Study of 1-butyl-3-methylimidazolium tetrafluoroborate for lithium battery electrolyte

I&EC 118

Nelly M. Giroud, nelly.giroud@cea.fr, GENEC/LSEC, Commissariat à l'Energie Atomique, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France, Hélène Rouault, hélène.rouault@cea.fr, GENEC/LSEC, CEA, 17 rue des Martyrs, 38054 Grenoble cedex 9, France, Eric Chainet, eric.chainet@lepmi.inpg.fr, LEPMI, Centre National de la Recherche Scientifique, 1301 rue de la piscine, 38402 Saint Martin d'Hères, France, and Jean-Claude Poignet, jean-claude.poignet@lepmi.inpg.fr, LEPMI, Ecole Nationale Supérieure d'Electrochimie et d'Electrométallurgie de Grenoble, 1301 rue de la piscine, 38402 Saint Martin d'Hères, France.
Ionic liquids (IL) possess unique properties that make them ideal battery electrolyte. As a result, ionic conductivity, dynamic viscosity, and electrochemical and thermal stability of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4) with or without lithium tetrafluoroborate (LiBF4) were studied. Thermogravimetric investigations showed that the ionic solutions are completely damaged above 450°C. Besides, original differential scanning calorimetric results were obtained, and allowed the observation of characteristic temperatures. Temperature and concentration in LiBF4 dependences of ionic conductivity and dynamic viscosity were analyzed thanks to impedance spectroscopy and rheometric methods, respectively. It was demonstrated that viscosity decreases with temperature, whereas specific conductivity increases. In the -10°C to 60°C temperature range, the conductivities values varied from 0.07 mS/cm to 10 mS/cm, while the viscosities values are bounded between 0.02 Pa.s and 3.9 Pa.s. Furthermore, fitting laws are proposed to describe the thermal behaviors. On the other hand, it was shown that an increase in ionic conductivity and a decrease in dynamic viscosity are expected when LiBF4 concentration increases. Cyclic voltammetry experiments indicated that the reduction of BMI+ on an iron working electrode occurred at 0.94 V vs. a Li/Li+ reference electrode, whereas BF4- was oxidized on a platinum working electrode at 5.67 V vs. a Li/Li+. Then LiCoO2/Li4Ti5O12 and LiFePO4/Li4Ti5O12 batteries using BMIBF4-LiBF4 in various concentrations as the electrolyte were assembled for cycling tests.