Électrolytes-gels pour piles au lithium système PVdF-HFP/SiO2/VL-LiTFSI

Les électrolytes-gels étudiés sont constitués du copolymère poly (fluorure de vinylidène-hexafluoropropylène) (PVdF-HFP) contenant où non de la silice et ayant absorbé un électrolyte liquide obtenu par dissolution du (trifluorométhyl sulfone) imidure de lithium (LiTFSI) dans la gamma-valérolactone (VL) ou dans le mélange VL:EC (90:10 en moles) (EC:carbonate d'éthylène). L'influence du pourcentage en sel de lithium dans l'électrolyte liquide, de la proportion de silice dans le copolymère sec et de la température sur la capacité d'absorption est étudiée. L'évolution de la conductivité en fonction de la composition de l'électrolyte-gel et de la température ainsi que l'étude de la solvatation de l'ion Li$^+$ par spectroscopie RAMAN ont permis de proposer un modèle de conductivité ionique pour ces matériaux. Après avoir déterminé le domaine d'électroactivité des gels, l'évolution des spectres d'impédance à l'interface Li / gel est interprétée par le modèle “couche polymère solide" (SPL)

Copper(II) complexation by micelle-solubilized long-chain complexing agents: Unusually slow reaction rates

We consider in this work the complexation of copper(II) by two different complexing agents [7-4(ethyl-1-methyloctyl)-8-hydroxyquinoline (C-11-HQ) and 6-(hexadecylamino)methyl-2-hydroxymethylpyridine (C16NHMePyr)] in different kinds of micellar surfactant solutions (SDS, C12EO6, CTAB and mixed CTAB/butanol). Stopped-flow kinetic experiments at controlled pH have provided values of the apparent rate constants for complex formation, which are discussed with reference to literature data in homogeneous solutions. They show considerable rate decreases, especially in CTAB micellar systems

Cycling Behavior of a High Voltage Spinel Using an Original Three Electrodes Li1-xNi0.4Mn1.6O4//Li//LiNi0.4Mn1.6O4 Symmetric Cell: Application to LiNi0.4Mn1.6O4 Electrolyte Interface Degradation Studies

International audienceThe interface between LiNi0.4Mn1.6O4 and alkylcarbonate-based electrolytes is investigated by ab initio calculations, ICP-AES measurements and electrochemical tests. Interface degradation is known to occur by both the electrolyte oxidation and the Mnn+ and Nin+ ion dissolution. Nevertheless, EC or PC oxidation, leading to a polymeric film formation, is able to contribute to the interface stabilization. Besides Li//LiNi0.4Mn1.6O4 half-cells, Li1-xNi0.4Mn1.6O4//LiNi0.4Mn1.6O4 symmetric cells are used in order to eliminate the effects from the strong reducing nature of lithium on the electrolyte. Systematic comparisons of fading and coulombic efficiency show that the main degradation mechanism in half-cells is the electrolyte oxidation, as a consequence of the continuous precipitation of metal ion-based compounds on the lithium electrode. The symmetric cell studies indicate that redox shuttles (Mn+ ↔ M(n-1)+, M=Mn or Ni) are mainly responsible for the LiNi0.4Mn1.6O4/electrolyte interface degradation despite the possible presence of a polymeric film. Symmetric cells also confirm EC superiority over other alkylcarbonates at the LiNi0.4Mn1.6O4 interface

Evaluate Sulfone-Based Reduction Sensitive Electrolytes with Lithium Li4Ti5O12/Li and Symmetric Li4+XTi5O12/Li4Ti5O12 Cells

International audienceBinary mixtures of cyclic or acyclic sulfones with EMC or DMC are used in electrolytes containing LiPF6 (1M) in both Li4Ti5O12/Li half-cells and Li4+xTi5O12/Li4Ti5O12 symmetrical cells and compared with standard EC/EMC or EC/DMC mixtures. In half-cells, sulfone-based electrolytes cannot be satisfactorily cycled owing to the formation of a resistive layer at the lithium interface, which is not stable and generates species (RSO2-, RSO3-) able to migrate toward the titanate electrode interface. Potentiostatic and galvanostatic tests in Li4Ti5O12/Li half-cells show that charge transfer resistance increases drastically when sulfones are used in the electrolyte composition. Moreover, cycling ability and coulombic efficiency are low. At the opposite, when symmetrical Li4+xTi5O12/Li4Ti5O12 cells are used, it is demonstrated that MIS- (methyl isopropyl sulfone) and TMS- (tetra methyl sulfone) based electrolytes exhibit reasonable electrochemical performances compared to the EC/DMC or EC/EMC standard mixtures. Surface analysis by XPS of both the Li4+xTi5O12 (partially oxidized) and Li7Ti5O12 (reduced) electrodes taken from symmetrical cells reveals that sulfones do not participate in the formation of surface layers. Alkylcarbonates (EMC or DMC), used as co-solvents in sulfone-based binary electrolytes, ensure the formation of surface layers at the titanate interfaces

Marine ecosystems’ responses to climatic and anthropogenic forcings in the Mediterranean

