Molecular Effects of Li⁺-Coordinating Binders and Negatively Charged Binders on the Li⁺ Local Mobility near the Electrolyte/LiFePO₄ Cathode Interface within Lithium-Ion Batteries

Abstract

The development of lithium-ion batteries (LIBs) is important in the realm of energy storage. Understanding the intricate effects of binders on the Li+ transport at the cathode/electrolyte interface in LIBs remains a challenge. This study utilized molecular dynamics simulations to compare the molecular effects of conventional polyvinylidene difluoride (PVDF), Li+-coordinating polyethylene oxide (PEO), and negatively charged polystyrene sulfonate (PSS) binders on local Li+ mobility at the electrolyte/LiFePO4 (LFP) cathode interface. By examining concentration profiles of Li+, three different polymer binders, and anions near Li+-rich LFP and Li+-depleted FePO4 (FP) surfaces, we found a superior performance of the negatively charged PSS on enhancing Li+ distribution near the Li+-depleted FP surface. The radial distribution function and coordination number analyses revealed the potent interactions of PEO and PSS with Li+ disrupting Li+ coordination with electrolyte solvents. Our simulations also revealed the effects of non-uniform binder dispersions on the Li+ local mobility near the cathode surface. The combined results provide a comparative insight into Li+ transport at the electrolyte/cathode interface influenced by distinct binder chemistries, offering a profound understanding of the binder designs for high-performance LIBs.

Keywords

• lithium-ion battery
• electrolyte–cathode interface
• functional binders
• molecular dynamics