Gas Additives for Silicon Anode Lithium-Ion Batteries
Authors: Soto Mel , Weddle Peter J , Colclasure Andrew M. , Tremolet de Villers Bertrand J. , Fink Kae 
Published: September 2023

While many organic liquid and electrolyte salt formulations have been explored to improve the stability of lithium-ion batteries, less research has been done to determine the role of evolved gasses in the performance of commercial Li-ion battery chemistries, let alone novel combinations of gas additives that may affect the solid-electrolyte interphase (SEI) formation and evolution.[1,2] Many gases are generated during Li-ion battery cycling, any of which could have possible beneficial or harmful effects on performance. Currently, only the effect of carbon dioxide (CO2) gas addition to Li-ion batteries with Si anodes has been studied.[3-4] In addition to CO2, ethylene gas (C2H4) is a promising additive for Si anode systems because it is a precursor in polyethylene polymerization reactions, nCH2=CH2 --> [-CH2-CH2-]n. In addition, polyethylene oxide (PEO) has been observed in the Si-anode SEI and contributes to its passivation while maintaining flexibility.[5] Therefore, creating polyethylene and increasing PEO concentration in situ via ethylene gas doping may yield an improved SEI and more-stable battery.

This work investigates the potential of gas-phase additives, including CO2 and C2H4, to improve the performance of Si anodes for Li-ion batteries. The pressure decay of the gasses at different starting pressures dissolving in GenF3 electrolyte (1.2 M LiPF6 in 3:7 wt:wt ethylene carbonate to ethyl methyl carbonate + 3 wt% fluoroethylene carbonate) was monitored to determine the saturation concentration of dissolved gas. The experimental pressure decay curve was fit to a model and extrapolated to predict the final pressure at equilibrium.[6] The relationship between partial pressure and concentration of dissolved gas in GenF3 at equilibrium was plotted and a curve was drawn to determine the Henry’s law constant. Varying volumes of gas were injected into battery pouch cells containing Si nanoparticle anodes and LiFePO4 (LFP) cathodes to pressurize them to different pressures. Electrochemical cycling and subsequent multi-phase analyses, including vibrational spectroscopy and X-ray characterization of the SEI surface layer and GC-MS/FID were conducted to determine the impact of gas doping on the capacity, SEI, and gas phase reaction products.

References:

[1] G. G. Eshetu and E. Figgemeier, ChemSusChem,
12 (12), 2515-2539 (2019).

[2] L. Bläubaum, P. Röse, L. Schmidt, and U. Krewer, ChemSusChem,
14 (14), 2943-2951 (2021).

[3] L. J. Krause, V. L. Chevrier, L. D. Jensen, and T. Brandt, J. Electrochem. Soc.,
164 (12), A2527-A2533 (2017).

[4] E. J. Hopkins, S. Frisco, R. T. Pekarek, C. Stetson, Z. Huey, S. Harvey, X. Li, B. Key, C. Fang, G. Liu, G. Yang, G. Teeter, N. R. Neale, and G. M. Veith, J. Electrochem. Soc.,
168 (3), 030534 (2021).

[5] M. C. Schulze, G. M. Carroll, T. R. Martin, K. Sanchez-Rivera, F. Urias, and N. R. Neale, ACS Applied Energy Materials,
4 (2), 1628-1636 (2021).

[6] E. Behzadfar and S. G. Hatzikiriakos, Energy & Fuels,
28 (2), 1304-1311 (2014).