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Sinturel C.,CNRS Center for Research on Divided Matter | Vayer M.,CNRS Center for Research on Divided Matter | Morris M.,University College Cork | Hillmyer M.A.,University of Minnesota | Hillmyer M.A.,LE STUDIUM Institute for Advanced Studies
Macromolecules | Year: 2013

This Perspective provides a critical analysis of the current knowledge concerning solvent vapor annealing (SVA) of block polymer thin films. Herein, we identify key challenges that will be important to overcome for future development of SVA as a practical, reliable, and universal technique for the valorization of block polymer thin films in a wide range of technologies. The Perspective includes a brief background on thin film block polymer self-assembly, a historical account of the SVA technique, an overview of the SVA fundamentals that are necessary to develop a more comprehensive picture of the overall process, and summaries of relevant and important contributions from the recent literature. We also offer our outlook on SVA and suggest important future directions. © 2013 American Chemical Society.


Raymundo-Pinero E.,CNRS Center for Research on Divided Matter | Cadek M.,Siemens AG | Wachtler M.,ZSW Zentrum fur Sonnenergie und Wasserstoff Forschung | Beguin F.,CNRS Center for Research on Divided Matter
ChemSusChem | Year: 2011

The advantages provided by multiwalled carbon nanotubes (CNTs) as backbones for composite supercapacitor electrodes are discussed. This paper particularly highlights the electrochemical properties of carbon composites obtained by pyrolysis of seaweed/CNTs blends. Due to the nanotexturing effect of CNTs, supercapacitors fabricated with electrodes from these composites exhibit enhanced electrochemical performances compared with CNT-free carbons. The cell resistance is dramatically reduced by the excellent conductivity of CNTs and by the good propagation of ions favored by the presence of opened mesopores. As a consequence, the specific power of supercapacitors based on these nanocomposites is very high. Another advantage related to the presence of CNTs is a better life cycle of the systems. The composite electrodes are resilient during the charge/discharge of capacitors; these are able to perfectly accommodate the dimensional changes appearing in the active material without mechanical damages. Carbonizing oxygen-rich seaweeds in the presence of carbon nanotubes (CNTs) adds several advantages to the electrochemical performance of carbon electrodes. Due to the excellent electrical conductivity of CNTs and the good propagation of ions favored by the presence of opened mesopores, the resistance of the cells is dramatically reduced and the specific power is enhance (see figure). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Anouti M.,University of Tours | Jacquemin J.,Queen's University of Belfast | Porion P.,CNRS Center for Research on Divided Matter
Journal of Physical Chemistry B | Year: 2012

We present a study on the transport properties through conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of two pure protic ionic liquids-pyrrolidinium hydrogen sulfate, [Pyrr][HSO 4], and pyrrolidinium trifluoroacetate, [Pyrr][CF3COO]-and their mixtures with water over the whole composition range at 298.15 K and atmospheric pressure. Based on these experimental results, transport mobilities of ions have been then investigated in each case through the Stokes-Einstein equation. From this, the proton conduction in these PILs follows a combination of Grotthuss and vehicle-type mechanisms, which depends also on the water composition in solution. In each case, the displacement of the NMR peak attributed to the labile proton on the pyrrolidinium cation with the PILs concentration in aqueous solution indicates that this proton is located between the cation and the anion for a water weight fraction lower than 8%. In other words, for such compositions, it appears that this labile proton is not solvated by water molecules. However, for higher water content, the labile protons are in solution as H3O+. This water weight fraction appears to be the solvation limit of the H+ ions by water molecules in these two PILs solutions. However, [Pyrr][HSO4] and [Pyrr][CF 3COO] PILs present opposed comportment in aqueous solution. In the case of [Pyrr][CF3COO], η, σ, D, and the attractive potential, Epot, between ions indicate clearly that the diffusion of each ion is similar. In other words, these ions are tightly bound together as ion pairs, reflecting in fact the importance of the hydrophobicity of the trifluoroacetate anion, whereas, in the case of the [Pyrr][HSO4], the strong H-bond between the HSO4 - anion and water promotes a drastic change in the viscosity of the aqueous solution, as well as on the conductivity which is up to 187 mS•cm-1 for water weight fraction close to 60% at 298 K. © 2012 American Chemical Society.


