Lithium solvation in a PMMA membrane plasticized by a lithium‐conducting ionic liquid based on 1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide

Abstract

The Raman and Infrared (IR) spectra of poly(methyl methacrylate) (PMMA) membranes plasticized by ionic liquids of the (1 − x)[1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI)],xLiTFSI type, where BMI + is the 1-butyl-3-methylimidazolium cation and TFSI− the bis(trifluoromethanesulfonyl)imide anion, are analyzed for a lithium bis(trifluoromethane sulfone)imide (LiTFSI) mole fraction x = 0.23 and PMMA contents from 0 to 50 wt%. The lithium is found to have an average coordination of about three C O groups and less than one TFSI − anion. It plays the role of a cross-linker between the ester groups of PMMA and the nonvolatile ionic liquid. Addition of PMMA to the (1 − x)(BMITFSI),xLiTFSI ionic liquid lowers the conductivity but might improve the lithium transference number by transforming the [Li(TFSI) 2 ] − anionic clusters present in the pure ionic liquid into a mixed coordination by ester groups and TFSI − anions.

Solvation of AgTFSI in 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid investigated by vibrational spectroscopy and DFT calculations

“…In contrast, the IR absorption spectra should exhibit more information about the nature of the ligands formed between the Ag + cation and surrounding anions. This finding shows the complementarity of both Raman scattering and IR absorption techniques in such investigations . In the following section, we attempt to determine quantitatively the type and stability of complexes formed in solution as well as their IR and Raman spectral signatures using the DFT approach.…”

“…This finding shows the complementarity of both Raman scattering and IR absorption techniques in such investigations. [40,56,57] In the following section, we attempt to determine quantitatively the type and stability of complexes formed in solution as well as their IR and Raman spectral signatures using the DFT approach.…”

Poly(methyl methacrylate)-Based Gel Polymer Electrolyte for High-Performance Solid State Li–O2 Battery with Enhanced Cycling Stability

“…The PP separator shows characteristic peaks at 2830–3000 and 1374 cm –1 belonging to the asymmetric stretching vibration and symmetric stretching vibrations of the −CH 3 and −CH 2 group, respectively . In contrast, the PMMA-modified PP exhibits characteristic peaks at 1726, 1142, and 1147 cm –1 , which are attributed to stretching vibrations of C=O, C–O–C, and the bending vibration of CH 2 of PMMA, respectively. , After PMMA soaked in the LE, the carbonyl peak of PMMA has a significant decrease in intensity at 1732 cm –1 , which could be attributed to the fact that the interaction of PMMA and the LE limits the stretching and vibration of the carbonyl group. − Furthermore, a new peak at 1650 cm –1 appears, which may caused by the interaction between PMMA and LiTFSI. , …”

Recent advances in linear and non‐linear Raman spectroscopy. Part III

“…As a probe of the local structure, the vibrational properties of the 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF 4 ] ionic liquid were studied by infrared and Raman spectroscopies and ab initio calculations by Holomb et al [185] In particular, Raman spectroscopy has proven the existence of unique [bmim] + conformers. Fourier-transform infrared and Raman spectroscopies have been used to investigate the role played by water on the structural organisation of 1-butyl-3-methyl-imidazolium tetrafluoroborate and H 2 O mixtures, over a wide composition range at room temperature by Fazio et al [186] Lithium solvation and diffusion in the 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid was studied by Duluard et al [187] Another paper [188] from the same laboratory dealt with lithium solvation in a PMMA membrane plasticised by a lithium-conducting ionic liquid based on 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. Raman spectroscopy of ionic liquids derived from 1-n-butyl-3-methylimidazolium chloride and niobium chloride or zinc chloride mixtures was performed by Alves et al [189] The low-wavenumber Raman spectra of aqueous solutions of carbohydrates (glucose, fructose, trehalose and dextran) have been investigated by Perticaroli et al [190] at different sugar concentrations.…”