Abstract: Metal-organic frameworks (MOFs) are intriguing host materials in composite electrolytes due to their ability for tailoring host-guest interactions by chemical tuning of the MOF backbone. Here, we introduce particularly high sodium ion conductivity into the zeolitic imidazolate framework ZIF-8 by impregnation with the sodium-salt-containing ionic liquid (IL) (Na0.1EMIM0.9)TFSI. We demonstrate an ionic conductivity exceeding 2 × 10−4 S · cm−1 at room temperature, with an activation energy as low as 0.26 eV, i.e., the highest reported performance for room temperature Na+-related ion conduction in MOF-based composite electrolytes to date. Partial amorphization of the ZIF-backbone by ball-milling results in significant enhancement of the composite stability towards exposure to ambient conditions, up to 20 days. While the introduction of network disorder decelerates IL exudation and interactions with ambient contaminants, the ion conductivity is only marginally affected, decreasing with decreasing crystallinity but still maintaining superionic behavior. This highlights the general importance of 3D networks of interconnected pores for efficient ion conduction in MOF/IL blends, whereas pore symmetry is a less stringent condition
