An electrolyte based on fluorinated carbonate solvents was evaluated with high voltage cathode materials at elevated temperature. The theoretically high anodic stability of these new electrolytes was supported by electrochemical evaluation results using LiNi 0.
We developed a unique class of non-Grignard, aluminum-free magnesium electrolytes based on a simple mixture of magnesium compounds: magnesium hexamethyldisilazide (Mg(HMDS)2) and magnesium chloride (MgCl2).
With the correlation between Li + solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation−solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li + , and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li + solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF 6 − , and tetrafluoroborate, BF 4 −) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.
A series of electrolyte formulations containing fluorinated cyclic carbonates and fluorinated linear carbonates with LiPF 6 has been evaluated as electrolyte solvents for high-voltage Li-ion batteries. The anodic stability of the new electrolytes on fully charged spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode was examined by electrochemical floating tests. The effects of fluorine substitution on the cyclic and linear carbonate, ratio of cyclic vs. linear carbonate, and LiPF 6 concentration on the electrolyte oxidation stability were investigated. Based on this study, the floating test proved to be an effective tool for identification of stable electrolyte materials. have been proposed. Because of the large number of candidates for high-voltage electrolyte solvents, screening the voltage stability of each solvent would be very labor-intensive. Traditional methods of measuring the oxidation potential of organic solvents usually involves linear/cyclic voltammetry using an inert electrode such as platinum and glassy carbon. However, such measurements are in many cases misleading, because interactions of these organic solvents with actual electrode materials are usually more complicated and may happen at a much lower potential due to the catalytic effect of the cathode material lowering the kinetic barrier of oxidation. Unfortunately, using active cathode material to run voltammetry measurement has a drawback in that the material itself is redox active and can interfere with the observation of electrolyte oxidation. Thus, developing a fast and effective method to screen the voltage stability of electrolyte solvents on actual cathode materials is of vital importance. Herein, we report a method using constant potential electrolysis with a slightly overcharged LNMO cathode as the working electrode, abbreviated as an "electrochemical floating test", where the cell potential is allowed to "float" at different values to evaluate the voltage stability of the electrolyte. For an ideal electrolyte with no impurities and no oxidation at the working electrode, the only current observed when a potential is applied is the capacitance current, which should decline to zero when the equilibrium is reached. However, in reality, the electrolytes are oxidized, and the current intensity measured corresponds to the severity of oxidation. As a result, the leakage currents of each electrolyte at different potentials can be compared to produce a voltage stability profile of a given solvent. The effect of different ratios of mixed solvents and lithium salt concentrations can also be probed. * Electrochemical Society Active Member.z E-mail: zzhang@anl.gov
Materials and MethodsTheoretical calculations.-The Gaussian 09 code was used for all calculations.14 Oxidation and reduction potentials were calculated by optimizing the geometries of the neutral and ionic species at the B3LYP/6-31G * level, followed by frequency calculations to determine gas-phase free energies. Solvation effects were taken into account by using a single-point B3LYP/6-31+G * PCM...
Animal studies have suggested that transient receptor potential ion channels and G-protein coupled receptors play important roles in itch transmission. TRPV3 gain-of-function mutations have been identified in patients with Olmsted syndrome, which is associated with severe pruritus. However, the mechanisms causing itch remain poorly understood. Here, we show that keratinocytes lacking TRPV3 impair the function of proteaseactivated receptor 2 (PAR2), resulting in reduced neuronal activation and scratching behavior in response to PAR2 agonists. Moreover, we show that TRPV3 and PAR2 were upregulated in skin biopsies from patients and mice with atopic dermatitis, whereas their inhibition attenuated scratching and inflammatory responses in mouse atopic dermatitis models. These results reveal a previously unrecognized link between TRPV3 and PAR2 in keratinocytes to convey itch information and suggest that a blockade of PAR2 or TRPV3 individually or both may serve as a potential approach for antipruritic therapy in atopic dermatitis.
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