Thermally Conductive Reduced Graphene Oxide Thin Films for Extreme Temperature Sensors

Reduced graphene oxide (RGO) films are promising in applications ranging from electronics to flexible sensors. Though high electrical and thermal conductivities have been reported for RGO films, existing thermal conductivity data for RGO films show large variations from 30 to 2600 W m^?1 K^?1. Further, there is a lack of data at low temperatures (<300 K), which is critical for the understanding of thermal transport mechanisms. In this work, a temperature‐dependent study of thermal (10–300 K) and electrical (10–3000 K) transport in annealed RGO films indicates the potential application of RGO films for sensing temperatures across an extremely wide range. The room‐temperature thermal conductivity increases significantly from 46.1 to 118.7 W m^?1 K^?1 with increasing annealing temperature from 1000 to 3000 K with a corresponding increase in the electrical conductivity from 5.2 to 1481.0 S cm^?1. In addition, films reduced at 3000 K are promising for sensing extreme temperatures as demonstrated through the measured electrical resistivity from 10 to 3000 K. Sensors based on RGO films are advantageous over conventional temperature sensors due to the wide temperature range and flexibility. Thus, this material is useful in many applications including flexible electronics and thermal management systems.     

Functional Free‐Standing Graphene Honeycomb Films

Fabricating free‐standing, three‐dimensional (3D) ordered porous graphene structure can service a wide range of functional materials such as environmentally friendly materials for antibacterial medical applications and efficient solar harvesting devices. A scalable solution processable strategy is developed to create such free‐standing hierarchical porous structures composed of functionalized graphene sheets via an “on water spreading” method. The free‐standing film shows a large area uniform honeycomb structure and can be transferred onto any substrate of interest. The graphene‐based free‐standing honeycomb films exhibit superior broad spectrum antibacterial activity as confirmed using green fluorescent protein labeled Pseudomonas aeruginosa PAO1 and Escherichia coli as model pathogens. Functional nanoparticles such as titanium dioxide (TiO₂) nanoparticles can be easily introduced into conductive graphene‐based scaffolds by premixing. The formed composite honeycomb film electrode shows a fast, stable, and completely reversible photocurrent response accompanying each switch‐on and switch‐off event. The graphene‐based honeycomb scaffold enhances the light‐harvesting efficiency and improves the photoelectric conversion behavior; the photocurrent of the composite film is about two times as high as that of the pure TiO₂ film electrode. Such composite porous films combining remarkably good electrochemical performance of graphene, a large electrode/electrolyte contact area, and excellent stability during the photo‐conversion process hold promise for further applications in water treatment and solar energy conversion.     

Free‐Standing Functionalized Graphene Oxide Solid Electrolytes in Electrochemical Gas Sensors

A free‐standing sulfonic acid functionalized graphene oxide (fSGO)‐based electrolyte film is prepared and used in an electrochemical gas sensor, an alcohol fuel cell sensor (AFCS), for the detection of alcohol. The fSGO electrolyte film‐based AFCS detects ethanol vapor with excellent response, linearity, and sensitivity, since it possesses a high proton conductivity (58 mS cm^?1 at 55 °C). An ethanol detection limit level as low as 25 ppm is achieved and high selectivity for ethanol over acetone is demonstrated. These results do not only show the promising potential of fSGO films in an electrochemical gas sensors, specifically a portable breathalyzer, but also open an alternative pathway to investigate the application of graphene derivatives in the field of gas sensors.     

Structured Reduced Graphene Oxide/Polymer Composites for Ultra‐Efficient Electromagnetic Interference Shielding

A high‐performance electromagnetic interference shielding composite based on reduced graphene oxide (rGO) and polystyrene (PS) is realized via high‐pressure solid‐phase compression molding. Superior shielding effectiveness of 45.1 dB, the highest value among rGO based polymer composite, is achieved with only 3.47 vol% rGO loading owning to multi‐facet segregated architecture with rGO selectively located on the boundaries among PS multi‐facets. This special architecture not only provides many interfaces to absorb the electromagnetic waves, but also dramatically reduces the loading of rGO by confining the rGO at the interfaces. Moreover, the mechanical strength of the segregated composite is dramatically enhanced using high pressure at 350 MPa, overcoming the major disadvantage of the composite made by conventional‐pressure (5 MPa). The composite prepared by the higher pressure shows 94% and 40% increment in compressive strength and compressive modulus, respectively. These results demonstrate a promising method to fabricate an economical, robust, and highly efficient EMI shielding material.     

