Synchrotron Infrared Nano-Spectroscopy and Imaging of Lithium Fluoride in the Solid Electrolyte Interphase on Li-Ion Anodes
Authors: Dopilka Andrew , Larson Jonathan M. , Cha Hyungyeon , Kostecki Robert 
Published: August 2024

The solid electrolyte interphase layer that forms on the surface of the negative electrode in Li-ion batteries is crucial for battery cycle/calendar life, rate performance and safety. This 10's of nanometers layer is formed from the decomposition of the liquid electrolyte and its passivation properties are very sensitive to its formation and aging conditions. Despite this critical role, there is still a lack of fundamental understanding of how its structure and composition relate to its stability and passivation performance.

Amongst the SEI products that form during the decomposition of liquid electrolyte, lithium fluoride (LiF) is a ubiquitous component and many attribute its presence to be a determining factor of a well passivated interface. Despite the importance, LiF’s nanostructure and distribution within the SEI layer is rarely investigated due to the lack of suitable characterization techniques. X-ray photoelectron spectroscopy (XPS) is the main tool to identify LiF in the SEI layer, but its micron scale lateral resolution precludes any nanometer scale mapping of LiF’s distribution which limits its ability to identify the role LiF plays in the SEI layer.

Recently our group has been characterizing the SEI layer of Li-ion negative electrodes with nano-Fourier transform infrared spectroscopy (nano-FTIR).1,2 Nano-FTIR is a scanning probe technique based in a typical atomic force microscope (AFM) in which a broadband laser illuminates a metallic tip/sample interface. The metallic tip acts as an antenna, focusing the infrared light adjacent to the interface and creating a near-field interaction. By operating in constant tapping mode and due to the nonlinearity of the near-field signal on the tip/sample distance, the corresponding backscattered light from the near-field interaction with the sample can be separated from the background with lock-in amplification. The result is IR reflection and absorption spectra with lateral resolution close to the tip radius (ca. 20 nm). This far exceeds the diffraction limited resolution of typical IR microscopy (~10’s µm) creating new opportunities for IR characterization on nanometer length scales.

In this talk, we’ll discuss our recent work related to utilizing synchrotron-based nano-FTIR to characterize and image LiF in the SEI layer of Li-ion based negative electrodes. The synchrotron infrared light source allows the detection of photons out to the far-IR (322 cm-1 limit) which enables the detection of the vibrational modes of Li containing inorganic phases such as LiF, Li2O, and LiH. By comparing model thin film LiF nano-FTIR spectra with experimental spectra take from the surfaces of Cu, Si thin film, and a novel metallic glass anode, we can gauge the heterogeneity of the LiF in the SEI layer and then suggest different LiF formation mechanisms. Based on the results, we believe that nano-FTIR with a synchrotron based light source will be a key tool to unravelling the nanoscale structure of the SEI layer due to its nanoscale chemical sensitivity and nondestructive nature.

This research was supported by the US Department of Energy (DOE)’s Vehicle Technologies Office under the Silicon Consortium Project directed by Brian Cunningham and managed by Anthony Burrell. This research used resources of the Advanced Light Source from beamline 2.4, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231.

References

(1) Dopilka, A.; Gu, Y.; Larson, J. M.; Zorba, V.; Kostecki, R. Nano-FTIR Spectroscopy of the Solid Electrolyte Interphase Layer on a Thin-Film Silicon Li-Ion Anode. ACS Appl. Mater. Interfaces
2023, 15 (5), 6755–6767.

(2) He, X.; Larson, J. M.; Bechtel, H. A.; Kostecki, R. In Situ Infrared Nanospectroscopy of the Local Processes at the Li/Polymer Electrolyte Interface. Nature Communications
2022, 13 (1), 1398.