ABSTRACT
Solid electrolytes are at the heart of future energy storage systems. Li-bearing argyrodites are frontrunners in terms of Li+ ion conductivity. Although many studies have investigated the effect of elemental substitution on ionic conductivity, we still do not fully understand the various origins leading to improved ion dynamics. Here, Li6+xP1-xGexS5I served as an application-oriented model system to study the effect of cation substitution (P5+ vs Ge4+) on Li+ ion dynamics. While Li6PS5I is a rather poor ionic conductor (10-6 S cm-1, 298 K), the Ge-containing samples show specific conductivities on the order of 10-2 S cm-1 (330 K). Replacing P5+ with Ge4+ not only causes S2-/I- anion site disorder but also reveals via neutron diffraction that the Li+ ions do occupy several originally empty sites between the Li rich cages in the argyrodite framework. Here, we used 7Li and 31P NMR to show that this Li+ site disorder has a tremendous effect on both local ion dynamics and long-range Li+ transport. For the Ge-rich samples, NMR revealed several new Li+ exchange processes, which are to be characterized by rather low activation barriers (0.1-0.3 eV). Consequently, in samples with high Ge-contents, the Li+ ions have access to an interconnected network of pathways allowing for rapid exchange processes between the Li cages. By (i) relating the changes of the crystal structure and (ii) measuring the dynamic features as a function of length scale, we were able to rationalize the microscopic origins of fast, long-range ion transport in this class of electrolytes.
ABSTRACT
Li6PS5I acts as a perfect model substance to study length scale-dependent diffusion parameters in an ordered matrix. It provides Li-rich cages which offer rapid but localized Li+ translational jump processes. As jumps between these cages are assumed to be much less frequent, long-range ion transport is sluggish, resulting in ionic conductivities in the order of 10-6 S cm-1 at room temperature. In contrast, the site disordered analogues Li6PS5X (X = Br, Cl) are known as fast ion conductors because structural disorder facilities intercage dynamics. As yet, the two extremely distinct jump processes in Li6PS5I have not been visualized separately. Here, we used a combination of 31P and 7Li NMR relaxation measurements to probe this bimodal dynamic behavior, that is, ultrafast intracage Li+ hopping and the much slower Li+ intercage exchange process. While the first is to be characterized by an activation energy of ca. 0.2 eV as directly measured by 7Li NMR, the latter is best observed by 31P NMR and follows the Arrhenius law determined by 0.44 eV. This activation energy perfectly agrees with that seen by direct current conductivity spectroscopy being sensitive to long-range ion transport for which the intercage jumps are the rate limiting step. Moreover, quantitative agreement in terms of diffusion coefficients is also observed. The solid-state diffusion coefficient D σ obtained from conductivity spectroscopy agrees very well with that from 31P NMR (D NMR ≈ 4.6 × 10-15 cm2 s-1). D NMR was directly extracted from the pronounced diffusion-controlled 31P NMR spin-lock spin-lattice relaxation peak appearing at 366 K.
ABSTRACT
High ionic conductivity, electrochemical stability and small interfacial resistances against Li metal anodes are the main requirements to be fulfilled in powerful, next-generation all-solid-state batteries. Understanding ion transport in materials with sufficiently high chemical and electrochemical stability, such as rhombohedral LiZr2(PO4)3, is important to further improve their properties with respect to translational Li ion dynamics. Here, we used broadband impedance spectroscopy to analyze the electrical responses of LiZr2(PO4)3 and Ca-stabilized Li1.4Ca0.2Zr1.8(PO4)3 that were prepared following a solid-state synthesis route. We investigated the influence of the starting materials, either ZrO2 and Zr(CH3COO)4, on the final properties of the products and studied Li ion dynamics in the crystalline grains and across grain boundary (g.b.) regions. The Ca2+ content has only little effect on bulk properties (4.2 × 10-5 S cm-1 at 298 K, 0.41 eV), but, fortunately, the g.b. resistance decreased by 2 orders of magnitude. Whereas, 7Li spin-alignment echo nuclear magnetic resonance (NMR) confirmed long-range ion transport as seen by conductivity spectroscopy, 7Li NMR spin-lattice relaxation revealed much smaller activation energies (0.18 eV) and points to rapid localized Li jump processes. The diffusion-induced rate peak, appearing at T = 282 K, shows Li+ exchange processes with rates of ca. 109 s-1 corresponding, formally, to ionic conductivities in the order of 10-3 S cm-1 to 10-2 S cm-1.
