Deep Eutectic Solvent‐Based Solid Polymer Electrolytes for High‐Voltage and High‐Safety Lithium Metal Batteries

Abstract Solid‐state electrolytes (SSE) exhibit great promise in enhancing the safety of Li metal batteries by replacing flammable liquid electrolytes. However, the practical application of SSE is hampered mainly due to the poor electrode–electrolyte interface, low ion conductivity, and inferior electrochemical stability. Herein, superior nonflammable solid polymer electrolytes are elaborately designed by in situ encapsulating succinonitrile (SN)‐based deep eutectic solvent (DES) into the ethoxylated trimethylolpropane triacrylate (ETPTA) matrix (DES‐ETPTA). Benefiting from strong polarity and high anti‐oxidation capability, as‐prepared DES‐ETPTA electrolyte shows high ionic conductivity (9.55 × 10⁻⁴ S cm⁻¹ at 30 °C), high Li⁺ transference number (0.68), and good electrochemical stability. As a result, the assembled LiFePO₄ || Li full cells based on the designed DES‐ETPTA electrolyte deliver a high reversible capacity and capacity retention at −10 °C and room temperature. Furthermore, considering the compatibility with high‐voltage layered oxide cathode, the electrochemical stability of the ETPTA is further improved through the decoration of cyanoacrylate (CA) with strong electron‐withdrawing characteristic of C≡N. Consequently, the constructed 4.5 V LiCoO₂ || Li full cells using DES‐ETPTA‐CA electrolyte deliver a high reversible capacity of 144 mAh g⁻¹ and a superior retention rate of 93% after 200 cycles at 0.5 C. This work paves a new pathway to design high‐safety and high‐voltage solid polymer electrolytes for lithium metal batteries.