Tuning Ceramic Surface to Minimize the Ionic Resistance at the Interface between PEO- and LATP-Based Ceramic Electrolyte.

New battery technologies are currently under development, and among them, all-solid-state batteries should deliver better electrochemical performance and enhanced safety. Composite solid electrolytes, combining a solid polymer electrolyte (SPE) and a ceramic electrolyte (CE), should then provide high ionic conductivity coupled to high mechanical stability. To date, this synergy has not yet been reached due to the complexity of the Li-ion transport within the hybrid solid electrolyte, especially at the SPE/CE interface currently considered the limiting step.

New Crosslinked Single-Ion Silica-PEO Hybrid Electrolytes.

New single-ion hybrid electrolytes have been synthetized via an original and simple synthetic approach combining Michael addition, epoxidation, and sol-gel polycondensation. We designed an organic PEO network as a matrix for the lithium transport, mechanically reinforced thanks to crosslinking inorganic (SiO) sites, while highly delocalized anions based on lithium vinyl sulfonyl(trifluoromethane sulfonyl)imide (VSTFSILi) were grafted onto the inorganic sites to produce single-ion hybrid electrolytes (HySI). The influence of the electrolyte composition in terms of the inorganic/organic ratio and the grafted VSTFSILi content on the local structural organization, the thermal, mechanical, and ionic transport properties (ionic conductivity, transference number) are studied by a variety of techniques including SAXS, DSC, rheometry, and electrochemical impedance spectroscopy.

Dense inorganic electrolyte particles as a lever to promote composite electrolyte conductivity.

Solid-state batteries are seen as key to the development of safer and higher-energy-density batteries, by limiting flammability and enabling the use of the lithium metal anode, respectively. Composite polymer-ceramic electrolytes are a possible solution for their realization, by benefiting from the combined mechanical properties of the polymer electrolyte and the thermal stability and high conductivity of the ceramic electrolyte. In this study we used different liquid electrolyte chemistries as models for the polymer electrolytes, and evaluated the effect of adding a variety of porous and dense ceramic electrolytes on the conductivity.

Electrochemical Impedance Spectroscopy of PEO-LATP Model Multilayers: Ionic Charge Transport and Transfer.

Solid-state batteries are seen as a possible revolutionary technology, with increased safety and energy density compared to their liquid-electrolyte-based counterparts. Composite polymer/ceramic electrolytes are candidates of interest to develop a reliable solid-state battery due to the potential synergy between the organic (softness ensuring good interfaces) and inorganic (high ionic transport) material properties. Multilayers made of a polymer/ceramic/polymer assembly are model composite electrolytes to investigate ionic charge transport and transfer.

Operando XPS: A Novel Approach for Probing the Lithium/Electrolyte Interphase Dynamic Evolution.

The coupling protocols combining photoemission spectroscopy and other characterization methods such as electrochemical, electrical, optical, thermal, or magnetic paved the way to considerable progress in the field of materials science. Access to complementary data on the same object is relevant, but in the vast majority of cases, it is carried out sequentially and separately. This raises the complex question of the equivalence of the analyzed surfaces subjected to these different characterizations.

Quantification of the Local Topological Variations of Stripped and Plated Lithium Metal by X-ray Tomography.

Lithium (Li) metal is the most promising negative electrode to be implemented in batteries for stationary and electric vehicle applications. For years, its use and subsequent industrialization were hampered because of the inhomogeneous Li ion reduction upon recharge onto Li metal leading to dendrite growth. The use of solid polymer electrolyte is a solution to mitigate dendrite growth.

New Interpretation of X-ray Photoelectron Spectroscopy of Imidazolium Ionic Liquid Electrolytes Based on Ionic Transport Analyses.

We reported a new perspective on the correlation between the electronic structure of an ionic liquid (IL)-based electrolyte probed by X-ray photoelectron spectroscopy and the transport properties analyzed by impedance spectroscopy. We highlighted the core level chemical shifts of 1-hexyl-3-methylimidazolium (bis(trifluoromethanesulfonyl)imide) (CCImTFSI), 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide (CCImFSI), and 1-hexyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide (CCCImTFSI) laden with LiTFSI salt and vinylene carbonate (VC) or fluoroethylene carbonate (FEC) with regard to the transport properties of cations and anions. We pointed out based on detailed binding energy shift analyses a clear effect of the anion on the local organization of Li ions.

