Removal of Surface Carbonate from Lithium-Ion Battery Cathode Materials via Vapor-Phase Fluorination

Abstract

Herein, ultrathin metal-fluoride barrier coatings on the surface of lithium-ion battery (LIB) cathodes can improve cycling stability and prevent corrosion by acidic byproducts in the electrolyte. Atomic layer deposition (ALD) is an effective method to deposit ultrathin metal fluoride coatings on LIB cathodes. Although numerous studies have demonstrated the benefit of ALD metal fluoride coatings to LIB performance, comparatively few works have examined the effect of individual ALD precursors on the cathode surface. This paper uses X-ray photoelectron spectroscopy (XPS) measurements to elucidate the surface chemical changes on LIB cathode material surfaces upon exposure to the ALD metal fluoride precursor, hydrogen fluorine pyridine (HFPy). We found a decrease in surface carbonate and an increase in surface fluoride after HFPy exposure suggesting the conversion of lithium carbonate (Li₂CO₃) to lithium fluoride (LiF). This conversion is desirable given that Li₂CO₃ degrades LIB performance, whereas LiF provides an excellent physio-chemical barrier against chemical attack during cycling. Scanning transmission electron microscopy, X-ray energy dispersive spectroscopy, and XPS measurements following HFPy exposure to Li₂CO₃ powder revealed the formation of a conformal LiF shell around the Li₂CO₃ particles. Finally, we confirmed the complete conversion of similar to 7 nm ALD Li₂CO₃ films on silicon from HFPy exposure using XPS and spectroscopic ellipsometry. The elimination of problematic Li₂CO₃ from LIB cathode surfaces and conversion into a protective LiF coating via a single precursor vapor treatment may provide a cost-effective method for enhancing LIB performance.