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Facile Reduction of Pseudo-Carbonates: Promoting Solid Electrolyte Interphases with Dicyanoketene Alkylene Acetals in Lithium-Ion Batteries

Wednesday, 1 June 2016: 09:45
Sapphire Ballroom A (Hilton San Diego Bayfront)
C. Forestier (Renault DEA-IREB, LRCS - CNRS UMR 7314, Université de Picardie Jules Verne), P. Jankowski (Warsaw Technical University, Faculty of Chemistry, Chalmers University of Technology), L. Coser (LRCS - CNRS UMR 7314, Université de Picardie Jules Verne), G. Gachot (CNRS RS2E FR3459, LRCS - CNRS UMR 7314, Université de Picardie Jules Verne), L. Sannier (Renault, DEA-IREB), P. Johansson (Chalmers University of Technology, LRCS - CNRS UMR 7314, Université de Picardie Jules Verne), S. Grugeon, S. Laruelle (CNRS RS2E FR3459, LRCS - CNRS UMR 7314, Université de Picardie Jules Verne), and M. Armand (LRCS - CNRS UMR 7314, Université de Picardie Jules Verne)
In recent years, greener transportation has become of major interest to limit air pollution and global warming. For this purpose, Li-ion batteries (LIBs) are considered as the most promising power source for electric vehicles (EV) and hybrid electric vehicles (HEV) due to their high energy density. The use of high-energy multi-cell battery packs imposes ever more stringent requirements on LIBs in term of safety and long-term cyclability.

The formation of an effective SEI passivation layer at the negative electrode / electrolyte interface was found to be of paramount importance in order to enable LIB long-life cycling and controlling the threshold for thermal runaway. This is why SEI-forming additives have been used in the electrolyte to reinforce these protective properties, with the most common additives being vinylene carbonate (VC) (1), fluoroethylene carbonate (FEC) (2), and vinyl ethylene carbonate (VEC) (3).

To our knowledge, the modification of EC and PC on the carbonyl group, rather than on the alkylene bridge as for VC, VEC, or FEC, has not previously been attempted.(4,5) It is known that the =C(CN)2 group is an “oxygen equivalent” being even slightly more electronegative than O itself and extending considerably the conjugation. Hence, we hypothesized that modified EC or PC, with C=C(CN)2 replacing the carbonyl groups, could lead to a more facile reduction at higher potentials and a stable SEI.

The dicyanoketene propylene (and ethylene) acetal, DCKPA (DCKEA), have both been synthesized according to a simple procedure.(6) The reduction process has been investigated for DCKPA by means of GC/MS and IR analysis and the efficiency as a SEI-reinforcing additive demonstrated by the analysis of the soluble products using liquid GC/MS.

The cycling tests using a pouch cell configuration at both 20 and 45°C were realized with only 0.5 wt.% of additive in the electrolyte and resulted in higher capacity retention.  Moreover, a post-mortem analysis by DSC revealed an improvement in term of safety due to an improved lithiated graphite/electrolyte interface.

[1] H.-H. Lee, Y.-Y. Wang, C.-C. Wan, M.-H. Yang, H.-C. Wu, D.-T. Shieh, Journal of Applied Electrochemistry. 35 (2005) 615–623.

[2] I.A. Profatilova, S.-S. Kim, N.-S. Choi, Electrochimica Acta. 54 (2009) 4445–4450.

[3] Y. Hu, W. Kong, H. Li, X. Huang, L. Chen, Electrochemistry Communications. 6 (2004) 126–131.

[4] C. Forestier, P. Jankowski, L. Coser, G. Gachot, L. Sannier, P. Johansson, et al., Journal of Power Sources. 303 (2016) 1–9.

[5] Pending patent

[6] W.J. Middleton, V.A. Engelhardt, Journal of the American Chemical Society. 80 (1958) 2788–2795.

 

Figure 1: Results of cycling tests at 45°C without and with 0.5 wt.% of DCKPA using a pouch cell configuration, and the post mortem DSC / liquid GC/MS analyses.

See more of: Electrolytes I
See more of: A02: Future and Present Advanced Lithium Batteries and Beyond – a Symposium in the Honor of Prof. Bruno Scrosati
See more of: Batteries and Energy Storage
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