Pre-oxidized and composite strategy greatly boosts performance of polyacrylonitrile/LLZO nanofibers for lithium-metal...

The active cyano-group in polyacrylonitrile has severe passivation of lithium anode under larger current density, which restricts the wide application of polyacrylonitrile(PAN) in lithium metal batteries. Herein, in order to address the excessive passivation of lithium metal by PAN, inspired by the pre-oxidation of carbon fibers, PAN was pre-oxidized at 230 °C, which transformed part of the cyano group into a more chemically stable cyclized structure. The electrochemical and mechanical properties of the composite solid electrolyte were effectively improved by introducing the fast ionic conductor Li_6.25La₃Zr₂Al_0.25O₁₂ into PAN by electrospinning. The oxidized PAN-based composite solid electrolyte presents high ionic conductivity (3.05 × 10^-3 S·cm^-1) and high lithium transference number of 0.79 at 25 °C, further contributing to a high electrochemical window (5.3 V). The solid-state batteries assembled by Li||10 wt%-LLZAO@230-oxy-PAN||NCM523 behave superb electrochemical performance, delivering a high initial discharge capacity of 157 mAh g^-1 at 0.2 C. After 100 cycles, the capacity retention was 93.3 %, indicating the electrolyte displays great electrochemical stability. This work provides new insights into the structural design of polymer-based high-voltage batteries.