September 4, 2025
Journal Article

Direct Prelithiation of Silicon-Based Composite Electrodes via Island-like Thermal Evaporation

Abstract

Irreversible losses of Li during solid electrolyte interface (SEI) conditioning is a key contributor to the lower specific capacities observed in silicon-containing Li-ion batteries. Herein, thermal evaporation of between 1 and 20 µm of Li onto Si-based composite anodes has been investigated as a prelithiation method to account for such losses. To account for mechanical strain caused by Li-Si alloying during the deposition, a stainless-steel mesh is applied to the electrodes before prelithiation to form “island-like” deposition on the electrode surface. The open circuit potential was also found to decrease as a function of increased Li evaporation, consistent with the potentials of electrochemically prepared LixSi alloys. Prelithiating to account for irreversible Li losses to SEI formation resulted in full cells with a 15.8% increase in initial coulombic efficiency and a 47.8% reduction in irreversible capacity loss after SEI formation cycling. Subsequent C/3 cycling showed up to a 62.9% increase in specific capacity in prelithiated cells. X-ray photoelectron spectroscopy (XPS) revealed differences in the SEI composition that was formed by electrochemical cycling and reactively formed in prelithiated cells upon exposure to Gen2 + 3% FEC electrolyte. The reactively formed SEI from the spontaneous reaction with lithiated silicon was carbonate-rich while the electrochemical SEI formation showed significantly more LiPFx species, which could play a role in overall cycling performance.

Published: September 4, 2025

Citation

Musgrove A., K. Browning, R.L. Sacci, A. Ulman, H.M. Meyer III, K. Musgrove, and J.P. Quinn, et al. 2025. Direct Prelithiation of Silicon-Based Composite Electrodes via Island-like Thermal Evaporation. Energy & Fuels 39, no. 10:4968–4982. PNNL-SA-206600. doi:10.1021/acs.energyfuels.4c06113