersible Carbon Superstructure with Excellent Conductivity

In this work, it is shown that the hydrophilic functionalized multiwall carbon nanotubes (MWCNs) can stabilize a large amount of pristine graphene nanosheets in pure water without the assistance of surfactants, ionic liquids, or hydrophilic polymers. Role of stabilizer is conveyed by highly hydrophilic carbon nanotubes, functionalized by dihydroxy phenyl groups, affording a stable dispersion at concentrations as high as 15 mg mL^?1. Such multidimensional (2D/1D) graphene/MWCN hybrid is found to be dispersible also in other polar organic solvents such as ethanol, isopropanol, N,N‐dimethylformamide, ethylene glycol, and their mixtures. High‐resolution transmission microscopy and atomic force microscopy (AFM) including a liquid mode AFM manifest several types of interaction including trapping of multiwalled carbon nanotubes between the graphene sheets or the modification of graphene edges. Molecular dynamic simulations show that formation of an assembly is kinetically controlled. Importantly, the hybrid can be deposited on the paper by drop casting or dispersed in water‐soluble polymers resulting in record values of electrical conductivity (sheet resistance up to R_s ≈ 25 Ω sq^?1 for free hybrid material and R_s ≈ 1300 Ω sq^?1 for a polyvinilalcohol/hybrid composite film). Thus, these novel water dispersible carbon superstructures reveal a high application potential as conductive inks for inkjet printing or as highly conductive polymers.     

Spontaneous Formation of Liquid Crystals in Ultralarge Graphene Oxide Dispersions

A novel process is developed to synthesize graphene oxide sheets with an ultralarge size based on a solution‐phase method involving pre‐exfoliation of graphite flakes. Spontaneous formation of lyotropic nematic liquid crystals is identified upon the addition of the ultralarge graphene oxide sheets in water above a critical concentration of about 0.1 wt%. It is the lowest filler content ever reported for the formation of liquid crystals from any colloid, arising mainly from the ultrahigh aspect ratio of the graphene oxide sheets of over 30 000. It is proposed that the self‐assembled brick‐like graphene oxide nanostructure can be applied in many areas, such as energy‐storage devices and nanocomposites with a high degree of orientation.     

Emulsifier‐Free Graphene Dispersions with High Graphene Content for Printed Electronics and Freestanding Graphene Films

A novel and highly versatile synthetic route for the production of functionalized graphene dispersions in water, acetone, and isopropanol (IPA), which exhibit long‐term stability and are easy to scale up, is reported. Both graphene functionalization (wherein the oxygen content can be varied from 4 to 16 wt%) and dispersion are achieved by the thermal reduction of graphite oxide, followed by a high‐pressure homogenization (HPH) process. For the first time, binders, dispersing agents, and reducing agents are not required to produce either dilute or highly concentrated dispersions of single graphene sheets with a graphene content of up to 15 g L^?1. High graphene content is essential for the successful printing of graphene dispersions by 3D microextrusion. Free‐standing graphene films and micropatterned graphene materials are successfully prepared using this method. Due to the absence of toxic reducing agents, the graphene exhibits no cytotoxicity and is biocompatible. Furthermore, the electrical conductivity of graphene is significantly improved by the absence of binders. Flexible microarrays can be printed on different substrates, producing microarrays that are mechanically stable and can be bent several times without affecting electrical conductivity.     

An Anisotropically High Thermal Conductive Boron Nitride/Epoxy Composite Based on Nacre‐Mimetic 3D Network

Polymer‐based thermal interface materials (TIMs) with excellent thermal conductivity and electrical resistivity are in high demand in the electronics industry. In the past decade, thermally conductive fillers, such as boron nitride nanosheets (BNNS), were usually incorporated into the polymer‐based TIMs to improve their thermal conductivity for efficient heat management. However, the thermal performance of those composites means that they are still far from practical applications, mainly because of poor control over the 3D conductive network. In the present work, a high thermally conductive BNNS/epoxy composite is fabricated by building a nacre‐mimetic 3D conductive network within an epoxy resin matrix, realized by a unique bidirectional freezing technique. The as‐prepared composite exhibits a high thermal conductivity (6.07 W m^?1 K^?1) at 15 vol% BNNS loading, outstanding electrical resistivity, and thermal stability, making it attractive to electronic packaging applications. In addition, this research provides a promising strategy to achieve high thermal conductive polymer‐based TIMs by building efficient 3D conductive networks.     

