Shih-Yuan Lu

A cost-effective supercapacitor material of ultrahigh specific capacitances: spinel nickel cobaltite aerogels from an epoxide-driven sol-gel process.

Adv. Mater. 2010, 22, 347–351 2010 WILEY-VCH Verlag Gm The ever worsening energy depletion and global warming issues call for not only urgent development of clean alternative energies and emission control of global warming gases, but also more advanced energy storage and management devices. Supercapacitors, offering transient but extremely high powers, are probably the most important next generation energy storage device. To boost the specific capacitance of supercapacitors, the specific surface area of the electrode materials needs to be as high as possible to promote the electric double-layer capacitances and to accommodate a large amount of superficial electroactive species to participate in faradaic redox reactions. In addition, suitable pore sizes, 2–5 nm, of the porous electrode materials are critical to ease the mass transfer of electrolytes within the pores for fast redox reactions and double-layer charging/discharging. Aerogels are a class of mesoporous materials possessing highly specific surface areas and porosities, from which promising applications in a wide range of areas have been investigated. They are composed of 3D networks of nanoparticles with an average pore size of several nanometers, adjustably falling within the optimal pore sizes of 2–5 nm. Consequently, aerogels are a promising candidate for supercapacitor applications. As to the electrode material, electroactive materials possessing multiple oxidation states/structures that enable rich redox reactions for pseudocapacitance generation are desirable for supercapacitors. Transition metal oxides are such a class of materials that have drawn extensive and intensive research attention in recent years. Among them, RuO2 is themost prominent one with a specific capacitance as high as 1580F g , probably the highest ever reported. The commercialization of RuO2 based supercapacitors, however, is not promising because of the high cost and rareness of Ru. Spinel nickel cobaltite (NiCo2O4) is a low-cost, environmentally friendly transition metal oxide, which has been employed in electrocatalytic water splitting (oxygen evolution) and lithium ion batteries. Its application in supercapacitors, however, received much less attention. Nickel cobaltite has been reported to possess a much better electronic conductivity, at least two orders of magnitude higher, and higher electrochemical activity than those of nickel oxides and cobalt oxides. It is expected to offer richer redox reactions, including contributions from both nickel and cobalt ions, than the two corresponding single component oxides and is a potential cost-effective alternative for RuO2. Based on the above considerations, one would expect nickel cobaltite aerogels, with anticipated good electronic conductivity, low diffusion resistance to protons/cations, easy electrolyte penetration, and high electroactive areas to be a promising candidate for the construction of next-generation, ultrahighperformance supercapacitors. Traditionally, aerogels are prepared with sol–gel processes by taking corresponding alkoxides as the precursors. Alkoxides are generally expensive and sensitive to moisture and heat, requiring careful handling. Recently, to tackle these drawbacks, the epoxide synthetic route, enabling the use of low-cost and stable metal salts as the precursors, was successfully developed to prepare metal oxide aerogels. In this work, we reported the first successful preparation of nickel cobaltite aerogels with the epoxide-driven sol–gel process. The effects of the post-gel-drying calcination temperature on the critical properties of the product aerogels were investigated. At a starting Ni/Co ratio of 0.5 and a post-gel-drying calcination temperature of 200 8C, an optimal combination of composition, crystallinity, specific surface area, pore volume, and pore size was achieved to afford the nickel cobaltite aerogels that showed an extremely high-specific capacitance of 1400 F g 1 under a mass loading of 0.4 mg cm 2 at a sweep rate of 25mV s 1 within a potential window of 0.04 to 0.52V in a 1 M NaOH solution. The excellent reversibility and cycle stability of the product aerogels were also demonstrated. A stoichiometric mixture of nickel and cobalt chlorides was used as the precursor for the preparation of the nickel cobaltite aerogels. After the gel is dried in supercritical carbon dioxide, a post-gel-drying calcination is generally required to acquire preferred composition and/or better crystallinity of the products. The post-gel-drying calcination temperature is thus an important processing parameter to be studied. For referring convenience, we term the product aerogels as Ni–Co–O–T, with Tdenoting the calcination temperature. The T block is omitted for as-prepared samples. Also, for comparison purposes, NiO and Co3O4 aerogels were prepared, termed as Ni–O–T and Co–O–T, respectively. Figure 1a shows the X-ray diffraction (XRD) patterns of the as-prepared product aerogels and those samples calcined at 200 and 300 8C. Surprisingly, nickel cobaltite was formed even at the as-prepared condition. The diffraction peak located at the 2u value

