Covalent organic frameworks (COFs) are attractive porous crystalline materials with extremely high stability, easy functionalization, and open channels, which are expected to be unique ion conductors/transporters in lithium ion batteries (LIBs). Despite recent advances, low ion conductivity and low transference number, resulting in low charging/discharging rate, low energy density, and short battery life, are the main issues that limit their direct application as solid electrolytes in LIBs. Here, we designed and synthesized a novel polyimide COF, namely, TAPA-PDI-COF, with abundant C=O groups, which has been successfully employed as high-performance solid electrolytes by doping TAPA-PDI-COF and succinonitrile (SN). Both the well-defined nanochannels of COFs and SN confined in the well-aligned channels restricted the free migration of anions, while C=O on COFs and CN groups of SN enhanced Li⁺ transport, thus achieving a high ion conductivity of 0.102 mS cm⁻¹ at 80 °C and a high lithium-ion transference number of 0.855 at room temperature. According to density functional theory (DFT) calculations, Li-ion migration mainly adopted in-plane transport rather than the axial pathway, which may be due to the shorter hopping distances in the planar pathway. The results suggest an effective strategy for the design and development of all-solid-state ionic conductors for achieving high-performance LIBs.

共价有机骨架（COF）是一种有吸引力的多孔晶体材料，具有极高的稳定性、易于功能化和开放通道，有望成为锂离子电池（LIB）中独特的离子导体/转运体。尽管最近取得了进展，但低离子电导率和低迁移数导致充放电速率低、能量密度低和电池寿命短，是限制其作为固体电解质在锂离子电池中直接应用的主要问题。在这里，我们设计并合成了一种新型聚酰亚胺COF，即TAPA-PDI-COF ，具有丰富的C=O基团，通过掺杂TAPA-PDI-COF和丁二腈（SN） ，它已成功用作高性能固体电解质。 COF和SN的明确纳米通道限制在排列良好的通道中，限制了阴离子的自由迁移，而COF上的C=O和SN的CN基团增强了Li ⁺传输，从而实现了0.102 mS cm的高离子电导率80 °C 时为^-1，室温下锂离子迁移数高达 0.855。根据密度泛函理论（DFT）计算，锂离子迁移主要采用平面内传输而不是轴向路径，这可能是由于平面路径中的跳跃距离较短。研究结果提出了设计和开发全固态离子导体以实现高性能锂离子电池的有效策略。