Highly Elastic and Conductive N‐Doped Monolithic Graphene Aerogels for Multifunctional Applications

The simple synthesis of ultralow‐density (≈2.32 mg cm^?3) 3D reduced graphene oxide (rGO) aerogels that exhibit high electrical conductivity and excellent compressibility are described herein. Aerogels are synthesized using a combined hydrothermal and thermal annealing method in which hexamethylenetetramine is employed as a reducer, nitrogen source, and graphene dispersion stabilizer. The N‐binding configurations of rGO aerogels increase dramatically, as evidenced by the change in pyridinic‐N/quaternary‐N ratio. The conductivity of this graphene aerogel is ≈11.74 S m^?1 at zero strain, whereas the conductivity at a compressive strain of ≈80% is ≈704.23 S m^?1, which is the largest electrical conductivity reported so far in any 3D sponge‐like low‐density carbon material. In addition, the aerogel has excellent hydrophobicity (with a water contact angle of 137.4°) as well as selective absorption for organic solvents and oils. The compressive modulus (94.5 kPa; ρ ≈ 2.32 mg cm^?3) of the rGO aerogel is higher than that of other carbon‐based aerogels. The physical and chemical properties (such as high conductivity, elasticity, high surface area, open pore structure, and chemical stability) of the aerogel suggest that it is a viable candidate for the use in energy storage, electrodes for fuel cells, photocatalysis, environmental protection, energy absorption, and sensing 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.     

Thermal Properties of the Binary‐Filler Hybrid Composites with Graphene and Copper Nanoparticles

The thermal properties of epoxy‐based binary composites comprised of graphene and copper nanoparticles are reported. It is found that the “synergistic” filler effect, revealed as a strong enhancement of the thermal conductivity of composites with the size‐dissimilar fillers, has a well‐defined filler loading threshold. The thermal conductivity of composites with a moderate graphene concentration of f_g = 15 wt% exhibits an abrupt increase as the loading of copper nanoparticles approaches f_Cu ≈ 40 wt%, followed by saturation. The effect is attributed to intercalation of spherical copper nanoparticles between the large graphene flakes, resulting in formation of the highly thermally conductive percolation network. In contrast, in composites with a high graphene concentration, f_g = 40 wt%, the thermal conductivity increases linearly with addition of copper nanoparticles. A thermal conductivity of 13.5 ± 1.6 Wm^?1K^?1 is achieved in composites with binary fillers of f_g = 40 wt% and f_Cu = 35 wt%. It has also been demonstrated that the thermal percolation can occur prior to electrical percolation even in composites with electrically conductive fillers. The obtained results shed light on the interaction between graphene fillers and copper nanoparticles in the composites and demonstrate potential of such hybrid epoxy composites for practical applications in thermal interface materials and adhesives.     

Stress Controllability in Thermal and Electrical Conductivity of 3D Elastic Graphene‐Crosslinked Carbon Nanotube Sponge/Polyimide Nanocomposite

Stress controllability in thermal and electrical conductivity is important for flexible piezoresistive devices. Due to the strength‐elasticity trade‐off, comprehensive investigation of stress‐controllable conduction in elastic high‐modulus polymers is challenging. Here presented is a 3D elastic graphene‐crosslinked carbon nanotube sponge/polyimide (G_w‐CNT/PI) nanocomposite. Graphene welding at the junction enables both phonon and electron transfer as well as avoids interfacial slippage during cyclic compression. The uniform G_w‐CNT/PI comprising a high‐modulus PI deposited on a porous templated network combines stress‐controllable thermal/electrical conductivity and cyclic elastic deformation. The uniform composites show different variation trends controlled by the porosity due to different phonon and electron conduction mechanisms. A relatively high k (3.24 W m^?1 K^?1, 1620% higher than PI) and suitable compressibility (16.5% under 1 MPa compression) enables the application of the composite in flexible elastic thermal interface conductors, which is further analyzed by finite element simulations. The interconnected network favors a high stress‐sensitive electrical conductivity (sensitivity, 973% at 9.6% strain). Thus, the G_w‐CNT/PI composite can be an important candidate material for piezoresistive sensors upon porosity optimization based on stress‐controllable thermal or electrical conductivity. The results provide insights toward controlling the stress‐induced thermal/electrical conductivities of 3D interconnected templated composite networks for piezoresistive conductors or sensors.     

