The science and technology of ultracapacitors are reviewed for a number of electrode materials, including carbon, mixed metal oxides, and conducting polymers. More work has been done using microporous carbons than with the other materials and most of the commercially available devices use carbon electrodes and an organic electrolytes. The energy density of these devices is 3¯5 Wh/kg with a power density of 300¯500 W/kg for high efficiency (90¯95%) charge/discharges. Projections of future developments using carbon indicate that energy densities of 10 Wh/kg or higher are likely with power densities of 1¯2 kW/kg. A key problem in the fabrication of these advanced devices is the bonding of the thin electrodes to a current collector such the contact resistance is less than 0.1 cm2. Special attention is given in the paper to comparing the power density characteristics of ultracapacitors and batteries. The comparisons should be made at the same charge/discharge efficiency.

Ultracapacitors: Why, How, and Where is the Technology

Owing to their immense potential in energy conversion and storage, catalysis, photocatalysis, adsorption, separation and life science applications, significant interest has been devoted to the design and synthesis of hierarchically porous materials. The hierarchy of materials on porosity, structural, morphological, and component levels is key for high performance in all kinds of applications. Synthesis and applications of hierarchically structured porous materials have become a rapidly evolving field of current interest. A large series of synthesis methods have been developed. This review addresses recent advances made in studies of this topic. After identifying the advantages and problems of natural hierarchically porous materials, synthetic hierarchically porous materials are presented. The synthesis strategies used to prepare hierarchically porous materials are first introduced and the features of synthesis and the resulting structures are presented using a series of examples. These involve templating methods (surfactant templating, nanocasting, macroporous polymer templating, colloidal crystal templating and bioinspired process, i.e. biotemplating), conventional techniques (supercritical fluids, emulsion, freeze-drying, breath figures, selective leaching, phase separation, zeolitization process, and replication) and basic methods (sol–gel controlling and post-treatment), as well as self-formation phenomenon of porous hierarchy. A series of detailed examples are given to show methods for the synthesis of hierarchically porous structures with various chemical compositions (dual porosities: micro–micropores, micro–mesopores, micro–macropores, meso–mesopores, meso–macropores, multiple porosities: micro–meso–macropores and meso–meso–macropores). We hope that this review will be helpful for those entering the field and also for those in the field who want quick access to helpful reference information about the synthesis of new hierarchically porous materials and methods to control their structure and morphology.

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Hierarchically porous materials: synthesis strategies and structure design

Liquid crystals of anisotropic colloids are of great significance in the preparation of their ordered macroscopic materials, for example, in the cases of carbon nanotubes and graphene. Here, we report a facile and scalable spinning process to prepare neat “core–shell” structured graphene aerogel fibers and three-dimensional cylinders with aligned pores from the flowing liquid crystalline graphene oxide (GO) gels. The uniform alignment of graphene sheets, inheriting the lamellar orders from GO liquid crystals, offers the porous fibers high specific tensile strength (188 kN m kg–1) and the porous cylinders high compression modulus (3.3 MPa). The porous graphene fibers have high specific surface area up to 884 m2 g–1 due to their interconnected pores and exhibit fine electrical conductivity (2.6 × 103 to 4.9 × 103 S m–1) in the wide temperature range of 5–300 K. The decreasing conductivity with decreasing temperature illustrates a typical semiconducting behavior, and the 3D interconnected network of 2D graph...

Strong, Conductive, Lightweight, Neat Graphene Aerogel Fibers with Aligned Pores

Electromagnetic Response and Energy Conversion for Functions and Devices in Low‐Dimensional Materials

