Contaminant-to-Protection: In Situ Built Tri-Component Barrier Enables Ultralong-Cycling NASICON-Based Sodium Metal Batteries

Abstract

NASICON-type Na₃Zr₂Si₂PO₁₂ (NZSP) is a promising electrolyte for solid-state sodium battery due to its high ionic conductivity and wide electrochemical window. Unfortunately, the sodiophobicity of NZSP leads to extremely poor interfacial contact, which represents a substantial hindrance to its practical application. Herein, a “one stone two birds” strategy is proposed to decompose the contamination layer of NZSP and form a super-sodiophilic and electron-blocking hybrid interlayer consisting of Na₃Sb alloy, NaCl and Na₂O. The hybrid interlayer can not only improve the wettability of NZSP to Na and promote the rapid migration of Na⁺ ions, but also effectively prevent the electron from intruding into the electrolyte at the interface and inhibit the growth of dendrites. Consequently, a dendrite-free sodium plating/stripping can be achieved even at critical current densities as high as 1.4 mA cm⁻² and the sodium symmetric cell can be stably cycled for more than 3600 h at 0.5 mA cm⁻²/0.5 mAh cm⁻². In addition, the solid-state full cell coupled with the Na₃V₂(PO₄)₃ cathode delivers capacities of 103.3 mAh g⁻¹ under 0.5 C for 300 cycles at room temperature. This work offers an effective and innovative strategy to address the interfacial issues of solid-state sodium metal batteries.

Keywords

hybrid interlayer / interface engineering / NASICON electrolytes / Sb₄O₅Cl₂ / solid-state sodium metal batteries

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