Confining Li⁺ Solvation in Core-Shell Metal-Organic Frameworks for Stable Lithium Metal Batteries at 100 °C.

The practical deployment of lithium metal batteries remains severely constrained, especially under elevated temperatures. Although metal-organic frameworks (MOFs) improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores, interparticle voids between MOF particles readily absorb liquid electrolyte, obscuring our understanding of the intrinsic role of nanopores in directing Li⁺ transport. To address this challenge, we introduce a one-dimensional (1D) MOF model architecture that eliminates interparticle effects and enables direct observation of Li⁺ solvation and de-solvation dynamics. Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors, supported by both experimental measurements and neural network potential-based molecular dynamics simulations. Building on these insights, we construct a hierarchical core-shell MOF architecture by integrating ZIF-8 (core) and HKUST-1 (shell) onto a hybrid fiber scaffold. This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways, directional Li⁺ conduction, and improved thermal and electrochemical resilience.