Spark plasma sintered carbon electrodes for electrical double layer capacitor applications

The spark plasma sintering (SPS) is an emerging process for shaping any type of materials (metals, ceramic, polymers and their composites). The advantage of such a process is to prepare densified ceramic materials in a very short time, while keeping the materials internal porosity. In the present work, we have used the SPS technique to prepare activated carbon-based electrodes for Electrochemical Double Layer Capacitor applications (EDLC). Self-supported 600 and 300µm-thick electrodes were prepared and characterized using of Electrochemical Impedance Spectroscopy and galvanostatic cycling in a non-aqueous 1.5MNEt4BF4 in acetonitrile electrolyte. Electrochemical performance of these sintered electrodes were found to be in the same range – or even slightly better – than the conventional tape-casted activated carbon electrodes. Although organic liquid electrolyte was used to characterize the electrochemical performance of the sintered electrodes, these results demonstrate that the SPS technique could be worth of interest in the ultimate goal of designing solid-state supercapacitors

Nanocrystallized ceria-based coatings prepared by electrochemistry on TA6V titanium alloy

Nanocrystallized ceria-based coatings were prepared on TA6V titanium alloy by using a three-step procedure: substrate pretreatment, electrochemical impregnation and final heat treatment. UV–vis and Raman in situ spectroscopies performed at the substrate interface during the electrochemical impregnation, showed experimentally for the first time that the interfacial deposit is made up of cerium hydroxide, incorporating also water molecules and nitrate ions coming from the electrolyte. Thermogravimetric analysis indicated also that the composition of the coating after the impregnation is given by the global formula CeO23.4H2O, while XRD analysis revealed that ceria with cubic fluorite crystalline structure is finally produced. Different preparation conditions were studied in view to control the nanosize of the supported ceria crystallites. It appeared that the final heat treatment is the most efficient operational parameter for the tuning of the particle size, that it can be thus well controlled from 5 to 30 nm between 300 and 700 8C

MnO2-coated Ni nanorods: Enhanced high rate behavior in pseudo-capacitive supercapacitor

Ni nanorods prepared by electrochemical growth through an anodized aluminium oxide membrane were used as substrate for the electrodeposition of MnO2 either in potentiostatic mode or by a pulsed method. Electrochemical deposition parameters were chosen for an homogeneous deposit onto Ni nanorods. Resulting Ni supportedMnO2 electrodes were tested for electrochemical performances as nanostructured negative electrodes for supercapacitors. They exhibited initial capacitances up to 190 F/g and remarkable performances at high charge/discharge rates

Qualitative electrochemical impedance spectroscopy study of ion transport into sub-nanometer carbon pores in electrochemical double layer capacitor electrodes

Ion adsorption onto high surface area microporous Carbide Derived Carbons (CDCs) with pore sizes in the sub-nanometer range was studied by means of the Electrochemical Impedance Spectroscopy (EIS) technique in two electrolytes, Tetraethylammonium Tetrafluoroborate (NEt4BF4) in Acetonitrile (AN) and in Propylene Carbonate (PC). Polarization at two bias voltages (0.5 V/Ref and -1 V/Ref) for EIS measurements enabled comparing the capacitive behaviors resulting from anions and cations adsorption, respectively, it was confirmed that the effective size of NEt4+ is bigger than the one of BF4-. Higher transport limitation was then observed for cations and was exalted in PC-based electrolyte. Although slow ion transport kinetics, it was found that the low frequency vertical line observed on the Nyquist plots was preserved meaning that carbon electrodes were fully charged. This study confirmed the importance of choosing an electrode carbon pore size adapted to the effective ion size. Finally, the best performances would be got in 1.5 M NEt4BF4 AN-based electrolyte with a 0.76 nm pore size negative electrode and a 0.68 nm pore size positive electrode

Effect of electric field polarization and temperature on the effective permittivity and conductivity of porous anodic aluminium oxide membranes

