Richard B. Kaner

Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage

The rapid development of miniaturized electronic devices has increased the demand for compact on-chip energy storage. Microscale supercapacitors have great potential to complement or replace batteries and electrolytic capacitors in a variety of applications. However, conventional micro-fabrication techniques have proven to be cumbersome in building cost-effective micro-devices, thus limiting their widespread application. Here we demonstrate a scalable fabrication of graphene micro-supercapacitors over large areas by direct laser writing on graphite oxide films using a standard LightScribe DVD burner. More than 100 micro-supercapacitors can be produced on a single disc in 30u2009min or less. The devices are built on flexible substrates for flexible electronics and on-chip uses that can be integrated with MEMS or CMOS in a single chip. Remarkably, miniaturizing the devices to the microscale results in enhanced charge-storage capacity and rate capability. These micro-supercapacitors demonstrate a power density of ~200u2009Wu2009cm-3, which is among the highest values achieved for any supercapacitor.

Flash welding of conducting polymer nanofibers

The absorption of light by a material generates heat through non-radiative energy dissipation and exothermic photochemical reactions1. In nanostructured materials, the heat generated through photothermal processes will be confined within the individual nanostructures when heat transfer to neighbouring nanostructures and the environment is slow. This leads to unprecedented photothermal effects that cannot be observed in bulk materials, especially when a strong, pulsed light source is used2,3. Here we demonstrate an enhanced photothermal phenomenon with conducting polymer nanofibres in which a camera flash causes instantaneous welding. Under flash irradiation, polyaniline nanofibres melt to form a smooth and continuous film from an originally random network of nanofibres. This photothermal effect can be used to form asymmetric nanofibre films, to melt-blend polymer–polymer nanocomposites rapidly and to photo-pattern polymer nanofibre films.

Tungsten tetraboride, an inexpensive superhard material

Tungsten tetraboride (WB4) is an interesting candidate as a less expensive member of the growing group of superhard transition metal borides. WB4 was successfully synthesized by arc melting from the elements. Characterization using powder X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) indicates that the as-synthesized material is phase pure. The zero-pressure bulk modulus, as measured by high-pressure X-ray diffraction for WB4, is 339 GPa. Mechanical testing using microindentation gives a Vickers hardness of 43.3 ± 2.9 GPa under an applied load of 0.49 N. Various ratios of rhenium were added to WB4 in an attempt to increase hardness. With the addition of 1 at.% Re, the Vickers hardness increased to approximately 50 GPa at 0.49 N. Powders of tungsten tetraboride with and without 1 at.% Re addition are thermally stable up to approximately 400 °C in air as measured by thermal gravimetric analysis.

Mechanochemical synthesis and thermoelectric properties of high quality magnesium silicide

Magnesium silicide and related alloys are attractive for thermoelectric applications due to their low toxicity, thermal stability, low density, relative abundance and low cost of production. Earlier work on the synthesis of Mg2Siviahigh energy ball milling resulted in incomplete product formation, oxide impurities, and contamination from milling media. Here we present an improved solid-state synthesis of n-type magnesium silicide using the mechanochemical technique of high energy ball milling of the elements followed by high pressure sintering using hot uniaxial compaction. This robust synthetic method permits a detailed investigation of thermoelectric properties as a function of Bi doping. The thermoelectric properties of Mg2Si1−xBix (0 ≤ x ≤ 0.021) samples are characterized from 300 K to 775 K. These results are analyzed within a single parabolic band (SPB) model to determine the effective conduction band parameters and identify regimes of non-SPB behavior.

Vapor-Phase Polymerization of Nanofibrillar Poly(3,4-ethylenedioxythiophene) for Supercapacitors

Nanostructures of the conducting polymer poly(3,4-ethylenedioxythiophene) with large surface areas enhance the performance of energy storage devices such as electrochemical supercapacitors. However, until now, high aspect ratio nanofibers of this polymer could only be deposited from the vapor-phase, utilizing extrinsic hard templates such as electrospun nanofibers and anodized aluminum oxide. These routes result in low conductivity and require postsynthetic template removal, conditions that stifle the development of conducting polymer electronics. Here we introduce a simple process that overcomes these drawbacks and results in vertically directed high aspect ratio poly(3,4-ethylenedioxythiophene) nanofibers possessing a high conductivity of 130 S/cm. Nanofibers deposit as a freestanding mechanically robust film that is easily processable into a supercapacitor without using organic binders or conductive additives and is characterized by excellent cycling stability, retaining more than 92% of its initial capacitance after 10,000 charge/discharge cycles. Deposition of nanofibers on a hard carbon fiber paper current collector affords a highly efficient and stable electrode for a supercapacitor exhibiting gravimetric capacitance of 175 F/g and 94% capacitance retention after 1000 cycles.

