Temperature Dependent Formation of the Graphite SEI with Vinylene Carbonate Electrolyte Additive

Autor: Lennart Reuter, Robert Morasch, Jonas Dickmanns, Filippo Maglia, Roland Jung, Hubert Andreas Gasteiger
Rok vydání: 2022
Zdroj: ECS Meeting Abstracts. :432-432
ISSN: 2151-2043
1945-7111
DOI: 10.1149/ma2022-012432mtgabs
Popis: The charge/discharge efficiency and the cycle life of lithium-ion batteries (LiBs) depends on a large number of competing interfacial processes. Probably the best-known interface in LiBs is the solid-electrolyte-interphase (SEI), which is a passivating layer formed at the negative electrode by electrolyte decomposition during the first cycles.[1–3] Since the SEI stability is a deciding factor with regards to cycle life, understanding and improving the SEI formation process is crucial. In order to yield an effective SEI, commercial battery cells undergo an extensive so-called formation procedure after cell assembly, which generally consist of multiple voltage-holds and current-steps at various temperatures.[4,5] During the first cycles of a LiB, the SEI is generated by the reduction products of the commonly used carbonate-based electrolyte components, such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).[6,7] Additionally, electrolyte additives are commonly added to form an SEI layer with increased cycling stability and reduced irreversible capacity loss during the first cycle.[6,8–10] Among a variety of additives, vinylene carbonate (VC) is the most prominent. Since the reduction of VC initiates at higher reduction potentials compared to alkyl carbonate solvents (e.g., EC), it is reduced preferentially during the first charge and thus strongly affects the SEI composition.[6,11] In the present study we investigated the effect of the formation temperature in a range between 10-60 °C on the performance characteristics of full-cells with a graphite anode (MAGE) and an NCM831205 cathode as well as of MAGE/Li half-cells, both with LP572 (1 M LiPF6 in EC:EMC 3:7wt/wt + 2wt% VC) electrolyte. These include the first-cycle irreversible capacity loss, the negative electrode impedance build-up, the gas evolution during formation, the rate capability, and the cycle life. Employing electrochemical impedance spectroscopy using a µ-reference electrode allowed us to determine the graphite intercalation resistance (R Int), representing the sum of the SEI resistance (R SEI) and of the charge transfer resistance (R CT), after two 0.1C formation cycles at a given temperature. The impedance spectrum was recorded at 25 °C and 40% SOC referenced to 190 mAh/gNCM reversible capacity. As depicted in Figure 1, both R Int of the graphite electrode in the MAGE/NCM83125 full-cell and the first-cycle irreversible Li-loss determined a MAGE/Li half-cell increase with increasing formation temperature. Additionally, on-line electrochemical mass spectrometry (OEMS) was applied to identify and quantify the gaseous reduction products for LP572 in a MAGE/NCM831205 full-cell during one 0.1C formation cycle at different temperatures. As displayed in Figure 1, the relative increase of the total gas evolved, which is the sum of hydrogen, ethylene, carbon monoxide, and carbon dioxide, follows the relative increase of the intercalation resistance. Next to the overall gas amounts, changes in the quantity of the individual gases give insights into the highly temperature dependent reduction mechanisms of VC. Acknowledgement: The authors thank BMW AG for their financial support. References: [1] E. Peled, J. Electrochem. Soc. 1979, 126, 2047–2051. [2] E. Peled, S. Menkin, J. Electrochem. Soc. 2017, 164, 1703–1719. [3] K. Edström, M. Herstedt, D. P. Abraham, J. Power Sources 2006, 153, 380–384. [4] T. Miura, S. Cottte, K. Masanori, Lithium-Ion Battery Formation Process, 2018, WO 2018/153449 Al. [5] S. Amiruddin, B. Li, High Capacity Lithium Ion Battery Formation Protocol and Corresponding Batteries, 2015, US 9,159,990 B2. [6] B. Zhang, M. Metzger, S. Solchenbach, M. Payne, S. Meini, H. A. Gasteiger, A. Garsuch, B. L. Lucht, J. Phys. Chem. C 2015, 119, 11337–11348. [7] B. Strehle, S. Solchenbach, M. Metzger, K. U. Schwenke, H. A. Gasteiger, J. Electrochem. Soc. 2017, 164, A2513–A2526. [8] D. Pritzl, S. Solchenbach, M. Wetjen, H. A. Gasteiger, J. Electrochem. Soc. 2017, 164, A2625–A2635. [9] T. Taskovic, L. Thompson, A. Eldesoky, M. Lumsden, J. R. Dahn, J. Electrochem. Soc. 2021, DOI 10.1149/1945-7111/abd833. [10] M. Nie, J. Demeaux, B. T. Young, D. R. Heskett, Y. Chen, A. Bose, J. C. Woicik, B. L. Lucht, J. Electrochem. Soc. 2015, 162, A7008–A7014. [11] K. U. Schwenke, S. Solchenbach, J. Demeaux, B. L. Lucht, H. A. Gasteiger, J. Electrochem. Soc. 2019, 166, A2035–A2047. Figure 1 . Formation temperature dependent relative increase (normalized to the formation at 10 °C) of the first-cycle irreversible Li-loss (black lines and dots) determined in MAGE/Li half-cells, of the intercalation resistance R Int at 25 °C and 40% SOC after two 0.1C formation cycles (yellow lines and dots) determined in MAGE/NCM8311205 full-cells with a µ-reference electrode, and of the total amount of gas evolved (sum of H2, C2H4, CO, and CO2; blue lines and dots) after one 0.1C formation cycle determined in a MAGE/NCM831205 OEMS cell. Figure 1
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