Probing the ionic structure of FLiNaK–ZrF4 salt mixtures by solid-state NMR
In this study, by applying 19F, 23Na and 7Li high-resolution NMR methods, the evolution of the [ZrxFy]4x−y local ionic structures in FLiNaK–ZrF4 salt mixtures were elucidated. K3ZrF7, Na3ZrF7 and Na7Zr6F31 crystal phases were identified when the melt salts were being solidified. The distribution of these [ZrxFy]4x−y species was dependent on the content of ZrF4 in FLiNaK eutectic salts. Moreover, K3ZrF7 phase transition from an orthorhombic lattice into a disordered cubic lattice was clarified, thereby causing dynamics of the coordinated F− ions to be reduced and the well-ordered crystal lattices to be destroyed. These mentioned results provide a further insight into the Zr–F based ionic structure and the formation of the disordered Zr–F structure in ZrF4-based eutectic salts.
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