Piezoelectric nanogenerator using CdS nanowires

Vertically grown cadmium sulfide (CdS) nanowire (NW) arrays were prepared using two different processes: hydrothermal and physical vapor deposition (PVD). The NWs obtained from the hydrothermal process were composed of alternating hexagonal wurtzite (WZ) and cubic zinc blende (ZB) phases with growth direction along WZ ⟨0001⟩ and ZB [111]. The NWs produced by PVD process are single crystalline WZ phase with growth direction along ⟨0001⟩. These vertically grown CdS NW arrays have been used to converting mechanical energy into electricity following a developed procedure [Z. L. Wang and J. Song Science 312, 242 (2006)]. The basic principle of the CdS NW nanogenerator relies on the coupled piezoelectric and semiconducting properties of CdS, and the data fully support the mechanism previously proposed for ZnO NW nanogenerators and nanopiezotronics.

Large enhancement in photon detection sensitivity via Schottky-gated CdS nanowire nanosensors

The Schottky contact based photon detection was demonstrated using CdS (visible light responsive), silicon (indirect n-type oxygen-non-adsorbing), and CuO (indirect p-type oxygen-adsorbing) nanowire nanosensors. With changing one of the two nanowire-electrode contacts from ohmic to Schottky, detection sensitivities as high as 105% were achieved by the CdS nanowire nanosensor operated at the reverse bias mode of −8 V, which was 58 times higher than that of the corresponding ohmic contact device. The reset time was also significantly reduced. In addition, originally light nonresponsive silicon and CuO nanowires became light responsive when fabricated as a Schottky contact device. These improvements in photon detection can be attributed to the Schottky gating effect realized in the present nanosensor system by introducing a Schottky contact.

EFFECTIVE CONDUCTIVITY OF COMPOSITES CONTAINING ALIGNED SPHEROIDAL INCLUSIONS OF FINITE CONDUCTIVITY

The effective conductivity of composites containing aligned spheroids of finite conductivity is determined with the pair interaction rigorously taken into account. The pair interaction is evaluated by solving a boundary‐value problem involving two aligned spheroids with a boundary collocation scheme. Our results are in the form of virial expansion in the inclusion volume fraction f, truncated at the O(f2) term. Effective conductivities obtained from this study agree well with Willis’s [J. Mech. Phys. Solids 25, 185 (1977)] bounds and Kim and Torquato’s [J. Appl. Phys. 74, 1844 (1993)] first‐passage‐time simulation results. An expression for the effective conductivity tensor based on an equivalent inclusion method originated by Hasselman and Johnson [J. Compos. Mater. 21, 508 (1987)] is also derived, from which a criterion for testing the virial expansion validity is constructed. The relevant series ratio is found to be a good measure of intensity of the system thermal interaction. The smaller the value of...

Manganese Oxide/Graphene Aerogel Composites as an Outstanding Supercapacitor Electrode Material

Graphene aerogels (GA), prepared with an organic sol-gel process, possessing a high specific surface area of 793 m(2)  g(-1) , a high pore volume of 3 cm(3)  g(-1) , and a large average pore size of 17 nm, were applied as a support for manganese oxide for supercapacitor applications. The manganese oxide was electrochemically deposited into the highly porous GA to form MnO2 /GA composites. The composites, at a high manganese oxide loading of 61 wt. %, exhibited a high specific capacitance of 410 F g(-1) at 2 mV s(-1) . More importantly, the high rate specific capacitances measured at 1000 mV s(-1) for these composites were two-fold higher than those obtained with samples prepared in the absence of the GA support. The specific capacitance retention ratio, based on the specific capacitance obtained at 25 mV s(-1) , was maintained high, at 85 %, even at the high scan rate of 1000 mV s(-1) , in contrast with the significantly lower value of 67 % for the plain manganese oxide sample. For the cycling stability, the specific capacitance of the composite electrode decayed by only 5 % after 50,000 cycles at 1000 mV s(-1) . The success of this MnO2 /GA composite may be attributed to the structural advantages of high specific surface areas, high pore volumes, large pore sizes, and three-dimensionally well-connected network of the GA support. These structural advantages made possible the high mass loading of the active material, manganese oxide, large amounts of electroactive surfaces for the superficial redox events, fast mass-transfer within the porous structure, and well-connected conductive paths for the involved charge transport.

