Thermal transport in MWCNT sheets and yarns

Laser flash and self-heating 3ω techniques were employed to determine the anisotropic thermal conductivity and thermal diffusivity of a highly oriented, free-standing multiwalled carbon nanotube (MWCNT) sheet and a yarn drawn from a sidewall of the MWCNT forest grown by chemical-vapor deposition. Normalized to ideal high density structure the thermal conductivity and the thermal diffusivity along the alignment are 50 ± 5 W/m K and 45 ± 5 mm²/s, respectively, and are mostly limited by dangling terminals of bundles, intrinsic defects of individual nanotubes and phonon scattering within the bundles, which form the supporting matrix of the MWCNT sheet. The high degree of tube–tube overlap substantially decreases the electrical and thermal interconnection resistance, which usually dominates in randomly deposited mat-like nanotube assemblies. The extremely high surface area of the MWCNT sheet leads to excessive radial heat radiation that does not allow transferring the heat energy along the MWCNT sheet by means of phonons to distances >2 mm. On the other hand, the high surface area and negligible heat capacitance make it a perfect material for bolometric sensing (r = 38 V/W) and heat dissipation.     

Effect of the nanostructure and surface chemistry on the gas adsorption properties of macroscopic multiwalled carbon nanotube ropes

The NO₂ adsorption properties of macroscopic multiwalled carbon nanotube (MWCNT) ropes and acid treated MWCNT ropes, obtained by the floating catalyst chemical vapour deposition process, have been examined. The structural characterisation shows that these ropes constitute bundles of MWCNTs. This bundled structure is found to control the electrical and gas adsorption properties of the material. The electrical resistance of these ropes decreases upon exposure to NO₂ with a high sensitivity even at room temperature. The adsorption of the NO₂ onto MWCNT bundles is found to be more stable with temperature in comparison to isolated MWCNTs revealing the complex nature of the adsorption process. These adsorption sites, which are created within the bundles of carbon nanotubes, are more stable requiring higher desorption energy. The surface of the MWCNT ropes is also modified with acid treatment, which increases the response to NO₂ by a factor 100% due to increased polar interactions between the gas molecules and the existing functionalised surface. These results suggest the possibility of using these macroscopic MWCNT ropes as low cost gas sensing materials.     

Preparation and thermal,electrical, and morphological properties of multiwalled carbon nanotubeand epoxy composites

Multiwalled carbon nanotube (MWCNT)/epoxy composites are prepared, and the characteristics and morphological properties are studied. Scanning electron microscopy microphotographs show that MWCNTs are dispersed on the nanoscale in the epoxy resin. The glass‐transition temperature (T_g) of MWCNT/epoxy composites is dramatically increased with the addition of 0.5 wt % MWCNT. The T_g increases from 167°C for neat epoxy to 189°C for 0.5 wt % CNT/epoxy. The surface resistivity and bulk resistivity are decreased when MWCNT is added to the epoxy resins. The surface resistivity of CNT/epoxy composites decreases from 4.92 × 10¹² Ω for neat epoxy to 3.03 × 10⁹ Ω for 1 wt % MWCNT/epoxy. The bulk resistivity decreases from 8.21 × 10¹⁶ Ω cm for neat epoxy to 6.72 × 10⁸ Ω cm for 1 wt % MWCNT/epoxy. The dielectric constant increases from 3.5 for neat epoxy to 5.5 for 1 wt % MWCNT/epoxy. However, the coefficient of thermal expansion is not affected when the MWCNT content is less than 0.5 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1272–1278, 2007     

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

Preparation, crystallization, electrical conductivity and thermal stability of syndiotactic polystyrene/carbon nanotube composites

A homogeneous dispersion of multi-walled carbon nanotubes (MWCNTs) in syndiotactic polystyrene (sPS) is obtained by a simple solution dispersion procedure. MWCNTs were dispersed in N-methyl-2-pyrrolidinone (NMP), and sPS/MWCNT composites are prepared by mixing sPS/NMP solution with MWCNT/NMP dispersion. The composite structure is characterized by scanning electron microscopy and transmission electron microscopy. The effect of MWCNTs on sPS crystallization and the composite properties are studied. The presence of MWCNTs increases the sPS crystallization temperature, broadens the crystallite size distribution and favors the formation of the thermodynamically stable β phase, whereas it has little effect on the sPS γ to α phase transition during heating. By adding only 1.0 wt.% pristine MWCNTs, the increase in the onset degradation temperature of the composite can reach 20 °C. The electrical conductivity is increased from 10^{−10∼−16} (neat sPS) to 0.135 S m⁻¹ (sPS/MWCNT composite with 3.0 wt.% MWCNT content). Our findings provide a simple and effective method for carbon nanotube dispersion in polymer matrix with dramatically increased electrical conductivity and thermal stability.     

