Dynamic Covalent Frameworks for Lithium Anode Protection: From Bonding Chemistry to Interface Engineering

ABSTRACT Lithium metal batteries are severely hindered by interfacial instability issues such as dendrite growth, unstable solid electrolyte interphase, and volume expansion. Crystalline dynamic covalent frameworks have emerged as a promising class of artificial solid electrolyte interphase materials to address these challenges, owing to their unique combination of reversible bond chemistry and ordered pore architectures. This synergy enables these frameworks to homogenize Li + flux, suppress dendrite penetration, accommodate volume changes, and even impart self‐healing capabilities. This review provides a comprehensive overview of recent advances in crystalline dynamic covalent frameworks for lithium anode protection, organized according to four representative dynamic covalent linkages: imine, boronate ester, N→B dative, and disulfide bonds. This review systematically discusses key design principles, including lithophile site engineering, pore structure, dynamic bond chemistry utilization, and framework processability. Finally, this review points out the current challenges and looks ahead to future directions, including multi‐dynamic hybrid frameworks, the design of processable solutions, machine learning to accelerate discovery, and intelligent stimulus‐response interfaces, all aimed at inspiring the development of high‐performance lithium metal anode protective layers.