Hard X-ray-induced damage on carbon–binder matrix for in situ synchrotron transmission X-ray microscopy tomography of Li-ion batteries

The electrode of Li-ion batteries is required to be chemically and mechanically stable in the electrolyte environment for in situ monitoring by transmission X-ray microscopy (TXM). Evidence has shown that continuous irradiation has an impact on the microstructure and the electrochemical performance of the electrode. To identify the root cause of the radiation damage, a wire-shaped electrode is soaked in an electrolyte in a quartz capillary and monitored using TXM under hard X-ray illumination. The results show that expansion of the carbon–binder matrix by the accumulated X-ray dose is the key factor of radiation damage. For in situ TXM tomography, intermittent X-ray exposure during image capturing can be used to avoid the morphology change caused by radiation damage on the carbon–binder matrix

Three-Dimensional Reconstruction and Analysis of All-Solid Li-Ion Battery Electrode Using Synchrotron Transmission X-ray Microscopy Tomography

A synchrotron transmission X-ray microscopy tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source was employed to obtain three-dimensional morphological data of all-solid Li-ion battery electrodes. The three-phase electrode was fabricated from a 47:47:6 (wt %) mixture of Li(Ni1/3Mn1/3Co1/3)O2 as active material, Li1.3Ti1.7Al0.3(PO4)3 as Li-ion conductor, and Super-P carbon as electron conductor. The geometric analysis show that particle-based all-solid Li-ion battery has serious contact interface problem which significantly impact the Li-ion transport and intercalation reaction in the electrode, leading to low capacity, poor rate capability and cycle life

Factors driving the biogeochemical budget of the Amazon River and its statistical modelling Facteurs denext term contrôle du bilan biogéochimique previous termdenext term l'Amazone et modélisation statistique associée

International audienceThe seasonal and interannual fluctuations of the biogeochemical budget (solutes, suspended matter, isotopes) of the Amazon River basin were analyzed, with a special focus on 44 physicochemical parameters monitored over the period 1982-1984 during the Carbon in the AMazon River Experiment (CAMREX) project. The relevant factors driving this variability were identified and sorted through the implementation of a statistical-regressive model coupled to variance analysis. Basically, the compositional fluctuations in the Amazon River are related (1) to the variable contribution of major tributaries (variable regional source) to the river flow but also (2) to the variable contribution of hydrological sources, (3) to river processes, i.e. in-stream diagenesis and sediment dynamics and (4) to the hydrological budget of the floodplains. Their respective contributions to the variability of chemical signals observed in the stream waters depend on which parameter was investigated but their combination explains on average 85% of the observed variability. The variability related to regional sources was captured by the compared measures of flow discharge and biogeochemical fluxes at the outlet of the major tributaries. The variability of hydrological sources was described by the variable contribution of three runoffs of distinct but constant composition: forwarded direct runoff, delayed floodplain runoff and baseflow. Several methods were tested to depict the seasonal and interannual variations of their individual discharges. Biologically-mediated processes were related to a hydrobiological index IBIO = [O2]-[CO2] which allows tracking the nature of the dominant ecological regime (autotrophy vs. heterotrophy). The alteration of chemical signals related to the intermittent discharge of the floodplains (where specific processes occur such as: gas exchanges at the air-water interface, sorption of dissolved organic matter, chemical weathering, deposition vs. remobilization of sediments, etc.) was simulated by taking into account the default of hydrological balance between inflows and outflows, used as a marker of floodplains discharge. This analysis shows that the chemical baseline observed in the waters of the Amazon River is mostly acquired upstream from the junction of major tributaries with the Amazon main reach. Les fluctuations saisonnières et interannuelles du bilan biogéochimique (solutés, matière particulaire, isotopes) du fleuve Amazone ont été analysées, avec une attention particulière apportée à 44 paramètres physicochimiques mesurés entre 1982 et 1984 dans le cadre du programme CAMREX. Les facteurs exerçant une influence significative sur cette variabilité ont été identifiés et hiérarchisés par le biais d'un modèle statistique couplé à une analyse previous termdenext term variance. Les variations previous termdenext term composition des eaux previous termdenext term l'Amazone sont fondamentalement associées (1) à previous termlanext term contribution variable previous termdenext term ses affluents majeurs (source régionale variable) au débit total, mais aussi (2) à previous termlanext term contribution variable des pôles previous termdenext term mélange hydrologiques, (3) à des processus fluviaux correspondant au régime hydrobiologique et à previous termlanext term dynamique sédimentaire et (4) au bilan hydrologique des plaines d'inondation. Leurs contributions respectives à previous termlanext term variabilité des signaux chimiques observés dans les eaux du fleuve dépendent du paramètre considéré, mais leur combinaison explique en moyenne 85 % previous termde lanext term variabilité observée. previous termLanext term variabilité associée aux contributions régionales variables est appréhendée en procédant aux bilans entrées-sorties des débits et flux biogéochimiques. previous termLanext term variabilité previous termdenext term contribution des pôles previous termdenext term mélange est décrite par previous termlanext term contribution variable previous termdenext term trois écoulements previous termdenext term compositions distinctes mais constantes : l'écoulement direct à expression précoce, l'écoulement local previous termdenext term vidange alluviale à expression différée et l'écoulement previous termdenext term base. Douze méthodes ont été testées afin previous termdenext term décrire les variations saisonnières et interannuelles des débits individuels previous termdenext term chaque pôle previous termdenext term mélange. Les processus contrôlés par le vivant sont appréhendés à partir d'un indice hydrobiologique IBIO = [O2]-[CO2] qui permet previous termdenext term déterminer previous termlanext term nature du régime hydro-écologique dominant (autotrophe vs. hétérotrophe). L'altération des signaux chimiques générée par previous termlanext term vidange intermittente des plaines d'inondation (au niveau desquelles ont lieu des processus spécifiques : échanges gazeux, sorption previous termdenext term matière organique dissoute, érosion chimique, dépôt vs. remise en suspension previous termdenext term sédiments, etc.) est simulée en prenant en compte le défaut previous termdenext term bilan hydrologique entrées-sorties utilisé comme marqueur previous termdenext term débit des plaines d'inondation. Cette analyse montre que le bruit previous termdenext term fond chimique observé dans les eaux du fleuve Amazone est principalement acquis en amont des confluences entre le tronçon fluvial étudié et les principaux affluents qui l'alimentent