Gao Q.,CNRS Center for Research on Divided Matter | Demarconnay L.,CNRS Center for Research on Divided Matter | Raymundo-Pinero E.,CNRS Center for Research on Divided Matter | Beguin F.,CNRS Center for Research on Divided Matter | Beguin F.,Poznan University of Technology
Energy and Environmental Science | Year: 2012

This study investigates the large voltage range of symmetric carbon/carbon capacitors in environmentally friendly aqueous lithium sulfate electrolyte. A high over-potential related to the hydrogen sorption mechanism at the negative electrode contributes usefully to enhance the operating voltage up to 1.9 V with an excellent stability during 10000 charge/discharge cycles. Such a voltage value is two times higher than the values generally demonstrated with symmetric carbon/carbon capacitors in conventional aqueous media, while avoiding the disadvantages of the corrosive properties of acidic and basic electrolytes. Temperature programmed desorption analysis of the electrodes after long-term cycling gives the evidence that the maximum voltage is essentially limited by an irreversible electro-oxidation process at the positive electrode. If the potential of the positive electrode goes beyond a given value during cell operation, a massive electro-oxidation of carbon leads to a further deleterious increase of the maximum potential of the electrode and an increase of electrode resistance resulting in a decrease of capacitance. Inconvenience can be sidestepped by performing a controlled chemical oxidation of the carbon surface using hydrogen peroxide. As a consequence, the maximum potential of the electrode remains stable during operation of the cell at 1.9 V, and the system can be charged/discharged during 10000 cycles with very moderate loss of capacitance or increase of resistance. © 2012 The Royal Society of Chemistry.


Al-Mukhtar M.,CNRS Center for Research on Divided Matter | Lasledj A.,CNRS Center for Research on Divided Matter | Alcover J.-F.,CNRS Center for Research on Divided Matter
Applied Clay Science | Year: 2010

A comprehensive series of laboratory tests were conducted on a highly expansive clay soil treated with lime in order to study the lime-soil reaction over a short term and the progression of the pozzolanic reaction over a longer term. Therefore, the results of this study allow determination of the minimal concentration of lime reacting with clay minerals in order to induce a substantial long term improvement in the treated clay soil.The tests were performed with different percentages of hydrated lime (0-20%) at the room temperature of 20°C. Plasticity Index, swelling pressure, unconfined compressive strength, wave velocity, pH, electrical conductivity and lime consumption were used to monitor the progression of the lime-clay reactions. X-ray diffraction tests were carried out in an attempt to identify the mineralogical changes and the reaction products formed in the treated soil.The experimental results indicate that 5% lime is sufficient for a short term reaction involving cation exchange, in this soil. This quantity corresponds to the amount needed for optimum change in soil properties after treatment. The excess of lime added promotes pozzolanic reactions and produces new minerals, such as calcium aluminate hydrates (CAH). This new mineral is identified by X-ray diffraction and its characteristic reflections intensities increase with lime added and curing time. Soil properties continue to be improved with lime addition. Finally, this study shows clearly that lime treatment can be used even for extremely expansive soil. © 2010 Elsevier B.V.


Porous materials are known to adsorb fluid and can be characterised by measurement of fluid adsorption isotherms. Many nanoporous materials exhibit linear pores such as MCM-41 and porous silicon or alumina. In such systems, data adsorption analysis is considered to be straightforward within the approximation of independent domains. This article, which reviews previous molecular simulation works, aims at showing that the presence of heterogeneities within the pores actually invalidates this hypothesis, with consequences for porosity characterisation. To enlighten the effects, starting from perfect cylinders, the number of heterogeneities is progressively increased, up to large numbers, for which specific simulation tools are used to take into account the interdependence between the domains. The adsorption/desorption isotherms are calculated and correlated to the appearance of an exponentially large number of metastable states. © 2014 Taylor & Francis.


