Flexible, solid-state, fiber-network-reinforced composite solid electrolyte for long lifespan solid lithium-sulfurized polyacrylonitrile battery

Solid lithium-sulfur batteries (SLSBs) show potential for practical application due to their possibility for high energy density. However, SLSBs still face tough challenges such as the large interface impedance and lithium dendrite formation. Herein, a high-performance SLSB is demonstrated by using a fiber network reinforced Li_6.75La₃Zr_1.75Ta_0.25O₁₂ (LLZTO) based composite solid electrolyte (CSE) in combination with sulfurized polyacrylonitrile (SPAN) cathode. The CSE consisting of an electrospun polyimide (PI) film, LLZTO ionically conducting filler and polyacrylonitrile (PAN) matrix, which is named as PI-PAN/LLZTO CSE, possesses high room-temperature ionic conductivity (2.75 × 10⁻⁴ S/cm), high Li⁺ migration number (t_Li⁺) of 0.67 and good interfacial wettability. SPAN is utilized due to its unique electrochemical properties: reasonable electronic conductivity and no polysulfides shuttle effect. The CSE enables a highly stable Li plating/stripping cycle for over 600 h and good rate performance. Moreover, the assembled SLSB exhibits good cycle performance of accomplishing 120 cycles at 0.2 C with the capacity retention of 474 mAh/g, good rate properties and excellent long-term cycling stability with a high capacity retention of 86.49% from 15^th to 1,000^th cycles at 1.0 C. This work rationalizes our design concept and may guide the future development of SLSBs.