Direct Visualization of the Solid Electrolyte Interphase and Its Effects on Silicon Electrochemical Performance

Fluoroethylene carbonate (FEC) as an electrolyte additive can considerably improve the cycling performance of silicon (Si) electrodes in Li‐ion batteries. However, the fundamental mechanism for how FEC contributes to solid electrolyte interphase (SEI) morphological changes and chemical composition is not well understood. Here, scanning transmission electron microscopy coupled with electron energy loss spectroscopy gives a comprehensive insight as to how FEC affects the SEI evolution in terms of composition and morphology throughout electrochemical cycling. In the first lithiation cycle, the electrode cycled in ethylene carbonate (EC): diethylene carbonate (DEC) forms a porous uneven SEI composed of mostly Li2CO3. However, the electrode cycled in EC/DEC/FEC is covered in a dense and uniform SEI containing mostly LiF. Interestingly, the intrinsic oxide layer (Li x SiO y ) is not observed at the interface of electrode cycled in EC/DEC/FEC after 1 cycle. This is consistent with fluoride anion formation from the reduction of FEC, which leads to the chemical attack of any silicon‐oxide surface passivation layer. Furthermore, surface sensitive helium ion microscopy and X‐ray photoelectron spectroscopy techniques give further insights to the SEI composition and morphology in both electrodes cycled with different electrolytes. Scanning transmission electron micro­scopy demonstrates the effect that adding fluoroethylene carbonate additive to traditional electrolyte ethylene carbonate/diethylene carbonate (EC/DEC) has on solid electrolyte interphase (SEI) morphology. In the first 5 cycles, the addition of FEC to the traditional electrolyte produces an SEI that is uniform and dense. Conversely, the electrochemical decomposition of EC/DEC electrolyte forms a porous, inhomogeneous SEI that exposes more Si nanoparticles to the electrolyte.