Operando characterization and theoretical modeling of metal|electrolyte interphase growth kinetics in solid-state batteries. Part II: Modeling

Understanding the interfacial dynamics of batteries is crucial to control degradation and increase electrochemical performance and cycling life. If the chemical potential of a negative electrode material lies outside of the stability window of an electrolyte (either solid or liquid), a decomposition layer (interphase) will form at the interface. To better understand and control degradation at interfaces in batteries, theoretical models describing the rate of formation of these interphases are required. This study focuses on the growth kinetics of the interphase forming between solid electrolytes and metallic negative electrodes in solid-state batteries. More specifically, we demonstrate that the rate of interphase formation and metal plating during charge can be accurately described by adapting the theory of coupled ion-electron transfer (CIET). The model is validated by fitting experimental data presented in the first part of this study. The data was collected operando as a Na metal layer was plated on top of a NaSICON solid electrolyte (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside an XPS chamber. This study highlights the depth of information which can be extracted from this single operando experiment and is widely applicable to other solid-state electrolyte systems

Operando characterization and theoretical modeling of Metal|Electrolyte interphase growth kinetics in solid-state batteries. Part I: experiments

To harness all of the benefits of solid-state battery (SSB) architectures in terms of energy density, their negative electrode should be an alkali metal. However, the high chemical potential of alkali metals makes them prone to reduce most solid electrolytes (SE), resulting in a decomposition layer called an interphase at the metal|SE interface. Quantitative information about the interphase chemical composition and rate of formation is challenging to obtain because the reaction occurs at a buried interface. In this study, a thin layer of Na metal (Na0) is plated on the surface of an SE of the NaSICON family (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside a commercial X-ray photoelectron spectroscopy (XPS) system while continuously analyzing the composition of the interphase operando. We identify the existence of a solid electrolyte interphase at the Na0|NZSP interface, and more importantly, we demonstrate for the first time that this protocol can be used to study the kinetics of interphase formation. A second important outcome of this article is that the surface chemistry of NZSP samples can be tuned to improve their stability against Na0. It is demonstrated by XPS and time-resolved electrochemical impedance spectroscopy (EIS) that a native NaxPOy layer present on the surface of as-sintered NZSP samples protects their surface against decomposition

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centers. We demonstrate how the single-ion electron paramagnetic resonance $\textbf{g}$ tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the $\textbf{g}$ tensor with density functional theory to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, $\textbf{σ}$$^{s}$. The method is applied to a series of olivine-type Li$\textit{TM}$PO$_{4}$ materials (with $\textit{TM}$=Mn, Fe, Co, and Ni) and the corresponding $^{7}$$\textbf{Li}$ and $^{31}$$\textbf{P}$ NMR spectra are simulated. We analyze the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the Li$\textit{TM}$PO$_{4}$ series, in which the magnitudes and signs of the nonrelativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.RP acknowledges financial support from the People Programme (Marie Curie Ac- tions) of the European Union’s Seventh Framework Pro- gramme (FP7/2007-2013) under REA grant agreement n◦ 317127. Via our membership of the U.K.’s HPC Materials Chemistry Consortium, which is funded by EPSRC (n ◦ EP/L000202), this work made use of the facilities of ARCHER, the U.K.’s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC’s High End Computing Programme. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Lab- oratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract n◦ DE-AC02-98CH10886

Electrophysical properties of nanoporous cerium dioxide–water system

The impedance of nanoporous cerium dioxide with adsorbed water is investigated in the frequency range 103–104 Hz at temperatures near the water–ice phase transition. Here we show that the manifestation of impedance peculiarities at phase transition is caused by the dielectric constant of the matrix

Gold and silver diffusion in germanium: a thermodynamic approach

Diffusion properties are technologically important in the understanding of semiconductors for the efficent formation of defined nanoelectronic devices. In the present study we employ experimental data to show that bulk materials properties (elastic and expansivity data) can be used to describe gold and silver diffusion in germanium for a wide temperature range (702–1177 K). Here we show that the so-called cBΩ model thermodynamic model, which assumes that the defect Gibbs energy is proportional to the isothermal bulk modulus and the mean volume per atom, adequately metallic diffusion in germanium

Impact of uniaxial strain and doping on oxygen diffusion in CeO2

Doped ceria is an important electrolyte for solid oxide fuel cell applications. Molecular dynamics simulations have been used to investigate the impact of uniaxial strain along the directions and rare-earth doping (Yb, Er, Ho, Dy, Gd, Sm, Nd, and La) on oxygen diffusion. We introduce a new potential model that is able to describe the thermal expansion and elastic properties of ceria to give excellent agreement with experimental data. We calculate the activation energy of oxygen migration in the temperature range 900-1900K for both unstrained and rare-earth doped ceria systems under tensile strain. Uniaxial strain has a considerable effect in lowering the activation energies of oxygen migration. A more pronounced increase in oxygen diffusivities is predicted at the lower end of the temperature range for all the dopants considered

