1053
A New Thermally Stable and Conducting Electrolyte Based on Litdi As Lithium Salt for Li-Ion Batteries

Thursday, 23 June 2016
Riverside Center (Hyatt Regency)
C. L. Berhaut (Laboratoire PCM2E (EA 6296)), G. Schmidt (Arkema CRRA), L. Timperman (Laboratoire PCM2E), D. Lemordant (PCM2E (EA6299) Université François Rabelais de Tours), and M. Anouti (PCM2E (EA6299) - Université François Rabelais de Tours)
Most of the LiBs used in electrical devices currently available contain lithium hexafluorophosphate (LiPF6) dissolved in a mixture of alkylcarbonates as the electrolyte. The main reasons for this [1] are the high conductivity of LiPF6 solutions, the formation of a protective SEI layer on graphite and its ability to passivate aluminum, a low-cost metal which can be used as a current collector. Other advantageous properties, which should also be observed by all LiB electrolytes, include low viscosity and a large life-span without safety risks, especially when damaged. However, the thermodynamic instability and moisture sensitivity of LiPF6 induce high risks of releasing HF and/or PF5 via its thermal decomposition or hydrolysis in the presence of traces of water. These drawbacks have been highly criticized justifying the importance in finding a replacement. Owing to (i) its high thermal stability, (ii) low sensitivity to the presence of water and (iii) its electrochemical stability [2], the lithium 4,5-dicyano-2-trifluoromethyl-imidazole (LiTDI) is seen as a promising substitute for LiPF6in LiBs.

In a previous study [3] the poor dissociation of ion pairs (IP) of LiTDI in electrolyte solutions was discussed and the IP dissociation coefficient was found to be around 30 % in an ethylene carbonate/dimethyl carbonate (EC/DMC) mixture. The power capability of LiTDI in EC/DMC with an added 2% FEC in half-cells, using either a NMC or a graphite electrode, and in full NMC/graphite systems was investigated and compared to that of LiPF6 in the same solvent mixture.  It was noticed that both lithium salts performed equally within graphite half-cells but not in the NMC half-cells where a greater capacity loss was observed in the case of the LiTDI based electrolyte when increasing the NMC lithiation speed. The reason was attributed to the lower IP dissociation of LiTDI; LiPF6 being 85% dissociated in EC/DMC. Taking into account this observation a new solvent mixtures is proposed. We present here the results obtained using this new solvent mixture allowing a better dissociation of LiTDI (37 %), a higher conductivity (8.5 mS.cm-1 instead of 6.1 mS.cm-1in EC/DMC at 25°C) and a lower viscosity (2.4 mPa.s instead of 2.8 mPa.s in EC/DMC at 25°C). In addition a better power capability is achieved at higher current rates.

1.            Eshetu, G.G., et al., LiFSI vs. LiPF6 electrolytes in contact with lithiated graphite: Comparing thermal stabilities and identification of specific SEI-reinforcing additives. Electrochimica Acta, 2013. 102(0): p. 133-141.

2.            Niedzicki, L., et al., New covalent salts of the 4V class for Li batteries. Journal of Power Sources, 2011. 196(20): p. 8696-8700.

3.            Berhaut, C.L., et al., LiTDI as electrolyte salt for Li-ion batteries: transport properties in EC/DMC. Electrochimica Acta, 2015. 180: p. 778-787.