Preparation and characterization of colorful graphene oxide papers and flexible N-doping graphene papers for supercapacitor and capacitive deionization

An efficient method that utilizes simple techniques,easy operation,and low-cost production to create flexible graphene-based materials is a worthy practical challenge.A rapid strategy for preparing flexible,functional graphene oxide(GO)is introduced using GO-ethanol dispersion filtration.The filtration process is highly efficient and drying time is significantly reduced by employing ethanol as solvent,due to the fact that ethanol is a volatile liquid.Freestanding GO papers can be harvested with ultralarge size(700 cm2),color variety,and writable characteristics.After reduction,N-doped graphene(NDG)papers still maintain good foldability with improved electric conductivity and porous structure.When used as an electrode for a supercapacitor,the flexible NDG paper device demonstrates good electrochemical performance even with size expansion and extreme double folding.Moreover,this NDG paper capacitor device shows a good electrosorption performance for capacitive deionization of sulfate and chromate in groundwater system.These flexible GO and NDG papers promise potential to facilitate the production of graphene-based materials for practical applications in energy and environmental related fields.

Corrugated Graphene Paper Reinforced Silicone Resin Composite for Efficient Interface Thermal Management

With the rapid development of high-power-density electronic devices,interface thermal resistance has become a critical barrier for effective heat management in high-performance electronic products.Therefore,there is an urgent demand for advanced thermal interface materials(TIMs)with high cross-plane thermal conductivity and excellent compressibility to withstand increasingly complex operating conditions.To achieve this aim,a promising strategy involves vertically arranging highly thermoconductive graphene on polymers.However,with the currently available methods,achieving a balance between low interfacial thermal resistance,bidirectional high thermal conductivity,and large-scale production is challenging.Herein,we prepared a graphene framework with continuous filler structures in in-plane and cross-plane directions by bonding corrugated graphene to planar graphene paper.The interface interaction between the graphene paper framework and polymer matrix was enhanced via surface functionalization to reduce the interface thermal resistance.The resulting three-dimensional thermal framework endows the polymer composite material with a cross-plane thermal conductivity of 14.4 W·m^(-1)·K^(-1)and in-plane thermal conductivity of 130W·m^(-1)·K^(-1)when the thermal filler loading is 10.1 wt%,with a thermal conductivity enhancement per 1 wt%filler loading of 831%,outperforming various graphene structures as fillers.Given its high thermal conductivity,low contact thermal resistance,and low compressive modulus,the developed highly thermoconductive composite material demonstrates superior performance in TIM testing compared with TFLEX-700,an advanced commercial TIM,effectively solving the interfacial heat transfer issues in electronic systems.This novel filler structure framework also provides a solution for achieving a balance between efficient thermal management and ease of processing.

Interface optimization of graphene paper-Cu composite prepared by electrodeposition

A room-temperature electrodeposition method with an organic electrolyte was developed to fabricate a HNO3-pretreated graphene paper Cu(GP'-Cu)composite.To improve the interfacial bonding of GP'-Cu composite,magnetron sputtering technology was used to create a"sandwich"structural gradient GP'-Cu composite.The selection of the intermediate transition layer metal was based on two-dimensional disregistry.Scanning electron microscopy,X-ray photoelectron spectroscopy,and other analytical methods confirmed that the addition of an intermediate transition metal(Cr,Ni)layer reduced the gap distance and enhanced the interfacial bonding of the GP'and Cu deposited layers.The GP'-Ni-Cu composite exhibited the largest increase in tensile strength and conductivity.In addition,it had the highest thermal diffusivity and elongation at break among the GP'-Cu,GP'-Cr-Cu and GP'-Ni-Cu composites.

Highly electrically conductive graphene papers via catalytic graphitization

The highly electrically conductive graphene papers prepared from graphene oxide have shown promising perspectives in flexible electronics,electromagnetic interference(EMI)shielding,and electrodes.To achieve high electrical conductivity,the graphene oxide precursor usually needs to be graphitized at extremely high temperature(~2,800°C),which severely increases the energy consumption and production costs.Here,we report an efficient catalytic graphitization approach to fabricate highly conductive graphene papers at lower annealing temperature.The graphene papers with boron catalyst annealed at 2,000°C show a high conductivity of~3,400 S·cm^(-1),about 47%higher than pure graphene papers.Boron catalyst facilitates the recovery of structural defects and improves the degree of graphitization by 80%.We further study the catalytic effect of boron on the graphitization behavior of graphene oxide.The results show that the activation energy of the catalytic graphitization process is as low as 80.1 kJ·mol^(–1)in the temperature ranges studied.This effective strategy of catalytic graphitization should also be helpful in the fabrication of other kinds of highly conductive graphene macroscopic materials.

