Lithium aluminium titanium phosphate (LATP) belongs to one of the most promising solid electrolytes.Besides sufficiently high electrochemical stability, its use in lithium-based all-solid-state batteries crucially depends on the ionic transport properties. While many impedance studies can be found in literature that report on overall ion conductivities, a discrimination of bulk and grain boundary electrical responses via conductivity spectroscopy has rarely been reported so far. Here, we took advantage of impedance measurements that were carried out at low temperatures to separate bulk contributions from the grain boundary responses. It turned out that bulk ion conductivity is by at least three orders of magnitude higher than ion transport across the grain boundary regions. At temperatures well below ambient long-range Li ion dynamics is governed by activation energies ranging from 0.26 to 0.29 eV depending on the sintering conditions. As an example, at temperatures as low as 173 K, the bulk ion conductivity, measured in N 2 inert gas atmosphere, is in the order of 8.1 Â 10 À6 S cm À1 . Extrapolating this value to room temperature yields ca. 3.4 Â 10 À3 S cm À1 at 293 K. Interestingly, exposing the dense pellets to air atmosphere over a long period of time causes a significant decrease of bulk ion transport.This process can be reversed if the phosphate is calcined at elevated temperatures again.
The development of all-solid-state electrochemical energy storage systems, such as lithiumion batteries with solid electrolytes, requires stable, electronically insulating compounds with exceptionally high ionic conductivities. Considering oxides, garnet-type Li7La3Zr2O12 and derivatives, see Zr-exchanged Li6La3ZrTaO12 (LLZTO), have attracted great attention because of its high Li + ionic conductivity of up to 1 mS · cm −1 . Despite numerous studies focusing on conductivities of powder samples, only a few use time-domain NMR methods to probe Li ion diffusion parameters in single crystals. Here we report, for the first time, on temperature-variable 7 Li NMR relaxometry measurements using both laboratory and spin-lock techniques to probe Li jump rates in monocrystalline Li-bearing garnets. Timedomain NMR offers the possibility to study Li ion dynamics on both the short-range and long-range length scale. The techniques applied yield a fully consistent picture of correlated Li ion jump diffusion in LLZTO; the data perfectly mirror a modified BPP-type relaxation response being based on a Lorentzian-shaped relaxation function. The rates measured could be parameterized with a single set of diffusion parameters. Dynamic information about the elementary jump processes, such as jump rates and activation energies, were extracted from complete diffusion-induced rate peaks that are obtained when the relaxation rate is plotted vs inverse temperature. Results from NMR are completely in line with ion transport parameters derived from conductivity spectroscopy. Acknowledgement. We thank our colleagues at the University of Hannover and the TU Graz for valuable discussions. Financial support by the Deutsche Forschungsgemeinschaft
Diffusive processes are ubiquitous in nature. In solid state physics, metallurgy and materials science the diffusivity of ions govern the functionality of many devices such as sensors or batteries. Motional processes on surfaces, across interfaces or through membranes can be quite different to that in the bulk. A direct, quantitative description of such local diffusion processes is, however, rare. Here, we took advantage of Li longitudinal nuclear magnetic relaxation to study, on the atomic length scale, the diffusive motion of lithium spins in the interfacial regions of nanocrystalline, orthorhombic LiBH. Magnetization transients and free induction decays revealed a fast subset of Li ions having access to surface pathways that offer activation barriers (0.18 eV) much lower than those in the crystalline bulk regions (0.55 eV). These observations make orthorhombic borohydride a new nanostructured model system to study disorder-induced enhancements in interfacial diffusion processes.
Lithium fluoride serves as a model substance to study Li and F hopping processes in a material solely composed of mobile ions with an opposite charge. In its microcrystalline form, it is known to be a very poor ionic conductor. Here, we tried to boost ion dynamics in LiF by taking advantage of size effects and the introduction of structural disorder. Compared to micro-LiF, we observed an increase of the ion conductivity by 2 orders of magnitude for nanocrystalline LiF prepared by high-energy ball milling. A further boost might be achieved in nanocrystalline two-phase systems consisting of LiF and an insulator, such as amphoteric γ-Al 2 O 3 . In such dispersed ionic conductors, percolating conductor/insulator pathways are anticipated enabling the ions to move quickly over long distances. Indeed, for nano-LiF:Al 2 O 3 , another drastic increase of ionic conductivity by 3 orders of magnitude (393 K) is achieved by interface engineering. The activation energy characterizing long-range ion transport is reduced from 0.98 eV (nanocrystalline LiF) to 0.79 eV for (LiF) 0.86 (Al 2 O 3 ) 0.14 . 7 Li nuclear magnetic resonance (NMR) measurements showed that Li + is mainly responsible for this increase seen for nano-LiF:Al 2 O 3 . 27 Al magic angle spinning NMR revealed that pentacoordinated Al species act as anchor sites for F − anions (and Li + ). This mechanism is assumed to lead to a 3D network of fast Li + diffusion pathways along the conductor/insulator interfaces.
In this paper the influence of different feedback (FB) and synchronization schemes on the timing phase noise (TPN) power spectral density (PSD) of a quantum-dot based passively mode-locked laser (MLL) is studied numerically and by experiments. The range of investigated schemes cover hybrid mode-locking, an opto-electrical feedback configuration, an all-optical feedback configuration and optical pulse train injection configuration by means of a master MLL. The mechanism responsible for TPN PSD reduction in the case of FB is identified for the first time for monolithic passively MLL and relies on the effective interaction of the timing of the intra-cavity pulse and the time-delayed FB pulse or FB modulation together with an statistical averaging of the independent timing deviations of both. This mechanism is quantified by means of simulation results obtained by introducing an universal and versatile simple time-domain model.
Crystalline ion conductors exhibiting fast ion dynamics are of utmost importance for the development of, e.g., sensors or rechargeable batteries. In some layer-structured or nanostructured compounds fluorine ions participate in remarkably fast self-diffusion processes. As has been shown earlier, F ion dynamics in nanocrystalline, defect-rich BaF 2 is much higher than that in the coarse-grained counterpart BaF 2 . The thermally metastable fluoride (Ba,Ca)F 2 , which can be prepared by joint high-energy ball milling of the binary fluorides, exhibits even better ion transport properties. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19 F nuclear magnetic resonance (NMR) spin-lattice relaxation is sensitive. The present paper aims at understanding ion dynamics in metastable, nanocrystalline (Ba,Ca)F 2 by correlating short-range ion hopping with long-range transport properties. Variable-temperature NMR line shapes clearly indicate fast and slow F spin reservoirs. Surprisingly, from an atomic-scale point of view increased ion dynamics at intermediate values of compo-sition is reflected by increased absolute spin-lattice relaxation rates rather than by a distinct minimum in activation energy. Hence, the pre-factor of the underlying Arrhenius relation, which is determined by the number of mobile spins, the attempt frequency and entropy effects, is identified as the parameter that directly enhances short-range ion dynamics in metastable (Ba,Ca)F 2 . Concerted ion migration could also play an important role to explain the anomalies seen in NMR spin-lattice relaxation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.