Solid Electrolytes Based on Fast Fluorine Ion Motions — 19F T1ρ NMR Relaxation vs Conductivity Measurements of Mechanosynthesized Nanocrystalline Ba0.6La0.4F2.4

The use of mechanosynthesis for the preparation of ion conductors provides access to new compounds whose properties are governed by chemical metastability, defects introduced and size effects present. The benefits of this valuable synthesis method manifest in enhanced ion transport properties of the prepared nanocrystalline ceramics. Such materials are useful candidates to act as solid electrolytes, e.g., in fluorine ion batteries [1]. Here, the introduction of large amounts of La³⁺ into the cubic structure of BaF₂ was carried out by using high-energy ball-milling. The replacement of Ba²⁺ with a trivalent cation leads to the formation of an increased number fraction of point defects in the metastable crystal structure, which resulted in an increase of the dc-conductivity when compared to pure, nano-sized BaF₂ [2]. Until now, only little is known about activation energies and jump rates of the elementary hopping processes of such materials. In the present study, we used broadband impedance spectroscopy and ¹⁹F NMR relaxometry to get to the bottom of ion jump diffusion proceeding on short-range and long-range length scales in Ba_0.6La_0.4F_2.4. The dielectric measurements revealed an activation energy of 0.57 eV for macroscopic ion transport, whilst NMR, which is sensitive to both long-range motion and localized jumps, gave much smaller activation energies [3]. This was confirmed by high-frequency impedance measurements carried out at frequencies as high as 3 GHz that enabled us to compare the results from complementary methods applied in the same time window.

[1] C. Rongeat, M. A. Reddy, R. Witter, and M. Fichtner, J. Phys. Chem. C, 117, 4943 (2013).

[2] A. Düvel, J. Bednarcik, V. Šepelák, and P. Heitjans, J. Phys. Chem. C, in press (2014), DOI: 10.1021/jp410018t.

[3] F. Preishuber-Pflügl, and M. Wilkening, Phys. Chem. Chem. Phys., in press (2014), DOI: 10.1039/C4CP00422A.