Radiation Chemistry Reveals the Reaction Mechanisms Involved in the Reduction of Vinylene Carbonate in the Solid Electrolyte Interphase of Lithium-Ion Batteries.

A safe and efficient lithium-ion battery requires including an additive in the electrolyte. Among the additives used, vinylene carbonate (VC) is particularly interesting, because it leads to the formation of a stable and protective solid electrolyte interphase (SEI) on the negative electrode. However, the reduction behavior of VC, resulting in polymer formation, is complex, and many questions remain as to the corresponding reaction mechanisms.

Effect of Crystalline Phase and Facet Nature on the Adsorption of Phosphate Species onto TiO Nanoparticles.

The current use of TiO nanoparticles raises questions about their impact on our health. Cells interact with these nanoparticles via the phospholipid membrane and, in particular, the phosphate head. This highlights the significance of understanding the interaction between phosphates and nanoparticles possessing distinct crystalline structures, specifically anatase and rutile.

Predicting Degradation Mechanisms in Lithium Bistriflimide "Water-In-Salt" Electrolytes For Aqueous Batteries.

Aqueous solutions are crucial to most domains in biology and chemistry, including in energy fields such as catalysis and batteries. Water-in-salt electrolytes (WISEs), which extend the stability of aqueous electrolytes in rechargeable batteries, are one example. While the hype for WISEs is huge, commercial WISE-based rechargeable batteries are still far from reality, and there remain several fundamental knowledge gaps such as those related to their long-term reactivity and stability.

UV-Visible photo-reactivity of permanently polarized inorganic nanotubes coupled to gold nanoparticles.

Hybrid aluminosilicate nanotubes (Imo-CH) have the ability to trap small organic molecules inside their hydrophobic internal cavity while being dispersed in water owing to their hydrophilic external surface. They also display a curvature-induced polarization of their wall, which favors reduction outside the nanotubes and oxidation inside. Here, we coupled bare plasmonic gold nanoparticles (GNPs) with Imo-CH and analyzed for the first time the redox reactivity of these hybrid nano-reactors upon UV illumination.

Radiolysis of Electrolytes in Batteries: A Quick and Efficient Screening Process for the Selection of Electrolyte-Additive Formulations.

Understanding aging phenomena in batteries is crucial to the design of efficient, safe, and reliable energy storage devices as a part of the current green energy transition. Among the different aspects of a battery, the behavior of the electrolyte is a key parameter. Therefore, screening the aging characteristics of different electrolytes is of major interest.

Experimental determination of the curvature-induced intra-wall polarization of inorganic nanotubes.

Inspired by a natural nano-mineral known as imogolite, aluminosilicate inorganic nanotubes are appealing systems for photocatalysis. Here, we studied two types of synthetic imogolites: one is completely hydrophilic (IMO-OH), while the other has a hydrophilic exterior and a hydrophobic interior (IMO-CH), enabling the encapsulation of organic molecules. We combined UV-Vis diffuse reflectance spectroscopy of imogolite powders and X-ray photoelectron spectroscopy of deposited imogolite films and isolated nanotubes agglomerates to obtain not only the band structure, but also the quantitative intra-wall polarization of both synthetic imogolites for the first time.

Radiolytic Approach for Efficient, Selective and Catalyst-free CO Conversion at Room Temperature.

The present study proposes a new approach for direct CO conversion using primary radicals from water irradiation. In order to ensure reduction of CO into CO by all the primary radiation-induced water radicals, we use formate ions to scavenge simultaneously the parent oxidizing radicals H and OH producing the same transient CO radicals. Conditions are optimized to obtain the highest conversion yield of CO .

Reaction Mechanisms of the Degradation of Fluoroethylene Carbonate, an Additive of Lithium-Ion Batteries, Unraveled by Radiation Chemistry.

Numerous additives are used in the electrolytes of lithium-ion batteries, especially for the formation of an efficient solid electrolyte interphase at the surface of the electrodes. Understanding the degradation processes of these compounds is thus important; they can be seen through radiolysis. In the case of fluoroethylene carbonate (FEC), picosecond pulse radiolysis experiments evidenced the formation of FEC .

