Publication date: 10th April 2024
All solid-state fluoride ion batteries are promising and suitable for electric vehicles and grid storage due to their high energy density. The use of very high fluoride ion conducting solid electrolyte is necessary to achieve the potential of fluoride ion batteries. Various fluoride ion conducting solid electrolytes in the tysonite, and fluorite structured systems are under development. Among these fluoride ion conducting solid electrolytes the fluorite structured materials especially PbSnF4 system shows high ionic conductivity at ambient temperatures (~10-3 Scm-1). Similar to PbSnF4, the barium variant (BaSnF4) which exists in the same structure as PbSnF4, also shows conductivity in the order of 10-4 Scm-1 at room temperatures. In recent years, further increase in conductivity has been achieved by varying the barium to tin ratio. Especially, the solid solutions Ba1-xSnxF4 prepared by mechanical milling technique (x=0.5-0.57) with Sn rich ratio shows ionic conductivity nearly in order of 10-2 Scm-1 at room temperature. Therefore, we have studied the fluoride ion diffusion coefficient in this system since the diffusion coefficient plays a vital role in the mass transfer during battery operation. In the present work, the 19F diffusion coefficient in Ba1-xSnxF4 solid solution with high ionic conductivity has been studied using 19F pulsed field gradient nuclear magnetic resonance Spectroscopy (PFG-NMR). The fluoride ion diffusion coefficient is found to be in the order of 10-12 m2s-1 at room temperature. Further, we have investigated the fluoride ion conduction mechanism in Ba1-xSnxF4 by comparing the diffusion coefficient measured by 19F PFG-NMR and calculated from ac impedance measurements and the results will be discussed in detail.
This presentation is based on results obtained from a project, JPNP21006, commissioned by the New Energy and Industrial Technology Development Organization (NEDO), Japan.
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