All-solid-state sodium-ion batteries (ASSSIBs) using composite polymer electrolytes (CPEs) are promising candidates for addressing the high cost, safety issues, and limited energy density of traditional lithium-ion batteries. The microstructure and morphology of active ceramic filler and cathode seriously affect the construction of ion/electron transport channels and electrochemical performance, while the contact tightness at the electrode/CPE interface determines the release of energy storage performance in ASSSIBs. Here, NASICON-type Na3.3La0.3Zr1.7Si2PO12 (NLZSP) ceramic nanofibers (NFs) and Na4MnCr(PO4)3@C (NMCP@C) NFs are prepared via electrospinning. NLZSP long NFs (L-NFs) can be uniformly dispersed in PVDF-HFP using ultrasonic treatment to create rapid ion transport pathways within the ceramic and polymer/ceramic interphases, enabling the CPE to achieve high ionic conductivity of 3.36 × 10−4 S·cm−1, wide electrochemical stability window (ESW) exceeding 5 V, low activation energy (Ea) of 0.28 eV and sodium-ion transference number (TNa+) of 0.65 at room temperature. Meanwhile, NMCP@C NFs can enhance electron conductivity and reduce the sodium ion migration path, and finally achieve a superhigh specific capacity (161 mAh·g−1) and energy density (534 Wh·kg−1) at 0.1C. Additionally, the integrated NMCP@C/CPE structure is incorporated into NMCP@C/CPE//Na solid state sodium metal batteries (SMBs), which exhibits excellent rate performance and high capacity retention of 78.8 % at 1C (1.4–4.3 V) and 70.5 % at 0.5C (1.4–4.6 V) after 200 cycles. This study offers valuable insights into constructing high-performance ASSSIBs.
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