This study introduces a Na⁺ fluorinated halide nanocomposite solid electrolyte (HNSE), ZrO₂-2Na₂ZrCl₅F, synthesized through a mechanochemical reaction using Na₂O. This HNSE exhibits a substantial improvement in Na⁺ conductivity (2.1 × 10^–5 S cm^–1 at 30 °C) compared to Na₂ZrCl₅F (2.0 × 10^–7 S cm^–1). The significant reduction in ionic conductivity of Na₂ZrCl₅F relative to Na₂ZrCl₆ (2.0 × 10^–5 S cm^–1) is elucidated through synchrotron pair distribution function (PDF) analysis. Structural insights, including the fine structure of the ZrO₂ nanograins embedded in an amorphous Na₂ZrCl₅F matrix and the potential O-substituted interphase, are revealed through X-ray absorption spectroscopy, PDF, and cryogenic transmission electron microscopy. Fluorinated HNSEs offer exceptional electrochemical oxidative stability up to 5 V (vs Na/Na⁺), enabling high-voltage cathode applications. Na_0.66Ni_0.1Co_0.1Mn_0.8O₂||Na₃Sn all-solid-state cells using ZrO₂-2Na₂ZrCl₅F as the catholyte demonstrate enhanced performance at 30 °C compared to cells using Na₂ZrCl₆ (47.4% capacity retention after 100 cycles vs 35.3% using Na₂ZrCl₆).

中文翻译：

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扩展用于 5 V 级全固态钠离子电池的 Na+ 卤化物纳米复合固体电解质的电化学窗口

本研究介绍了一种Na ⁺氟化卤化物纳米复合固体电解质（HNSE）ZrO ₂ -2Na ₂ ZrCl _{5 F，它是通过使用Na 2} O的机械化学反应合成的。这种HNSE表现出Na ⁺电导率的显着改善（2.1 × 10 ^–5 S cm ^{–1 (30 °C)) 与 Na} ₂ ZrCl ₅ F (2.0 × 10 ^–7 S cm ^–1 )相比。通过同步加速器对分布函数 (PDF) 分析，阐明了Na ₂ ZrCl ₅ F 的离子电导率相对于 Na ₂ ZrCl ₆ (2.0 × 10 ^–5 S cm ^–1 )显着降低。通过 X 射线吸收光谱、PDF 和低温透射电子显微镜揭示了结构见解，包括嵌入无定形 Na ₂ ZrCl _{5 F 基质中的 ZrO 2}纳米颗粒的精细结构和潜在的 O 取代中间相。氟化 HNSE 具有高达 5 V（相对于 Na/Na ⁺）的出色电化学氧化稳定性，可实现高压阴极应用。使用 ZrO ₂ -2Na ₂ ZrCl ₅ F 作为阴极电解液的Na _0.66 Ni _0.1 Co _0.1 Mn _0.8 O ₂ ||Na ₃ Sn 全固态电池与使用 Na ₂ ZrCl _{6 的}电池相比，在 30 °C 时表现出更高的性能（47.4 100次循环后的容量保留百分比与使用Na ₂ ZrCl ₆的35.3%相比。