Recent observations by our group show the creation of a reversible shuttle species in LFP/graphite and NMC811/graphite cells with 3:7 ethylene carbonate:dimethyl carbonate (EC:DMC) based electrolytes. This is indicated by a high reversible self-discharge of these cells in the absence of electrolyte additives. Electrolyte extraction from pouch cells after formation allowed to directly investigate the electrolytes for redox shuttle currents. For this purpose, the extracted electrolytes were inserted into coin cells with an Al foil as the working electrode (WE) and a Li foil as the counter electrode (CE). The measured cyclic voltammetry (CV) of the coin cells show a clear relationship between high formation temperature and high shuttle currents. Interestingly, the addition of vinylene carbonate (VC) to the electrolyte completely prevents the shuttle current, even at elevated formation temperatures. [1]

In this study, we systematically investigate the effect of various electrolyte additives on the generation of shuttle molecules. LFP/graphite and NMC811/graphite pouch cells were filled with electrolyte consisting of 3:7 EC:DMC with 1.5 M lithium hexafluorophosphate (LiPF₆) and different additives. The pouch cells were formed at different temperatures, T_F. The electrolytes were then extracted and inserted into the aforementioned coin cell setup for CV measurements.

We have found that additives such as VC, fluoroethylene carbonate (FEC), ethylene sulfate (DTD), prop-1-ene-1,3-sultone (PES), and triallyl phosphate (TAP), which are known to create a stable solid electrolyte interphase (SEI), [2-4] prevent shuttle current in the CV. On the other hand, additives such as succinonitrile (SN) and trimethylsilyl isothiocyanate (TMSNCS), which do not contribute to the formation of a better SEI, [5,6] cannot prevent the shuttle current. This suggests that the formation of the shuttles is due to a poor SEI and therefore occurs at the interface between electrolyte and graphite anode.

Analogue experiments with DMC as only solvent instead of 3:7 EC:DMC show similar shuttle currents in CVs, which suggests that linear carbonates such as DMC are required to form the shuttle.

Figure 1 shows CVs for 1.5 M LiPF₆ DMC electrolyte. The shuttle current appears to be the same for electrolyte extracted from LFP/graphite and NMC811/graphite cells ranging up to 6 μA in both cases. This indicates that the shuttle is formed independently of the cathode material, and therefore gives rise to the hypothesis that it is formed at the anode-electrolyte interface. Figure 1 also shows that the shuttle current increases with higher formation temperatures T_F.

References:

1. Boulanger, A. Eldesoky. S. Buechele, T. Taskovic, S. Azam, C. Aiken, E. Logan, M. Metzger, Investigation of redox shuttle generation in LFP/graphite and NMC811/graphite cells, Submitted (2022).
2. Song, J. Harlow, E. Logan, H. Hebecker, M. Coon, L. Molino, M. Johnson, J. Dahn, M. Metzger, A Systematic Study of Electrolyte Additives in Single Crystal and Bimodal LiNi 0.8 Mn 0.1 Co 0.1 O 2 /Graphite Pouch Cells , J. Electrochem. Soc. 168 (2021) 090503. doi:10.1149/1945-7111/ac1e55.
3. J. Nelson, J. Xia, J.R. Dahn, Studies of the Effect of Varying Prop-1-ene-1,3-sultone Content in Lithium Ion Pouch Cells, J. Electrochem. Soc. 161 (2014) A1884–A1889. doi:10.1149/2.0791412jes.
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5. Chen, F. Liu, Y. Chen, Y. Ye, Y. Huang, F. Wu, L. Li, An investigation of functionalized electrolyte using succinonitrile additive for high voltage lithium-ion batteries, J. Power Sources. 306 (2016) 70–77. doi:10.1016/j.jpowsour.2015.10.105.
6. G. Han, M.Y. Jeong, K. Kim, C. Park, C.H. Sung, D.W. Bak, K.H. Kim, K.M. Jeong, N.S. Choi, An electrolyte additive capable of scavenging HF and PF5 enables fast charging of lithium-ion batteries in LiPF6-based electrolytes, J. Power Sources. 446 (2020) 227366. doi:10.1016/j.jpowsour.2019.227366.

Acknowledgements

This work was funded under the auspices of the NSERC/Tesla Canada Alliance Grant program.