International audienceThe semi-enclosed nature of the Mediterranean Sea, together with its smaller inertia due to the relative short residence time of its water masses, make it highly reactive to external forcings, in particular variations of water, energy and matter fluxes at the interfaces. This region, which has been identified as a “hotspot” for climate change, is therefore expected to experience environmental impacts that are considerably greater than those in many other places around the world. These natural pressures interact with the increasing demographic and economic developments occurring heterogeneously in the coastal zone, making the Mediterranean even more sensitive. This review paper aims to provide a review of the state of current functioning and responses of Mediterranean marine biogeochemical cycles and ecosystems with respect to key natural and anthropogenic drivers and to consider the ecosystems’ responses to likely changes in physical, chemical and socio-economical forcings induced by global change and by growing anthropogenic pressure at the regional scale. The current knowledge on and expected changes due to single forcing (hydrodynamics, solar radiation, temperature and acidification, chemical contaminants) and combined forcing (nutrient sources and stoichiometry, extreme events) affecting the biogeochemical fluxes and ecosystem functioning are explored. Expected changes in biodiversity resulting from the combined action of the different forcings are proposed. Finally, modeling capabilities and necessity for modeling are presented. A synthesis of our current knowledge of expected changes is proposed, highlighting relevant questions for the future of the Mediterranean ecosystems that are current research priorities for the scientific community. Finally, we discuss how these priorities can be approached by national and international multi-disciplinary research, which should be implemented on several levels, including observational studies and modeling at different temporal and spatial scales

3,5-Bis(ethynyl)pyridine and 2,6-bis(ethynyl)pyridine spanning two Fe(Cp*)(dppe) units: role of the nitrogen atom on the electronic and magnetic couplings.

International audienceThe role of the nitrogen atom on the electronic and magnetic couplings of the mono-oxidized and bi-oxidized pyridine-containing complex models [2,6-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) and [3,5-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) is theoretically tackled with the aid of density-functional theory (DFT) and multireference configuration interaction (MR-CI) calculations. Results are analyzed and compared to those obtained for the reference complex [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+). The mono-oxidized species show an interesting behavior at the borderline between spin localization and delocalization and one through-bond communication path among the two involving the central ring, is favored. Investigation of the spin state of the dicationic complexes indicates ferromagnetic coupling, which can differ in magnitude from one complex to the other. Very importantly, electronic and magnetic properties of these species strongly depend not only upon the location of the nitrogen atom in the ring versus that of the organometallic end-groups but also upon the architectural arrangement of one terminus, with respect to the other and/or vis-à-vis the central ring. To help validate the theoretical results, the related families of compounds [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+), [2,6-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+), [3,5-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+) (n = 0-2) were experimentally synthesized and characterized. Electrochemical, spectroscopic (infrared (IR), Mössbauer), electronic (near-infrared (NIR)), and magnetic properties (electron paramagnetic resonance (EPR), superconducting quantum interference device (SQUID)) are discussed and interpreted in the light of the theoretical data. The set of data obtained allows for many strong conclusions to be drawn. A N atom in the long branch increases the ferromagnetic interaction between the two Fe(III) spin carriers (J > 500 cm(-1)), whereas, when placed in the short branch, it dramatically reduces the magnetic exchange in the di-oxidized species (J = 2.14(5) cm(-1)). In the mixed-valence compounds, when the N atom is positioned on the long branch, the intermediate excited state is higher in energy than the different ground-state conformers and the relaxation process provides exclusively the Fe(II)/Fe(III) localized system (H(ab) ≠ 0). Positioning the N atom on the short branch modifies the energy profile and the diabatic mediating state lies just above the reactant and product diabatic states. Consequently, the LMCT transition becomes less energetic than the MMCT transition. Here, the direct coupling does not occur (H(ab) = 0) and only the coupling through the bridge (c) and the reactant (a) and product (b) diabatic states is operating (H(ac) = H(bc) ≠ 0)

Hexatriynediyl Chain Spanning Two Cp*(dppe) M Termini (M= Fe, Ru): Evidence for the Dependence of Electronic and Magnetic Couplings on the Relative Orientation of the Termini

The binuclear complexes Cp*(dppe)FeC-CC-CC-CM(dppe)Cp* (6, M = Fe; 8, M = Ru) were obtained in good yield by treatment of the iron chloro complex Cp*(dppe)Fe-Cl (5) in the presence of KF with the bis(silylated) hexatriyne Me3SiC-CC-CC-CSiMe3 and the ruthenium complex Cp*(dppe)RuC-CC-CC-CSiMe3 (7), respectively. The oxidized species 6(PF6)n (n = 1, 2) and 8(PF6) were obtained in ca. 80% yield by treatment of the parent neutral compounds with 1 or 2 equiv of [Cp2Fe](PF6) in THF or dichloromethane at -78 °C. The CV of these compounds show three reversible waves with a separation larger than 0.5 V. The salts 6(PF6)n (n = 1, 2), and 8(PF6) were characterized by XRD. Quantum chemistry calculations performed at the DFT level on the oxidized species show a strong contribution of the -C6- spacer to the delocalization of the spin density. IR spectra analyzed with the support of TD-DFT calculations are consistent with the delocalization of the odd electron on the fast IR time scale for the two mixed-valence complexes 6(PF6) and 8(PF6). Combined ESR measurements on rigid glass and on single crystal samples clearly establish that the electronic properties of MV species and particularly their magnetic anisotropies depend on the conformation of the molecules. In the case of the doubly oxidized species 6(PF6)2, which carries two unpaired electrons, it is shown that the singlet vs triplet ground states can be inverted by the rotation of one metal end with respect to the other around the all-carbon chain axis. Very strong NIR bands are found for the symmetric 6(PF6) and nonsymmetric 8(PF6) MV (mixed-valence) derivatives allowing the determination of very large electronic couplings (Hab = 3070 and 4025 cm-1, respectively). © 2014 American Chemical Society