Thickness Dependence of the Mechanical Properties of Free‐Standing Graphene Oxide Papers

Graphene oxide (GO) papers are candidates for structural materials in modern technology due to their high specific strength and stiffness. The relationship between their mechanical properties and structure needs to be systematically investigated before they can be applied to the broad range fields where they have potential. Herein, the mechanical properties of GO papers with various thicknesses (0.5–100 μm) are investigated using bulge and tensile test methods; this includes the Young's modulus, fracture strength, fracture strain, and toughness. The Young's modulus, fracture strength, and toughness are found to decrease with increasing thickness, with the first two exhibiting differences by a factor of four. In contrast, the fracture strain slightly increases with thickness. Transmission electron, scanning electron, and atomic force microscopy indicate that the mechanical properties vary with thickness due to variations in the inner structure and surface morphology, such as crack formation and surface roughness. Thicker GO papers are weaker because they contain more voids that are produced during the fabrication process. Surface wrinkles and residual stress are found to result in increased fracture strain. Determination of this structure–property relationship provide improved guidelines for the use of GO‐based thin‐film materials in mechanical structures.     

Self‐Healing Reduced Graphene Oxide Films by Supersonic Kinetic Spraying

The industrial scale application of graphene and other functional materials in the field of electronics has been limited by inherent defects, and the lack of simple deposition methods. A simple spray deposition method is developed that uses a supersonic air jet for a commercially available reduced graphene oxide (r‐GO) suspension. The r‐GO flakes are used as received, which are pre‐annealed and pre‐hydrazine‐treated, and do not undergo any post‐treatment. A part of the considerable kinetic energy of the r‐GO flakes entrained by the supersonic jet is used in stretching the flakes upon impact with the substrate. The resulting “frozen elastic strains” heal the defects (topological defects, namely Stone‐Wales defect and C₂ vacancies) in the r‐GO flakes, which is reflected in the reduced ratio of the intensities of the D and G bands in the deposited film. The defects can also be regenerated by annealing.     

Electrical Conductivity and Ferromagnetism in a Reduced Graphene–Metal Oxide Hybrid

The rare coexistence of ferromagnetism and electrical conductivity is observed in the reduced graphene oxide–metal oxide hybrids, rGO‐Co, rGO‐Ni, and rGO‐Fe, using chemical reduction with hydrazine or ultraviolet photoirradiation of the graphene oxide–metal complexes, GO‐Co, GO‐Ni, and GO‐Fe. The starting and final materials are characterized by X‐ray photoelectron spectroscopy, transmission electron microscopy (TEM), elemental analysis, Mössbauer spectroscopy, and Raman spectroscopy. In contrast to graphene, where the electrical conductivity and magnetic properties are controlled by carrier (electron or hole) doping, those of graphene oxide can be controlled by complexation with Co²⁺, Ni²⁺, and Fe³⁺ cations through the strong electrostatic affinity of negatively charged graphene oxide towards metal cations. The presence of ferromagnetism and electrical conductivity in these hybrids can promote significant applications including magnetic switching and data storage.     

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.     

A Controllable Self‐Assembly Method for Large‐Scale Synthesis of Graphene Sponges and Free‐Standing Graphene Films

A simple method to prepare large‐scale graphene sponges and free‐standing graphene films using a speed vacuum concentrator is presented. During the centrifugal evaporation process, the graphene oxide (GO) sheets in the aqueous suspension are assembled to generate network‐linked GO sponges or a series of multilayer GO films, depending on the temperature of a centrifugal vacuum chamber. While sponge‐like bulk GO materials (GO sponges) are produced at 40 °C, uniform free‐standing GO films of size up to 9 cm² are generated at 80 °C. The thickness of GO films can be controlled from 200 nm to 1 µm based on the concentration of the GO colloidal suspension and evaporation temperature. The synthesized GO films exhibit excellent transparency, typical fluorescent emission signal, and high flexibility with a smooth surface and condensed density. Reduced GO sponges and films with less than 5 wt% oxygen are produced through a thermal annealing process at 800 °C with H₂/Ar flow. The structural flexibility of the reduced GO sponges, which have a highly porous, interconnected, 3D network, as well as excellent electrochemical properties of the reduced GO film with respect to electrode kinetics for the [Fe(CN)₆]^3?/4? redox system, are demonstrated.     

Regulating Cellular Behavior on Few‐Layer Reduced Graphene Oxide Films with Well‐Controlled Reduction States

Understanding the effect of graphene on cellular behavior is important for enabling a range of new biological and biomedical applications. However, due to the complexity of cell responses and graphene surface states, regulating cellular behaviors on graphene or its derivatives is still a great challenge. To address this challenge we have developed a novel, facile route to regulate the cellular behaviors on few‐layer reduced graphene oxide (FRGO) films by controlling the reduction states of graphene oxide. Our results indicate that the surface oxygen content of FRGO has a strong influence on cellular behavior, with the best performance for cell attachment, proliferation and phenotype being obtained in moderately reduced FRGO. Cell performance decreased significantly as the FRGO was highly reduced. Moderate performance was found in non‐reduced pure graphene oxide and control glass slides. Our results highlight the important role of surface physicochemical characteristics of graphene and its derivatives in their interactions with biocomponents, and may have great potential in enabling the utility of graphene based materials in various biomedical and bioelectronic applications.     