Direct functionalization with 3,5‐substituted benzoic acids of multiwalled carbon nanotube/epoxy composites

Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (T_p) and exothermic heat of reaction (ΔH). The values of activation energy (E_a) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (f_g) decreased, resulting in dramatic increase of glass transition temperatures (T_g) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers     

Synthesis and properties of new polyamide/multiwalled carbon nanotube nanocomposites containing a pyridine group

The effects of multiwalled carbon nanotubes (MWCNTs) on the thermal properties and flame retardancy of a new polyamide (PA) derived from glutaric acid and aromatic diamine were investigated in this work. The synthesized PA containing pyridine and trialkylamine groups was characterized by ¹H NMR and SEC. The PA unit structure was geometrically optimized at the B₃LYP/6‐311⁺⁺G(d, p) level of theory. PA showed a glass transition temperature of 151 ºC. PA nanocomposites containing two different amounts of MWCNTs were prepared via the solution intercalation technique with the solvent N,N‐dimethylacetamide. Transmission electron microscopy showed that MWCNTs were exfoliated in the polymer matrix, resulting in well‐dispersed morphologies at 3 wt% MWCNT content. The redox behaviors of PA and the nanocomposites were examined using cyclic voltammetry (CV). PA showed a reversible oxidation process in the CV scan. Thermal and flammability properties of the nanocomposites were studied by TGA in nitrogen and air, DSC and with a microscale combustion calorimeter. The TGA results showed that the addition of MWCNTs resulted in a substantial increase in the thermal stability and char yields of the nanocomposites compared with neat PA. The heat release rate and total heat release were significantly reduced in the presence of MWCNTs. © 2013 Society of Chemical Industry     

固化石墨的渗透率测试

为了测试混合吸附剂的传质特性,设计了一套测试吸附剂渗透率的试验装置。在研究渗透率之前,先用平面热源法测试了散装石墨在不同膨胀温度及不同膨胀时间下的热导率,优选出了膨胀石墨的最佳膨胀工艺。然后采用最佳工艺对石墨进行膨胀,采用压力机与压制模具对石墨进行固化,而后以氮气作为气源,对膨胀石墨进行了固化及渗透率测试研究,研究发现,膨胀石墨的固化密度不同时,渗透率的大小差别较大,密度从100 kg.m-3到400 kg.m-3变化时,渗透率介于10-14～10-12m2之间变化。     

Surface modification of MWCNT and its influence on properties of paraffin/MWCNT nanocomposites as phase change material

Multiwalled carbon nanotubes (MWCNTs) were modified by an organo-silane in order to improve their dispersion state and stability in paraffin wax. A family of paraffin-based phase change material (PCM) composites filled with MWCNTs was prepared with different loadings (0, 0.1, 0.5, and 1 wt%) of pristine MWCNTs and organo-silane modified MWCNTs (Si-MWCNT). Structural analyses were performed by means of Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and rheological studies using temperature sweeps. Moreover, phase change transition temperatures and heat of fusion as well as thermal and electrical conductivities of the developed PCM nanocomposites were determined. The SEM micrographs and FTIR absorption bands appearing at approximately 1038 and 1112 cm⁻¹ confirmed the silane modification. Differential scanning calorimetery (DSC) results indicate that the presence of Si-MWCNTs leads to slightly favorable enhancement in the energy storage capacity at the maximum loading. It was also shown that the thermal conductivity of the PCM nanocomposites, in both solid and liquid phases, increased with increasing the MWCNT content independent of the kind of MWCNTs by up to about 30% at the maximum loading of MWCNTs. In addition, the modification of MWCNTs made the samples completely electrically nonconductive, and the electrical surface resistivity of the PCMs containing pristine MWCNTs decreased with increasing MWCNTs loading. Furthermore, the rheological assessment under consecutive cyclic phase change demonstrated that the samples containing modified MWCNTs are more stable compared to the PCM containing pristine MWCNTs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48428.     

