Te-Yu Wei

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

Supersensitive, Fast-Response Nanowire Sensors by Using Schottky Contacts

A Schottky barrier can be formed at the interface between a metal electrode and a semiconductor. The current passing through the metal-semiconductor contact is mainly controlled by the barrier height and barrier width. In conventional nanodevices, Schottky contacts are usually avoided in order to enhance the contribution made by the nanowires or nanotubes to the detected signal. We present a key idea of using the Schottky contact to achieve supersensitive and fast response nanowire-based nanosensors. We have illustrated this idea on several platforms: UV sensors, biosensors, and gas sensors. The gigantic enhancement in sensitivity of up to 5 orders of magnitude shows that an effective usage of the Schottky contact can be very beneficial to the sensitivity of nanosensors.

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.

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.

Mesoporous Fluorocarbon-Modified Silica Aerogel Membranes Enabling Long-Term Continuous CO2 Capture with Large Absorption Flux Enhancements

The use of a membrane contactor combined with a hydrophobic porous membrane and an amine absorbent has attracted considerable attention for the capture of CO2 because of its extensive use, low operational costs, and low energy consumption. The hydrophobic porous membrane interface prevents the passage of the amine absorbent but allows the penetration of CO2 molecules that are captured by the amine absorbent. Herein, highly porous SiO2 aerogels modified with hydrophobic fluorocarbon functional groups (CF3 ) were successfully coated onto a macroporous Al2 O3 membrane; their performance in a membrane contactor for CO2 absorption is discussed. The SiO2 aerogel membrane modified with CF3 functional groups exhibits the highest CO2 absorption flux and can be continuously operated for CO2 absorption for extended periods of time. This study suggests that a SiO2 aerogel membrane modified with CF3 functional groups could potentially be used in a membrane contactor for CO2 absorption. Also, the resulting hydrophobic SiO2 aerogel membrane contactor is a promising technology for large-scale CO2 absorption during the post-combustion process in power plants.

Titania and Pt/titania aerogels as superior mesoporous structures for photocatalytic water splitting

The highly porous, three-dimensionally well-connected through-pore structure of TiO2 aerogels is proven a superior material form for applications in photocatalytic water splitting for hydrogen production. At the reaction temperature of 30 °C, the specific hydrogen evolution rate achieved by the TiO2 aerogel is 3.40 and 9.63 times those obtained by hydrothermally prepared TiO2 nanocrystals and commercial P25 TiO2 nanoparticles, respectively. Decoration of Pt nanocrystals onto the backbone of the TiO2 aerogel leads to a one-order of magnitude improvement in hydrogen evolution rate over the plain TiO2 aerogel. Two methods are developed for the Pt decoration: a polyol process and an immersion-calcination-reduction process. The latter produces smaller sized Pt nanocrystals of around 1.9 nm, versus 4.7 nm from the polyol process, and achieves the same level of maximum specific hydrogen evolution rates as the polyol process at only a 1/10 Pt loading.

Aerogels for Energy Saving and Storage

Aerogels have drawn a great deal of research attention in recent years because their unique and advantageous structural characteristics of high porosity, high specific surface area, and mesopores, find a wide range of potential applications. Among them, their timely and imperative applications in energy saving and energy storage are particularly important to respond to the ever worsening issues of fossil energy depletion and global warming. In this chapter, aerogels serving as thermal insulation materials for energy saving and as electrode materials for supercapacitors and lithium ion batteries for energy storage are reviewed and discussed.