High Potential of Aerosol-Made 3D Graphene-Based Composites for Enhanced Energy Storage.

Recently, many researchers have developed advanced energy storage and energy conversion systems to address the increased demand for energy resources. The performance of these electrochemical energy storage and conversion devices depends considerably on the properties of their unique electrode materials. Among electrode materials, graphene (GR) has attracted much attention due to its unique properties of high flexibility, a large specific surface area, and superior electric conductivity rates that are well-suited to energy storage systems. Specifically, aerosol-made 3D GR composites are known to be more resistant to compressive forces such as paper balls owing to their stronger and harder compressive tolerance levels and higher and more stable surface areas compared to 2D GR sheets. These unique properties of 3D GR composites result in enhanced electrochemical performances for energy storage systems. This review focuses on recent studies of aerosol-made 3D GR-based composites for energy storage systems such as supercapacitors, lithium-ion batteries, and sodium-ion batteries.

K2Ti6O13 Nanoparticle-Loaded Porous rGO Crumples for Supercapacitors.

One-dimensional alkali metal titanates containing potassium, sodium, and lithium are of great concern owing to their high ion mobility and high specific surface area. When those titanates are combined with conductive materials such as graphene, carbon nanotube, and carbon nanofiber, they are able to be employed as efficient electrode materials for supercapacitors. Potassium hexa-titanate (K2Ti6O13, KTO), in particular, has shown superior electrochemical properties compared to other alkali metal titanates because of their large lattice parameters induced by the large radius of potassium ions. Here, we present porous rGO crumples (PGC) decorated with KTO nanoparticles (NPs) for application to supercapacitors. The KTO NP/PGC composites were synthesized by aerosol spray pyrolysis and post-heat treatment. KTO NPs less than 10 nm in diameter were loaded onto PGCs ranging from 3 to 5 µm. Enhanced porous structure of the composites was obtained by the activation of rGO by adding an excessive amount of KOH to the composites. The KTO NP/PGC composite electrodes fabricated at the GO/KOH/TiO2 ratio of 1:3:0.25 showed the highest performance (275 F g-1) in capacitance with different KOH concentrations and cycling stability (83%) after 2000 cycles at a current density of 1 A g-1.

Stacking-Controlled Assembly of Cabbage-Like Graphene Microsphere for Charge Storage Applications.

Nanostructured graphene electrodes generally have a low density, which can limit the volumetric performance for energy storage devices. The liquid-phase mild reduction process of graphene oxide sheets is combined with the continuous aerosol densification process to produce high-density graphene agglomerates in the form of microspheres. The produced graphene assembly shows the cabbage-like morphology with a high density of 0.75 g cm-3 . In spite of such high density, the cabbage-like graphene microspheres have narrow-ranged mesopores and a high surface area. The cabbage-like graphene microsphere exhibits both high gravimetric and volumetric energy densities due to the optimized microstructure, which shows a high gravimetric capacitance of 177 F g-1 and volumetric capacitance of 117 F cm-3 in supercapacitors. As a cathode for lithium-ion capacitors, the cabbage-like graphene delivers a reversible capacity of ≈176 mAh g-1 . The stacking-control approach provides a new pathway to control the microstructure of the graphene assembly and corresponding charge storage characteristics for energy storage applications.

3 D Network-Structured Crumpled Graphene/Carbon Nanotube/Polyaniline Composites for Supercapacitors.

Crumpled graphene (CGR) is considered a promising supercapacitor material to achieve high power and energy density because it could overcome the disadvantages of 2 D GR sheets such as aggregation during the electrode fabrication process, reduction of the available surface area, and limitation of the electron and ion transport. Even though CGR shows good results, carbon materials are limited in terms of their capacitance performance. Here, we report highly enhanced supercapacitor materials by fabricating a 3 D composite containing CGR, carbon nanotubes (CNTs), and polyaniline (PANI). The CNTs increased the basal spacing and bridged the defects for electron transfer between the GR sheets in CGR. PANI can enhance the rate of conduction of electrons and offer high pseudocapacitance originating from its redox reactions. The synergistic effect of the CNTs and PANI may also result in a higher electrochemical capacitance and better stability than each individual component as electrode materials for supercapacitors in a two-electrode system. More importantly, the performance of the supercapacitors can be further enhanced by employing 2 D GR as the binder for the composite electrodes, resulting in specific capacitance of 456 F g-1 , rate capability of 89 %, and cyclic stability of 97 % after 1000 cycles.

