Due to the polymer plasticizing ability and ionic nature of ionic liquids (bistrifluoromethanesulfonimidate salts of 1-butyl-2,3-dimethylimidazolium and dodecylethyldiphenylphosphonium, BDMIm Tf 2 N and DEDPP Tf 2 N, respectively), they were found to be excellent compounds for preparing ion-selective membrane electrodes. Membrane polymers studied were poly(methyl methacrylate) and poly(vinyl chloride). The electrodes demonstrated good and extremely stable response to both cations and anions (including surfactants) and were successfully applied to the analysis of detergents.
4-methyl-2- [(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane with the oxidation number of phosphorous (III) is used as an oxidative additive (OA) to a standard carbonate-based electrolyte for the high-voltage Li-ion cells with the overlithiated layered oxide Li 1.20 Ni 0.18 Mn 0.53 Co 0.09 O 2 (OLO) as a positive electrode. Electrochemical stability of electrolytes with and without OA is compared by linear sweep voltammetry, and characteristics of coin half and full cells are examined by means of cycling tests and electrochemical impedance spectroscopy. Presence of OA in electrolyte mixture provides noticeable improvement in Coulombic efficiency, capacity retention, and rate properties of the cells, most likely, through the formation of an interface layer on the OLOsurface due to the decomposition of OA. Morphology of OLO after cycling with OA-containing electrolyte is investigated by scanning electron microscopy and the presence of amorphous coating is observed; 31 P NMR analysis reveals that the products by the oxidation of OA are present on the cathode's surface. Differential scanning calorimetry data point out the substantially improved thermal stability of the OLO cathode after cycling in OA-containing electrolyte. Therefore, substituted dioxaphosphinanes may be considered as a promising structural pattern for design of new additives for the development of high-voltage electrolytes.
Ionic liquids that melt slightly above room temperature (and may be called low-melting ionic solids, LMISs) were used as sensing materials for the detection of ions in aqueous solutions. A simple procedure based on the consecutive melting and further solidification of the LMISs was applied to prepare solid-contact ion-sensitive electrodes. A potentiometric response toward a number of anions was observed, and the possibility of altering the selectivity by incorporating additional ionophores into the LMIS matrix was demonstrated.
Electrochemical performance of Li-ion cells with LiMn 2 O 4 cathodes and graphite anodes with carbonates electrolytes containing quaternary ammonium-based room temperature ionic liquids (ILs) is investigated. Eight different ILs based on tetraalkylammonium, pyrrolidinium or piperidinium cations paired with bis(trifluoromethylsulfonyl)imide or tris(pentafluoroethyl)trifluorophosphate anions are examined in combination with dimethyl carbonate as a main solvent and fluoroethylene carbonate as a solid electrolyte interface forming agent. It is shown that cycling properties of the cells are strongly affected by the content of ILs in the electrolyte mixtures and its increase corresponds to lower discharge capacity retention. Since viscosity and conductivity of ILs are of a great importance for the electrolytes formulation, some kind of combined parameter should be used for the assessment of IL applicability and calculated values of Walden products for neat ILs represent one of the possible options. Besides, positive effect of ILs on reduction of flammability and enhancement of thermal stability of electrolytes in contact with charged electrodes have been demonstrated by means of self-extinguishing time test and differential scanning calorimetry respectively.
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