Lithium–sulfur (Li–S) batteries hold significant
promise as rechargeable energy storage systems due to their exceptionally
high theoretical specific capacity and energy density. However, the
widespread adoption of Li–S batteries has been impeded by challenges
such as the diffusion of long-chain polysulfides and the formation
of lithium dendrites when organic liquid electrolytes. To address
these problems, a composite polymer electrolyte reinforced with Li6.28La3Al0.24Zr2O12 nanofiber (LLAZO NF) was developed. This electrolyte, featuring
a garnet nanofiber filler within a PEO-based polymer system, exhibited
superior ionic conductivity. The well-interconnected organic–inorganic
network facilitated rapid and uninterrupted pathways for lithium-ion
conduction, achieving a high Li-ion transference number. The incorporation
of LLAZO NFs not only enhanced the electrochemical stability and mechanical
properties of the composite polymer electrolyte, effectively mitigating
lithium dendrite formation, but also contributed to the suppression
of polysulfide diffusion during cycling. As a result, the all-solid-state
Li–S battery utilizing this garnet-type composite polymer electrolyte
demonstrated robust cycling stability and excellent rate performance
at room temperature.