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Volume 116
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Interfacial regulation and cycling performance of PVDF@NZSPO composite solid electrolyte for sodium metal batteries
Jing Zhang a b 1, Haiqiang Bai a 1 *, Jingwen Huang a c, Ling Kang a c, Lei Ai d, Rui Ding a b, Xiaohua Wang a b, Yunhua Xu a c
a College of New Energy, Yulin University, Yulin, 719000, China
b School of Chemistry and Chemical Engineering, Yulin University, Yulin, 719000, China
c School of Material Science and Engineering, Xi'an University of Technology, Xi'an, 710048, China
d Administrative Committee of Yulin Economic and Technological Development Zone (Yushen Industrial Zone), Yulin, 719000, China
10.1016/j.partic.2026.06.028
Volume 116, September 2026, Pages 240-248
Received 21 May 2026, Revised 19 June 2026, Accepted 24 June 2026, Available online 1 July 2026, Version of Record 10 July 2026.
E-mail: baihaiqiang0107@163.com
Highlights

• NASICON-type NZSPO particles are uniformly incorporated into a PVDF matrix.

• NZSPO particles effectively induce α-to-β phase transition of PVDF.

• A high ionic conductivity of 3.83 × 10−4 S cm−1 and a Na+ transference number of 0.56 are achieved.

• Composite solid electrolyte enables stable cycling of Na//Na symmetric cells for 200 h.


Abstract

Composite solid-state electrolytes (CSSEs) are one of the effective strategies to address the safety hazards of liquid electrolytes and the low ionic conductivity of polymer electrolytes. However, the mismatch in ion transport capability between the inorganic filler and the polymer matrix often leads to uneven Na flux distribution, and the side reactions at the electrolyte/electrode interface easily induce sodium dendrite growth. To address these issues, this work designs a solid-state electrolyte by incorporating NASICON-type Na3Zr2Si2PO12 (NZSPO) particles into a poly (vinylidene fluoride) (PVDF) matrix. This design effectively promotes homogeneous Na migration, enabling the optimized PN@NZSPO-30% CSSE to achieve an ionic conductivity of 3.83 × 10−4 S cm−1 and a Na transference number of 0.56 at room temperature. Meanwhile, the PVDF matrix forms a stable interfacial structure upon contact with the sodium metal anode, effectively suppressing dendrite growth. The Na//PN@NZSPO-30%//Na symmetric cell achieves stable cycling for 50 to 200 h under different current densities, and the Na//PN@NZSPO-30%//NVP full cell exhibits a capacity retention of 95.8% after 100 cycles at 1 C, along with excellent rate reversibility in the range of 0.1-1 C. This study provides a new approach for constructing solid-state sodium metal batteries with high performance and suppressed sodium dendrite growth.

Graphical abstract
Keywords
Composite solid-state electrolyte; Polyvinylidene fluoride; NASICON; Sodium metal battery; Ionic conductivity; Interfacial stability
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