PolyHIPEs: Recent advances in emulsion-templated porous polymers

Freeze drying is a process whereby solutions are frozen in a cold bath and then the frozen solvents are removed via sublimation under vacuum, leading to formation of porous structures. Pore size, pore volume and pore morphology are dependent on variables such as freeze temperature, solution concentration, nature of solvent and solute, and the control of the freeze direction. Aqueous solutions, organic solutions, colloidal suspensions, and supercritical CO2 solutions have been investigated to produce a wide range of porous and particulate structures. Emulsions have recently been employed in the freeze drying process, which can exert a systematic control on pore morphology and pore volume and can also lead to the preparation of organic micro- and nano-particles. Spray freezing and directional freezing have been developed to form porous particles and aligned porous materials. This review describes the principles, latest progress and applications of materials prepared by controlled freezing and freeze drying. First of all the basics of freeze drying and the theory of freezing are discussed. Then the materials fabricated by controlled freezing and freeze drying are reviewed based on their morphologies: porous structures, microwires and nanowires, and microparticles and nanoparticles. The review concludes with new developments in this area and a brief look into the future. Copyright © 2010 Society of Chemical Industry

Controlled freezing and freeze drying: a versatile route for porous and micro-/nano-structured materials

Random composites with nickel networks hosted randomly in porous alumina are proposed to realize double negative materials. The random composite for DNMs (RC-DNMs) can be prepared by typical processing of material, which makes it possible to explore new DNMs and potential applications, and to feasibly tune their electromagnetic parameters by controlling their composition and microstructure. Hopefully, various new RC-DNMs with improved performance will be proposed in the future.

Random Composites of Nickel Networks Supported by Porous Alumina Toward Double Negative Materials

While metal is the most common conductive constituent element in the preparation of metamaterials, one-dimensional conductive carbon nanotubes (CNTs) provide alternative building blocks. Here alumina (Al2O3) nanocomposites with multi-walled carbon nanotubes (MWCNTs) uniformly dispersed in the alumina matrix were prepared by hot-pressing sintering. As the MWCNT content increased, the formed conductive MWCNT networks led to the occurrence of the percolation phenomenon and a change of the conductive mechanism. Two different types of negative permittivity (i.e., resonance-induced and plasma-like) were observed in the composites. The resonance-induced negative permittivity behavior in the composite with a low nanotube content was ascribed to the induced electric dipole generated from the isolated MWCNTs. The frequency dispersions of such negative permittivity can be fitted well by the Lorentz model, while the observed plasma-like negative permittivity behavior in the composites with MWCNT content exceeding the percolation threshold could be well explained by the low frequency plasmonic state generated from conductive nanotube networks using the Drude model. This work is favorable to revealing the generation mechanism of negative permittivity behavior and will greatly facilitate the practical applications of metamaterials.

Radio frequency negative permittivity in random carbon nanotubes/alumina nanocomposites

Urchin-like NiO–NiCo2O4 microspheres with heterostructures were successfully synthesized through a facile hydrothermal method, followed by thermal treatment. The unique structure of NiO–NiCo2O4 with the synergetic effect between NiCo2O4 and NiO, and the heterostructure favour the catalytic activity towards Li–O2 batteries. NiCo2O4 is helpful for boosting both the oxygen reduction reaction and oxygen evolution reaction for the Li–O2 batteries and NiO is likely to promote the decomposition of certain by-products. The special urchin-like morphology facilitates the continuous oxygen flow and accommodates Li2O2. Moreover, benefitting from the heterostructure, NiO–NiCo2O4 microspheres are able to promote the transport of Li ions and electrons to further improve battery performance. Li–O2 batteries utilizing a NiO–NiCo2O4 microsphere electrode show a much higher specific capacity and a lower overpotential than those with a Super P electrode. Moreover, they exhibit an enhanced cycling stability. The electrode can be continuously discharged and charged without obvious terminal voltage variation for 80 cycles, as the discharge capacity is restricted at 600 mA h g−1, suggesting that NiO–NiCo2O4 is a promising catalyst for Li–O2 batteries.

Lei Qian

Papers

Controlled freezing and freeze drying: a versatile route for porous and micro-/nano-structured materials

Random Composites of Nickel Networks Supported by Porous Alumina Toward Double Negative Materials

Radio frequency negative permittivity in random carbon nanotubes/alumina nanocomposites

Urchin-like NiO–NiCo2O4 heterostructure microsphere catalysts for enhanced rechargeable non-aqueous Li–O2 batteries

Green synthesis of chitosan-based nanofibers and their applications