Heterogeneity-Segment Charge-Induced-Coupling Catalysis of Component-Selective-Type Covalent Organic Frameworks Interface toward Stabilizing Lithium Metal Anode.

Serialized lithium traveling on the solid electrolyte interphase (SEI) of the metal anode plays a dominant role in high-energy-density lithium metal batteries. Unsatisfactorily, irregular native SEI suffers from the Li local deposition and possesses low inorganic component content, which exacerbates the growth of lithium dendrites and leads to poor battery performance. Purposefully, we fabricated the porphyrin-based covalent organic frameworks (COF-366 and COF-367) as lithium metal anode interfaces. Concretely, heterogenetic segments within COFs nodes allocate electron situations to induce component-selective catalysis, of which electron-rich nitrogen atom sites urge the N-S cleavage of bis(trifluoromethylsulfonyl)azanide (TFSI) and C-C breakage of 1,2-dimethoxyethane (DME), while electron-deficient benzene sites facilitate the C-O cleavage of 1,3-dioxolane (DOL), constructing a rich LiO/LiF-rich modification of COFs interface. The well-constructed interface facilitates rapid Li migration, distributes charge evenly, and further increases the Li flux, which achieves uniform Li deposition and suppresses dendrite growth. Consequently, the COF-366@Li anode displayed outstanding capacity stability at a high current density of 5C after 400 cycles with a capacity of 53.37 mAh g (70.99%). The COF-366@Li||LFP pouch cell further validated its practical application with an impressive capacity of 120.37 mAh g and an excellent capacity retention of 92.42% after 43 cycles with a high cathode loading of 295.2 mg. This study demonstrates the feasibility of heterogeneity-segment of customized-type COFs to induce component-selective charge-coupling catalysis toward electrolytes and manipulate SEI inorganic components for stabilizing lithium metal anode.