Solid-state lithium-metal batteries (SSLMBs) have been regarded as one of the most promising battery systems due to their high energy density and excellent safety. However, the low ionic conductivity of solid electrolyte (normally < 1 mS cm⁻¹) does not meet the practical application of SSLMBs. Herein, we propose a vertically-aligned composite solid electrolytes (VA-CSE) with dual Li⁺ transportation paths: one dimensional (1D) Li⁺-transportation highway in lithium montmorillonite (Li-MMT) layer along aligned poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) channels and unique Li⁺ hopping path created by aggregated ions pairs in polymerized vinyl ethylene carbonate-based electrolyte. This Li-MMT/PVDF-HFP solid electrolyte (Li-MPSE) exhibits superionic conductivity of 1.99 mS cm⁻¹ and high lithium transference number (0.73) at 30 °C. With this superior Li-MPSE electrolyte, Li/LiFePO₄ solid-state batteries stably cycle 200 times with 99.7% capacity retention at 0.5 C and pouch cell also presents excellent electrochemical performance and safety.

固态锂金属电池（SSLMB）因其高能量密度和出色的安全性而被认为是最有前途的电池系统之一。然而，固体电解质的低离子电导率（通常<1 mS cm ^-1）不能满足SSLMB的实际应用。^{在此，我们提出了一种具有双Li +}传输路径的垂直排列复合固体电解质（VA-CSE） ：沿排列的聚（偏二氟乙烯-钴）锂蒙脱石（Li-MMT）层中的一维（1D）Li ⁺传输高速公路-六氟丙烯）（PVDF-HFP）通道和独特的Li ⁺由聚合的碳酸乙烯亚乙酯基电解质中聚集的离子对产生的跳跃路径。这种Li-MMT/PVDF-HFP固体电解质（Li-MPSE）在30℃下表现出1.99 mS cm ^{-1的超离子电导率和高锂迁移数（0.73）。}凭借这种卓越的Li-MPSE电解质，Li/LiFePO ₄固态电池可稳定循环200次，在0.5 C下容量保持率为99.7%，软包电池还呈现出优异的电化学性能和安全性。