XPS and TOF-SIMS characterization of the surface of aluminum foil anode after cycling in a localized high-concentration Li+-electrolyte
DOI:
https://doi.org/10.15407/hftp17.03.334Keywords:
X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, localized high-concentration Li+-electrolytes, aluminum foil, anode, lithium and lithium-ion batteriesAbstract
Traditional dilute LiPF6-organocarbonate electrolytes used in lithium-ion batteries (LIB) with graphite anode are unable to provide the safety, long service life, and power of the novel high-energy lithium batteries (LB), including those that initially have not lithium metal on the anode’s current collector. Improved properties are demonstrated by high concentration electrolytes (HCE), but the ultra-high salt concentration leads to low ionic conductivity and poor electrode wettability. This study shows for the first time the capability of localized high-concentration Li+-electrolyte (LHCE), such as 1.5 М LiN(SO2F)2 (LiFSI) solution in 1,2-dimethoxyethane (DME) diluted with 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), dramatically increase the cycling of a cheap and high-energy aluminum foil anode (as an active material and current collector) to 1200 cycles with capacity loading 1 mАh cm–2 and current density 1 mА сm–2, with average Coulombic efficiency of cycles (CEav) equal to 99.2 %, even without prelithiation. Moreover, the Al anode in this electrolyte withstands cycling with 10 mА сm-2, and is also capable of operating at –20 °С without deterioration of electrochemical parameters. These achievements are made possible by the formation of a highly effective passivating layer with the function of a solid electrolyte (SEI) on the surface. For its characterization X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were used, which indicate inorganic nature of the nanometer-thick SEI enriched with LiF, Li3N, and Li2SO3. Not only does it rapidly transport ions, but it also functions as a strong self-healing shield, providing improved interfacial stability. Among other things, the study shows the possibilities and limitations of the applied analysis methods.
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