Following up the great success of lithium ion batteries (LIBs) in the field of consumer electronics in the recent decades, LIBs are today also widely used as energy storage devices for various types of electric vehicles (EVs). However, it is believed that a substantial breakthrough of the electromobility can only take place, if EVs are able to achieve driving ranges of more than 500 km and, therefore, gaining greater consumer acceptance. To achieve these driving ranges, the energy content of the used LIBs needs to be increased to values of 350 Wh/kg and 750 Wh/L at the cell level. These improvements can be achieved by replacing the state-of-the-art graphite anode by high-capacity anode materials like silicon (Si), which is able to provide a nearly 10 times higher specific capacity compared to graphite.[1] However, due to huge volume changes of up to 300% upon lithiation/de-lithiation, Si-based anodes often suffer from poor cycling performance related to cracking and pulverization of the Si particles and continuous solid electrolyte interphase (SEI) re-formation.

Typically, these issues are addressed by decreasing the size of the active material particles to the nanoscale (i.e. nanoparticles, nanowires or thin films) or the fabrication of composites like intermetallic Si phases or Si/carbon composite materials to decrease the overall volume changes.[2] Although these strategies are reported to be effective to improve the performance of Si electrodes, it was revealed that the dominating failure mechanism of full cells containing Si-based negative electrodes lies in the consumption active lithium from the cathode related to continuous electrolyte reduction at the Si negative electrode. The addition of appropriate electrolyte additives such as fluoroethylene carbonate (FEC) or vinylene carbonate (VC) can significantly improve the capacity retention and Coulombic efficiency of Si-based full cells by forming a more stable SEI on the Si negative electrode.[3, 4] Recently, Krause et al. demonstrated that the addition of carbon dioxide in the form of dry ice significantly improved the performance of Si-based full cells and even outperformed the most commonly used additive FEC.[5] However, the exact working mechanism of the carbon dioxide additive and especially the reductive decomposition reactions including the resulting morphology and/or chemical composition of the formed SEI layer are still uncertain.

Within this study, thin film Si electrodes prepared via magnetron sputtering are employed as model electrodes (i.e. no binder or conductive additive) therefore, possible effects of the carbon dioxide can be correlated to the Si active material. These Si thin film electrodes are coupled with NMC-111 positive electrodes to Si/NMC-111 full cells, which are used for the electrochemical investigations. As the solubility of carbon dioxide in the organic carbonate based electrolytes is rather low, diethylpyrocarbonate is added to the baseline electrolyte, as pyrocarbonates are known as carbon dioxide generators and, therefore, the carbon dioxide is released in-situ within the assembled full cell. The addition of the diethylpyrocarbonate electrolyte additive leads to significantly improved performance of the Si/NMC-111 full cells in terms of Coulombic efficiency and capacity retention full cells during prolonged cycling compared to the baseline electrolyte. The chemical composition of the SEI layer formed on the Si negative electrodes is investigated by means of X-ray photoelectron spectroscopy (XPS). The XPS investigations reveal that the improved performance of the carbon dioxide containing cells is related the improved passivation of the negative electrode by the formation of mainly lithium carbonate at the Si surface.

References:

[1] D. Andre, H. Hain, P. Lamp, F. Maglia, B. Stiaszny, Future high-energy density anode materials from an automotive application perspective, Journal of Materials Chemistry A, 5 (2017) 17174-17198.

[2] M.N. Obrovac, V.L. Chevrier, Alloy Negative Electrodes for Li-Ion Batteries, Chemical Reviews, 114 (2014) 11444-11502.

[3] R. Nölle, A.J. Achazi, P. Kaghazchi, M. Winter, T. Placke, Pentafluorophenyl Isocyanate as an Effective Electrolyte Additive for Improved Performance of Silicon-Based Lithium-Ion Full Cells, ACS Applied Materials & Interfaces, 10 (2018) 28187-28198.

[4] M. Klett, J.A. Gilbert, S.E. Trask, B.J. Polzin, A.N. Jansen, D.W. Dees, D.P. Abraham, Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li_1.03(Ni_0.5Co_0.2Mn_0.3)_0.97O₂/Silicon-Graphite Full Cells, Journal of The Electrochemical Society, 163 (2016) A875-A887.

[5] L.J. Krause, V.L. Chevrier, L.D. Jensen, T. Brandt, The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy, Journal of The Electrochemical Society, 164 (2017) A2527-A2533.