Barbara Daffos

On-chip and freestanding elastic carbon films for micro-supercapacitors

Flexible power for flexible electronics A challenge for flexible electronics is to couple devices with power sources that are also flexible. Ideally, they could also be processed in a way that is compatible with current microfabrication technologies. Huang et al. deposited a relatively thick layer of TiC on top of an oxide-coated Si film. After chlorination, most, but importantly not all, of the TiC was converted into a porous carbon film that could be turned into an electrochemical capacitor. The carbon films were highly flexible, and the residual TiC acted as a stress buffer with the underlying Si film. The films could be separated from the Si to form free-floating films, with the TiC providing a support layer. Science, this issue p. 691 Porous carbon-based supercapacitors are directly fabricated onto silicon substrates. Integration of electrochemical capacitors with silicon-based electronics is a major challenge, limiting energy storage on a chip. We describe a wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors, fully compatible with current microfabrication and silicon-based device technology. Capacitance of those films reaches 410 farads per cubic centimeter/200 millifarads per square centimeter in aqueous electrolyte and 170 farads per cubic centimeter/85 millifarads per square centimeter in organic electrolyte. We also demonstrate preparation of self-supported, mechanically stable, micrometer-thick porous carbon films with a Young’s modulus of 14.5 gigapascals, with the possibility of further transfer onto flexible substrates. These materials are interesting for applications in structural energy storage, tribology, and gas separation.

Highly confined ions store charge more efficiently in supercapacitors

Liquids exhibit specific properties when they are adsorbed in nanoporous structures. This is particularly true in the context of supercapacitors, for which an anomalous increase in performance has been observed for nanoporous electrodes. This enhancement has been traditionally attributed in experimental studies to the effect of confinement of the ions from the electrolyte inside sub-nanometre pores, which is accompanied by their partial desolvation. Here we perform molecular dynamics simulations of realistic supercapacitors and show that this picture is correct at the microscopic scale. We provide a detailed analysis of the various environments experienced by the ions. We pick out four different adsorption types, and we, respectively, label them as edge, planar, hollow and pocket sites upon increase of the coordination of the molecular species by carbon atoms from the electrode. We show that both the desolvation and the local charge stored on the electrode increase with the degree of confinement.

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%.

On the dynamics of charging in nanoporous carbon-based supercapacitors.

Supercapacitors are electricity storage systems with high power performances. Their short charge/discharge times are due to fast adsorption/desorption rates for the ions of the electrolyte on the electrode surface. Nanoporous carbon electrodes, which give larger capacitances than simpler geometries, might be expected to show poorer power performances because of the longer times taken by the ions to access the electrode interior. Experiments do not show such trends, however, and this remains to be explained at the molecular scale. Here we show that carbide-derived carbons exhibit heterogeneous and fast charging dynamics. We perform molecular dynamics simulations, with realistically modeled nanoporous electrodes and an ionic liquid electrolyte, in which the system, originally at equilibrium in the uncharged state, is suddenly perturbed by the application of an electric potential difference between the electrodes. The electrodes respond by charging progressively from the interface to the bulk as ions are exchanged between the nanopores and the electrolyte region. The simulation results are then injected into an equivalent circuit model, which allows us to calculate charging times for macroscopic-scale devices.

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

From molecule-based (super)conductors to thin films, nanowires and nanorings

Thin films of (TTF)(TCNQ) (TTF=tetrathiafulvalene, TCNQ=tetracyanoquinodimethane) are deposited on Si (001), KBr, and stainless steel conversion coatings (SSCC) using chemical vapor deposition. These films are characterized by IR, XRD, conductivity measurements, and SEM. Conducting nanowires and nanorings of (TTF)(TCNQ) and nanowires of (TTF)[Ni(dmit) 2 ] 2 (typically, 20 nm×20 μm) are prepared by successively dipping SSCC in acetonitrile solutions of TTF and TCNQ, or (TTF) 3 (BF 4 ) and (Bu 4 N)[Ni(dmit) 2 ], respectively. These nanowires are observed by SEM. The (TTF)(TCNQ) nanowires are also observed by TEM and AFM and characterized by current-voltage measurements. Nanowires of (TTF)[Ni(dmit) 2 ] 2 are also obtained on silicon conversion coatings (SiCC) and characterized by Raman spectroscopy.

TiC-carbide derived carbon electrolyte adsorption study by ways of X-ray scattering analysis

Understanding ion adsorption in nanoporous carbon electrodes is of great importance for designing the next-generation of high energy density electrical double-layer capacitors. In this work, X-ray scattering is used for investigating the impregnation of nanoporous carbons with electrolytes in the absence of applied potential. We are able to show that interactions between the carbon surface and electrolytes allow adsorption to take place in sub-nanopores, thus confirming experimentally for the first time the results predicted by molecular dynamic simulations.

Improved electro-grafting of nitropyrene onto onion-like carbon via in situ electrochemical reduction and polymerization: tailoring redox energy density of the supercapacitor positive electrode

Herein, we report a improved method for the physical grafting of 1-nitropyrene (Pyr-NO2) onto highly graphitized carbon onion. This is achieved through a lowering of the onset potential of the pyrene polymerization via in situ reduction of the NO2 group. The additional redox activity pertaining to the reduced NO2 enables exceeding the faradaic capacity which is associated with the p-doping of the grafted pyrene backbone, as observed for pyrene, 1-aminopyrene, and unreduced Pyr-NO2. Theoretical calculations demonstrate the charge transfer and binding enthalpy capabilities of Pyr-NO2, which are significantly higher than those of the other two species, and which allow for improved p-stacking on the carbon surface. Upon 20 wt % grafting of Pyr-NO2, the capacity of the electrode jumps from 20 mAh g-1 electrode to 38 mAh g-1 electrode, which corresponds to 110 mAh g-1 per mass of Pyr-NO2 and the average potential is increased by 200 mV. Very interestingly, this high performance is also coupled with outstanding retention with respect to both the initial capacity for more than 4000 cycles, as well as the power characteristics, demonstrating the considerable advantages of employing the present in situ grafting technique.