Flexible and Transparent Nanocomposite of Reduced Graphene Oxide and P(VDF‐TrFE) Copolymer for High Thermal Responsivity in a Field‐Effect Transistor

A new class of temperature‐sensing materials is demonstrated along with their integration into transparent and flexible field‐effect transistor (FET) temperature sensors with high thermal responsivity, stability, and reproducibility. The novelty of this particular type of temperature sensor is the incorporation of an R‐GO/P(VDF‐TrFE) nanocomposite channel as a sensing layer that is highly responsive to temperature, and is optically transparent and mechanically flexible. Furthermore, the nanocomposite sensing layer is easily coated onto flexible substrates for the fabrication of transparent and flexible FETs using a simple spin‐coating method. The transparent and flexible nanocomposite FETs are capable of detecting an extremely small temperature change as small as 0.1 °C and are highly responsive to human body temperature. Temperature responsivity and optical transmittance of transparent nanocomposite FETs were adjustable and tuneable by changing the thickness and R‐GO concentration of the nanocomposite.     

High Performance Three‐Dimensional Chemical Sensor Platform Using Reduced Graphene Oxide Formed on High Aspect‐Ratio Micro‐Pillars

The sensing performance of chemical sensors can be achieved not only by modification or hybridization of sensing materials but also through new design in device geometry. The performance of a chemical sensing device can be enhenced from a simple three‐dimensional (3D) chemiresistor‐based gas sensor platform with an increased surface area by forming networked, self‐assembled reduced graphene oxide (R‐GO) nanosheets on 3D SU8 micro‐pillar arrays. The 3D R‐GO sensor is highly responsive to low concentration of ammonia (NH₃) and nitrogen dioxide (NO₂) diluted in dry air at room temperature. Compared to the two‐dimensional planar R‐GO sensor structure, as the result of the increase in sensing area and interaction cross‐section of R‐GO on the same device area, the 3D R‐GO gas sensors show improved sensing performance with faster response (about 2%/s exposure), higher sensitivity, and even a possibly lower limit of detection towards NH₃ at room temperature.     

Polyoxometalate‐Modified Sponge‐Like Graphene Oxide Monolith with High Proton‐Conducting Performance

Graphene oxide (GO) contains abundant oxygen‐containing functional groups acting as hydrogen bond acceptors for proton conduction on its basal plane. However, the dilemma in realizing bulk in‐plane conduction and the metastability at room temperature of GO films both obstruct its application. Polyoxometalate‐modified sponge‐like GO monolith (PEGO) with 3D cross‐linking inner structure, which exhibits unique “shrink‐expand” effect to polar solvent, are synthesized. Owing to the introduction of polyoxometalates and the replacement of unstable epoxy groups by ethylenediamine, PEGO exhibits hitherto the highest proton conductivity under low relative humidity (1.02 × 10^?2 S cm^?1 at 60% relative humidity) and excellent long‐term stability (more than 1 month). The outstanding conductivity originates from 3D transporting pathways, high‐density hopping sites, and eliminated grain boundary resistance. This study provides a practical way to design GO‐based proton‐conducting material dominated by in‐plane diffusion.     

Multi‐Alternating Organic Semiconducting Films with High Electric Conductivity

High electric conductivity is observed in multilayer stack of m‐MTDATA/F₁₆CuPc. Impedance data shows that the circuit resistance is significantly dropped by three orders of magnitude from ～0.2 MΩ to ～0.4 kΩ when the number of alternating units is increased from one to six, keeping a total thickness of 300 nm. Impedance results show that as the number of alternating units increases, the organic stack shows an increasing capacitance and a decreasing resistance. This result suggests the increasing charges accumulate at the heterojunctions, leading to reduction in overall film resistance. The application of the high conductive units in OLED device results in stability enhancement.     