Porous graphene paper for supercapacitor applications

Graphene paper shows a great promise for the electrical energy storage. However, the high stability, purity and specific surface area have become stringent requirements for supercapacitor applications. Finding methods to tackle these problems is rather challenging. Here, we develop a facile method to prepare porous graphene papers with a thickness 0.5 mm by a thermal shock to the layer-structure graphene paper self-assembled on Cu foil under nitrogen flowing. The as-prepared porous graphene paper exhibits a large specific capacitance of 100 Fg-1at the scan rate of 100 mVs-1with high stability and purity without any residual chemical reagents, showing a promising potential for supercapacitor applications. The high electrochemical properties are mainly attributed to the high-specific area and the improved conductivity of the porous graphene paper performed by the multieffect of reducing, cleaving and expanding to the layer-structure graphene paper by high-energy thermal heating during the thermal shock process. This work paves a pathway to the facile preparation of porous graphene paper for supercapacitor applications.

Strong and tough graphene papers constructed with pyrene-containing small molecules via π-π/Hbonding synergistic interactions

Lightweight yet strong paper with high toughness is desirable especially for impact protection. Herein we demonstrated electrically conductive and mechanically robust paper(AP/PB-GP) made of reduced graphene oxide via interfacial crosslinking with 1-aminopyrene(AP) and 1-pyrenebutyrat(PB) small molecules. The AP/PB-GP with thickness of over ten micrometer delivers a record-high toughness(~69.67 ± 15.3 MJ m^(-3) in average), simultaneously with superior strength(close to 1 GPa), allowing an impressive specific penetration energy absorption(~0.17 MJ kg^(-1)) at high impact velocities when used for ballistic impact protection. Detailed interfacial and structural analysis reveals that the reinforcement is synergistically determined by π-π interaction and H-bonding linkage between adjacent graphene lamellae. Especially, the defective pores within the graphene platelets benefit the favorable adsorption of the pyrene-containing molecules, which imperatively maximizes the interfacial binding, facilitating deflecting crack and plastic deformation under loading. Density functional theory simulation suggests that the coupling between the polar functional groups, e.g., –COOH, at the edges of graphene platelets and –NH_(2) and –COOH of AP/PB are critical to the formation of hydrogen bonding network.

3D hierarchically porous NiO/Graphene hybrid paper anode for long-life and high rate cycling flexible Li-ion batteries

With the rapid emergence of wearable devices, flexible lithium-ion batteries(LIBs) are much more needed than ever. Free-standing graphene-based composite paper electrodes with various active materials have appealed wide applications in flexible LIBs. However, due to the prone-to-restacking feature of graphene layers, a long cycle life at high current densities is rather difficult to be achieved. Herein, a unique threedimensional(3D) hierarchically porous NiO micro-flowers/graphene paper(fNiO/GP) electrode is successfully fabricated. The resulting fNiO/GP electrode shows superior long-term cycling stability at high rates(e.g., storage capacity of 359 mAh/g after 600 cycles at a high current density of 1 A/g). The facile 3D porous structure combines both the advantages of the graphene that is highly conductive and flexible to ensure rapid electrons/ions transfer and buffer the volume expansion of NiO during charge/discharge,and of the micro-sized NiO flowers that induces hierarchical between-layer pores ranging from nanomicro meters to promote the penetration of the electrolyte and prevent the re-stacking of graphene layers. Such structural design will inspire future manufacture of a wide range of active materials/graphene composite electrodes for high performance flexible LIBs.

A Facile Route for the Large Scale Fabrication of Graphene Oxide Papers and Their Mechanical Enhancement by Cross-linking with Glutaraldehyde

A facile route for the large scale production of graphene oxide(GO) papers and their mechanical enhancement has been presented in this work. The novel paper-like GO made from individual GO sheets in aqueous suspension can be achieved in large scale by a simple drop casting method on hydrophobic substrates.Significant enhancement in mechanical stiffness(341%) and fracture strength(234%) of GO paper have been achieved upon modification with a small amount(less than 10 wt%) of glutaraldehyde(GA). The cross-linking reaction takes place between hydroxyl groups on the surface of GO and aldehyde groups of GA, through forming hemiacetal structure, which can result in distinct mechanical enhancement of the GO papers.

