Carving Metal–Organic–Framework Glass Based Solid–State Electrolyte Via a Top–Down Strategy for Lithium–Metal Battery

Abstract Traditional polymer solid electrolytes (PSEs) suffer from low ions conductivity, poor kinetics and safety concerns. Here, we present a novel porous MOF glass gelled polymer electrolyte (PMG‐GPE) prepared via a top‐down strategy, which features a unique three‐dimensional interconnected graded‐aperture structure for efficient ions transport. Comprehensive analyses, including time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), Solid‐state 7Li magic‐angle‐spinning nuclear magnetic resonance (MAS NMR), Molecular Dynamics (MD) simulations, and electrochemical tests, quantify the pore structures, revealing their relationship with ions conductivity that increases and then decreases as macropore proportion rises. The introduced dispersed macropores (17 % fraction) can serve as bridges, connecting adjacent transport units to accelerate ions transport. Taking advantage of the cross‐linked ion‐conductive paths constructed by hierarchical pore structures, the PMG‐GPE achieves a high ions conductivity of 1.9 mS cm−1. Additionally, the robust mechanical properties of PMG‐GPE effectively suppress dendrite growth and penetration, outperforming crystal MOF‐based electrolytes. The prepared Li symmetric batteries with PMG‐GPE demonstrate a high critical current density of 5.1 mA cm−2 (two times higher than crystal MOF‐electrolytes) and stable cycling for over 6000 hours without short circuits. Furthermore, a Li/PMG‐GPE/LFP half‐cell exhibits exceptional capacity retention of 83.12 % after 1400 cycles. These findings highlight the potential of structural design in advancing PSE performance, offering a promising pathway for the commercialization of high‐performance solid‐state batteries.