Solvent‐Free Mechano‐Thermal Synthesis of a Li‐Zn Phosphonate Cathode Framework

A key challenge in synthesizing alkali‐ion metal–organic frameworks (MOFs) lies in the multistep procedures typically required, often involving solvothermal crystallization, desolvation, post‐synthetic alkali‐metalation, and controlled drying. To address this, a solvent‐free mechano‐thermal method is reported that combines solid‐state grinding of precursors with thermal annealing under vacuum. This direct, scalable route offers a more sustainable alternative while enabling stoichiometric precision. We demonstrate this approach for the synthesis of Li 4 ‐Zn‐ p ‐DOBDP_mt (LZP 3 ; p ‐DOBDP 6− = 2,5‐dioxido‐1,4‐benzenediphosphate), in which lithium is incorporated during MOF formation. The resulting material exhibits better crystallinity compared to its conventionally synthesized counterpart and retains its key functional properties, including a reversible capacity of 130 mAhg − 1 at 3.2 V versus Li + /Li and a quasi‐solid‐state ionic conductivity of 10 −6 S cm − 1 at 303 K. These results underscore the viability of solid‐state synthesis for constructing alkali‐ion‐containing organic electrode materials with reduced processing complexity.