Effect of low‐content carbon nanotubes on the dielectric and microwave absorption properties of graphite/polymer nanocomposites

Honeycomb cores (HCs) coated with graphite and multiwalled carbon nanotubes (MWCNTs) filled in a thermoplastic resin are proposed as microwave absorbers. The MWCNT contents varied from 0.2 to 0.6 wt % in a graphite‐filled (15 wt %) thermoplastic resin. The HCs were coated with three different types of coating materials for the sake of comparison: graphite, MWCNTs, and graphite plus MWCNTs. The dielectric properties [the real and imaginary parts of complex permittivity (ε′ and ε″, respectively)] and reflection loss (RL) of all of the coated HCs were measured and compared. We observed that the permittivities and RL increased significantly with increased weight percentage of the MWCNTs in the graphite‐filled thermoplastic resin. The RL measurements showed a maximum loss of ?20 dB around 7 GHz and a bandwidth of 2.7 GHz at ?10 dB in the HCs coated with the 0.4 wt % MWCNT plus graphite. There was also a shift in the RL peak position from the x band to the c band after the increase of MWCNT content. We also observed from the measurements that a combination of graphite and MWCNTs resulted in a broadband microwave absorber; a bandwidth of 13 GHz was observed for 80% RL when the MWCNT content increased to 0.6 wt % in the graphite‐incorporated resin. The possible mechanism that increased RL with the incorporation of MWCNTs in the graphite‐mixed thermoplastic resin is discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40891.     

Thermal properties and transition studies of multi-wall carbon nanotube/nylon-6 composites

Transition behavior and thermal properties of a multi-wall carbon nanotube (MWCNT)/nylon-6 composite (P-composite) made by in situ polymerization and subsequently structurally modified by high-pressure–high-temperature treatment have been established. The thermal conductivity (κ) of nylon-6 improved ∼27% by the addition of 2.1 wt.% MWCNT filler simultaneously as the heat capacity per unit volume decreased ∼22% compared with that of nylon-6 at 1 atm and 298 K. Moreover, the MWCNT filler raises the glass transition temperature (T_g) of nylon-6, but the pressure dependence of T_g remains unchanged. A model for κ indicates that the interfacial thermal resistance between the MWCNT filler and the nylon-6 matrix decreases 20% up to 1 GPa and most significantly above 0.8 GPa. P-composite was structurally modified by a sluggish cold-crystallization transition at 1.0 GPa, 530 K, which further increased κ by as much as ∼37% as the crystallinity of nylon-6 improved from 31% to 58% with a preferred crystal orientation and increased crystal size.     

Porous graphite matrix for chemical heat pumps

Expanded graphite powders were prepared by rapid heating of expandable graphite powders intercalated with sulfuric acid at different heat treatment temperatures (HTT). Porous graphite matrices with 100–400 kg m⁻³ of bulk density were fabricated by pressing expanded graphite powders in order to use as heat conductive media. They were characterized using an C/S analyzer, inductively coupled plasma spectroscopy, X-ray diffraction, scanning electron microscopy, Fourier transform infrared (FTIR), nitrogen adsorption, optical microscopy and helium pycnometer before and after heat treatment. Gas permeability and thermal conductivity were measured for porous graphite matrices with different HTT and bulk densities. Chemical analysis and FTIR showed that as the HTT of expandable graphite powders increase, the residual sulfur content decreased remarkably. Nitrogen adsorption experiments for expanded graphite powders showed that specific surface area and total pore volume increased with HTT. Helium penetration results showed that porous graphite matrices with different HTT have noticeably different open porosities which were attributed to the different degrees of expansion of graphite layers. The gas permeability of porous graphite matrices was in the range of 10⁻¹²–10⁻¹⁵ m² and exhibited higher values with low HTT. Thermal conductivity values in the axial and the radial directions were in the range of 4.1–20.0 and 4.6–42.3 W mK⁻¹, respectively. A semi-empirical model was developed that can be used to correlate with the thermal conductivity of graphite matrix on the basis of solid conductivity, bulk density and porosity.     

Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites

In this work the thermal properties of poly (l-lactide)/multi-wall carbon nanotube (PLLA/MWCNT) composites have been investigated. Thermal conductivity was determined after measuring specific heat capacity (C_p), thermal diffusivity (D) and bulk density (ρ) of composites. Thermal conductivity rises up to 0.345 W/m K at 5 wt.% after reaching a minimum value of about 0.12 W/m K at 0.75 wt.%. In order to understand the heat-conduction process, experimentally obtained thermal conductivities were fitted to an existing theoretical model. The much lower thermal conductivity of composites compared with the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction could be explained in terms of the obtained large thermal resistance (R_k) of 1.8 ± 0.3 × 10^?8 m² K/W at nanotube–matrix interface. The CNT dispersion in the composites was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Although the thermal resistance dramatically reduces the estimated bulk thermal conductivity of composites, the existence of an interconnected conductive nanotube network for thermal diffusion in PLLA/MWCNT composites demonstrates that the addition of carbon nanotubes represents an efficient strategy in order to successfully enhance the thermal conductivity of insulator polymers.     

