Hollow Graphene as an Expansion-Inhibiting Electrical Interconnector for Silicon Electrodes in Lithium-Ion Batteries.

Huge volume changes of silicon particles upon alloying and dealloying reactions with lithium are a major reason for the poor cycle performance of silicon-based anodes for lithium-ion batteries. To suppress dimensional changes of silicon is a key strategy in attempts to improve the electrochemical performance of silicon-based anodes. Here, we demonstrate that a conductive agent can be exploited to offset the mechanical strain imposed on silicon electrodes caused by volume expansion of silicon associated with lithiation. Hollow graphene particles as a conductive agent inhibit volume expansion by absorbing the swelling of silicon upon lithiation through flattening the free voids surrounded by the graphene shell. As a result, silicon electrodes with hollow graphene showed a height expansion of 20.4% after full lithiation with a capacity retention of 69% after 200 cycles, while the silicon electrode with conventional carbon black showed an expansion of 76.8% under the same conditions with a capacity retention of 38%. Some of the deflated hollow graphene returns to its initial shape on delithiation due to the mechanical flexibility of the graphene shell layer. Such a robust microstructure of a silicon electrode incorporating hollow graphene that serves as both an expansion inhibitor and a conductive agent greatly improves capacity retention compared with silicon electrodes with the conventionally used carbon black.

Self-Healing Microcapsule-Thickened Oil Barrier Coatings.

Low-viscosity oils could potentially act as self-healing barrier coatings because they can readily flow and reconnect to heal minor damage. For the same reason, however, they typically do not form stable coatings on metal surfaces. Increasing viscosity helps to stabilize the oil coating, but it also slows down the healing process. Here, we report a strategy for creating highly stable oil coatings on metal surfaces without sacrificing their remarkable self-healing properties. Low-viscosity oil films can be immobilized on metal surfaces using lightweight microcapsules as thickeners, which form a dynamic network to prevent the creep of the coating. When the coating is scratched, oil around the opening can rapidly flow to cover the exposed area, reconnecting the particle network. Use of these coatings as anticorrosion barriers is demonstrated. The coatings can be easily applied on metal surfaces, including those with complex geometries, both in air or under water, and remain stable even in turbulent water. They can protect metal in corrosive environments for extended periods of time and can self-heal repeatedly when scratched at the same spot. Such a strategy may offer effective mitigation of the dangerous localized corrosion aggravated by minor imperfections or damage in protective coatings, which are typically hard to prevent or detect, but can drastically degrade metal properties.

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.

Disassembly-Reassembly Approach to RuO2 /Graphene Composites for Ultrahigh Volumetric Capacitance Supercapacitor.

A porous, yet compact, RuO2 /graphene hybrid is successfully prepared by using a disassembly-reassembly strategy, achieving effective and uniform loading of RuO2 nanoparticles inside compact graphene monolith. The disassembly process ensures the uniform loading of RuO2 nanoparticles into graphene monolith, while the reassembly process guarantees a high density yet simultaneously unimpeded ion transport channel in the composite. The resulting RuO2 /graphene hybrid possesses a density of 2.63 g cm-3 , leading to a record high volumetric capacitance of 1485 F cm-3 at the current density of 0.1 A g-1 . When the current density is increased to 20 A g-1 , it remains a high volumetric capacitance of 1188 F cm-3 . More importantly, when the single electrode mass loading is increased to 12 mg cm-2 , it still delivers a high volumetric capacitance of 1415 F cm-3 at the current density of 0.1 A g-1 , demonstrating the promise of this disassembly-reassembly approach to create high volumetric performance materials for energy storage applications.

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.

Hierarchical networks of redox-active reduced crumpled graphene oxide and functionalized few-walled carbon nanotubes for rapid electrochemical energy storage.

Crumpled graphene is known to have a strong aggregation-resistive property due to its unique 3D morphology, providing a promising solution to prevent the restacking issue of graphene based electrode materials. Here, we demonstrate the utilization of redox-active oxygen functional groups on the partially reduced crumpled graphene oxide (r-CGO) for electrochemical energy storage applications. To effectively utilize the surface redox reactions of the functional groups, hierarchical networks of electrodes including r-CGO and functionalized few-walled carbon nanotubes (f-FWNTs) are assembled via a vacuum-filtration process, resulting in a 3D porous structure. These composite electrodes are employed as positive electrodes in Li-cells, delivering high gravimetric capacities of up to ∼170 mA h g(-1) with significantly enhanced rate-capability compared to the electrodes consisting of conventional 2D reduced graphene oxide and f-FWNTs. These results highlight the importance of microstructure design coupled with oxygen chemistry control, to maximize the surface redox reactions on functionalized graphene based electrodes.

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.

Self-dispersed crumpled graphene balls in oil for friction and wear reduction.

Ultrafine particles are often used as lubricant additives because they are capable of entering tribological contacts to reduce friction and protect surfaces from wear. They tend to be more stable than molecular additives under high thermal and mechanical stresses during rubbing. It is highly desirable for these particles to remain well dispersed in oil without relying on molecular ligands. Borrowing from the analogy that pieces of paper that are crumpled do not readily stick to each other (unlike flat sheets), we expect that ultrafine particles resembling miniaturized crumpled paper balls should self-disperse in oil and could act like nanoscale ball bearings to reduce friction and wear. Here we report the use of crumpled graphene balls as a high-performance additive that can significantly improve the lubrication properties of polyalphaolefin base oil. The tribological performance of crumpled graphene balls is only weakly dependent on their concentration in oil and readily exceeds that of other carbon additives such as graphite, reduced graphene oxide, and carbon black. Notably, polyalphaolefin base oil with only 0.01-0.1 wt % of crumpled graphene balls outperforms a fully formulated commercial lubricant in terms of friction and wear reduction.