One-Step Synthesis of Pt/Graphene Composites from Pt Acid Dissolved Ethanol via Microwave Plasma Spray Pyrolysis.

Pt nanoparticles-laden graphene (Pt/GR) composites were synthesized in the gas phase from a mixture of ethanol and Pt precursor by microwave plasma spray pyrolysis. The morphology of Pt/GR composites has the shape of wrinkled sheets of paper, while Pt nanoparticles (Pt NPs) that are less than 2.6 nm in the mean diameter are uniformly well deposited on the surface of GR sheets stacked in only three layers. The Pt/GR composite prepared with 20 wt% of Pt had the highest specific surface area and electrochemical surface area of up to 402 m(2) g(-1) and 77 m(2) g(-1) (Pt), respectively. In addition, the composite showed superior electrocatalytic activity compared with commercial Pt-carbon black. The excellent electrocatalytic activity was attributed to the high specific surface area and electrochemical surface area of the Pt/GR composite directly produced by microwave plasma spray pyrolysis. Thus, it is clearly expected that the Pt/GR composite is a promising material for DMFC catalysts.

One-Step Formation of Silicon-Graphene Composites from Silicon Sludge Waste and Graphene Oxide via Aerosol Process for Lithium Ion Batteries.

Over 40% of high-purity silicon (Si) is consumed as sludge waste consisting of Si, silicon carbide (SiC) particles and metal impurities from the fragments of cutting wire mixed in ethylene glycol based cutting fluid during Si wafer slicing in semiconductor fabrication. Recovery of Si from the waste Si sludge has been a great concern because Si particles are promising high-capacity anode materials for Li ion batteries. In this study, we report a novel one-step aerosol process that not only extracts Si particles but also generates Si-graphene (GR) composites from the colloidal mixture of waste Si sludge and graphene oxide (GO) at the same time by ultrasonic atomization-assisted spray pyrolysis. This process supports many advantages such as eco-friendly, low-energy, rapid, and simple method for forming Si-GR composite. The morphology of the as-formed Si-GR composites looked like a crumpled paper ball and the average size of the composites varied from 0.6 to 0.8 µm with variation of the process variables. The electrochemical performance was then conducted with the Si-GR composites for Lithium Ion Batteries (LIBs). The Si-GR composites exhibited very high performance as Li ion battery anodes in terms of capacity, cycling stability, and Coulombic efficiency.

A swelling-suppressed Si/SiOx nanosphere lithium storage material fabricated by graphene envelopment.

A swelling-suppressed, Si nanocrystals-embedded SiOx nanospheres lithium storage material was prepared by graphene envelopment. The free void spaces formed between the graphene envelope and Si/SiOx nanospheres effectively accommodated the volume changes of Si/SiOx nanospheres during cycling, which significantly suppresses the swelling behavior and improves the capacity retention up to 200 cycles.

Aerosol-assisted extraction of silicon nanoparticles from wafer slicing waste for lithium ion batteries.

A large amount of silicon debris particles are generated during the slicing of silicon ingots into thin wafers for the fabrication of integrated-circuit chips and solar cells. This results in a significant loss of valuable materials at about 40% of the mass of ingots. In addition, a hazardous silicon sludge waste is produced containing largely debris of silicon, and silicon carbide, which is a common cutting material on the slicing saw. Efforts in material recovery from the sludge and recycling have been largely directed towards converting silicon or silicon carbide into other chemicals. Here, we report an aerosol-assisted method to extract silicon nanoparticles from such sludge wastes and their use in lithium ion battery applications. Using an ultrasonic spray-drying method, silicon nanoparticles can be directly recovered from the mixture with high efficiency and high purity for making lithium ion battery anode. The work here demonstrated a relatively low cost approach to turn wafer slicing wastes into much higher value-added materials for energy applications, which also helps to increase the sustainability of semiconductor material and device manufacturing.

