Energetically preferred Li+ ion jump processes in crystalline solids: Site-specific hopping in β-Li3VF6 as revealed by high-resolution 6Li 2D EXSY NMR

The visualization of atomic or ionic jump processes on the Ångström length scale is important to identify the preferred diffusion pathways in solid electrolytes for energy storage devices. Two-dimensional high-resolution 6Li nuclear magnetic resonance (NMR) spectroscopy is highly suited to yield unprecedented site-specific insights into local Li+ exchange processes within a single measurement. Here, the beta-modification of Li3VF6 is used as a model system for such an investigation as it provides a range of important Li+ geometric environments in one and the same crystal structure useful to elucidate qualitatively a ranking of energetic preferences of the Li+ exchange processes. In Li3VF6 the Li+ ions are subject to diffusive exchange processes among five crystallographically and magnetically inequivalent Li sites: LiFn (n = 6, 4). By using a sample with a natural concentration of the 6Li isotope, we suppressed unwanted spin-diffusion processes and visualized the various exchange processes on the ms time scale. We were able to verify the following ranking experimentally: Li+ ion jumps between face-shared polyhedra are preferred, followed by Li+ exchange between edge-shared configurations for which interstitial sites are needed to jump from site to site. Surprisingly, Li+ exchange between corner-shared polyhedra and Li+ hopping involving almost isolated LiF4 polyhedra do contribute to overall Li+ self-diffusion as well. In this sense, the current study experimentally verifies current predictions by theory but also extends our understanding of ion dynamics between corner-shared Li-bearing polyhedra

Direct Assessment of Ultralow Li+ Jump Rates in Single Crystalline Li3N by Evolution-Time-Resolved 7Li Spin-Alignment Echo NMR

Diffusion processes of small cations and anions play important roles in many applications such as batteries and sensors. Despite the enormous progress we have witnessed over the past years in characterizing the irregular movement of ions such as Li+, new methods able to sharpen our view and understanding of fast and slow diffusion phenomena are steadily developed. Still, very few techniques are, however, available to directly sense extremely slow Li+ diffusion processes. Here, we took advantage of 1D evolution-time resolved 7Li spin-alignment echo NMR that is able to probe the extremely slow interlayer Li+ hopping process in layer-structured Li3N, which served as a model substance for our purposes. The use of single crystals enabled us to study this translational process without being interfered by the fast intralayer Li+ motions. At 318 K the corresponding jump rate of interlayer dynamics turned out to be in the order of 2500(200) s−1 resulting in a diffusion coefficient as low as 1×10−17 m2 s−1, which is in excellent agreement with results from literature. The method, comparable to 1D and 2D NMR exchange spectroscopy, relies on temporal fluctuations of electric interactions the jumping ions are subjected to. 7Li single crystal 1D SAE NMR offers new opportunities to precisely quantify slow Li+ diffusion processes needed to validate theoretical models and to develop design principles for new solid electrolytes

Broadband impedance spectroscopy of Li4Ti5O12: from nearly constant loss effects to long-range ion dynamics

Li4Ti5O12 (LTO) is known as one of the most robust and long-lasting anode materials in lithium-ion batteries. As yet, the Li-ion transport properties of LTO are, however, not completely understood. Here, we used broadband impedance spectroscopy spanning a wide temperature range to investigate the full electrical response of LTO over a wide frequency range. It turned out that the isotherms recorded entail information about two relaxation processes. While at high temperatures the isotherms show a frequency independent plateau that corresponds to poor long-range ion transport (<10−11 S cm−1 (298 K), 0.79 eV), they reveal a second region, seen at lower temperatures and higher frequencies, which we attribute to short-range ion dynamics (10−8 S cm−1) with a significantly reduced activation energy of ca. 0.51 eV. At even lower temperatures, the isotherms are fully governed by nearly constant loss behavior, which has frequently been explained by cage-like dynamics. The present results agree with those earlier presented by 7Li NMR spin-lattice relaxation measurements being sensitive to dynamic processes taking place on quite different length scales. Our findings unveil complex Li+ ion dynamics in LTO and help understand its superior electrochemical properties

Ion dynamics in Al-Stabilized Li7La3Zr2O12 single crystals – Macroscopic transport and the elementary steps of ion hopping

