Lithium-ion batteries have been the gold standard and ubiquitous driving force behind almost all electronic devices for over two decades. A typical lithium-ion battery consist of a graphite anode, a transition metal oxide cathode, and an electrically insulating and ionically conducting nonaqueous organic electrolyte that acts as an ionic path between the two. One key to understanding a battery's electrochemistry is its electrode/electrolyte interface, which controls critical aspects of performance and is thus a target for improvement. The decomposition of organic electrolyte molecules at the electrode surface yields a passivation layer called the solid electrolyte interphase (SEI). Understanding the SEI layer formation, composition, and growth over multiple time and length scales is essential for the design of next-generation safe and performant lithium-ion batteries. The most common electrolytes are mixtures of alkyl carbonates such as ethylene carbonate (EC) or propylene carbonate (PC), and lithium salts such as LiAsF 6 or LiPF 6 . Both components undergo chemical reactions that contribute to the composition of the SEI. The choice of an electrolyte is partially based on its compatibility with the electrode materials used, such that the electrolyte should either be electrochemically stable or form a stable and well-understood SEI at the electrode surface, necessitating a thorough understanding of the electrolyte stability and decomposition pathways. However, it is experimentally challenging to directly capture reactive processes leading to the formation of SEI. Alternatively, atomistic simulations, including electronic structure theory and molecular dynamics, have the potential to contribute to a fundamental understanding of the electrolyte decomposition pathways responsible for the SEI. Although density functional theory (DFT) has become a standard approach due to the steep computational scaling of more accurate wavefunction (WF) methods that explicitly describe electron correlation, the results can vary depending on the density functional approximation used and the system of interest. Therefore, the selection of a particular density functional approximation for a specific application requires rigorous benchmarking studies. In this work, we carry out such a study for the problem of organic electrolyte decomposition in the presence of lithium.