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Carbon aerogels (CAs) combine unique properties including ultra-high surface area, high electrical conductivity, corrosion resistance, and robust mechanical properties making them ideal materials for electrochemical applications. Traditional CA synthesis results in isotropic, random nanoporous networks that work well for applications relying on diffusional mass transport. However, many applications would benefit from integration of engineered macroporous network structures that enable directed pressure-gradient-driven mass transport. Here, we report on using 3D-printed sacrificial polymeric templates to generate templated CAs (t-CAs) with integrated engineered nonrandom macroporous network structures. Specifically, we used projection micro-stereo-lithography (PμSL) and two-photon polymerization direct laser writing (2PP-DLW) to fabricate millimeter-to-centimeter-sized 3D sacrificial polymeric templates with features ranging from tens of microns (PμSL) to 100s of nanometers (2PP-DLW). T-CAs were fabricated by infiltrating the templates with resorcinol-formaldehyde (RF) precursor solution, followed by carbonization at 1050 °C to simultaneously convert the RF gel to a CA and decompose the 3D-printed template, leaving an embedded templated macroporous network structure behind. X-ray computer tomography confirms integration of the macroporous architecture defined by the template. The templated macroporous architecture improves mass transport in t-CAs compared to traditional bulk CA as demonstrated by more uniform activation and their response in electrochemical cyclic voltammetry and galvanostatic charge-discharge tests.

Water absorption-desorption-resorption and swelling were studied for a DGEBA-based amine-cured epoxy resin filled with four types of carbon nanoparticles: multiwall carbon nanotubes (MWCNT), graphite nano-platelets (GnP), expanded graphite platelets, and carbon black. Nanocomposites are characterised by lower diffusivity (down to 20% for epoxy/GnP) and increased water sorption capacity compared to the neat epoxy. Anomalous water absorption and swelling of nanocomposites is finely described by the diffusion-relaxation model. The relaxation times, considered as quantitative indicators of changes in segmental mobility of the polymer, increased with addition of nanoparticles and decreased with temperature. Epoxy/MWCNT composites are characterised by the longest relaxation times (twofold increase) and highest Deborah numbers compared to the neat epoxy and other nanocomposites. Hydrothermal ageing effects and efficiency of nanoparticles on thermal and thermomechanical properties of the epoxy were estimated. Water uptake in nanocomposites is accompanied by several competing processes: plasticization, after-cure, and physical ageing of the polymer matrix.

Summary Retaining sound electrochemical performance of electrodes at high mass loading holds significant importance to energy storage. Pseudocapacitive materials such as manganese oxide (MnO2) deposited on current collectors have achieved outstanding gravimetric capacitances, sometimes even close to their theoretical values. Yet, this is only achievable with very small mass loading of active material typically less than 1 mg cm−2. Increasing mass loading often leads to drastic decay of capacitive performance due to sluggish ion diffusion in bulk material. Here, we demonstrate a 3D printed graphene aerogel electrode with MnO2 loading of 182.2 mg cm−2, which achieves a record-high areal capacitance of 44.13 F cm−2. Most importantly, this 3D printed graphene aerogel/MnO2 electrode can simultaneously achieve excellent capacitance normalized to area, gravimetry, and volume, which is the trade-off for most electrodes. This work successfully validates the feasibility of printing practical pseudocapacitive electrodes, which might revolutionize pseudocapacitor fabrication.

Electrochemical energy storage (EES) devices, such as lithium-ion batteries and supercapacitors, are emerging as primary power sources for global efforts to shift energy dependence from limited fossil fuels towards sustainable and renewable resources. These EES devices, while renowned for their high energy or power densities, portability, and long cycle life, are still facing significant performance hindrance due to manufacturing limitations. One major obstacle is the ability to engineer macroscopic components with designed and highly resolved nanostructures with optimal performance, via controllable and scalable manufacturing techniques. 3D printing covers several additive manufacturing methods that enable well-controlled creation of functional nanomaterials with three-dimensional architectures, representing a promising approach for fabrication of next-generation EES devices with high performance. In this review, we summarize recent progress in fabricating 3D functional electrodes utilizing 3D printing-based methodologies for EES devices. Specifically, laser-, lithography-, electrodeposition-, and extrusion-based 3D printing techniques are described and exemplified with examples from the literatures. Current challenges and future opportunities for functional materials fabrication via 3D printing techniques are also discussed.

A successful exploitation of nanocomposite materials founds on the development of models capable of predicting the macroscopic mechanical behaviour as a function of the nanostructure. To this end the most critical issue to overcome is the identification of the inherent mechanisms at the very nanoscale which might depend on the type, the morphology and the functionalisation of the nanofilleras well as on the loading conditions. Within this scenario, this work aims to review the main damage mechanisms reported in the literature for nano-reinforced thermosetting polymers, to include new insights and to discuss predictive models incorporating these mechanisms.

Aerographite (AG) is a mechanically robust, lightweight synthetic cellular material, which consists of a 3D interconnected network of tubular carbon [1]. The presence of open channels in AG aids to infiltrate them with polymer matrices, thereby yielding an electrical conducting and lightweight composite. Aerographite produced with densities in the range of 7-15 mg/cm(3) was infiltrated with a low viscous epoxy resin by means of vacuum infiltration technique. Detailed morphological and structural investigations on synthesized AG and AG/epoxy composite were performed by scanning electron microscopic techniques. The present study investigates the fracture and failure of AG/epoxy composites and its energy absorption capacity under compression. The composites displayed an extended plateau region when uni-axially compressed, which led to an increase in energy absorption of similar to 133% per unit volume for 1.5 wt% of AG, when compared to pure epoxy. Preliminary results on fracture toughness showed an enhancement of similar to 19% in K-IC for AG/epoxy composites with 0.45 wt% of AG. Observations of fractured surfaces under scanning electron microscope gives evidence of pull-out of arms of AG tetrapod, interface and inter-graphite failure as the dominating mechanism for the toughness improvement in these composites. These observations were consistent with the results obtained from photoelasticity experiments on a thin film AG/epoxy model composite. Published by Elsevier Ltd.