Fingerprinting Mean Composition of Lithium Polysulfide Standard Solutions by Applying High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy.

In a lithium/sulfur (Li/S) battery, the reduction of sulfur during discharge involves a particular mechanism, where the active material successively dissolves into the electrolyte to form lithium polysulfide intermediate species (LiS), with being a function of the state of charge. In this work, sulfur K-edge resonant inelastic X-ray scattering measurements were performed for the characterization of different LiS polysulfide standard solutions. High-energy resolution fluorescence detected X-ray absorption spectroscopy allowed clear separation the pre-edge absorption peak corresponding to terminal sulfur atoms from the main absorption peak due to internal atoms and allowed quantitative evaluation of the evolution of the peak area ratio as a function of the polysulfide chain length.

Magic-angle-spinning-induced local ordering in polymer electrolytes and its effects on solid-state diffusion and relaxation NMR measurements.

Magic-angle-spinning (MAS) enhances sensitivity and resolution in solid-state nuclear magnetic resonance (NMR) measurements. MAS is obtained by aerodynamic levitation and drive of a rotor, which results in large centrifugal forces that may affect the physical state of soft materials, such as polymers, and subsequent solid-state NMR measurements. Here, we investigate the effects of MAS on the solid-state NMR measurements of a polymer electrolyte for lithium-ion battery applications, poly(ethylene oxide) (PEO) doped with the lithium salt LiTFSI.

Electrochemical Impedance Spectroscopy and X-ray Photoelectron Spectroscopy Study of Lithium Metal Surface Aging in Imidazolium-Based Ionic Liquid Electrolytes Performed at Open-Circuit Voltage.

Lithium reactivity toward an electrolytic media and dendrite growth phenomenon constitutes the main drawback for its use as an anode material for the lithium battery technology. Ionic liquids (ILs) were pointed out as promising electrolyte solvent candidates to prevent thermal runaway in a lithium battery system. However, the reactivity of lithium toward such a kind of an electrolyte is still under debate.

A 1,2,3-triazolate lithium salt with ionic liquid properties at room temperature.

A triethylene glycol-based 1,2,3-triazolate lithium salt with ionic liquid properties at room temperature is synthesized in three steps including copper-catalysed cycloaddition between alkyne-functionalized monomethoxy-triethylene glycol and azidomethyl pivalate, followed by the deprotection of the methyl pivalate group and further lithiation of the 1H-1,2,3-triazole intermediate. The resulting lithium 1,2,3-triazolate is characterized by NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, broadband dielectric spectroscopy, electrochemical impedance spectroscopy and cyclic voltamperometry. This approach provides new opportunities for the further development of highly functional molecular and macromolecular lithium salts.

Restricted lithium ion dynamics in PEO-based block copolymer electrolytes measured by high-field nuclear magnetic resonance relaxation.

The intrinsic ionic conductivity of polyethylene oxide (PEO)-based block copolymer electrolytes is often assumed to be identical to the conductivity of the PEO homopolymer. Here, we use high-field Li nuclear magnetic resonance (NMR) relaxation and pulsed-field-gradient (PFG) NMR diffusion measurements to probe lithium ion dynamics over nanosecond and millisecond time scales in PEO and polystyrene (PS)-b-PEO-b-PS electrolytes containing the lithium salt LiTFSI. Variable-temperature longitudinal (T) and transverse (T) Li NMR relaxation rates were acquired at three magnetic field strengths and quantitatively analyzed for the first time at such fields, enabling us to distinguish two characteristic time scales that describe fluctuations of the Li nuclear electric quadrupolar interaction.

Non-operative treatment of four-part fractures of the proximal end of the humerus: results of a prospective and retrospective multicentric study.

Purpose: The aim of this study was to evaluate the short- and medium-term results of non-operative treatment of four-part fractures of the proximal end of the humerus. The initial hypothesis was that non-operative treatment of fractures with little or no displacement is equivalent or superior to surgical treatment, and that non-operative treatment is probably insufficient for displaced fractures.

