The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na₂O₂–MCl_y, M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na₂O₂–MCl_y electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm⁻¹, wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na₂O₂–HfCl₄ electrolyte and a Na_0.85Mn_0.5Ni_0.4Fe_0.1O₂ cathode exhibit a superior rate capability and long-term cycle stability, with 78% capacity retention after 700 cycles under 0.2 C (1C = 120 mA g⁻¹) at room temperature. The discoveries in this work could trigger a new wave of enthusiasm for exploring new superionic conductors beyond those based on a single-anion framework.

钠 （Na） 超离子导体是可能彻底改变传统钠离子电池能量密度和安全性的关键部件。然而，现有的 Na 超离子导体主要基于单阴离子框架，每种导体都存在固有的优点和缺点。在这里，我们介绍了一个基于氯氧双阴离子框架的非晶态钠离子导体（Na₂O 2-MCl_y、M = Hf、Zr 和 Ta）。得益于双阴离子化学和由此产生的独特结构，Na₂O 2-MCl_y 电解质表现出高达 2.0 mS ^cm-1 的室温离子电导率、较宽的电化学稳定性窗口和理想的机械性能。采用非晶态 Na₂O 2-HfCl₄ 电解质和 Na_0.85Mn_{0.5 Ni 0.4}Fe_0.1O₂ 阴极的全固态钠离子电池表现出卓越的倍率能力和长期循环稳定性，在 0.2 C 下循环 700 次后容量保持率为 78% （1C = 120 mA ^g-1） 在室温下。这项工作中的发现可能会引发新一轮的热情，以探索基于单阴离子框架的新型超离子导体。