Electrolyte Design Enabling a High‐Safety and High‐Performance Si Anode with a Tailored Electrode–Electrolyte Interphase

Silicon (Si) anodes are advantageous for application in lithium-ion batteries in terms of their high theoretical capacity (4200 mAh g^-1 ), appropriate operating voltage (<0.4 V vs Li/Li⁺ ), and earth-abundancy. Nevertheless, a large volume change of Si particles emerges with cycling, triggering unceasing breakage/re-formation of the solid-electrolyte interphase (SEI) and thereby the fast capacity degradation in traditional carbonate-based electrolytes. Herein, it is demonstrated that superior cyclability of Si anode is achievable using a nonflammable ether-based electrolyte with fluoroethylene carbonate and lithium oxalyldifluoroborate dual additives. By forming a high-modulus SEI rich in fluoride (F) and boron (B) species, a high initial Coulombic efficiency of 90.2% is attained in Si/Li cells, accompanied with a low capacity-fading rate of only 0.0615% per cycle (discharge capacity of 2041.9 mAh g^-1 after 200 cycles). Full cells pairing the unmodified Si anode with commercial LiFePO₄ (≈13.92 mg cm^-2 ) and LiNi_0.5 Mn_0.3 Co_0.2 O₂ (≈17.9 mg cm^-2 ) cathodes further show extended service life to 150 and 60 cycles, respectively, demonstrating the superior cathode-compatibility realized with a thin and F, B-rich cathode electrolyte interface. This work offers an easily scalable approach in developing high-performance Si-based batteries through Si/electrolyte interphase regulation.