Li7La3Zr2O12 (LLZO) garnet-type ceramics are considered as very promising candidates for solid electrolytes and have been extensively studied in the past few years. Several studies report on an increase in ionic conductivity by doping with ions, such as Al3+ and Ga3+, to stabilize the cubic modification of LLZO. Unfortunately, so far ion dynamics have mainly been studied using powdered samples. Such studies may suffer from chemical heterogeneities concerning Al distribution. Here, we took advantage of Al-stabilized LLZO single crystals to throw light on the elementary steps of ion hopping. We used 7Li nuclear magnetic resonance (NMR) spin-lattice relaxation measurements and conductivity spectroscopy to probe dynamic parameters from both a microscopic and macroscopic point of view. At 293 K the total conductivity turned out to be 0.082 mS cm−1, which is remarkably good for LLZO exhibiting an Al-content of only 0.37 wt%. Most importantly, 7Li NMR spin-lock transients revealed two overlapping diffusion-induced processes. Overall, activation energies from spin-lock NMR excellently agree with that from conductivity measurements; both techniques yield values around 0.36 eV. The corresponding diffusion coefficients deduced from NMR and conductivity measurements almost coincide. The magnetic spin fluctuations sensed by NMR provide an in-depth look at the elementary jump processes, which can barely be revealed by macroscopic impedance spectroscopy providing average values. In particular, we were able to precisely measure the local hopping barrier (0.20 eV) characterizing forward-backward jumps between the sites 24d and 96h. © 2019 The Author(s

High Li+ and Na+ Conductivity in New Hybrid Solid Electrolytes based on the Porous MIL-121 Metal Organic Framework

Solid-state electrolytes (SSEs) can leapfrog the development of all-solid-state batteries (ASSBs), enabling them to power electric vehicles and to store renewable energy from intermittent sources. Here, a new hybrid Li+ and Na+ conducting SSE based on the MIL-121 metal-organic framework (MOF) structure is reported. Following synthesis and activation of the MOF, the free carboxylic units along the 1D pores are functionalized with Li+ or Na+ ions by ion exchange. Ion dynamics are investigated by broadband impedance spectroscopy and by Li-7 and Na-23 NMR spin-lattice relaxation. A crossover at 50 degrees C (Li+) and at 10 degrees C (Na+) from correlated to almost uncorrelated motion at higher temperature is observed, which is in line with Ngai\u27s coupling model. Alternatively, in accordance to the jump relaxation model of Funke, at low temperature only a fraction of the jump processes are successful as lattice rearrangement in the direct vicinity of Li+ (Na+) is slow. H-1 NMR unambiguously shows that Li+ is the main charge carrier. Conductivities reach 0.1 mS cm(-1) (298 K, Na+) while the activation energies are 0.28 eV (Li+) and 0.36 eV (Na+). The findings pave the way towards development of easily tunable and rationally adjustable high-performance MOF-based hybrid SSEs for ASSBs

Evaluation of the MOCAGE Chemistry Transport Model during the ICARTT/ITOP Experiment

We evaluate the Meteo-France global chemistry transport 3D model MOCAGE (MOdele de Chimie Atmospherique a Grande Echelle) using the important set of aircraft measurements collected during the ICARRT/ITOP experiment. This experiment took place between US and Europe during summer 2004 (July 15-August 15). Four aircraft were involved in this experiment providing a wealth of chemical data in a large area including the North East of US and western Europe. The model outputs are compared to the following species of which concentration is measured by the aircraft: OH, H2O2, CO, NO, NO2, PAN, HNO3, isoprene, ethane, HCHO and O3. Moreover, to complete this evaluation at larger scale, we used also satellite data such as SCIAMACHY NO2 and MOPITT CO. Interestingly, the comprehensive dataset allowed us to evaluate separately the model representation of emissions, transport and chemical processes. Using a daily emission source of biomass burning, we obtain a very good agreement for CO while the evaluation of NO2 points out incertainties resulting from inaccurate ratio of emission factors of NOx/CO. Moreover, the chemical behavior of O3 is satisfactory as discussed in the paper

A hierarchical and modular approach to the discovery of robust associations in genome-wide association studies from pooled DNA samples

[Background] One of the challenges of the analysis of pooling-based genome wide association studies is to identify authentic associations among potentially thousands of false positive associations. [Results] We present a hierarchical and modular approach to the analysis of genome wide genotype data that incorporates quality control, linkage disequilibrium, physical distance and gene ontology to identify authentic associations among those found by statistical association tests. The method is developed for the allelic association analysis of pooled DNA samples, but it can be easily generalized to the analysis of individually genotyped samples. We evaluate the approach using data sets from diverse genome wide association studies including fetal hemoglobin levels in sickle cell anemia and a sample of centenarians and show that the approach is highly reproducible and allows for discovery at different levels of synthesis. [Conclusion] Results from the integration of Bayesian tests and other machine learning techniques with linkage disequilibrium data suggest that we do not need to use too stringent thresholds to reduce the number of false positive associations. This method yields increased power even with relatively small samples. In fact, our evaluation shows that the method can reach almost 70% sensitivity with samples of only 100 subjects.Supported by NHLBI grants R21 HL080463 (PS); R01 HL68970 (MHS); K-24, AG025727 (TP); K23 AG026754 (D.T.)