Carine Davoisne

Cathode composites for Li-S batteries via the use of oxygenated porous architectures.

Li-S rechargeable batteries are attractive for electric transportation because of their low cost, environmentally friendliness, and superior energy density. However, the Li-S system has yet to conquer the marketplace, owing to its drawbacks, namely, soluble polysulfide formation. To tackle this issue, we present here a strategy based on the use of a mesoporous chromium trimesate metal-organic framework (MOF) named MIL-100(Cr) as host material for sulfur impregnation. Electrodes containing sulfur impregnated within the pores of the MOF were found to show a marked increase in the capacity retention of Li-S cathodes. Complementary transmission electron microscopy and X-ray photoelectron spectroscopy measurements demonstrated the reversible capture and release of the polysulfides by the pores of MOF during cycling and evidenced a weak binding between the polysulphides and the oxygenated framework. Such an approach was generalized to other mesoporous oxide structures, such as mesoporous silica, for instance SBA-15, having the same positive effect as the MOF on the capacity retention of Li-S cells. Besides pore sizes, the surface activity of the mesoporous additives, as observed for the MOF, appears to also have a pronounced effect on enhancing the cycle performance. Increased knowledge about the interface between polysulfide species and oxide surfaces could lead to novel approaches in the design and fabrication of long cycle life S electrodes.

Growth of single-crystal copper sulfide thin films viaelectrodeposition in ionic liquid media for lithium ion batteries

By exploiting the ability of ionic liquids to solubilize molecular sulfur at the melting point, we report the electrodeposition of CuS in an [EMIm]TFSI (1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) electrolytic bath containing Cu(TFSI)2 salt and elemental sulfur. Single-crystal and preferentially oriented covellite CuS thin films with flake morphology have been successfully obtained. Li/CuS coin cells using the deposits after carbon coating as the positive electrode show a discharge capacity of 350 mA h g−1 with capacity retention of 54.4% after 20 cycles.

Room-Temperature Synthesis of Iron-Doped Anatase TiO2 for Lithium-Ion Batteries and Photocatalysis

Iron-doped nanocrystalline particles of anatase TiO2 (denoted x% Fe-TiO2, with x the nominal [Fe] atom % in solution) have been successfully synthesized at room temperature by a controlled two-step process. Hydrolysis of titanium isopropoxide is first achieved to precipitate Ti(OH)4 species. A fine control of the pH allows one to maintain (i) soluble iron species and (ii) a sluggish solubility of Ti(OH)4 to promote a dissolution and condensation of titanium clusters incorporating iron, leading to the precipitation of iron-doped anatase TiO2. The pH does then influence both the nature and crystallinity of the final phase. After 2 months of aging at pH = 2, well-dispersed nanocrystalline iron-doped TiO2 particles have been achieved, leading to 5-6 nm particle size and offering a high surface area of ca. 280 m(2)/g. This dissolution/recrystallization process allows the incorporation of a dopant concentration of up to 7.7 atom %; the successful incorporation of iron in the structure is demonstrated by X-ray diffraction, high-resolution transmission electron microscopy, and Mössbauer spectroscopy. This entails optical-band-gap narrowing from 3.05 to 2.30 eV. The pros and cons effects of doping on the electrochemical properties of TiO2 versus lithium are herein discussed. We reveal that doping improves the power rate capability of the electrode but, in turn, deserves the electrolyte stability, leading to early formation of SEI. Finally, we highlight a beneficial effect of low iron introduction into the anatase lattice for photocatalytic applications under standard AM1.5G visible-light illumination.