3D label-free prostate specific antigen (PSA) immunosensor based on graphene-gold composites.

Highly sensitive and label-free detection of the prostate specific antigen (PSA) remains a challenge in the diagnosis of prostate cancer. Here, a novel three-dimensional (3D) electrochemical immunosensor capable of sensitive and label-free detection of PSA is reported. This unique immunosensor is equipped with a highly conductive graphene (GR)-based gold (Au) composite modified electrode. The GR-based Au composite is prepared using aerosol spray pyrolysis and the morphology of the composite is the shape of a crumpled GR ball decorated with Au nanoparticles. Unlike the previous research, this novel 3D immunosensor functions very well over a broad linear range of 0-10 ng/mL with a low detection limit of 0.59 ng/mL; furthermore, it exhibits a significantly increased electron transfer and high sensitivity toward PSA. The highest rate of current change with respect to the PSA concentration is 5 µA/(ng/mL). Satisfactory selectivity, reproducibility, and stability of the 3D immunosensor are also exhibited.

A novel recovery of silicon nanoparticles from a waste silicon sludge.

As the semiconductor and photovoltaic industry undergo rapid growth, a large amount of silicon sludge is generated from the cutting process of silicon ingots. However, it is not effectively recycled. Recovery of nanometer-sized silicon (Si) particles from the sludge has become an important concern because the silicon sludge contains valuable resources including high purity silicon. In the present study, we investigated the novel recovery of Si nanoparticles from waste silicon sludge. The waste silicon sludge also contained surfactant, silicon carbide particles and metallic fragments. After removal of the surfactant by distillation, the Si nanoparticles were recovered by applying controlled ultrasonic waves and centrifugation in series. Metallic impurities in the recovered Si nanoparticles were purified by HCl treatment. The overall maximum yield and purity of the Si nanoparticles were about 80% and 99.7%, respectively.

A glucose biosensor based on TiO2-Graphene composite.

A novel glucose biosensor was developed based on the adsorption of glucose oxidase at a TiO(2)-Graphene (GR) nanocomposite electrode. A TiO(2)-GR composite was synthesized from a colloidal mixture of TiO(2) nanoparticles and graphene oxide (GO) nanosheets by an aerosol assisted self-assembly (AASA). The particle morphology of all TiO(2)-GR composites was spherical in shape. It was observed that micron-sized TiO(2) particles were encapsulated by GR nanosheets and that the degree of encapsulation was proportional to the ratio of GO/TiO(2). The amperometric response of the glucose biosensor fabricated by the TiO(2)-GR composite was linear against a concentration of glucose ranging from 0 to 8mM at -0.6 V. The highest sensitivity was noted at about 6.2 µA/mMcm(2). The as prepared glucose biosensor based on the TiO(2)-GR composite showed higher catalytic performance for glucose redox than a pure TiO(2) and GR biosensor.

Oil absorbing graphene capsules by capillary molding.

Oil absorbing graphene capsules are synthesized by capillary molding of graphene oxide (GO) sheets against a polystyrene bead template in evaporating aerosol droplets, followed by simultaneous reduction of GO and decomposition of the polymer template during ultrasonic spray pyrolysis.

Preparation of nanoporous SiO2 particles and their application in drug release control.

Nanoporous SiO2 particles which have different pore size and volume were prepared from a colloidal mixture of nano-sized silica particles by a spray heating method. The prepared nanoporous SiO2 particles were employed as a drug carrier to investigate the release behaviors of methylene blue (MB) as a model drug for a selected period of time. The concentration of released MB from the porous particles was measured by a UV-Vis spectroscopy with respect to time. The release of MB from the porous particles was maintained for 400 hours and the maximum amount of the released MB was 0.8 mg at 1.56 cm3/g of pore volume. As pore volume of the nanoporous particles increased, the release rate of MB increased.

Preparation and characterization of vanadium-doped ZnO nanoparticles for environmental application.

