Prelithiation Effects in Enhancing Silicon-Based Anodes for Full-Cell Lithium-Ion Batteries Using Stabilized Lithium Metal Particles

Silicon (Si) has been considered as one of the most promising replacements for graphite anodes in next-generation lithium-ion batteries due to its superior specific capacity. However, the irreversible consumption of lithium (Li) ions in Si-based anodes, which is associated with a large volume expansion upon lithiation and the continuous formation of the solid electrolyte interphase (SEI), is especially detrimental to full-cell batteries, whose Li-ion reserve is limited. This study demonstrates the application of stabilized lithium metal particles (SLMPs) as a prelithiation method for Si anodes that can be readily incorporated into large-scale industrial battery manufacturing. Particularly, a surfactant-stabilized SLMP dispersion was designed to be spray-coated onto prefabricated Si composite anodes, forming a uniformly distributed and well-adhered SLMP layer for in situ prelithiation. In full-cells with lithium iron phosphate (LFP) cathodes, the Si-based anodes demonstrated an improved 1st cycle Coulombic efficiency and cycle life with SLMP prelithiation using capacity-control cycling. However, when cycling over the full potential range, prelithiation with high SLMP loading was found to initially increase battery capacity while inducing accelerated fading in later cycles. This phenomenon was caused by Li trapping in the Li–Si alloy associated with higher SLMP-enabled Li diffusion kinetics. Additionally, cycled Si anodes from full-cells were also examined by surface analysis techniques, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), demonstrating SLMP effects in modifying the SEI by increasing the inorganic content, particularly LiF, which had been widely credited with improving SEI morphology and Li-ion diffusion through the interphase. Our findings provide valuable insights into the design of prelithiation and cycling strategies for high-capacity Si-based full-cell batteries to utilize the benefits of SLMP while avoiding the Li trapping phenomenon.