Methods: This was a multicentric, prospective and retrospective study, based on 384 four-part proximal humerus fractures, 58 of which involved non-operative treatments - 37 in the prospective study (Pro-CT4) and 21 in the retrospective study (Retro-CT4).

Impact of the solute exclusion on the bed longitudinal diffusion coefficient and particle intra-tortuosity determined by ISEC.

The effective diffusion coefficient of non retained toluene and polystyrenes compounds was measured by the peak parking method for two columns packed with mesoporous silica. Different models used to predict the effective diffusion are compared. These models include the conventional Knox time-averaged model and some effective medium theory models such as Maxwell, Landauer, Garnett or Torquato models.

Effect of interfaces on the melting of PEO confined in triblock PS-b-PEO-b-PS copolymers.

Block copolymers form nanostructures that have interesting physical properties because they combine, for a single compound, the complementary features brought by each block. However, in order to fully exploit these properties, the physical state of each kind of domain must be precisely controlled. In this work, triblock PS-b-PEO-b-PS copolymers consisting of a central poly(ethylene oxide) (PEO) block covalently bonded to polystyrene (PS) blocks were synthesized by Atom Transfer Radical Polymerization.

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries.

Electrochemical energy storage is one of the main societal challenges of this century. The performances of classical lithium-ion technology based on liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues. Solid polymer electrolytes would be a perfect solution to those safety issues, miniaturization and enhancement of energy density.

Copper systematics in arc magmas and implications for crust-mantle differentiation.

Arc magmas are important building blocks of the continental crust. Because many arc lavas are oxidized, continent formation is thought to be associated with oxidizing conditions. On the basis of copper's (Cu's) affinity for reduced sulfur phases, we tracked the redox state of arc magmas from mantle source to emplacement in the crust.

Posterior approach and dislocation rate: a 213 total hip replacements case-control study comparing the dual mobility cup with a conventional 28-mm metal head/polyethylene prosthesis.

Introduction: Dislocation is a frequent complication of total hip arthroplasties (THA) especially in older patients, especially when using a posterior approach. In these cases, dual mobility (DM) cups developed by Gilles Bousquet in 1975 can be indicated to reduce this complication risk.

Hypothesis: Dual mobility cups reduce the rate of dislocation in primary total hip arthroplasty using posterior approach in a single-surgeon series.

Influence of molecule size on its transport properties through a porous medium.

The mass transfer kinetics of toluene and polystyrenes (of which the M(w) varies from 162 to 1.85 x 10(6) g mol(-1)) through columns filled with silica porous spheres were studied by inverse size exclusion chromatography. The mass transfer parameters were measured by modeling the band broadening of the chromatograms.

Tortuosity of porous particles.

Tortuosity is often used as an adjustable parameter in models of transfer properties through porous media. This parameter, not reducible to classical measured microstructural parameters like specific surface area, porosity, or pore size distribution, reflects the efficiency of percolation paths, which is linked to the topology of the material. The measurement of the effective conductivity of a bed of particles saturated with an electrolyte is a simple way to evaluate tortuosity.

Local atomic and electronic structure in nanocrystalline Sn-doped anatase TiO2.

Tin-doped anatase TiO(2) nanopowders and nanoceramics with particle sizes between 12 and 30 nm are investigated by X-ray absorption fine-structure (EXAFS) and Mössbauer spectroscopies. Furthermore, ab initio calculations based on the density functional theory are performed to analyze changes in the electronic structure due to Sn doping. The three approaches consistently show that Sn is dissolved on substitutional bulk sites with a slight increase of the bond lengths of the inner coordination shells.

[Familial palmo-plantar keratoderma with epidermolytic hyperkeratosis (author's transl)].

Three cases of palmo-plantar keratoderma coming from three different families are reported; Clinical features were those of Thost-Unna's disease; histo-pathological and ultrastructural aspects resembled those of the epidermolytic hyperkeratosis. The literature, 13 cases within 7 families with the same clinical and histopathological characteristics (though without study of the ultrastructure), have been reported. The authors propose to term "familial palmo-plantar keratoderma with epidermolytic hyperkeratosis", those cases of palmo-plantar keratoderma with dominant autosomal transmission and the histopathological aspects of the epidermolytic hyperkeratosis (Frost and Van Scott).