Highly Conductive Carbon Nanotube‐Graphene Hybrid Yarn

An efficient procedure for the fabrication of highly conductive carbon nanotube/graphene hybrid yarns has been developed. To start, arrays of vertically aligned multi‐walled carbon nanotubes (MWNT) are converted into indefinitely long MWNT sheets by drawing. Graphene flakes are then deposited onto the MWNT sheets by electrospinning to form a composite structure that is transformed into yarn filaments by twisting. The process is scalable for yarn fabrication on an industrial scale. Prepared materials are characterized by electron microscopy, electrical, mechanical, and electrochemical measurements. It is found that the electrical conductivity of the composite MWNT‐graphene yarns is over 900 S/cm. This value is 400% and 1250% higher than electrical conductivity of pristine MWNT yarns or graphene paper, respectively. The increase in conductivity is asssociated with the increase of the density of states near the Fermi level by a factor of 100 and a decrease in the hopping distance by an order of magnitude induced by grapene flakes. It is found also that the MWNT‐graphene yarn has a strong electrochemical response with specific capacitance in excess of 111 Fg^?1. This value is 425% higher than the capacitance of pristine MWNT yarn. Such substantial improvements of key properties of the hybrid material can be associated with the synergy of MWNT and graphene layers in the yarn structure. Prepared hybrid yarns can benefit such applications as high‐performance supercapacitors, batteries, high current capable cables, and artificial muscles.     

Graphene‐Based Devices for Thermal Energy Conversion and Utilization

Thermal energy conversion and utilization of integrated circuits is a very important research topic. Graphene is a new 2D material with superior electrical, mechanical, thermal, and optical properties, which is expected to continue Moore's law and make breakthroughs in the direction of “More than Moore.” Graphene‐based functionalized devices are applied in various aspects, including breakthroughs in thermal devices, due to their high thermal conductivity and thermal rectification. According to the coupling of different physical quantities, graphene‐based thermal devices can be divided into four categories: uncoupled thermal devices, thermoacoustic coupling devices, thermoelectric coupling devices, and thermo‐optical coupling devices. The structure, working mechanism, and performance of these devices are discussed, as well as the coupling methods of physical quantities. Moreover, scale‐up production of graphene and prospect for future graphene‐based thermal devices are summarized. In‐depth study of the development tendency of these graphene‐based thermal devices is expected to contribute to the development of new high‐performance thermal nanoelectronic devices in the future.     

Dynamic application of novel electro-optic switchable device modulation by graphene oxide dispersed liquid crystal cell assembling CdS nanowires

In nanotechnology, the novel creation of nanostructures consistently feeds back into efforts to fabricate novel complex hybrid nanomaterials. Two-dimensional graphene oxide dispersed liquid crystalline materials (GDLC) module assembled with CdS nanowires(NW's) have received widespread unprecedented attention due to their exceptional mechanical, electrical, thermal properties. However, making macroscopic graphene oxide (GO) sheets with average diameter 2.1 μm, CdS nanowires (15–20 nm) requires novel technology to fabricate few layered graphene oxide (FGO)-sheets were uniformly distributed as macroscopically ordered structures. Aqueous GDLC-CdS nanowires are continuously twist to obtain macroscopic GO-sheets. Subsequently chemical reduction gave first macroscopic neat graphene sheets with high conductivity and good mechanical performance. Liquid crystal formation is the most viable approach to produce macroscopic, periodic self-assembled materials from oriented graphene sheets. We discovered well-soluble FLG-sheets can exhibit nematic liquid crystallinity into Dimethyl sulfoxide (DMSO), first established isotropic-nematic solid phase diagram demonstrated by optical microscopy textural evidences of switching and relevant spectroscopic characterizations. GO utilizes light absorption and nanoscale heat source to thermally induced phase transition with LC from homogeneous alignment to isotropic phase. Thus, volume contraction occurred over the surface area of the GDLC-nanowires hybrid complex module due to photothermal effect. Thus, an excellent conductor as well as high contrast electro-optic switchable cell also deserves most promising applications. These novel findings shed focus on microscopically assembled graphene-LC based semiconductor nanomaterial's textural phase behavior, which can only be realized as the field moves forward and makes more significant advances.     

