Porous organic cages (POCs) with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior, yet their feasibility as solid-state electrolytes has never been testified in a practical battery. Herein, we design and fabricate a quasi-solid-state electrolyte (QSSE) based on a POC to enable the stable operation of Li-metal batteries (LMBs). Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC, the resulting POC-based QSSE exhibits a high Li⁺ transference number of 0.67 and a high ionic conductivity of 1.25 × 10⁻⁴ S cm⁻¹ with a low activation energy of 0.17 eV. These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h. As a proof of concept, the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85% capacity retention after 1000 cycles. Therefore, our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems, such as Na and K batteries.

具有永久孔隙率和优异主客体特性的多孔有机笼 （POC） 在调节离子传输行为方面具有巨大潜力，但它们作为固态电解质的可行性从未在实际电池中得到证实。在此，我们设计和制造了一种基于 POC 的准固态电解质 （QSSE），以实现锂金属电池 （LMB） 的稳定运行。得益于 POC 的有序通道和空腔诱导的阴离子捕获效应，所得的基于 POC 的 QSSE 表现出 0.67 的高 Li⁺ 转移数和 1.25 × ^10-4 S ^cm-1 的高离子电导率和 0.17 eV 的低活化能。这些允许均匀的锂沉积和高度可逆的锂电镀/剥离超过 2000 小时。作为概念验证，与基于 POC 的 QSSE 组装的 LMB 表现出极其稳定的循环性能，在 1000 次循环后仍能保持 85% 的容量。因此，我们的工作证明了 POC 作为 LMB 的 SSE 的实际适用性，并且可以扩展到其他储能系统，例如 Na 和 K 电池。