Temperature and alkaline hydroxide treatment effects on hydrogen sorption characteristics of multi-walled carbon nanotube–graphite mixture

Temperature and alkaline hydroxide treatment effects on the surface area and pore structure of the cathode deposit multi-walled carbon nanotube (MWCNT)–graphite mixture were investigated in a temperature range of 600–800 °C. Hydrogen sorption properties of the MWCNT–graphite mixture samples were studied by varying the alkaline hydroxide-activation temperature. Pore characterization of modified MWCNT–graphite mixture was performed with the observation of adsorption–desorption isotherms of N₂ at 77 K. Hydrogen sorption of the non-treated and treated MWCNT–graphite mixture was carried out using a volumetric apparatus at 77 K. The highest surface area of the sample was obtained as 275 m² g^?1 by treatments with KOH at 600 °C. The increase in the specific surface area of MWCNT–graphite sample mixture was about 13 times. The maximum amount of hydrogen adsorbed on the MWCNT–graphite sample mixture was found as 0.75 and 0.54 wt.% by chemical treatments with KOH at 600 °C and NaOH at 700 °C, respectively whereas it was 0.01 wt.% for the original sample. The hydrogen sorption capacity was enhanced considerably by KOH treatments at 600 °C.     

Thermal properties of alkali‐activated aluminosilicate composite with lightweight aggregates at elevated temperatures

Thermal diffusivity, specific heat capacity and linear thermal expansion coefficient of a lightweight composite with alkali‐activated aluminosilicate binder and heat‐resistant aggregate mixture of expanded vermiculite and electrical porcelain are measured in a wide temperature range. Experimental results show that the studied material has good prerequisites for high‐temperature applications. The apparent thermal diffusivity at one‐sided heating is significantly lower than at room temperature, and decreases for temperatures higher than 400^°C. The effective specific heat capacity at elevated temperatures increases with temperature in almost the whole analyzed temperature range. The linear thermal expansion coefficient is substantially lower compared with common cement‐based composites. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of compatibilizer on morphology,thermal, and rheological properties of polypropylene/functionalized multi‐walled carbon nanotubes composite

Multi‐walled carbon nanotubes (MWCNTs) filled polypropylene (PP) composites were prepared by a corotating intermeshing twin screw extruder. To improve the dispersion of MWCNTs, the surface of MWCNT was modified with 1,10‐diaminodecane, and maleic anhydride grafted polypropylene (MA‐g‐PP) was used as a compatibilizer. Micrographs of well dispersed functionalized MWCNTs (diamine‐MWCNT) were observed due to the reaction between MA‐g‐PP and diamine‐MWCNT in PP/MA‐g‐PP/diamine‐MWCNTs composites. The different behaviors in crystallization and melting temperatures of PP/MA‐g‐PP/diamine‐MWCNTs composite were observed compared to PP and PP/neat‐MWCNT. Especially, the decomposition temperature of the composite was increased by 50°C compared to PP. PP/MA‐g‐PP/diamine‐MWCNTs composite showed the highest complex viscosity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheology,crystallization behaviors,and thermal stabilities of poly(butylene succinate)/pristine multiwalled carbon nanotube composites obtained by melt compounding

