The Effects of Temperature and Fluoroethylene Carbonate Concentration on the Formation of the Graphite SEI and Its Impact on the Full-Cell Performance
Authors: Geserer Michael , Reuter Lennart , Dickmanns Jonas L. S. , Hartmann Louis , Maglia Filippo , Jung Roland , Gasteiger Hubert Andreas 
Published: August 2024

Extending the cycle-life of state-of-the-art lithium-ion batteries (LiBs) is, amongst other aspects, predicated on optimizing the properties of the solid electrolyte interphase (SEI), such as its stability and resistance.[1] It is formed at the negative electrode during the first cycles by electrolyte decomposition and acts as a passivating layer between the electrode surface and the electrolyte.[2,3] Since the SEI formation is accompanied by an irreversible loss of cyclable lithium, its stability during cycling is crucial for improving the charge/discharge efficiency of LiBs. Furthermore, the arising resistance associated with the SEI formation, predominantly depending on the SEI thickness, its chemical composition, and its lithium-ion conductivity, all impact the rate performance of the anode.[4]

Two of the most crucial factors impacting SEI formation are temperature and electrolyte composition (i.e., using electrolyte additives).[5] Additives are added to the electrolyte to inhibit the predominant reduction of other electrolyte constituents and thereby form an SEI with improved stability during cycling.[1,6,7] One of the most prominent additives for LiBs is fluoroethylene carbonate (FEC), which is preferentially reduced compared to common carbonate solvents (e.g., ethylene carbonate, ethyl methyl carbonate) due to its higher reduction potential.[7]

In this study, we investigated the influence of the formation temperature between 10 and 60 °C, as well as the concentration of FEC (2 and 20 %wt in EC:EMC 3:7 wt/wt with 1 M LiPF6, Gotion, USA) on the characteristics of a synthetic graphite (SMG-A5, Resonac, Japan) anode, both in SMG/Li half-cells and in Ni-rich NCM/SMG full cells.

We quantified the first-cycle irreversible capacity loss (ICL) in SMG/Li half cells with a lithium reference electrode after two 0.1 C formation cycles and compared the FEC containing electrolytes to the baseline- (LP-57) and an LP-572 (1 M LiPF6 in EC:EMC 3:7 wt/wt + 2 %wt vinylene carbonate (VC), Gotion, USA) electrolyte. Employing electrochemical impedance spectroscopy in an SMG/Li half-cell setup with a µ-reference electrode and a free-standing graphite electrode,[8,9] we could further quantify the intercalation resistance (R
Int, representing the sum of the charge-transfer and the SEI resistance) after an identical formation protocol at 40 % SOC. Both quantities, the ICL and R
Int, increase with increasing formation temperature and higher FEC content.

The impact of an increasing R
Int on the rate performance was tested in Ni-rich NCM/SMG full cells with a lithium reference electrode, revealing a decreased rate capability and higher susceptibility for lithium plating for cells that were formed at higher temperatures and contained 20 %wt FEC. Additionally, the cycling stability of Ni-rich NCM/SMG full cells at 25 °C was assessed in coin cells. Despite an increased ICL and R
Int after formation, cells that were formed at elevated temperatures and contained 20 %wt FEC showed enhanced cycling stability compared to those that were formed at a lower temperature and contained less FEC.

Finally, on-line electrochemical mass spectrometry (OEMS) was employed to quantify the evolved gases during the formation of a Ni-rich NCM/SMG full cell containing either of the FEC-containing electrolytes at different temperatures. In accordance with an increased ICL and R
Int, a higher formation temperature, as well as a higher FEC content, gave rise to a more pronounced gas evolution during formation.

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Acknowledgements:

This work is financially supported by BMW AG. The authors thank BMW AG for their financial support.