Supramolecular Mineralization Strategy for Engineering Covalent Organic Frameworks with Superior Zn-I2 Battery Performances

Construction of covalent organic frameworks (COFs) with fine-tuning pore structures and crystalline orientations at the nano-/meso-scale is vital for their potential applications, but common synthesis routes for COFs always result in the unpredictable nucleation growth and aggregation of small crystals with arbitrary orientations and geometries. Here, we develop a supramolecular mineralization strategy for controllable fabrication of semiconducting COF nanoarchitectures by pre-assembly and subsequent in situ covalent locking of supramolecules. This strategy allows us to change the dynamic covalent chemistry reaction path by reducing the entropy of the system, thus facilitating control over the growth and crystallization of COFs on demand (including 1D, 2D, etc.). The tailor-made COF can effectively suppress the shuttle effect and accelerate the conversion of polyiodide through strong intrinsic electron-pair induce interactions, thereby delivering an outstanding performance in zinc-iodine batteries. The studies create a link between supramolecular chemistry and polymer science for the controllable construction of COF and supramolecular materials.