Vanadium-doped ZnO nanoparticles (ZnO:V) were prepared via flame spray pyrolysis (FSP) from a mixed aqueous solution of zinc hydroxide and vanadyl (IV) acetylacetonate. The morphological, structural and optical properties of the ZnO:V photocatalyst were characterized via transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and UV-visible diffused reflection spectrum (DRS). The photocatalytic activity of ZnO:V was evaluated via photocatalytic degradation of methylene blue (MB). The results showed that the hexagonal wurtzite-structured ZnO:V nanoparticles were successfully synthesized via FSP. The morphology of the as-prepared nanoparticles was polyhedral and non-hollow. The average diameter of ZnO:V, which was calculated from BET result, was 11.7 nm when the molar ratio of V/Zn was 0.1. The maximum decomposition of MB by the ZnO:V nanoparticles was 99.4% after 180 min under UV irradiation, whereas the decomposition of MB by the pure ZnO nanoparticles was 96.6%.

Fabrication of porous nanostructured TiO2 particles by an aerosol templating method.

An aerosol templating method was applied to fabricate the spherical nanostructured TiO2 particles containing both mesopores and macropores using two kinds of colloidal mixture such as polystyrene latex (PSL) particles and TiO2 nanoparticles (P25), and PSL and a titanium hydroxybislactato (TC315). As the weight ratio of PSL/P25 increased from 0 to 1.30, morphology of the as-prepared particles changed from mesoporous particles to particles containing mesopores and macropores. As the furnace temperature decreased from 800 to 600 degrees C at the fixed process conditions, the increase of mesopore volume and specific surface area were determined. The TiO2 particles fabricated from a mixture of TC315 and PSL were composed of lots of mesopores and a few macropores. The width of UV-absorption spectra of the porous particles synthesized from two colloidal mixtures decreased a little with respect to the increase of the weight ratio. The complete decomposition of p-xylene of 97.9 ppm was accomplished within 2 h under the illumination of UV-light by all the porous particles.

Pore size-controlled synthesis and characterization of nanostructured silica particles.

Silica nano-materials with meso- and macroporosity are of great interest due to their variety of potential applications. For the application as a catalytic supporter, nanostructured spherical silica particles having both mesopores and macropores were prepared by using an aerosol templating method with colloidal mixtures of polystyrene latex (PSL) particles and silica nanoparticles. The as-prepared particles showed bimodal size distribution consisting of mesopores ranging 2-20 nm and macropores ranging 60-160 nm. As the PSL size decreased, mesopore size increased due to a reduction in packing rates of primary SiO(2) nanoparticles composing the walls of nanostructured porous particles. With an increment of the weight ratio of PSL/SiO(2), mesopores size increased but mesopore volume decreased due to the broken structure of particles and reduction in packing rates. Mesopores disappeared when the furnace temperature was 900 degrees C. The residuals of organic template were detected when furnace temperature and flow rate of carrier gas were below 600 degrees C and above 3 l/min, respectively.

Calibration of Polarization-Sensitive and Dual-Angle Laser Light Scattering Methods Using Standard Latex Particles.

A polarization-sensitive laser light scattering (PSLLS) method and a dual-angle laser light scattering (DALLS) method have been studied for in situ measurement of submicrometer hydrosol and aerosol particles. By using standard monodisperse polystyrene latex particles suspended in water and air as test particles, calibration of systems built based on the above methods have been performed. The effects of light scattered by agglomerated aerosol particles (multiplets) were corrected by considering the fraction of multiplets as determined with an aerosol measurement technique using a differential mobility analyzer. The change in the measured intensities of scattered light with particle diameter was then determined by calculations based on Mie theory. It was shown that the PSLLS system can determine particle diameters as small as approximately 60 nm for the test hydrosol particles and approximately 100 nm for test aerosol particles, respectively. The DALLS system can determine smaller diameters than the PSLLS system for test particles with no light absorption. The change in scattered light intensities with particle diameter was also investigated by theoretical calculations with various refractive indexes and scattering angles. The PSLLS and DALLS systems promise to become routine measurement tools for absorbing and nonabsorbing particles, respectively. Copyright 2001 Academic Press.