Résumé
The importance of the solid–electrolyte-interphase (SEI) is well-established in lithium-ion (Li-ion) batteries, but the technical story behind its formation remains incomplete. Current research has largely focused on the nature of the deposited layer, while the formation dynamics, particularly those occurring in the solution phase, remain elusive. Here, by employing operando infrared fiber evanescent wave spectroscopy (IR-FEWS) to conduct real-time monitoring of the chemical dynamics of ethylene carbonate-based electrolytes and graphite anodes, we reveal that the assembly of the SEI layer follows a classical heterogeneous nucleation and growth process under appropriate kinetic constraints. Our findings, supported by various other in situ/ex situ techniques, show that during charging, the newly generated species (e.g. lithium ethylene dicarbonate (LEDC) and Li2CO3), that are destined for the SEI, can also diffuse away from the graphite–electrolyte interface into the electrolyte. The deposition of the species occurs via a heterogeneous nucleation process with the low-solubility inorganic species (e.g. Li2CO3) preferentially nucleating on the graphite surface, followed by more-soluble organic species (e.g. LEDC). Limiting diffusion to promote the deposition is crucial for facilitating efficient SEI formation with competitive deposition kinetics depending not only on the charging rate and temperature, but also the electrolyte quantity. When the formation parameter-space is intentionally modified by employing a high current pulse during initial charging followed immediately by an ageing step, a more stable SEI with lower resistance is developed, leading to longer lifetimes for the Li-ion pouch cells prepared with this new protocol. Collectively, these findings deepen our mechanistic understanding of SEI formation from the “solution” phase perspective and offer an enriched framework for defining initial charging protocols for battery manufacturing.