The quaternary antimony (Sb)-based sulfide sodium solid electrolyte Na₁₁Sn₂SbS₁₂ with good moisture stability is attractive for practical application in all-solid-state sodium batteries. However, the Na₁₁Sn₂SbS₁₂ exhibits low room temperature ionic conductivity and it is difficult to obtain pure phase due to the limited solubility of Sb in the Na₁₁Sn₂SbS₁₂ crystal structure. Herein, titanium (Ti)-doping Na_11+xSn₂Sb_1-xTi_xS₁₂ (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0) materials are systematically investigated, and the highest room temperature ionic conductivity of 1.01 mS cm⁻¹ is achieved when x = 0.5 (Na_11.5Sn₂Sb_0.5Ti_0.5S₁₂), which is 3 times higher than that of pristine Na₁₁Sn₂SbS₁₂. X-ray diffraction and alternating current impedance analyses reveal that the substitution of Sb with Ti can prevent the formation of the NaSbS₂ impurity, determining high ionic conductivity. Meanwhile, the Na_11.5Sn₂Sb_0.5Ti_0.5S₁₂ demonstrates good air stability with limited H₂S gas evolution. Besides, the activation energy, electronic conductivity and electrochemistry stability window for Na_11.5Sn₂Sb_0.5Ti_0.5S₁₂ are also evaluated. Moreover, a high reversible capacity and stable cyclic performance of TiS₂ based all-solid-state sodium battery using Na_11.5Sn₂Sb_0.5Ti_0.5S₁₂ are demonstrated, showing an initial discharge capacity of 177.6 mAh g⁻¹ at 0.1C with a capacity retention of 83.5% based on the second discharge capacity after 50 cycles at 25 °C.

具有良好湿稳定性的季锑（Sb）基硫化钠固体电解质Na ₁₁ Sn ₂ SbS ₁₂在全固态钠电池的实际应用中具有吸引力。然而，Na ₁₁ Sn ₂ SbS _{12 的}室温离子电导率较低，并且由于Sb在Na ₁₁ Sn ₂ SbS ₁₂晶体结构中的溶解度有限，难以获得纯相。在此，钛 (Ti) 掺杂 Na _{11+ x} Sn ₂ Sb _{1- x} Ti _x S ₁₂ ( x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0) 材料，当x  = 0.5 (Na _11.5 Sn ₂ Sb _0.5 Ti _0.5)时，室温离子电导率最高可达 1.01 mS cm ^-1 S ₁₂ )，比原始 Na ₁₁ Sn ₂ SbS ₁₂高 3 倍。X 射线衍射和交流阻抗分析表明，用 Ti 取代 Sb 可以防止形成 NaSbS ₂杂质，从而确定高离子电导率。同时，Na _11.5 Sn ₂ Sb _0.5Ti _0.5 S ₁₂表现出良好的空气稳定性，且H ₂ S 气体逸出有限。此外，还评估了Na _11.5 Sn ₂ Sb _0.5 Ti _0.5 S ₁₂的活化能、电子电导率和电化学稳定性窗口。此外，使用Na _11.5 Sn ₂ Sb _0.5 Ti _0.5 S ₁₂的TiS ₂基全固态钠电池具有高可逆容量和稳定的循环性能，初始放电容量为177.6 mAh g ^-1 在 0.1C 下，在 25°C 下循环 50 次后，基于第二次放电容量的容量保持率为 83.5%。