Khomenko V.,CNRS Center for Research on Divided Matter | Raymundo-Pinero E.,CNRS Center for Research on Divided Matter | Beguin F.,CNRS Center for Research on Divided Matter
Journal of Power Sources | Year: 2010

A new type of low cost and high energy asymmetric capacitor based on only activated carbons for both electrodes has been developed in a safe and environment friendly aqueous electrolyte. In such electrolyte, the charges are stored in the electrical double-layer and through fast faradaic charge transfer processes. By taking profit of different redox reactions occurring in the positive and negative ranges of potential, it is possible to optimize the capacitor either by balancing the mass of the electrodes or by using different optimized carbons for the positive and negative electrodes. The best results are obtained in the latter case, by utilizing different pseudo-faradaic properties of carbons in order to increase the capacitance and to shift the potentials of water decomposition and destructive oxidation of activated carbon to more negative and positive values, respectively. After an additional adjustment of potentials by mass-balancing the two electrodes, the electrochemical capacitor can be reversibly charged/discharged at 1.6 V in aqueous medium, with energy densities close to the values obtained with electrical double-layer capacitors working in organic electrolytes, while avoiding their disadvantages. © 2010 Elsevier B.V. All rights reserved.


Demarconnay L.,CNRS Center for Research on Divided Matter | Raymundo-Pinero E.,CNRS Center for Research on Divided Matter | Beguin F.,CNRS Center for Research on Divided Matter
Journal of Power Sources | Year: 2011

The electrodes mass ratio of MnO2/activated carbon supercapacitors has been varied in order to monitor its influence on the potential window of both electrodes and consequently to optimize the operating voltage. It appeared that the theoretical mass ratio (R = 2), calculated considering an equivalent charge passed across both electrodes, is underestimated. It was demonstrated that R values of 2.5-3 are better adapted for this system; the extreme potential reached for each electrode is close to the stability limits of the electrolyte and active material, allowing a maximum voltage to be reached. During galvanostatic cycling up to 2 V, the best performance was obtained with R = 2.5. The specific capacitance increased from 100 to 113 F g-1 during the first 2000 cycles, then decayed up to 6000 cycles and finally stabilized at 100 F g-1. SEM images of the manganese based electrode after various numbers of thousands cycles exhibited dramatic morphological modifications. The later are suspected to be due to Mn(IV) oxidation and dissolution at high potential values. Hence, the evolution of specific capacitance during cycling of the asymmetric capacitor is ascribed to structural changes at the positive electrode. © 2010 Elsevier B.V.


Demarconnay L.,CNRS Center for Research on Divided Matter | Raymundo-Pinero E.,CNRS Center for Research on Divided Matter | Beguin F.,CNRS Center for Research on Divided Matter
Electrochemistry Communications | Year: 2010

A high voltage symmetric carbon/carbon supercapacitor was built using a Na 2SO 4 aqueous solution. This system exhibits an excellent cycle life during thousands of cycles up to voltage values as high as 1.6 V. Three-electrode investigations show a particularly high potential window, ΔE = 2 V, for the considered activated carbon in Na 2SO 4. However, in a two-electrode cell, when the voltage is higher than 1.6 V, the potential of the positive electrode is beyond the oxidation potential of water, and AC is oxidized. These results demonstrate the potentialities of Na 2SO 4 for developing high energy density systems. © 2010 Elsevier B.V.


Puibasset J.,CNRS Center for Research on Divided Matter
Journal of Physics Condensed Matter | Year: 2011

An improved approach is proposed to analyze the density of metastable states within any hysteresis loop, such as those observed in magnetic materials or for adsorption in porous materials. Except for a few analytically tractable models, most calculations have to be performed numerically on finite systems. The main points to be addressed thus concern the average over various material samples (the so-called realizations of the disorder), and the finite size analysis to estimate the thermodynamic limit. As an improvement of previously existing methods, it is proposed to introduce the Fourier transform of the density of metastable states (characteristic function). Its logarithm is shown to be additive and can straightforwardly be averaged over disorder. This procedure leads to a new definition of the complexity in finite size, giving the usual quenched complexity in the thermodynamic limit, while being better suited to performing finite size analysis. The calculations are illustrated on a molecular simulation based model for a simple fluid adsorbed in heterogeneous siliceous tubular pores mimicking mesoporous materials like MCM-41 or porous silicon. This approach is expected to be of general interest for hysteresis phenomena, including magnetic materials. © 2011 IOP Publishing Ltd.

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