Electrophoretic Deposition as a Versatile Low-Cost Tool to Construct a Synthetic Polymeric Solid-Electrolyte Interphase on Silicon Anodes: A Model System Investigation.

The cycling of next-generation, high-capacity silicon (Si) anodes capable of 3579 mAh·g -1 is greatly hindered by the instability of the solid-electrolyte interphase (SEI). The large volume changes of Si during (de)lithiation cause continuous cracking of the SEI and its reconstruction, leading to loss of lithium inventory and extensive consumption of electrolyte. The SEI formed in situ during cell cycling is mostly composed of molecular fragments and oligomers, the structure of which is difficult to tailor. In contrast, ex situ formation of a synthetic SEI provides greater flexibility to deposit long-chain, polymeric, and elastomeric components potentially capable of maintaining integrity against the large ∼350% volume expansion of Si while also enabling electronic passivation of the surface for longer cycling and calendar life. Furthermore, polymers are amenable to structural modifications, and the desired elasticity can be targeted by selection of the SEI polymer feedstock. Herein, electrophoretic deposition (EPD) is used to apply chitosan as a synthetic SEI on model Si thin film electrodes. Comparison of synthetic SEIs obtained without (Si/Chit) and with CH 3 COOLi (Si/Chit+CH 3 COOLi) added during EPD is performed to demonstrate a facile route to tuning of the polymer SEI chemistry. Atomic force and scanning electron microscopy reveal that addition of CH 3 COOLi at EPD assists in conformal deposition of the synthetic SEI. During electrochemical cycling, the Chit+CH 3 COOLi coating nearly doubles the capacity retention versus the reference bare Si thin film. X-ray photoelectron and Fourier transform infrared spectroscopy reveal that CH 3 COOLi caps the -NH 2 groups of chitosan through amidation during EPD, which suppresses the catalytic reduction of the electrolyte. The presented approach demonstrates and validates EPD as a low-capital route to achieving and chemistry-tuning synthetic SEIs on Si electrodes. More broadly, the method is a promising avenue toward controlled and tailored polymeric SEIs on various conversion-type electrodes with high particle volumetric expansion.