Abstract Na based all-solid-state batteries are one of the most promising candidates for large-scale electrochemical energy storage owing to their low cost and outstanding safety properties. The key enabler of this technology is solid electrolyte with sufficiently high ionic conductivity at room temperature. In this work, the design, synthesis, characterization, and testing of a series of novel fast Na-ion conductors, Na4-x-ySn1-xAxS4-yXy with aliovalent cation (P5+/Sb5+) and anion (Cl−/Br−) substitutions of the parent compound Na4SnS4 are reported. The doped samples crystalize in a new phase with space group I41/acd and show ionic conductivities that are one to four orders of magnitude higher than that of undoped Na4SnS4. R. t. conductivity of 0.64 mS cm−1 is achieved in Na3.7Sn0.8Sb0.2S3.9Cl0.1 with a low activation energy of 0.26 eV. Rietveld refinement against high resolution synchrotron X-ray powder diffraction data reveals that the distribution of the doping ions and the resulted Na vacancies are underlying causes of the enhanced conductivity.

中文翻译：

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Na4SnS4 阴离子和阳离子共掺杂作为钠超离子导体

摘要 钠基全固态电池由于其低成本和出色的安全性能而成为最有前途的大规模电化学储能候选者之一。该技术的关键推动因素是在室温下具有足够高离子电导率的固体电解质。在这项工作中，设计、合成、表征和测试了一系列具有异价阳离子 (P5+/Sb5+) 和阴离子 (Cl−/Br−) 的新型快速 Na 离子导体 Na4-x-ySn1-xAxS4-yXy报告了母体化合物 Na4SnS4 的取代。掺杂的样品在具有 I41/acd 空间群的新相中结晶，并显示出比未掺杂的 Na4SnS4 高一到四个数量级的离子电导率。R.T. 在 Na3.7Sn0.8Sb0.2S3.9Cl0.1 中实现了 0.64 mS cm-1 的电导率，具有 0.26 eV 的低活化能。