固态钠离子电池 NASICON 电解质纳米颗粒的旋流雾化火焰合成

Swirling Spray Flame Synthesis of NASICON-Type Electrolyte Nanoparticles for Solid-State Sodium Batteries

摘要

NASICON 型 Na₃Zr₂Si₂PO₁₂（NZSP）作为目前全固态钠离子电池最具前途的固态电解质材料，目前仍缺乏可靠的纳米粉体规模化制备方法。本工作采用旋流雾化火焰合成装置规模化制备了 NZSP 电解质纳米颗粒，并通过反应烧结得到了致密的固态电解质。添加 EHA 的 NZSP 颗粒因气相-颗粒相生成机制而具有较大的比表面积和最小约为 10 nm 的颗粒粒径。因不同元素气固转换温度的巨大差异，合成颗粒呈现出核-壳式结构。采用非 NASICON 结构的原粉直接压制成型并反应烧结得到 NASICON 晶相。化学当量的 P 元素添加 EHA 的 NZSP 固态电解质常温（25^∘C）下具有最高的 0.56mS/cm 的离子电导率，并通过掺杂少量 Mg 元素进一步提升至 1.4mS/cm 。旋流雾化火焰合成的固态电解质粉体展现出优良的电化学性能和高产率易放大特性使得其成为拓宽 NZSP 固态电解质应用的极具潜力的合成方法.

Abstract

NASICON-type Na₃Zr₂Si₂PO₁₂（NZSP），as a promising solid electrolyte for all-solid-state sodium bat-teries，still lacks scalable synthesis method.In this work，NZSP electrolyte nanoparticles are synthesized by swirling spray flame synthesis，and then sintered for dense solid electrolytes by reactive sintering method.NZSP nanoparti-cles with 2-ethylhexanoic acid（EHA）added have the largest specific surface area（SSA）and smallest size of about 10 nm for the gas-to-particle formation route.As-synthesized nanoparticles exhibit a core-shell structure due to distinctive gas-to-solid transformation temperature of different elements.The raw as-synthesized non-NASICON structural nanopowders are then directly molded and sintered to form NASICON crystalline after reactive sintering. EHA added NZSP solid electrolyte with stoichiometric P element amount exhibits the highest ionic conductivity of 0.56mS/cm at room temperature（25^∘C），and the conductivity is promoted to 1.4mS/cm with a little Mg element doped.The excellent electrochemical performance of synthesized solid-state electrolyte nanopowders and the high yield and scalability of swirling spray flame synthesis make it a potential synthesis method to expand the applica-tion of NZSP solid electrolyte.

关键词

Na₃Zr₂Si₂PO₁₂ 固态电解质 / 旋流雾化火焰合成 / 离子电导率 / 固态 Na⁺离子电池

Key words

Na₃Zr₂Si₂PO₁₂ solid electrolyte / spray flame synthesis / ionic conductivity / solid-state Na⁺ionic batteries

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基金资助

国家自然科学基金资助项目(52130606)

国家自然科学基金资助项目(52322608)

中国博士后科学基金资助项目(2023M741894)