Rechargeable solid-state lithium-oxygen (Li-O₂) batteries are considered promising candidates for next-generation energy storage systems. However, the development of solid-state Li-O₂ batteries has been limited by the lack of solid-state electrolytes (SSEs) with high ionic conductivities and high stability toward air/metal Li. To address this challenge, we report the three-dimensional covalent organic framework (3D COF) CD-COF-Li with a prominent Li-ion conductivity of 2.7 × 10⁻³ S cm⁻¹ as the SSE for Li-O₂ batteries. The ion transport in the porous COFs is clarified through two-dimensional exchange nuclear magnetic resonance spectroscopy (2D-EXSY NMR), which provides a method at the forefront for understanding Li-ion transport in the molecular channel. Solid-state Li-O₂ batteries with CD-COF-Li deliver a high specific capacity (9,340 mAh g⁻¹) and a record cycling life (100 cycles). These findings pave the way for the application of COFs as superior Li-ion conductors in other next-generation solid-state energy storage systems.

可充电固态锂氧 (Li-O ₂ ) 电池被认为是下一代储能系统的有前途的候选者。然而，由于缺乏具有高离子电导率和对空气/金属 Li 的高稳定性的固态电解质 (SSE)，固态 Li-O _{2电池的发展受到限制。}^{为了应对这一挑战，我们报告了具有 2.7 × 10 -3} S cm ^-1的突出锂离子电导率的三维共价有机骨架 (3D COF) CD-COF-Li 作为 Li-O 2的_SSE电池。通过二维交换核磁共振光谱 (2D-EXSY NMR) 阐明了多孔 COF 中的离子传输，这为理解分子通道中的锂离子传输提供了一种最前沿的方法。采用 CD-COF-Li 的固态 Li-O ₂电池具有高比容量 (9,340 mAh g ⁻¹ ) 和创纪录的循环寿命（100 次循环）。这些发现为 COF 作为优质锂离子导体在其他下一代固态储能系统中的应用铺平了道路。