• • The PEG-mediated asymmetric interchain interaction disrupts the ordered ANF hydrogen-bond network, suppressing inert aggregate formation and enhancing Li+ transport efficiency, as evidenced by stable Li||Li cycling for over 1600 h with low polarization voltage.
• • The composite electrolyte retains a yield stress of 3.25 MPa, ensuring mechanical robustness against lithium dendrite penetration, a critical requirement for safe all-solid-state batteries.
• • In LCO||Li cells at 65 °C, the modified electrolyte delivers 82.7% capacity retention after 300 cycles at 1 C, compared to only 35.5% for the unmodified counterpart, demonstrating a 2.3-fold improvement in cycling stability.
• • Destructive tests on pouch cells (puncturing, cutting) show the LED remains illuminated, confirming enhanced safety and mechanical integrity under physical damage, a key step toward practical applications.