Interface Stability of a TiO2/3‐Methoxypropionitrile‐Based Electrolyte: First Evidence for Solid Electrolyte Interphase Formation and Implications

We report an in-depth study focusing on the stability of a benchmark electrolyte composition based on a low-volatile 3-methoxypropionitrile (MPN) solvent employed in dye-sensitized solar cells. In the presence of TiO2, the semi-conductor surface plays a catalytic role in the thermal degradation of the electrolyte, which induces, among other effects, the nucleation and growth of a uniform solid electrolyte interphase (SEI) layer that wraps TiO2. On the basis of our actual understanding, we argue that SEI formation is responsible for triiodide depletion in the electrolyte during ageing and also has a simultaneous impact on TiO2 optoelectronic properties through the onset of a visible-light absorption tail, energy modification of intraband trap states, and the induction of an increase in both electron lifetime and transport time in TiO2. In-depth characterization of this layer by using XPS and ToF-SIMS indicates that the chemical composition of this SEI results from solvent and additive degradation, that is, iodide, sulfur, cyano, nitrogen, carbon, and imidazolium rings. The SEI thickness, its content, and the concentration profile strongly vary depending on the ageing conditions. The outcome of this new finding is discussed in comparison with literature observations and stresses the difficulties in reaching long-term stability at 85 °C by using MPN-based electrolytes unless new interfacial engineering is accomplished to impede pinholes between dye molecules on TiO2.

Chemical and morphological evolution of a silicate surface under low-energy ion irradiation

Aims. Olivine surfaces have been subjected to low-energy ion irradiation with H + ,H e + and Ar + at energies within the keV range in order to simulate the effects of energetic gas-grain interactions within shocked regions of the interstellar medium. Methods. The induced modifications in the chemical composition and the bonding configuration of the upper and the near surface regions were monitored in situ by X-ray photoelectron spectroscopy (XPS). The associated morphological evolution of the samples was studied by atomic force microscopy (AFM). Results. Results show that the surface chemistry evolves during irradiation with a noticeable Mg enrichment relative to Si. This evolution is interpreted as coming from magnesium atom diffusion driven by the electric field caused by the positive ion implantation. The iron valence state is also strongly affected by irradiation, with reduction occurring at relatively high fluxes. However, at low fluxes the iron is found to oxidise from Fe 2+ to Fe 3+ due to a charge transfer between the incident positive ions and the iron in the sample. The atomic force microscopy results show that the surface roughness tends to increase with irradiation and that this roughness influences the surface chemical reactivity of the grains, as shown by the enhanced formation of carbonate on the surfaces when they are exposed to a CO2 atmosphere. The implications for the evolution of interstellar dust include an enhanced dust catalytic activity. These effects would arise from modification under irradiation of the surface reactivity and an increase in the available grain surface area.

Phase stability frustration on ultra-nanosized anatase TiO2.

This work sheds light on the exceptional robustness of anatase TiO2 when it is downsized to an extreme value of 4 nm. Since at this size the surface contribution to the volume becomes predominant, it turns out that the material becomes significantly resistant against particles coarsening with temperature, entailing a significant delay in the anatase to rutile phase transition, prolonging up to 1000 °C in air. A noticeable alteration of the phase stability diagram with lithium insertion is also experienced. Lithium insertion in such nanocrystalline anatase TiO2 converts into a complete solid solution until almost Li1TiO2, a composition at which the tetragonal to orthorhombic transition takes place without the formation of the emblematic and unwished rock salt Li1TiO2 phase. Consequently, excellent reversibility in the electrochemical process is experienced in the whole portion of lithium content.

Ferromagnetic inclusions in silicate thin films: insights into the magnetic properties of cosmic grains

Context. We recently reported the formation of metallic inclusions in an amorphous and/or crystalline silicate matrix by thermal annealing of thin films in reducing atmospheres. Experimentally, the obtained microstructures closely resemble those of the glass with embedded metal and sulphides (GEMS) found in chondritic porous interplanetary dust particles (CP IDPs). We present here the magnetic properties of these synthetic samples. Aims. In this paper we report the detection and measurements of single domain and super paramagnetic ferromagnetic inclusions (SD/SP) in annealed silicate thin films of composition analogous to interstellar silicates and discuss the implications for the alignment of cosmic grains in astrophysical environments, in the presence of weak magnetic fields. Methods. We investigate the magnetic properties of synthesized laboratory silicate samples by measuring their magnetization when subjected to a given magnetic field. The measurements were performed at different temperatures including those compatible with interstellar dust. Results. The high values of remanent magnetization at saturation obtained in this work suggest the ability of our samples to indefinitely maintain a significant magnetization which may contribute to their alignment in weak magnetic fields. Conclusions. From our laboratory experimental simulation we propose that interstellar grains contain iron in form of nm-sized metallic beads. This can explain the non-detection of iron in interstellar grains. These inclusions could play a role in the alignment of grains. We propose a possible scenario for the magnetization of the cosmic grains and give a minimum value for the magnetic susceptibilty for GEMS.

