Enhancing the Performance and Stability of Li-Ion Batteries with Fluorinated Electrolytes: Insights from MD Simulation and Experimental Analysis

Abstract

The significance of using fluorinated electrolytes, particularly fluorinated ethylene carbonate (FEC) and difluoro ethylene carbonate (DFEC), in the electrolyte system of 1.2 M LiPF6 in dimethyl carbonate (DMC)/fluorinated solvent (FEC/DFEC), was explored using classical molecular dynamic (MD) simulation and density functional theory (DFT) calculation in this work. Various parameters, such as radial distribution function (RDF), integral over RDF, transference number, coordination number, and solvation energy, were analyzed. The study demonstrated that DFEC enhances the reduction in binding energy of the solvation sheath compared to FEC. Additionally, the electrochemical performance of a practical full-cell 18650 of LiNi0.88Co0.10Al0.02O4 (NCA) cathode and graphite anode batteries was examined, confirming that 1.2 M LiPF6 in DMC/FEC/DFEC (4:0.5:0.5 %v) demonstrated the highest capacity retention after 1,000 cycles, surpassing 1.2M LiPF6 in DMC/fluorinated (4:1 %v, FEC and DFEC, respectively) and the previous electrolyte 1.2 M LiPF6 in EC/EMC/DEC/FEC (1:1:1:1.3 %V). Spectroscopy techniques, including DEMS, NMR, and GC-MS, were utilized to investigate the electrolyte decomposition, revealing CO2 and H2 as the main gas products during decomposition. NMR results identified some species, such as HF, H2O, acetal, formaldehyde, and unknown products, while GC-MS confirmed that all the solvents in the electrolyte take part in the decomposition process. This study highlights the potential of fluorinated electrolytes in battery systems and provides insight into their decomposition mechanism, contributing to the development of more efficient and stable battery systems.