Lithium ion batteries (LIBs) are considered as key technology for stationary energy storage systems and especially as power supply for electric vehicles (EVs). Even though LIBs are already used in EVs, there is a need of further improvements of the LIBs to achieve driving ranges of more than 500 km, what is considered to be a value for greater consumer acceptance of EVs. To reach this goal, the specific energy and energy density of LIBs need to be increased to approximately 350 Wh kg^-1 and 750 Wh L^-1 at cell level, respectively. The use of alternative anode materials to replace the state-of-the-art graphite anode, is considered as an efficient strategy to increase the energy density of LIBs. Silicon (Si) turns out to be the most promising material for advanced anodes in LIBs, as it offers a nearly 10 times higher specific capacity compared to graphite. However, the implementation of electrode materials containing contents of more than 5-10% Si in commercial LIBs is still hampered by huge volume changes leading to a continuous solid electrolyte interphase (SEI) re-formation, loss of active lithium and, therefore, to a poor capacity retention.[1]

The application of nano-sized Si materials like nanoparticles, nanowires or thin films is reported to significantly improve the performance of Si based anodes, due to better accommodation of the huge volume changes upon lithiation/de-lithiation. Additionally, Si thin film electrodes exhibit improved specific capacities in comparison to typical composite-based electrodes, because of the absence of inactive components like binder and conductive additives.[2] An additional approach to improve the performance of Si based electrodes is the addition of additives to the electrolyte. Electrolyte additives like fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are commonly known to enhance the capacity retention of Si electrodes by forming a more stable SEI, thus, preventing ongoing electrolyte decomposition and continuous active lithium loss.[3] Isocyanate compounds are able to undergo reductive polymerization and, therefore, may be considered as effective electrolyte additives for Si anodes. Actually, several isocyanates were reported to function as effective film-forming additives for graphite-based negative electrodes.[4]

Within this work, magnetron sputtering was utilized for the preparation of thin film Si anodes, which contain neither a binder nor a conductive agent. Therefore, the effect of the electrolyte additive can be directly related to the Si active material. Since it was recently reported, that lithium consumption related to SEI reformation is the main failure mechanism of lithium ion full cells containing a Si anode[5], the electrochemical performance of these Si thin film electrodes was investigated in Si/NMC-111 full cells using different electrolyte formulations. DFT calculations (HOMO/LUMO energies) were performed prior to electrochemical investigations for reductive and oxidative stability predictions of the electrolyte solvent and additive molecules. The addition of the pentafluorophenyl isocyanate electrolyte additive leads to an increased Coulombic efficiency and a significantly enhanced capacity retention of the LIB full cells during prolonged cycling, in comparison to the baseline electrolyte. Post-mortem investigations of the negative Si electrodes by means of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were performed to study the SEI layer, formed in the different electrolyte formulations. The enhanced cycling performance of the full cells can be correlated to an improved SEI formation.

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] S. Dalavi, P. Guduru, B.L. Lucht, Performance Enhancing Electrolyte Additives for Lithium Ion Batteries with Silicon Anodes, Journal of The Electrochemical Society, 159 (2012) A642-A646.

[4] C. Korepp, W. Kern, E.A. Lanzer, P.R. Raimann, J.O. Besenhard, M.H. Yang, K.C. Möller, D.T. Shieh, M. Winter, Isocyanate compounds as electrolyte additives for lithium-ion batteries, Journal of Power Sources, 174 (2007) 387-393.

[5] 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.