Confined water radiolysis in aluminosilicate nanotubes: the importance of charge separation effects.

Imogolite nanotubes are potentially promising co-photocatalysts because they are predicted to have curvature-induced, efficient electron-hole pair separation. This prediction has however not yet been experimentally proven. Here, we investigated the behavior upon irradiation of these inorganic nanotubes as a function of their water content to understand the fate of the generated electrons and holes.

Dynamics in hydrated inorganic nanotubes studied by neutron scattering: towards nanoreactors in water.

Water dynamics in inorganic nanotubes is studied by neutron scattering technique. Two types of aluminosilicate nanotubes are investigated: one is completely hydrophilic on the external and internal surfaces (IMO-OH) while the second possesses an internal cavity which is hydrophobic due to the replacement of Si-OH bonds by Si-CH ones (IMO-CH), the external surface being still hydrophilic. The samples have internal radii equal to 7.

Influence of confinement on free radical chemistry in layered nanostructures.

The purpose of the present work was to study how chemical reactions and the electronic structure of atoms are affected by confinement at the sub-nanometer scale. To reach this goal, we studied the H atom in talc, a layered clay mineral. Talc is a highly 2D-confining material with the width of its interlayer space close to angstrom.

Observation and Simulation of Transient Anion Oligomers (LiClO) (n = 1-4) in Diethyl Carbonate LiClO Solutions.

NMR measurements show that diethyl carbonate (DEC, a solvent with a low dielectric constant) solutions of LiClO contain (LiClO) oligomers. The reduction of these species by solvated and presolvated electrons is followed by picosecond pulse radiolysis measurements. The data analysis shows that several anions absorbing in the near-infrared (NIR) and visible range are formed after the 7 ps electron pulse.

Degradation of an Ethylene Carbonate/Diethyl Carbonate Mixture by Using Ionizing Radiation.

The reactivity of ethylene carbonate (EC) and of a EC/diethyl carbonate (DEC) mixture was studied under ionizing radiation to mimic the aging phenomena that occur in lithium-ion batteries. Picosecond-pulse radiolysis experiments showed that the attachment of the electron to the EC molecule is ultrafast (k(e +EC)=1.3×10  L mol  s at 46 °C).

In situ and time-resolved infrared detection of the reactivity induced by electrons in polymer films.

The real time and in situ analysis of chemical reactions such as polymerization reactions, polymer degradation, and oxidation of polymers is of utmost importance. Surprisingly, only few experimental tools allowing this are available. To bridge this gap, we have developed a new experimental setup coupling a 60 keV electron gun with an infrared spectrometer operating in the mid-IR region (800-4000 cm) and associated with the rapid scan mode.

Ionosilicas as efficient sorbents for anionic contaminants: Radiolytic stability and ion capacity.

Ammonium based hybrid ionosilicas were prepared from tetrasilylated ammonium precursors. The formed material exhibited high specific surface area together with mesoporosity. Our results indicate that ionosilicas display high exchange capacity for iodide.

Picosecond Pulse Radiolysis of Propylene Carbonate as a Solute in Water and as a Solvent.

The ester propylene carbonate (PC) is a solvent with a high static dielectric constant where the charges generated by ionizing radiation are expected to be long-lived at room temperature. Time-resolved optical absorption spectroscopy after picosecond electron pulses reveals the formation of a UV band, within less than two nanoseconds, that is assigned to the radical anion PC(-•), arising from a fast attachment reaction of electrons onto PC. Assignment and reactivity of PC(-•) in neat solvent and solutions are discussed in relation with data obtained in solutions of PC in water under reducing or oxidizing conditions and in solutions in PC of aromatic scavengers with various reduction potentials.

Identification of Transient Radical Anions (LiClO4)(n)(-) (n = 1-3) in THF Solutions: Experimental and Theoretical Investigation on Electron Localization in Oligomers.

