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 (approximate to 13.92 mg cm(-2)) and LiNi0.5Mn0.3Co0.2O2 (approximate to 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.

Automated summary

This study demonstrates the superior cyclability of silicon anodes in lithium-ion batteries using a nonflammable ether-based electrolyte with dual additives. By forming a high-modulus SEI rich in fluoride and boron species, the Si/Li cells achieve a high initial Coulombic efficiency and low capacity-fading rate. Additionally, full cells pairing the unmodified Si anode with commercial cathodes show extended service life, highlighting the potential for developing high-performance Si-based batteries through Si/electrolyte interphase regulation.