Mode-Locked Thulium Ytterbium Co-Doped Fiber Laser with Graphene Oxide Paper Saturable Absorber

A mode-locked thulium ytterbium co-doped fiber laser （TYDFL） is proposed and demonstrated by using a commercial graphene oxide （GO） paper as saturable absorber （SA）. The GO paper is sandwiched between two fiber ferrules and incorporates a ring laser cavity to generate soliton pulse train operating at 1942.0nm at a threshold multimode pump power as low as 1.8 W. The mode-locked TYDFL has a repetition rate of 22.32 MHz and the calculated pulse width of 1.1 ns. Even though the SA has a low damage threshold, the easy fabrication of GO paper should promote its potentiM application in ultrafast photonics.

Graphene oxide paper as a saturable absorber for Er-and Tm-doped fiber lasers

In this work pulse generation in both the 1.5 and 2 μm spectral ranges using a graphene oxide(GO)-paper-based saturable absorber in Er-and Tm-doped fiber lasers is presented. The article describes the fabrication method of GO paper and its characterization. The performance of both lasers is discussed in detail. Stable, mode-locked operation provides 613 fs and 1.36 ps soliton pulses centered at 1565.9 and 1961.6 nm in Er-and Tm-doped fiber lasers, respectively. Furthermore, scaling of spectral width, and hence the pulse duration, by increasing the number of GO paper layers in the Er-doped laser is described. The versatility and simplicity of GO paper fabrication combined with the possibility of scaling the optical spectrum full width at half-maximum are essential features that make it a good candidate for ultrafast low-power mode-locked lasers operating in different spectral regions.

FACILE REGULATION OF GLUTARALDEHYDE-MODIFIED GRAPHENE OXIDE FOR PREPARING FREE-STANDING PAPERS AND NANOCOMPOSITE FILMS

Colloidal suspensions of glutaraldehyde （GA） crosslinked or grafted graphene oxide （GO） sheets were fabricated by simply tailoring the feed sequence. The different structures were confirmed by Fourier transform infrared spectra and X-ray diffraction. As demonstration of the utilities, the different colloidal suspensions were used to prepare free-standing papers by flow-directed filtration and poly（vinyl alcohol） （PVA）-based nanocomposite films by casting. Free-standing papers from GA crosslinked GO sheets exhibited better mechanical properties than unmodified GO paper, while nanocomposite films from GA grafted GO exhibit higher tensile strength and Young＇s modulus.

Eco-friendly non-acid intercalation and exfoliation of graphite to graphene nanosheets in the binary-peroxidant system for EMI shielding

The development of the preparation strategy for high-quality and large-size graphene via eco-friendly routes is still a challenging issue.Herein,we have successfully developed a novel route to chemically exfoliate natural graphite into high-quality and large-size graphene in a binary-peroxidant system.This system is composed of urea peroxide(CO(NH_(2))_(2)·H_(2)O_(2))and hydrogen peroxide(H_(2)O_(2)),where CO(NH_(2))_(2)·H_(2)O_(2)is used in preparing graphene for the first time.Benefiting from the complete decomposition of CO(NH_(2))_(2)·H_(2)O_(2)and H_(2)O_(2)into gaseous species under microwave(MW)irradiation,no water-washing and effluent-treatment are needed in this chemical exfoliation procedure,thus the preparation of graphene in an eco-friendly way is realized.The resultant graphene behaves a large-size,high-quality and few-layer feature with a yield of~100%.Then 4µm-thick ultrathin graphene paper fabricated from the as-exfoliated graphene is used as an electromagnetic interference(EMI)shielding material.And its absolute effectiveness of EMI shielding(SSE/t)is up to 34,176.9 dB cm^(2)/g,which is,to the best of our knowledge,among the highest values so far reported for typical EMI shielding materials.The EMI shielding performance demonstrates a great application potential of graphene paper in meeting the ever-increasingly EMI shielding demands in miniaturized electronic devices.