Picosecond pulse radiolysis measurements of tetrahydrofuran (THF) solutions containing LiClO4 over a wide range of concentration are performed to investigate the formation of transient species. The (35)Cl NMR measurements of these solutions prior to irradiation show that the salt is in the form of (LiClO4)n oligomers. Kinetics and transient absorption spectra of intermediates in each solution are obtained on the time scale from 10 to 3800 ps.

Ultrafast Decay of the Solvated Electron in a Neat Polar Solvent: The Unusual Case of Propylene Carbonate.

The behavior of carbonates is critical for a detailed understanding of aging phenomena in Li-ion batteries. Here we study the first reaction stages of propylene carbonate (PC), a cyclical carbonate, by picosecond pulse radiolysis. An absorption band with a maximum around 1360 nm is observed at 20 ps after the electron pulse and is shifted to 1310 nm after 50 ps.

Electrolytes Ageing in Lithium-ion Batteries: A Mechanistic Study from Picosecond to Long Timescales.

The ageing phenomena occurring in various diethyl carbonate/LiPF6 solutions are studied using gamma and pulse radiolysis as a tool to generate similar species as the ones occurring in electrolysis of Li-ion batteries (LIBs). According to picosecond pulse radiolysis experiments, the reaction of the electron with (Li(+), PF6(-)) is ultrafast, leading to the formation of fluoride anions that can then precipitate into LiF(s). Moreover, direct radiation-matter interaction with the salt produces reactive fluorine atoms forming HF(g) and C2H5F(g).

Radiolysis as a solution for accelerated ageing studies of electrolytes in Lithium-ion batteries.

Diethyl carbonate and dimethyl carbonate are prototype examples of eco-friendly solvents used in lithium-ion batteries. Nevertheless, their degradation products affect both the battery performance and its safety. Therefore, it is of paramount importance to understand the reaction mechanisms involved in the ageing processes.

The effect of myoglobin crowding on the dynamics of water: an infrared study.

Solutions containing 8 and 32 wt% myoglobin are studied by means of infrared spectroscopy, as a function of temperature (290 K and lower temperatures), in the mid- and far-infrared spectral range. Moreover, ultrafast time-resolved infrared measurements are performed at ambient temperature in the O-D stretching region. The results evidence that the vibrational properties of water remain the same in these myoglobin solutions (anharmonicity, vibrational relaxation lifetime…) and in neat water.

Water radiolysis in exchanged-montmorillonites: the H2 production mechanisms.

The radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H2 production under electron irradiation. It is shown that the main factor influencing this H2 production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy.

A trapped water network in nanoporous material: the role of interfaces.

The infrared spectra of water confined in well controlled pore glasses were recorded as a function of the pore size ranging from 8 to 320 nm and in the 30-4000 cm(-1) spectral range using the ATR technique. The experiments prove that even in the large pores, the water network is significantly perturbed. The energy of the connectivity (or hindered translation) band (around 150 cm(-1)) is found to increase when the pore size decreases, indicating that confinement increases the H-bonding between neighbouring water molecules.

Uranium carcinogenicity in humans might depend on the physical and chemical nature of uranium and its isotopic composition: results from pilot epidemiological study of French nuclear workers.

Objective: To study the cancer risk related to protracted, low-dose exposure to different industrial uranium compounds, paying attention to their isotopic composition and solubility.

Methods: Two thousand and ninety-seven workers employed at the AREVA NC uranium processing plant (France) were followed up for mortality from 1960 to 2006. Historical exposure to uranium and other carcinogenic chemical and physical pollutants was assessed on the basis of the plant-specific job-exposure matrix.

H(2) formation by electron irradiation of SBA-15 materials and the effect of Cu(II) grafting.

Measurement of H(2) production from electron irradiation (10 MeV) on SBA-15 materials has shown that adsorbed water is attacked preferentially. Silanol groups are only attacked when they are in the majority with respect to adsorbed water, however they are much less efficient at producing H(2). The comparison between water content before and after electron irradiation and the corresponding H(2) production indicates that water desorption is the main route to adsorbed water loss for SBA-15 materials.