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

This review article aims to provide an updated and comprehensive description of the development of the Electric Current Activated/assisted Sintering technique (ECAS) for the obtainment of dense materials including nanostructured ones. The use of ECAS for pure sintering purposes, when starting from already synthesized powders promoters, and to obtain the desired material by simultaneously performing synthesis and consolidation in one-step is reviewed. Specifically, more than a thousand papers published on this subject during the past decades are taken into account. The experimental procedures, formation mechanisms, characteristics, and functionality of a wide spectrum of dense materials fabricated by ECAS are presented. The influence of the most important operating parameters (i.e. current intensity, temperature, processing time, etc.) on product characteristics and process dynamics is reviewed for a large family of materials including ceramics, intermetallics, metal–ceramic and ceramic–ceramic composites. In this review, systems where synthesis and densification stages occur simultaneously, i.e. a fully dense product is formed immediately after reaction completion, as well as those ones for which a satisfactory densification degree is reached only by maintaining the application of the electric current once the full reaction conversion is obtained, are identified. In addition, emphasis is given to the obtainment of nanostructured dense materials due to their rapid progress and wide applications. Specifically, the effect of mechanical activation by ball milling of starting powders on ECAS process dynamics and product characteristics (i.e. density and microstructure) is analysed. The emerging theme from the large majority of the reviewed investigations is the comparison of ECAS over conventional methods including pressureless sintering, hot pressing, and others. Theoretical analysis pertaining to such technique is also proposed following the last results obtained on this topic.

Consolidation/synthesis of materials by electric current activated/assisted sintering

Field-assisted sintering technology/Spark plasma sintering is a low voltage, direct current (DC) pulsed current activated, pressure-assisted sintering, and synthesis technique, which has been widely applied for materials processing in the recent years. After a description of its working principles and historical background, mechanical, thermal, electrical effects in FAST/SPS are presented along with the role of atmosphere. A selection of successful materials development including refractory materials, nanocrystalline functional ceramics, graded, and non-equilibrium materials is then discussed. Finally, technological aspects (advanced tool concepts, temperature measurement, finite element simulations) are covered.

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Field-Assisted Sintering Technology/Spark Plasma Sintering: Mechanisms, Materials, and Technology Developments

The mechanical behaviour of nanocrystalline materials (that is, polycrystals with a grain size of less than 100 nm) remains controversial. Although it is commonly accepted that the intrinsic deformation behaviour of these materials arises from the interplay between dislocation and grain-boundary processes, little is known about the specific deformation mechanisms. Here we use large-scale molecular-dynamics simulations to elucidate this intricate interplay during room-temperature plastic deformation of model nanocrystalline Al microstructures. We demonstrate that, in contrast to coarse-grained Al, mechanical twinning may play an important role in the deformation behaviour of nanocrystalline Al. Our results illustrate that this type of simulation has now advanced to a level where it provides a powerful new tool for elucidating and quantifying--in a degree of detail not possible experimentally--the atomic-level mechanisms controlling the complex dislocation and grain-boundary processes in heavily deformed materials with a submicrometre grain size.

Dislocation processes in the deformation of nanocrystalline aluminium by molecular-dynamics simulation.

Molecular-dynamics simulations have recently been used to elucidate the transition with decreasing grain size from a dislocation-based to a grain-boundary-based deformation mechanism in nanocrystalline f.c.c. metals. This transition in the deformation mechanism results in a maximum yield strength at a grain size (the 'strongest size') that depends strongly on the stacking-fault energy, the elastic properties of the metal, and the magnitude of the applied stress. Here, by exploring the role of the stacking-fault energy in this crossover, we elucidate how the size of the extended dislocations nucleated from the grain boundaries affects the mechanical behaviour. Building on the fundamental physics of deformation as exposed by these simulations, we propose a two-dimensional stress-grain size deformation-mechanism map for the mechanical behaviour of nanocrystalline f.c.c. metals at low temperature. The map captures this transition in both the deformation mechanism and the related mechanical behaviour with decreasing grain size, as well as its dependence on the stacking-fault energy, the elastic properties of the material, and the applied stress level.

Deformation-mechanism map for nanocrystalline metals by molecular-dynamics simulation.

Spark plasma sintering of transparent alumina

High-strain-rate superplasticity describes the ability of a material to sustain large plastic deformation in tension at high strain rates of the order of 10-2 to 10-1 s-1 and is of great technological interest for the shape-forming of engineering materials. High-strain-rate superplasticity has been observed in aluminium-based and magnesium-based alloys. But for ceramic materials, superplastic deformation has been restricted to low strain rates of the order of 10-5 to 10-4 s-1 for most oxides and nitrides with the presence of intergranular cavities leading to premature failure. Here we show that a composite ceramic material consisting of tetragonal zirconium oxide, magnesium aluminate spinel and alpha-alumina phases exhibits superplasticity at strain rates up to 1 s-1. The composite also exhibits a large tensile elongation, exceeding 1,050 per cent for a strain rate of 0.4 s-1. The tensile flow behaviour and deformed microstructure of the material indicate that superplasticity is due to a combination of limited grain growth in the constitutive phases and the intervention of dislocation-induced plasticity in the zirconium oxide phase. We suggest that the present results hold promise for the application of shape-forming technologies to ceramic materials.

A high-strain-rate superplastic ceramic

Fabrication of transparent MgAl2O4 spinel polycrystal by spark plasma sintering processing

Microstructure and optical properties of transparent alumina

Commercial alumina powder was densified by spark plasma sintering (SPS) at 1150 °C. During SPS processing, the effects of the heating rate were examined on microstructure and transparency. With decreasing heating rate, the grain size and the residual porosity decreased, while the transparency increased. At a heating rate of 2 °C/min, the grain size was 0.29 μm, and the in-line transmission was 46% for a wavelength of 640 nm. The mechanisms for the fine microstructure and low porosity at slow heating, which are conflicting with some existing results, were explained by considering the role of defect concentration and grain-boundary diffusion during densification.

Byung-Nam Kim

Papers

Spark plasma sintering of transparent alumina

A high-strain-rate superplastic ceramic

Fabrication of transparent MgAl2O4 spinel polycrystal by spark plasma sintering processing

Microstructure and optical properties of transparent alumina

Effects of heating rate on microstructure and transparency of spark-plasma-sintered alumina