Transparent, Hydrophobic Composite Aerogels with High Mechanical Strength and Low High-Temperature Thermal Conductivities

A facile one-step polymer-incorporation sol-gel process, together with a surface modification and an ambient pressure drying processes, was developed to prepare silica-poly(vinylpyrrolidone) composite aerogels. These composite aerogels are with high hydrophobicity (static contact angle >120 degrees), good mechanical strength (Youngs modulus of bending >30 MPa), and low high-temperature thermal conductivity (0.063 W/m-K at 300 degrees C), which are critical characteristics for practical applications of aerogels, particularly in energy saving areas, for long-term usage and large scale production.

Wafer Scale Phase-Engineered 1T-and 2H-MoSe2/Mo Core-Shell 3D-Hierarchical Nanostructures toward Efficient Electrocatalytic Hydrogen Evolution Reaction

The necessity for new sources for greener and cleaner energy production to replace the existing ones has been increasingly growing in recent years. Of those new sources, the hydrogen evolution reaction has a large potential. In this work, for the first time, MoSe2 /Mo core-shell 3D-hierarchical nanostructures are created, which are derived from the Mo 3D-hierarchical nanostructures through a low-temperature plasma-assisted selenization process with controlled shapes grown by a glancing angle deposition system.

Cu2O-Decorated Mesoporous TiO2 Beads as a Highly Efficient Photocatalyst for Hydrogen Production

Cu2O‐decorated mesoporous TiO2 beads (MTBs) are developed as a low‐cost, highly efficient photocatalyst for H2 production. MTBs with a high specific surface area of 189 m2 g−1, a large pore volume of 0.43 cm3 g−1 and a suitable pore size of 8.9 nm are decorated with band‐structure‐matched Cu2O nanocrystals through a simple, fast and low‐cost chemical bath deposition process. The Cu2O nanocrystals serve as an electron–hole separation centre to promote H2 evolution. Under optimal operation conditions, an ultra‐high specific H2 evolution rate of 223 mmol h−1 g−1 is achieved. The success is attributed to the structural advantages of the MTBs of high specific surface areas, large pore volumes and suitable pore sizes together with the much improved electron–hole separation and light utilisation of the Cu2O‐decorated MTBs. The H2 evolution rates achieved with the Cu2O‐decorated MTBs are one order of magnitude higher than those achieved by commercial P25 TiO2.

Ultralow overpotentials for oxygen evolution reactions achieved by nickel cobaltite aerogels

An ultralow overpotential of 0.184 V at 100 mA cm−2 for oxygen evolution reactions in an alkaline solution, 1 M KOH at 25 °C, is achieved by nickel cobaltite aerogels. The success is attributed to the structural advantages of the aerogel materials, including high specific surface areas and a well-connected three-dimensional through-pore structure.

Polymer nanocomposite containing CdS-ZnS core-shell particles: Optical properties and morphology

Composites of nanosized CdS–ZnS core–shell particles well dispersed in polycetyl- p-vinylbenzyldimethylammonium chloride (PCVDAC) were fabricated and their optical properties and morphology were studied. The core-shell particles of less than 10 nm in size were prepared with the reverse micellar solutions formed by a polymerizable anionic surfactant, CVDAC, and a direct thermal radical polymerization of the micellar solution led to the nanocomposite containing well-dispersed core–shell particles. The shell was inferred from small angle x-ray scattering to be around a monolayer thick. This monolayer coating, however, was enough to produce an appreciable enhancement in photoluminescence for the ZnS-coated CdS system (wider band gap material on narrower band gap material), and a degradation in photoluminescence for the CdS-coated ZnS system. However, a complete coverage of the CdS core with ZnS was required to realize the photoluminescence enhancement for the ZnS-coated CdS system. The polymer domains in the ...