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

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 6.25 La 3 Zr 2 Al 0.25 O 12 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.