Poly(butylene succinate) (PBS)/pristine raw multiwalled carbon nanotube (MWCNT) composites were prepared in this work via simple melt compounding. Morphological observations indicated that the MWCNTs were well dispersed in the PBS matrix. Moreover, the incorporation of MWCNTs did not affect the crystal form of PBS as measured by wide‐angle X‐ray diffraction. The rheology, crystallization behaviors, and thermal stabilities of PBS/MWCNT composites were studied in detail. Compared with neat PBS, the incorporation of MWCNTs into the matrix led to higher complex viscosities (|η*|), storage modulus (G′), loss modulus (G″), shear thinning behaviors, and lower damping factor (tan δ) at low frequency range, and shifted the PBS/MWCNT composites from liquid‐like to solid‐like, which affected the crystallization behaviors and thermal stabilities of PBS. The presence of a very small quantity of MWCNTs had a significant heterogeneous‐nucleation effect on the crystallization of PBS, resulting in the enhancement of crystallization temperature, i.e., with the addition of 0.5 wt % MWCNTs, the values of T_c of PBS/MWCNT composites could attain to 90°C, about 6°C higher than that of neat PBS, whereas the values of T_c increased slightly with further increasing the MWCNTs content. The thermogravimetric analysis illustrated that the thermal stability of PBS was improved with the addition of MWCNTs compared with that of neat PBS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of molecular weight,stereo configuration of PLA,and processing on the dispersion of multiwalled carbon nanotubes and properties of corresponding nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were dispersed and distributed via a co-rotating twin-screw extruder (TSE) in high (h)- and low (l)-molecular-weight amorphous and semicrystalline polylactides (PLAs) (aPLA and scPLA, respectively). Effects of PLA molecular weight and D-lactic acid equivalents content (D-content), as well as processing parameters, were examined on the MWCNT dispersion quality in PLA. The effectiveness of the MWCNT dispersion in various PLA matrices was investigated using scanning electron microscopy (SEM) and small-amplitude oscillatory and transient shear flow rheometry in the molten state. The results showed a better dispersion of MWCNTs in the low-molecular-weight PLA grades (aPLAl and scPLAl). In addition, better MWCNT dispersion was observed in aPLA grades when processed at a higher temperature of 190°C than at 150°C. At 150°C, while MWCNT bundles in aPLAl could be broken down, a good dispersion could not be achieved in aPLAh due to the lower molecular mobility at such a temperature. The electrical conductivity of the samples was also shown to increase as the MWCNT dispersion was improved. The existence of crystallites in scPLA-based nanocomposites, however, disrupted the connectivity of the MWCNTs and decreased the final electrical conductivity. The lower molecular weight aPLAl prepared at 190°C showed the highest electrical conductivity (~10⁻⁵ S/m) at a low loading of 0.5 wt.% MWCNTs.     

Reduction of percolation threshold through double percolation in melt‐blended polycarbonate/acrylonitrile butadiene styrene/multiwall carbon nanotubes elastomer nanocomposites

We demonstrate a method that involves melt blending of polycarbonate (PC) and melt‐blended acrylonitrile butadiene styrene (ABS) with multiwall carbon nanotubes (MWCNTs) to prepare electrically conducting PC/MWCNT nanocomposites at significantly low MWCNT loading. The partial solubility of ABS in PC led to a selective dispersion of the MWCNTs in the ABS phase after melt‐blending PC and ABS. Thus, a sudden rise in electrical conductivity (∼10⁸ orders of magnitude) of the nanocomposites was found at 0.328 vol% of MWCNT, which was explained in terms of double percolation phenomena. By optimizing the ratio of PC and the ABS–MWCNT mixture, an electrical conductivity of 5.58 × 10⁻⁵ and 7.23 × 10⁻³ S cm⁻¹ was achieved in the nanocomposites with MWCNT loading as low as 0.458 and 1.188 vol%, respectively. Transmission electron microscopy revealed a good dispersion and distribution of the MWCNTs in the ABS phase, leading to the formation of continuous MWCNT network structure throughout the matrix even at very low MWCNT loading. Storage modulus and thermal stability of the PC were also increased by the presence of a small amount of MWCNTs in the nanocomposites.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

A flexible graphene/multiwalled carbon nanotube film as a high performance electrode material for supercapacitors

A flexible graphene/multiwalled carbon nanotube (GN/MWCNT) film has been fabricated by flow-directed assembly from a complex dispersion of graphite oxide (GO) and pristine MWCNTs followed by the use of gas-based hydrazine to reduce the GO into GN sheets. The GN/MWCNT (16 wt.% MWCNTs) film characterized by Fourier transformation infrared spectra, X-ray diffraction and scanning electron microscope has a layered structure with MWCNTs uniformly sandwiched between the GN sheets. The MWCNTs in the obtained composite film not only efficiently increase the basal spacing but also bridge the defects for electron transfer between GN sheets, increasing electrolyte/electrode contact area and facilitating transportation of electrolyte ion and electron into the inner region of electrode. Electrochemical data demonstrate that the GN/MWCNT film possesses a specific capacitance of 265 F g⁻¹ at 0.1 A g⁻¹ and a good rate capability (49% capacity retention at 50 A g⁻¹), and displays an excellent specific capacitance retention of 97% after 2000 continuous charge/discharge cycles. The results of electrochemical measurements indicate that the freestanding GN/MWCNT film has a potential application in flexible energy storage devices.