High-Yield Spreading of Water-Miscible Solvents on Water for Langmuir-Blodgett Assembly.

Langmuir-Blodgett (LB) assembly is a classical molecular thin-film processing technique, in which the material is spread onto water surface from a volatile, water-immiscible solvent to create floating monolayers that can be later transferred to solid substrates. LB has also been applied to prepare colloidal thin films with an unparalleled level of microstructural control and thickness, which has enabled the discovery of many exciting collective properties of nanoparticles and the construction of bulk nanostructured materials. To maximize the benefits of LB assembly, the nanoparticles should be well dispersed in both the spreading solvent and on water. This is quite challenging since colloids usually need contrasting surface properties in order to be stable in the water-hating organic solvents and on water surface. In addition, many organic and polymeric nanostructures dissolve in those organic solvents and cannot be processed directly. Using water-liking spreading solvents can avoid this dilemma. However, spreading of water-miscible solvents on water surface is fundamentally challenging due to extensive mixing, which results in significant material loss. Here we report a conceptually simple strategy and a general technique that allows nearly exclusive spreading of such solvents on water surface using electrospray. Since the volume of these aerosolized droplets is reduced by many orders of magnitude, they are readily depleted during the initial spreading step before any significant mixing could occur. The new strategy drastically reduces the burden of material processing prior to assembly and broadens the scope of LB assembly to previously hard-to-process materials. It also avoids the use of toxic volatile organic spreading solvents, improves the reproducibility, and can be readily automated, making LB assembly a more robust tool for colloidal assembly and thin-film fabrication.

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.

Synthesis and characterization of hollow silica particles from tetraethyl orthosilicate and sodium silicate.

We herein introduce an effective method to synthesize hollow silica particles (HSPs) from tetraethyl orthosilicate (TEOS) and sodium silicate (Na2SiO3) as silica sources using a sacrificial template method with a simple modification. The advantage of the method is that it can be applied to synthesize HSPs from not only TEOS but also Na2SiO3 silica sources without changing the method adopted to obtain the sacrificial polymeric templates. Polystyrene particles are adopted as sacrificial templates to synthesize the HSPs, and a conventional dispersion polymerization method is used to synthesis polystyrene particles in an oil medium. Size control of HSPs is enabled by modulation of the polymerization initiator content (2,2'-Azoisobutyronitrile). The particle size, shell thickness, and morphology are analyzed. Light reflection spectra are measured to obtain the light reflection properties of the HSPs. The results indicate that the hollow architecture is the most important factor in determining the light reflection properties of the particles. Such particles are potential candidates for use in light reflectors and heat insulators, as they may reduce energy consumption in heating and cooling applications.

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.

Effect of sheet morphology on the scalability of graphene-based ultracapacitors.

Graphene is considered a promising ultracapacitor material toward high power and energy density because of its high conductivity and high surface area without pore tortuosity. However, the two-dimensional (2D) sheets tend to aggregate during the electrode fabrication process and align perpendicular to the flow direction of electrons and ions, which can reduce the available surface area and limit the electron and ion transport. This makes it hard to achieve scalable device performance as the loading level of the active material increases. Here, we report a strategy to solve these problems by transforming the 2D graphene sheet into a crumpled paper ball structure. Compared to flat or wrinkled sheets, the crumpled graphene balls can deliver much higher specific capacitance and better rate performance. More importantly, devices made with crumpled graphene balls are significantly less dependent on the electrode mass loading. Performance of graphene-based ultracapacitors can be further enhanced by using flat graphene sheets as the binder for the crumpled graphene balls, thus eliminating the need for less active binder materials.

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.

Aerosol synthesis of cargo-filled graphene nanosacks.

Water microdroplets containing graphene oxide and a second solute are shown to spontaneously segregate into sack-cargo nanostructures upon drying. Analytical modeling and molecular dynamics suggest the sacks form when slow-diffusing graphene oxide preferentially accumulates and adsorbs at the receding air-water interface, followed by capillary collapse. Cargo-filled graphene nanosacks can be nanomanufactured by a simple, continuous, scalable process and are promising for many applications where nanoscale materials should be isolated from the environment or biological tissue.

Crumpled Graphene-Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes.

Submicrometer-sized capsules made of Si nanoparticles wrapped by crumpled graphene shells were made by a rapid, one-step capillary-driven assembly route in aerosol droplets. Aqueous dispersion of micrometer-sized graphene oxide (GO) sheets and Si nanoparticles were nebulized to form aerosol droplets, which were passed through a preheated tube furnace. Evaporation-induced capillary force wrapped graphene (a.k.a., reduced GO) sheets around the Si particles, and heavily crumpled the shell. The folds and wrinkles in the crumpled graphene coating can accommodate the volume expansion of Si upon lithiation without fracture, and thus help to protect Si nanoparticles from excessive deposition of the insulating solid electrolyte interphase. Compared to the native Si particles, the composite capsules have greatly improved performance as Li ion battery anodes in terms of capacity, cycling stability, and Coulombic efficiency.