Density Modeling of Battery Electrolyte Mixtures

Lithium-ion battery (LIB) electrolytes are generally composed of a mixture of organic hydrocarbons and lithium salt (e.g., LiPF6). Experimental density data for basic and realistic multicomponent mixtures are scarce in the literature, and a predictive model for electrolyte solution density is not yet widely available. This work resolves to create a simple predictive method that can be used to estimate the density of these mixtures. A model that accounts for intermolecular forces in the electrolyte mixture was developed and fitted to density data available in the literature that was internally vetted for consistency. The model exhibited high accuracy for single-component electrolyte mixtures, with most predictions falling within 1% of measured values and all predictions falling within 5%. The model was further extended to more realistic, multi-solvent electrolyte mixtures that exhibited similar accuracy. In addition, a novel, accurate method for computing absolute molar and mass fractions of multi-solvent mixtures with specified volumetric concentrations (e.g., 1.2 M LiPF6 in 1:1:1% vol. ethylene carbonate-EC/diethyl carbonate-DEC/dimethyl carbonate-DMC) is also described. The two separate approaches were combined to yield a modeling framework capable of computing molar concentrations and densities of all LIB electrolyte solutions based on LiPF6 loaded in any combination of EC, EMC, DEC, DMC, and PC. Additional ionic salt data for NaPF6 and LiFSI were also evaluated to illustrate the adaptability of the model to different salts and electrolytes. Once again, the model was successful, with most density predictions falling within 1% error and all falling within 5%. This work ultimately provides a simple, adaptable modeling framework for accurate prediction of electrolyte mixture densities.