Structural and optical characterization of electrodeposited CdSe in mesoporous anatase TiO2 for regenerative quantum-dot-sensitized solar cells

We investigated CdSe-sensitized TiO(2) solar cells by means of electrodeposition under galvanostatic control. The electrodeposition of CdSe within the mesoporous film of TiO(2) gives rise to a uniform, thickness controlled, conformal layer of nanostructured CdSe particles intimately wrapping the anatase TiO(2) nanoparticles. This technique has the advantage of providing not only a fast method for sensitization ( < 5 min) but also being easily scalable to the sensitization of large-area panels. XRD together with SAED analysis highlight that the deposit of CdSe is exclusively constituted of the hexagonal polymorph. In addition, hierarchical growth has also been shown, starting from the formation of a TiO(2)-CdSe core-shell structure followed by the growth of an assembly of CdSe nanoparticles resembling cauliflowers. This assembly exhibits at its core a mosaic texture with crystallites of about 3 nm in size, in contrast to a shell composed of well-crystallized single crystals between 5 and 10 nm in size. Preliminary results on the photovoltaic performance of such a nanostructured composite of TiO(2) and CdSe show 0.8% power conversion efficiency under A.M.1.5 G conditions-100 mW cm(-2) in association with a new regenerative redox couple based on cobalt(+III/+II) polypyridil complex (V(oc ) = 485 mV, J(sc ) = 4.26 mA cm (-2), ff=0.37).

Low-temperature electrodeposition approach leading to robust mesoscopic anatase TiO2 films.

Anatase TiO2, a wide bandgap semiconductor, likely the most worldwide studied inorganic material for many practical applications, offers unequal characteristics for applications in photocatalysis and sun energy conversion. However, the lack of controllable, cost-effective methods for scalable fabrication of homogeneous thin films of anatase TiO2 at low temperatures (ie. < 100 °C) renders up-to-date deposition processes unsuited to flexible plastic supports or to smart textile fibres, thus limiting these wearable and easy-to-integrate emerging technologies. Here, we present a very versatile template-free method for producing robust mesoporous films of nanocrystalline anatase TiO2 at temperatures of/or below 80 °C. The individual assembly of the mesoscopic particles forming ever-demonstrated high optical quality beads of TiO2 affords, with this simple methodology, efficient light capture and confinement into the photo-anode, which in flexible dye-sensitized solar cell technology translates into a remarkable power conversion efficiency of 7.2% under A.M.1.5G conditions.

Nitroxide supported on nanometric metal oxides as new hybrid catalysts for selective sugar oxidation

A new series of supported organocatalysts, prepared by a simple method, were used for selective sugar oxidation. This approach is based on the immobilization of a nitroxide derivative through a carboxylic function on nanometric metal oxides (TiO2, Al2O3 and CeO2), allowing the recovery of the catalyst. These hybrid materials were carefully characterized by Diffuse Reflectance FT-IR spectroscopy (DRIFT), ThermoGravimetric Analysis (TGA), X-Ray Diffraction (XRD), Brunauer-Emmet-Teller surface area measurements (B.E.T.), elemental and electrochemical analyses, showing different characteristics and behaviors depending on the nature of the metal oxide used. The activity of the supported nitroxide catalyst was evaluated on methyl α-d-glucoside oxidation, used as model reaction. In all cases, high catalytic activity was highlighted, with up to 25 times less nitroxyl radical required for complete conversion than under homogeneous conditions. The influence of several experimental conditions such as the use of phosphate buffer and recyclability of the catalyst were also investigated.