Determining the Oxidation Stability of Electrolytes for Lithium-Ion Batteries Using Quantum Chemistry and Molecular Dynamics

Determining the oxidation potential (OP) of lithium-ion battery (LIB) electrolytes using theoretical methods will significantly speed up and simplify the process of creating a new generation high-voltage battery. The algorithm for calculating OP should be not only accurate but also fast. Our work proposes theoretical principles for evaluating the OP of LIB electrolytes by considering LiDFOB solutions with different salt concentrations in EC/DMC solvent mixtures. The advantage of the new algorithm compared to previous versions of the theoretical determination of the oxidation potential of electrolyte solutions used in lithium-ion batteries for calculations of statistically significant complexes, the structure of which was determined by the molecular dynamics method. This approach significantly reduces the number of atomic–molecular systems whose geometric parameters need to be optimized using quantum chemical methods. Due to this, it is possible to increase the speed of calculations and reduce the power requirements of the computer performing the calculations. The theoretical calculations included a set of approaches based on the methods of classical molecular mechanics and quantum chemistry. To select statistically significant complexes that can make a significant contribution to the stability of the electrochemical system, a thorough analysis of molecular dynamics simulation trajectories was performed. Their geometric parameters (including oxidized forms) were optimized by QM methods. As a result, oxidation potentials were assessed, and their dependence on salt concentration was described. Here, we once again emphasize that it is difficult to obtain, by calculation methods, the absolute OP values that would be equal (or close) to the OP values estimated by experimental methods. Nevertheless, a trend can be identified. The results of theoretical calculations are in full agreement with the experimental ones.