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

Darapaneni, Pragathi; Mane, Anil U.; Hood, Zachary D.; Elam, Jeffrey W.

doi:10.1021/acsaem.2c01205

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

Journal Article · Fri Aug 05 00:00:00 EDT 2022 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.2c01205· OSTI ID:1910153

^[1]; Mane, Anil U. ^[1];

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Argonne National Lab. (ANL), Argonne, IL (United States)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1910153

Journal Information:: ACS Applied Energy Materials, Vol. 5, Issue 8; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
cathode materials
surface carbonate
fluorination
atomic layer deposition
lithium fluoride shell
X-ray photoelectron spectra
battery performance

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

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