Insight into the Isoreticularity of Li-MOFs for the Design of Low-Density Solid and Quasi-Solid Electrolytes

Isoreticularity in metal organic frameworks (MOFs) allows the design of the framework structure and tailoring the pore aperture at the molecular level. The optimal pore volume, long-range order of framework expansion, and crystallite size (grain size) could enable improving Li-ion conduction, thereby providing a unique opportunity to design high-performance solid and quasi-solid electrolytes. However, definitive understanding of the pore aperture, framework expansion, and crystallite size on the Li-ion conduction and its mechanism in MOFs remains at the exploratory stage. Among the different MOF subfamilies, Li-MOFs created by the isoreticular framework expansion using dicarboxylates of benzene, naphthalene, and biphenyl building blocks emerge as low-density porous solids with exceptional thermal stability to study the solid-state Li⁺ transport mechanisms. Herein, we report the subtle effect of the isoreticularity in Li-MOFs on the performance of solid and quasi-solid-state Li⁺ conduction, providing new insight into Li⁺ transport mechanisms in MOFs for the first time. Our experimental and computational results show that the reticular design on an isostructural extended framework structure with the optimal pore aperture and crystallite size can influence the Li⁺ conductivity, exhibiting comparable ionic conductivities to solid polymer electrolytes at room temperature. Aligning with the computational studies, our experimental absorption spectral traces of solid electrolytes prepared by encapsulating lithium salt (LiClO₄) and the plasticizer (ethylene carbonate) with Li-MOFs confirm the participation of the free and bound states of Li⁺ in a pore filling-driven ion conduction mechanism. We postulate that porous channels of Li-MOFs aid free Li⁺ to move through the pores via a vehicle-type mechanism, in which the pore-filled plasticizer acts as a carrier for mobile Li⁺ while the framework's functional sites transport the bound state of Li⁺ via an ion hopping mechanism from one crystallite site to another. Our computational studies performed on the Li⁺ conduction pathway validated the postulated pore filling mechanism and confirmed the involvement of bridging complexes, formed by binding Li⁺ onto the framework's functional sites as well as to the pore-filled ethylene carbonates. The Li⁺ diffusion energy barrier profiles along with the respective conformational changes during the diffusion of Li⁺ in solid electrolytes prepared from Li-BDC MOF and Li-NDC MOF strongly support the cooperative movement of Li⁺ ions via ion hopping along the framework's edges and vehicle-type transfer, involving the pore-filled plasticizer. Our findings suggest that cooperative function of the optimal pore volume, framework expansion, and crystallite size play a unique role in Li-ion conduction, thereby providing design guidelines for the low-density solid and quasi-solid electrolytes.