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Ionic liquids based electrolytes for lithium ion battery. Nelly M.

Giroud1, Hlne Rouault1, Eric Chainet2, JeanClaude Poignet2 1 Commissariat l'Energie Atomique (CEA), Direction de la Recherche Technologique (DRT-LITEN), 17 rue des Martyrs, 38054 Grenoble Cedex 9, France, 2 LEPMI, Centre National de la Recherche Scientifique (CNRS), 1130 rue de la piscine, 38402 Saint-Martin dHres, France

Although Walden identified ionic liquids in 1914, their scientific interest has become more obvious for ten years [1] . Indeed ionic liquids offer lots of numerous properties, which make them attractive for various applications in the fields of green chemistry, metal electrodepositing [2,3] and for energy devices (batteries, fuel cells, supercapacitors). Their significant properties are nonflammability, low vapor pressure, good thermal and chemical stability, moderate ionic conductivity and relatively wide electrochemical window [4-7]. As a result, ionic conductivity, dynamic viscosity and electrochemical and thermal stability of several ionic liquids with or without lithium salts were studied. Thermogravimetric investigations showed that the ionic liquids solutions are damaged above 450C which is very interesting for electric vehicle applications. On the other hand the lithium insertion and deinsertion process was observed in various insertion materials commonly used in lithium ion batteries (Cgr, LiFePO4, Li4Ti5O12). First results seem to show that the lithium insertion-deinsertion process occurs in two stages and that the reduction and oxidation potentials are different compared with organic electrolytes ones (figure 1). As a consequence, operating potentials for ionic liquids electrolytes lithium ion batteries may be higher than conventional lithium ion batteries. Temperature and concentration in lithium salt dependences of ionic conductivity and dynamic viscosity were analyzed by means of impedance spectroscopy and rheometric methods, respectively. It was demonstrated that viscosity decreases with temperature, whereas specific conductivity increases. Furthermore, fitting laws are proposed to describe the thermal behaviors. On the other hand, it was shown that ionic conductivity goes down and that dynamic viscosity increases with a rising lithium salt content. This loss of conductivity can be explained by the presence of aggregates that trap the lithium and reducing consequently its ionic mobility [8-10]. This assumption was confirmed by NMR-PGSE experiments. According to their electrochemical stability, and physicochemical properties some ionic liquids were selected. Then ionic liquids electrolytes were developed for Cgr/LiFePO4, Li4Ti5O12/LiFePO4 and Li4Ti5O12/LiNi0.5Mn1.5O4 (figure 2) lithium ion technologies. Very encouraging results were obtained notably for the Cgr/LiFePO4 technology. Indeed the ionic liquid electrolyte developed shows better cycling performances than organic electrolyte: more than 80 % of the expected capacity are recovered at C/10 after ten cycles at 60C against 65 % for EC/PC/DMC with 1 M LiPF6.

Figure 1: cyclic voltamperometry (0.1 mV.s-1) of an ionic liquid at a graphite electrode.

Figure 2: percentage of discharging capacity vs. cycle number during cycling ability at C/20 and C/10 of Li4Ti5O12//LiNi0.5Mn1.5O4 coin cells. [1]: P. Walden, Bulletin de lAcadmie Impriale des Sciences de St-Petersbourg, (1914), pp. 405-422, [2]: W. Dobbs, J. M. Suisse, L. Douce, R. Welter, Angew. Chem. Int. Ed., 2006, pp. 4179-4182, [3]: P.-Y. Chen, C. L. Hussey, Electrochim. Acta , 49 (2004) 5125-5138, [4]: Y. Hu, H. Li, X. Huang, L. Chen, Electrochem. Commun., 6 (2004) 28-32, [5]: H.L. Ngo, K. LeCompte, L. Hargens, A.B. McEwen, Thermochim. Acta 357358, (2000) 97-102, [6]: R.T. Carlin, J. Fuller, Battery Conference on Applications and Advances, Publisher IEE., 1997, pp. 221-226, [7]: J. Fuller, R.T. Carlin, R.A. Osteryoung, J. Electrochem. Soc., 144 (1997) 3881-3886 [8]: T.E. Sutto, H.C. De Long, P.C. Trulove, Z. Natursforsh., 57a, (2002) 839-846, [9]: J.C. Lassegues, J. Gondrin, D. Talaga, Phys. Chem.Chem. Phys., 8, (2006 ) 5629-5632, [10]: A. Noda, K. Hayamizu, M. Watanabe, J. Phys. Chem. B, 105, (2001) 4603-4610.