Why Ammoniated Lithium Borohydrides Liquefy and Resolidify?

Ammonia ($\mathrm{NH_3}$) absorption drives $\mathrm{LiBH_4}\!\cdot\!x\mathrm{NH_3}$ through a re-entrant "solid-liquid-solid" transition: $\mathrm{LiBH_4\cdot NH_3}$ is a well-defined solid ammoniate, compositions near $\mathrm{LiBH_4\cdot 2NH_3}$ are liquid-like or partially liquefied, whereas $\mathrm{LiBH_4\cdot 3NH_3}$ returns to a more rigid, non-liquid ammoniate state. However, the microscopic origin of this unintuitive response remains a long-lasting mystery. Here, we uncover its mechanism. Cross-database analysis identifies borohydrides as a particularly state-diverse and composition-responsive material family. Structure prediction and ab initio molecular simulations reveal that $\mathrm{NH_3}$ progressively replaces $\mathrm{BH_4^-}$ in the Li coordination shell. The liquid-like state emerges not at the highest $\mathrm{NH_3}$ loading but near $x \approx 2$, where Li-N and Li-B coordination modes are strongly mixed, coordination memory is weakest, and the sampled Li-N/N$\cdots$B coordination landscape is broadest. Further ammoniation produces Li-N-dominant coordination and slows $\mathrm{BH_4^-}/\mathrm{NH_3}$ contact renewal, resulting in increased network persistence and recovery of a rigid ammoniate state. Pressure-composition isotherm, $^1\mathrm{H}$ and $^{11}\mathrm{B}$ nuclear magnetic resonance, and Raman measurements support this non-monotonic state evolution and the associated $\mathrm{BH_4^-}/\mathrm{NH_3}$ reorganization. These findings transform ammonia-induced liquefaction from an empirical phase anomaly into a competition among native-network disruption, mixed-coordination frustration, and ligand-built network reconstruction, providing a framework for chemically switching between transport-favouring fluidity and stability-favouring rigidity in hydrogen-rich materials.