Porous insulators offer new opportunities for the controlled guest–host synthesis of nanowires for future integrated circuits characterized by low propagation delay, crosstalk and power consumption. We propose a method to estimate the effect of the electric field polarization and temperature on the electrical properties of different types of synthesized porous anodic aluminium oxide membranes. It results that the effective permittivity along the pore axis is generally 20% higher than the one in the orthogonal direction. The type of solution and the voltage level applied during anodization are the main parameters affecting the AAO templates characteristics, i.e. their porosity and chemical content. The values of permittivity of the final material, are typically in the range 2.6–3.2 for large pore diameter membranes including phosphorus element and having a low water content, and in the range 3.5–4 for the ones with smaller pores, and showing sulphur element incorporation. Moreover, the dc conductivity of the different membranes appears to be correlated to the pore density

One-step synthesis of highly reduced graphene hydrogels for high power supercapacitor applications

Graphene hydrogels with high electrical conductivity were prepared by a one-step process using hydrazine hydrate as gel assembly agent (GH-HD). Conventional two-step process of gel formation and further reduction to prepare highly conducting gels was replaced by a single step involving equivalent amount of hydrazine. Optimized graphene oxide concentration was established to facilitate such monolith formation. Extensive characterization and control studies enabled understanding of the material properties and gel formation mechanism. The synthesized gel shows a high electrical conductivity of 1141 S/m. The supercapacitor based on GH-HD delivers a high specific capacitance of 190 F/g at a current density of 0.5 A/g and 123 F/g at very high current density of 100 A/g. Furthermore, excellent power capability and cyclic stability were also observed. 3D macroporous morphology of GH-HD makes it ideal for high rate supercapacitor applications

Nanoarchitectured 3D cathodes for Li-Ion microbatteries

Microbatteries with large area capacity and no power limitation can be obtained by designing 3D structured batteries. 3D electrodes composed of 30 nm-thick films of LiCoO2 coating free-standing columns of Al current collector were achieved. By comparison with a planar electrode presenting an equivalent nominal capacity, a 3D electrode exhibits improved capacity retention: 68% of the nominal capacity at 8C instead of 11%

A SAXS outlook on disordered carbonaceous materials for electrochemical energy storage

Ordered and disordered carbonaceous materials cover a wide range of the energy storage materials market. In this work a thorough analysis of the Small Angle X-ray Scattering (SAXS) patterns of a number of carbon samples for energy storage (including graphite, soft carbon, hard carbon, activated carbon, glassy carbon and carbide-derived carbon) is shown. To do so, innovative geometrical models to describe carbon X-ray scattering have been built to refine the experimental SAXS data. The results obtained provide a full description of the atomic and pore structures of these carbons that in some cases challenge more traditional models. The correlative analysis of the descriptors here used provide novel insight into disordered carbons and can be used to shed light in charge storage mechanisms and to design improved carbonaceous materials

Solvent-Free Electrolytes for Electrical Double Layer Capacitors

A mechanically-stable non-aqueous inorganic gel polymer electrolyte that is based on association of sol-gel agents and Ionic Liquid is considered here for application in solid-state solvent free supercapacitors. The first part is devoted to the electrochemical characterization of the ionogel bulk properties. In the second part, an electrochemical cell using activated carbon as active materials and the new ionogel electrolyte has been characterized over a wide temperature range using cyclic voltammetry and electrochemical impedance spectroscopy. The use of high IL content (70%) has led to an increase of both the operating voltage window (up to 3 V)and the electrolyte ionic conductivity (around 4.7 mS/cm). The resulting double layer capacitance of the microporous activated carbon device was found to be as high as 80 F/g; even more important, this quasi solid electrolyte works well over a wide temperature range (namely, from −30 to more than 80◦C)

Outstanding room-temperature capacitance of biomass-derived microporous carbons in ionic liquid electrolyte

A remarkable capacitance of 180 F·g−1 (at 5 mV·s−1) in solvent-free room-temperature ionic liquid electrolyte, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, was achieved in symmetric supercapacitors using microporous carbons with a specific surface area of ca. 2000 m2·g−1 calculated from gas sorption by the 2D-NLDFT method. The efficient capacitive charge storage was ascribed to textural properties: unlike most activated carbons, high specific surface area was made accessible to the bulky ions of the ionic liquid electrolyte thanks to micropores (1–2 nm) enabled by fine-tuning chemical activation. From the industrial perspective, a high volumetric capacitance of ca. 80 F·cm−3 was reached in neat ionic liquid due to the absence of mesopores. The use of microporous carbons from biomass waste represents an important advantage for large-scale production of high energy density supercapacitors