Large‐Area Reduced Graphene Oxide Composite Films for Flexible Asymmetric Sandwich and Microsized Supercapacitors

Asymmetric supercapacitors have attracted tremendous attention in energy storage devices since they have an enhanced energy density in comparison with symmetric supercapacitor devices. Furthermore, the development of diverse and flexible electronic devices requires the asymmetric supercapacitor devices to be flexible and in various configurations. However, it is still a challenge to develop a universal strategy to obtain both capacitive and Faradic electrodes with various architectures. Herein, a spontaneously reducing/assembling strategy in an alkaline condition is developed to fabricate large‐area reduced graphene oxide (RGO) and RGO–metal oxide/hydroxide composite films or microsized structures. As a proof of concept, the large‐area pure RGO and RGO/Mn₃O₄ composite films with porous structure and superior mechanical property are achieved by such strategy. These RGO‐based films can directly serve as the anodes and cathodes of the flexible asymmetric film supercapacitors. Furthermore, the interdigital RGO and RGO/Mn₃O₄ patterns are also obtained via a selectively reducing/assembling process to achieve the asymmetric microsized supercapacitors. These asymmetric supercapacitors with different configurations possess good electrochemical performance and excellent flexibility. Therefore, such reducing and assembling strategy provides a route to achieve large‐area RGO‐based films and microsized structures for the applications in the various fields such as energy storage and photocatalysis.     

Self‐Assembly of Flexible Free‐Standing 3D Porous MoS2‐Reduced Graphene Oxide Structure for High‐Performance Lithium‐Ion Batteries

Flexible freestanding electrodes are highly desired to realize wearable/flexible batteries as required for the design and production of flexible electronic devices. Here, the excellent electrochemical performance and inherent flexibility of atomically thin 2D MoS₂ along with the self‐assembly properties of liquid crystalline graphene oxide (LCGO) dispersion are exploited to fabricate a porous anode for high‐performance lithium ion batteries. Flexible, free‐standing MoS₂–reduced graphene oxide (MG) film with a 3D porous structure is fabricated via a facile spontaneous self‐assembly process and subsequent freeze‐drying. This is the first report of a one‐pot self‐assembly, gelation, and subsequent reduction of MoS₂/LCGO composite to form a flexible, high performance electrode for charge storage. The gelation process occurs directly in the mixed dispersion of MoS₂ and LCGO nanosheets at a low temperature (70 °C) and normal atmosphere (1 atm). The MG film with 75 wt% of MoS₂ exhibits a high reversible capacity of 800 mAh g^?1 at a current density of 100 mA g^?1. It also demonstrates excellent rate capability, and excellent cycling stability with no capacity drop over 500 charge/discharge cycles at a current density of 400 mA g^?1.     

Ultrahigh Electrical Conductivity of Graphene Embedded in Metals

Highly efficient conductors are strongly desired because they can lead to higher working performance and less energy consumption in their wide range applications. However, the improvements on the electrical conductivities of conventional conductors are limited, such as purification and growing single crystal of metals. Here, by embedding graphene in metals (Cu, Al, and Ag), the trade‐off between carrier mobility and carrier density is surmount in graphene, and realize high electron mobility and high electron density simultaneously through elaborate interface design and morphology control. As a result, a maximum electrical conductivity three orders of magnitude higher than the highest on record (more than 3,000 times higher than that of Cu) is obtained in such embedded graphene. As a result, using the graphene as reinforcement, an electrical conductivity as high as ≈117% of the International Annealed Copper Standard and significantly higher than that of Ag is achieved in bulk graphene/Cu composites with an extremely low graphene volume fraction of only 0.008%. The results are of significance when enhancing efficiency and saving energy in electrical and electronic applications of metals, and also of interest for fundamental researches on electron behaviors in graphene.     

Fabrication of Highly Flexible,Scalable, and High‐Performance Supercapacitors Using Polyaniline/Reduced Graphene Oxide Film with Enhanced Electrical Conductivity and Crystallinity

With developments in technology, tremendous effort has been devoted to produce flexible, scalable, and high‐performance supercapacitor electrode materials. This report presents a novel fabrication method of highly flexible and scalable electrode material for high‐performance supercapacitors using solution‐processed polyaniline (PANI)/reduced graphene oxide (RGO) hybrid film. SEM, TEM, Raman, and XPS analyses show that the PANI/RGO film is successfully synthesized. The percentages of the PANI component in the film are controlled (88, 76, and 60%), and the maximum electrical conductivity (906 S cm^?1) is observed at the PANI percentage of 76%. Notably, electrical conductivity of the PANI/RGO film (906 S cm^?1) is larger than both PANI (580 S cm^?1) and RGO (46.5 S cm^?1) components. XRD analysis demonstrates that the strong π–π interaction between the RGO and the PANI cause more compact packing of the PANI chains by inducing more fully expanded conformation of the PANI chains in the solution, leading to increase in the electrical conductivity and crystallinity of the film. The PANI/RGO film also displays diverse advantages as a scalable and flexible electrode material (e.g., controllable size and great flexibility). During the electrochemical tests, the film exhibits high capacitance of 431 F g^?1 with enhanced cycling stability.