sox9b Is a Key Regulator of Pancreaticobiliary Ductal System Development

The pancreaticobiliary ductal system connects the liver and pancreas to the intestine. It is composed of the hepatopancreatic ductal (HPD) system as well as the intrahepatic biliary ducts and the intrapancreatic ducts. Despite its physiological importance, the development of the pancreaticobiliary ductal system remains poorly understood. The SRY-related transcription factor SOX9 is expressed in the mammalian pancreaticobiliary ductal system, but the perinatal lethality of Sox9 heterozygous mice makes loss-of-function analyses challenging. We turned to the zebrafish to assess the role of SOX9 in pancreaticobiliary ductal system development. We first show that zebrafish sox9b recapitulates the expression pattern of mouse Sox9 in the pancreaticobiliary ductal system and use a nonsense allele of sox9b, sox9bfh313, to dissect its function in the morphogenesis of this structure. Strikingly, sox9bfh313 homozygous mutants survive to adulthood and exhibit cholestasis associated with hepatic and pancreatic duct proliferation, cyst formation, and fibrosis. Analysis of sox9bfh313 mutant embryos and larvae reveals that the HPD cells appear to mis-differentiate towards hepatic and/or pancreatic fates, resulting in a dysmorphic structure. The intrahepatic biliary cells are specified but fail to assemble into a functional network. Similarly, intrapancreatic duct formation is severely impaired in sox9bfh313 mutants, while the embryonic endocrine and acinar compartments appear unaffected. The defects in the intrahepatic and intrapancreatic ducts of sox9bfh313 mutants worsen during larval and juvenile stages, prompting the adult phenotype. We further show that Sox9b interacts with Notch signaling to regulate intrahepatic biliary network formation: sox9b expression is positively regulated by Notch signaling, while Sox9b function is required to maintain Notch signaling in the intrahepatic biliary cells. Together, these data reveal key roles for SOX9 in the morphogenesis of the pancreaticobiliary ductal system, and they cast human Sox9 as a candidate gene for pancreaticobiliary duct malformation-related pathologies

Diversity and Functional Traits of Lichens in Ultramafic Areas: A Literature Based Worldwide Analysis Integrated by Field Data at the Regional Scale

While higher plant communities found on ultramafics are known to display peculiar characteristics, the distinguishability of any peculiarity in lichen communities is still a matter of contention. Other biotic or abiotic factors, rather than substrate chemistry, may contribute to differences in species composition reported for lichens on adjacent ultramafic and non-ultramafic areas. This work examines the lichen biota of ultramafics, at global and regional scales, with reference to species-specific functional traits. An updated world list of lichens on ultramafic substrates was analyzed to verify potential relationships between diversity and functional traits of lichens in different Köppen–Geiger climate zones. Moreover, a survey of diversity and functional traits in saxicolous communities on ultramafic and non-ultramafic substrates was conducted in Valle d’Aosta (North-West Italy) to verify whether a relationship can be detected between substrate and functional traits that cannot be explained by other environmental factors related to altitude. Analyses (unweighted pair group mean average clustering, canonical correspondence analysis, similarity-difference-replacement simplex approach) of global lichen diversity on ultramafic substrates (2314 reports of 881 taxa from 43 areas) displayed a zonal species distribution in different climate zones rather than an azonal distribution driven by the shared substrate. Accordingly, variations in the frequency of functional attributes reflected reported adaptations to the climate conditions of the different geographic areas. At the regional scale, higher similarity and lower species replacement were detected at each altitude, independent from the substrate, suggesting that altitude-related climate factors prevail over putative substrate–factors in driving community assemblages. In conclusion, data do not reveal peculiarities in lichen diversity or the frequency of functional traits in ultramafic areas

Sediment source fingerprinting: benchmarking recent outputs, remaining challenges and emerging themes

Abstract: Purpose: This review of sediment source fingerprinting assesses the current state-of-the-art, remaining challenges and emerging themes. It combines inputs from international scientists either with track records in the approach or with expertise relevant to progressing the science. Methods: Web of Science and Google Scholar were used to review published papers spanning the period 2013–2019, inclusive, to confirm publication trends in quantities of papers by study area country and the types of tracers used. The most recent (2018–2019, inclusive) papers were also benchmarked using a methodological decision-tree published in 2017. Scope: Areas requiring further research and international consensus on methodological detail are reviewed, and these comprise spatial variability in tracers and corresponding sampling implications for end-members, temporal variability in tracers and sampling implications for end-members and target sediment, tracer conservation and knowledge-based pre-selection, the physico-chemical basis for source discrimination and dissemination of fingerprinting results to stakeholders. Emerging themes are also discussed: novel tracers, concentration-dependence for biomarkers, combining sediment fingerprinting and age-dating, applications to sediment-bound pollutants, incorporation of supportive spatial information to augment discrimination and modelling, aeolian sediment source fingerprinting, integration with process-based models and development of open-access software tools for data processing. Conclusions: The popularity of sediment source fingerprinting continues on an upward trend globally, but with this growth comes issues surrounding lack of standardisation and procedural diversity. Nonetheless, the last 2 years have also evidenced growing uptake of critical requirements for robust applications and this review is intended to signpost investigators, both old and new, towards these benchmarks and remaining research challenges for, and emerging options for different applications of, the fingerprinting approach