Covalently Bonded Graphene Sheets on Carbon Nanotubes: Direct Growth and Outstanding Properties

Integrating 1D carbon nanotubes (CNTs) and 2D graphene with covalent bonds can inherit the outstanding properties of both components and obtain additional advantages. Here, this work reports the preparation of covalently bonded graphene/CNT (G/CNT) structure by a normal chemical vapor deposition method. Specifically, the pre-synthesized defects on the sidewall of CNTs act as nucleation sites for the growth of graphene sheets to form a branch-leaf structure. Graphene leaves restrict the sliding and re-stacking of CNTs, endowing G/CNT hybrid demonstrates excellent anti-agglomeration properties that are not present in either graphene or CNTs. In addition, the covalently bonded structure and high graphitization degree of graphene sheets and CNTs significantly enhance the comprehensive properties of the G/CNT hybrid material, such as large specific surface area, excellent thermal stability, and high electrical conductivity. Consequently, the microwave absorption properties of G/CNT are significantly enhanced compared with CNTs. This work provides a feasible pathway to synthesize high-performance covalently bonded G/CNT hybrids.     

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.     

High Surface Area MoS2/Graphene Hybrid Aerogel for Ultrasensitive NO2 Detection

A MoS₂/graphene hybrid aerogel synthesized with two‐dimensional MoS₂ sheets coating a high surface area graphene aerogel scaffold is characterized and used for ultrasensitive NO₂ detection. The combination of graphene and MoS₂ leads to improved sensing properties with the graphene scaffold providing high specific surface area and high electrical and thermal conductivity and the single to few‐layer MoS₂ sheets providing high sensitivity and selectivity to NO₂. The hybrid aerogel is integrated onto a low‐power microheater platform to probe the gas sensing performance. At room temperature, the sensor exhibits an ultralow detection limit of 50 ppb NO₂. By heating the material to 200 °C, the response and recovery times to reach 90% of the final signal decrease to <1 min, while retaining the low detection limit. The MoS₂/graphene hybrid also shows good selectivity for NO₂ against H₂ and CO, especially when compared to bare graphene aerogel. The unique structure of the hybrid aerogel is responsible for the ultrasensitive, selective, and fast NO₂ sensing. The improved sensing performance of this hybrid aerogel also suggests the possibility of other 2D material combinations for further sensing applications.     

Growth of Vertically Aligned Tunable Polyaniline on Graphene/ZrO2 Nanocomposites for Supercapacitor Energy‐Storage Application

In‐situ hydrothermal method is employed to synthesize graphene/zirconium oxide composite from respective precursors graphene oxide and zirconium oxy‐nitrate. In this method, the graphene oxide is reduced itself to graphene and simultaneously metal oxide gets anchor on the graphene sheets. A novel method is also developed for the preparation of vertically aligned tunable polyaniline on the graphene/zirconium oxide nanocomposite, which leads to achieve high surface area (207.1 m² g^?1), high electrical conductivity (70.8 S cm^?1), high specific capacitance (1359.99 Fg^?1 at 1 mV s^?1), and high electrochemical performances as supercapacitor electrode materials. This vertically aligned conducting polymer gets easy contact with electrolyte ions and provides numerous redox active sites during charging and discharging. Moreover, such a simple and low cost assembly approach can be a pioneer for the large‐scale production of various functional architectures for energy storage and conversions.     

Electromechanical Actuators Based on Graphene and Graphene/Fe3O4 Hybrid Paper

Exceptionally high specific surface area, mechanical strength, electrical conductivity, and a special two‐dimensional structure make graphene a highly promising material for electromechanical actuators. Electromechanical actuators are fabricated using flexible graphene‐based paper prepared via a filtration process, and the stroke of these graphene‐based actuators is directly measured during electrochemical double‐layer charge injection. Actuation strain up to 0.064% was obtained for pristine graphene paper in response to an applied potential of –1 V in 1 M NaCl solution. Double‐layer charge injection in graphene sheets is believed to induce actuation strain through a combination of coulombic and quantum‐chemical‐based expansion. To increase electrochemical‐double‐layer capacitance and actuator performance, Fe₃O₄ nanoparticles were used to partially prevent graphene sheets from restacking and allow the electrolyte ions to infiltrate the resulting magnetic graphene paper more easily. The magnetic graphene paper exhibits actuation strain as large as 0.1% at –1 V applied potential, which is about 56% higher than that of the pristine graphene paper.