Alessandra Fernicola

Phase behavior and ionic conductivity in lithium bis(trifluoromethanesulfonyl)imide-doped ionic liquids of the pyrrolidinium cation and Bis(trifluoromethanesulfonyl)imide anion.

The phase behavior and the ionic conductivity of ionic liquids (ILs) of the N-alkyl-N-alkylpyrrolidinium (PYR(xy)) cation and the bis(trifluoromethanesulfonyl)imide (TFSI) anion are investigated upon addition of LiTFSI salt. We compare the case of two new ILs of the PYR(2y) cation (where 2 is ethyl and y is butyl or propyl) with that of the PYR(14) (where 1 is methyl and 4 is butyl). We find that the addition of LiTFSI increases the glass transition temperature, decreases the melting temperature and the heat of fusion and, in the ILs of the PYR(2y) family, suppresses crystallization. In the solid state, significant ionic conductivities are found, being as high as 10(-5) S cm(-1), strongly increasing with Li(+) concentration. The opposite trend is found in the liquid state, where the conductivity is on the order of 10(-3)-10(-2) S cm(-1) at room temperature. A T(g)-scaled Arrhenius plot shows that the liquid-state ionic conductivity in these systems is mainly governed by viscosity and that the fragility of the liquids is slightly influenced by the structural modifications on the cation.

Lithium-Ion-Conducting Electrolytes: From an Ionic Liquid to the Polymer Membrane

This work concerns the design, the synthesis, and the characterization of the N-butyl-N-ethylpiperidinium N,N-bis(trifluoromethane)sulfonimide (PP(24)TFSI) ionic liquid (IL). To impart Li-ion transport, a suitable amount of lithium N,N-bis-(trifluoromethane)sulfonimide (LiTFSI) is added to the IL. The Li-IL mixture displays ionic conductivity values on the order of 10(-4) S cm(-1) and an electrochemical stability window in the range of 1.8-4.5 V vs Li(+)/Li. The voltammetric analysis demonstrates that the cathodic decomposition gives rise to a passivating layer on the surface of the working electrode, which kinetically extends the stability of the Li/IL interface as confirmed by electrochemical impedance spectroscopy measurements. The LiTFSI-PP(24)TFSI mixture is incorporated in a poly(vinylidene fluoride-co-hexafluoropropylene) matrix to form various electrolyte membranes with different LiTFSI-PP(24)TFSI contents. The ionic conductivity of all the membranes resembles that of the LiTFSI-IL mixture, suggesting an ionic transport mechanism similar to that of the liquid component. NMR measurements demonstrate a reduction in the mobility of all ions following the addition of LiTFSI to the PP(24)TFSI IL and when incorporating the mixture into the membrane. Finally, an unexpected but potentially significant enhancement in Li transference number is observed in passing from the liquid to the membrane electrolyte system.

Composite Gel-Type Proton Membranes An Overview of Their Properties in View of Application in Fuel Cells

This paper reviews the properties of a new microporous, composite proton-conducting gel membrane, formed by swelling with aqueous acid solutions suitable polymer matrices containing dispersed ceramic fillers. The data reported show that these membranes have a high and stable conductivity, a proton transport intrinsically provided by the absorbed acid solution not strictly influenced by the external humidity level, and a projected very low cost. Tests in a hydrogen-air laboratory cell also demonstrate that the membranes are basically suitable for application in polymer electrolyte fuel cells.