High Surface Area Tunnels in Hexagonal WO3

High surface area in h-WO3 has been verified from the intracrystalline tunnels. This bottom-up approach differs from conventional templating-type methods. The 3.67 Å diameter tunnels are characterized by low-pressure CO2 adsorption isotherms with nonlocal density functional theory fitting, transmission electron microscopy, and thermal gravimetric analysis. These open and rigid tunnels absorb H(+) and Li(+), but not Na(+) in aqueous electrolytes without inducing a phase transformation, accessing both internal and external active sites. Moreover, these tunnel structures demonstrate high specific pseudocapacitance and good stability in an H2SO4 aqueous electrolyte. Thus, the high surface area created from 3.67 Å diameter tunnels in h-WO3 shows potential applications in electrochemical energy storage, selective ion transfer, and selective gas adsorption.

Rediscovering the Crystal Chemistry of Borides

For decades, borides have been primarily studied as crystallographic oddities. With such a wide variety of structures (a quick survey of the Inorganic Crystal Structure Database counts 1253 entries for binary boron compounds!), it is surprising that the applications of borides have been quite limited despite a great deal of fundamental research. If anything, the rich crystal chemistry found in borides could well provide the right tool for almost any application. The interplay between metals and the boron results in even more varied materials properties, many of which can be tuned via chemistry. Thus, the aim of this review is to reintroduce to the scientific community the developments in boride crystal chemistry over the past 60 years. We tie structures to material properties, and furthermore, elaborate on convenient synthetic routes toward preparing borides.

Three-Dimensional Core–Shell Hybrid Solar Cells via Controlled in Situ Materials Engineering

Three-dimensional core-shell organic-inorganic hybrid solar cells with tunable properties are demonstrated via electropolymerization. Air-stable poly(3,4-ethylenedioxythiophene) (PEDOT) shells with controlled thicknesses are rapidly coated onto periodic GaAs nanopillar arrays conformally, preserving the vertical 3D structure. The properties of the organic layer can be readily tuned in situ, allowing for (1) the lowering of the highest occupied molecular orbital level (|ΔE| ∼ 0.28 eV), leading to the increase of open-circuit voltage (V(OC)), and (2) an improvement in PEDOT conductivity that results in enhanced short-circuit current densities (J(SC)). The incorporation of various anionic dopants in the polymer during the coating process also enables the tailoring of the polymer/semiconductor interface transport properties. Systematic tuning of the device properties results in a J(SC) of 13.6 mA cm(-2), V(OC) of 0.63 V, peak external quantum efficiency of 58.5%, leading to a power conversion efficiencies of 4.11%.

Graphene-Assisted Solution Growth of Vertically Oriented Organic Semiconducting Single Crystals

Vertically oriented structures of single crystalline conductors and semiconductors are of great technological importance due to their directional charge carrier transport, high device density, and interesting optical properties. However, creating such architectures for organic electronic materials remains challenging. Here, we report a facile, controllable route for producing oriented vertical arrays of single crystalline conjugated molecules using graphene as the guiding substrate. The arrays exhibit uniform morphological and crystallographic orientations. Using an oligoaniline as an example, we demonstrate this method to be highly versatile in controlling the nucleation densities, crystal sizes, and orientations. Charge carriers are shown to travel most efficiently along the vertical interfacial stacking direction with a conductivity of 12.3 S/cm in individual crystals, the highest reported to date for an aniline oligomer. These crystal arrays can be readily patterned and their current harnessed collectively over large areas, illustrating the promise for both micro- and macroscopic device applications.

Extrinsic Hardening of Superhard Tungsten Tetraboride Alloys with Group 4 Transition Metals

Alloys of tungsten tetraboride (WB4) with the group 4 transition metals, titanium (Ti), zirconium (Zr), and hafnium (Hf), of different concentrations (0-50 at. % on a metals basis) were synthesized by arc-melting in order to study their mechanical properties. The phase composition and purity of the as-synthesized samples were confirmed using powder X-ray diffraction (PXRD) and energy dispersive X-ray spectroscopy (EDS). The solubility limit as determined by PXRD is 20 at. % for Ti, 10 at. % for Zr, and 8 at. % for Hf. Vickers indentation measurements of WB4 alloys with 8 at. % Ti, 8 at. % Zr, and 6 at. % Hf gave hardness values, Hv, of 50.9 ± 2.2, 55.9 ± 2.7 and 51.6 ± 2.8 GPa, respectively, compared to 43.3 GPa for pure WB4 under an applied load of 0.49 N. Each of the aforementioned compositions are considered superhard (Hv > 40 GPa), likely due to extrinsic hardening that plays a key role in these superhard metal borides. Furthermore, these materials exhibit a significantly reduced indentation size effect, which can be seen in the plateauing hardness values for the W1-xZrxB4 alloy. In addition, W0.92Zr0.08B4, a product of spinoidal decomposition, possesses nanostructured grains and enhanced grain hardening. The hardness of W0.92Zr0.08B4 is 34.7 ± 0.65 GPa under an applied load of 4.9 N, the highest value obtained for any superhard metal at this relatively high loading. In addition, the WB4 alloys with Ti, Zr, and Hf showed a substantially increased oxidation resistance up to ∼460 °C, ∼510 °C, and ∼490 °C, respectively, compared to ∼400 °C for pure WB4.