Improving Cycle Life and Capacity Retention in PVMPO‖Li Dual‐Ion Lithium‐Organic Batteries Using an EC‐Free and FEC Additive Containing Electrolyte

Abstract Electrolytes critically influence the electrochemical performance and cycle life of lithium ion batteries (LIBs). This holds especially for organic redox polymer‐based batteries, such as those employing poly(3‐vinyl‐ N ‐methylphenoxazine) (PVMPO), where solubility limits performance in conventional ethylene carbonate (EC)/ dimethyl carbonate (DMC)‐based electrolytes. Reducing EC content has shown solubility suppression when using ethyl methyl carbonate (EMC) as a co‐solvent, however, capacity fading persists due to PVMPO electrode degradation. To address this degradation, this study explores the use of EC‐free electrolytes, with and without fluoroethylene carbonate (FEC). Electrochemical investigations, UltraViolet/Visible (UV/Vis) spectroscopy, post‐ cycling Scanning Electron Microscopy (SEM), Energy Dispersive X‐ray Spectroscopy (EDS) mapping, and X‐ray Photoelectron Spectroscopy (XPS) analyses are employed to evaluate solubility, interfacial properties, and electrode integrity. The EC‐free electrolyte system with FEC retains 95 mAh g ‒1 , while that without FEC retains 86 mAh g ‒1 , outperforming the 76 mAh g ‒1 observed in EC‐based systems after 500 cycles at 1C. FEC containing electrolyte systems display reduced interfacial resistance, fewer surface cracks, and minimal electrode degradation. These findings demonstrate that EC‐free electrolytes, particularly with FEC, effectively suppress electrode degradation and enhance the cycle life of organic LIBs.