The present study investigates the effect of addition of three different types on carbon nano-fillers on fracture toughness ( K IC ) and failure mechanism of epoxy based polymer nano-composites. The carbon nano-fillers were dispersed in the epoxy matrix using a three-roll mill and the three nano-fillers used for this experiment were (i) thermally reduced graphene oxide (TRGO); (ii) graphite nano-platelets (GNP); and (iii) multi-wall carbon nano-tubes (MWCNT). The fracture toughness was measured as a function of weight percentage of the filler using single edge notch three-point-bending tests. The toughening effect of TRGO was most significant resulting in 40% increase in K IC for 0.5 wt% of filler. On the other hand, the enhancements in toughness were 25% for GNP/epoxy and 8% for MWCNT/epoxy. Investigations on fracture surface revealed that crack pinning or bi-furcation by TRGO and crack face separation initiated from TRGO contributed to enhance the fracture toughness. Based on the observations, a schematic explaining the crack propagation in graphene/epoxy composite and the interaction of crack front with graphene particles was proposed.

Epoxy based polymer nano-composite was prepared by dispersing graphite nano-platelets (GNPs) using two different techniques: three-roll mill (3RM) and sonication combined with high speed shear mixing (Soni_hsm). The influence of addition of GNPs on the electrical and thermal conductivity, fracture toughness and storage modulus of the nano-composite was investigated. The GNP/epoxy prepared by 3RM technique showed a maximum electrical conductivity of 1.8 × 10 −03 S/m for 1.0 wt% which is 3 orders of magnitude higher than those prepared by Soni_hsm. The percentage of increase in thermal conductivity was only 11% for 1.0 wt% and 14% for 2.0 wt% filler loading. Dynamic mechanical analysis results showed 16% increase in storage modulus for 0.5 wt%, although the Tg did not show any significant increase. Single edge notch bending (SENB) fracture toughens ( K IC ) measurements were carried out for different weight percentage of the filler content. The toughening effect of GNP was most significant at 1.0 wt% loading, where a 43% increase in K IC was observed. Among the two different dispersion techniques, 3RM process gives the optimum dispersion where both electrical and mechanical properties are better.

In this study fibre reinforced laminates with a graphene oxide modified epoxy matrix were manufactured using a filament winding technology for prepreg production. Dispersion of the nano-particles was achieved with a three roll mill. Cross-ply laminates with carbon and glass fibres and different nano-particle loadings were produced. Impact damage was introduced with an instrumented drop weight tower. Prior to mechanical testing damage size was determined using ultrasonic c-scans and pulse phase thermography. The defect size was reduced significantly with increasing graphene oxide loading in the matrix. Residual compressive properties of the laminates improved significantly for the modified specimen, with the glass fibre laminates showing the highest improvement of 55% when compared to unmodified specimens. In addition to the improved mechanical properties the matrix modification also improved the phase contrast of the thermography data thus enabling better detection of defects and improved detection limits.

The effect of thermally reduced graphene oxide (TRGO) on the electrical percolation threshold of multi wall carbon nanotube (MWCNT)/epoxy cured composites is studied along with their combined rheological/electrical behavior in their suspension state. In contrast to MWCNT and carbon black (CB) based epoxy composites, there is no prominent percolation threshold for the bi-filler (TRGO–MWCNT/epoxy) composite. Furthermore, the electrical conductivity of the bi-filler composite is two orders of magnitude lower (∼1 × 10 −5 S/m) than the pristine MWCNT/epoxy composites (∼1 × 10 −3 S/m). This result is primarily due to the strong interaction between TRGO and MWCNTs. Optical micrographs of the suspension and scanning electron micrographs of the cured composites indicate trapping of MWCNTs onto TRGO sheets. A morphological model describing this interaction is presented.

This study is focused on the investigation of thermo-mechanical properties of an epoxy resin filled with thermally reduced graphene oxide (TRGO) and multi-wall carbon nanotubes (MWCNT) after exposure of samples to hot distilled water. Addition of low contents of TRGO and MWCNTs greatly reduces the water sorption capacity of the epoxy polymer and improves its resistance to hydrothermal ageing. The glassy and rubbery moduli of the neat epoxy decreased for about 20% and 80%, respectively, while TRGO-based epoxy filled with 0.3 wt.% of TRGO showed only 6% reduction of both moduli. Hydrothermal ageing resulted in an enormous drop in the glass transition temperature (Tg) of the neat epoxy, by about 90 °C, while the shift in Tg of the nanocomposites did not exceed 8 °C. After re-drying of samples, the position and shape of the peak was completely recovered for the nanocomposites. Irreversibility of water influence on the neat polymer appeared in the broadened and shifted glass transition region. The improvement of the thermo-mechanical properties of the neat epoxy from the addition of TRGO is higher than that achieved by incorporating MWCNTs. This trend is valid in both unexposed state and after hydrothermal ageing of the nanocomposites.