Geometric Characteristics of Lithium Ion Battery Electrodes with Different Packing Densities

poster abstractThe microstructure of electrodes plays a critical role in determining the performance of lithium ion batteries (LIBs), because the microstructure can affect the transport and electrochemical processes within electrodes (1-3). Increasing the volume fraction of active materials in the electrode will increase the energy density. However, the electrodes’ structural properties could also be changed significantly and the critical physical and electrochemical processes in LIBs will be affected. Therefore, the performance of a LIB can be optimized for a specific operating condition by designing electrode microstructures. For instance, Hellweg suggested a spatially varying porous electrode model to improve lithium ion transport in electrolyte phase at high charge/discharge rates (4). He showed that the power density of the graded porosity electrode was higher than a homogeneous porosity electrode without energy loss. In this study, we investigate the realistic geometric characteristics of electrode microstructures under different packing densities and the effect of packing density on the performance of LIBs. Moreover, a spatially varying porous electrode will be studied to increase the electrode energy density without losing rate capability. To investigate geometric characteristics of porous microstructures, cathode electrodes were fabricated from a 94:3:3 (weight %) mixture of LiCoO2 (average particle radius = 5 μm), PVDF, and super-P carbon black. To change the packing density, initial thickness of the electrodes was set in a range of 40 ~ 80 μm. Then all electrodes were pressed down to 40 μm by using a rolling press machine. A synchrotron X-ray nano-computed tomography instrument (nano-CT) at the Advanced Phothon Source of Argonne National Lab was employed to obtain morphological data of the electrodes, with a spatial resolution of 60 nm. The morphology data sets were quantitatively analyzed to characterize their geometric properties. Fig. 1 shows the porosity (ε), specific surface area (As, μm-1), tortuosity (τ), and pore size distribution of 4 different electrode microstructures. The pore size distribution of the un-pressed electrode (ε =0.56, black color) demonstrates nonuniformly dispersed active material. The highest packing density electrode (ε =0.36, red color) shows the highest tortuosity. The charge/discharge experiments were also conducted for these 4 different electrodes. The geometric properties and cell testing results will be analyzed and reported. Acknowledgments: This work was supported by US National Science Foundation under Grant No. 1335850. Fig. 1 Geometric characteristics (porosity ε, specific surface area As, tortuosity τ, pore size distribution) of xray generated porous electrode microstructure with different packing densities

Combining X-ray Nano-CT and XANES Techniques for 3D Operando Monitoring of Lithiation Spatial Composition evolution in NMC Electrode

In this study, we present a well-defined methodology for conducting Operando X-ray absorption near-edge structure spectroscopy (XANES) in conjunction with transmission X-ray nano computed tomography (TXM-nanoCT) experiments on the LiNi$_{0.5}$Mn$_{0.3}$Co$_{0.2}$O$_2$ (NMC) cathode electrode. To minimize radiation-induced damage to the sample during charge and discharge cycles and to gain a comprehensive 3D perspective of the (de)lithiation process of the active material, we propose a novel approach that relies on employing only three energy levels, strategically positioned at pre-edge, edge, and post-edge. By adopting this technique, we successfully track the various (de)lithiation states within the three-dimensional space during partial cycling. Furthermore, we are able to extract the nanoscale lithium distribution within individual secondary particles. Our observations reveal the formation of a core-shell structure during lithiation and we also identify that not all surface areas of the particles exhibit activity during the process. Notably, lithium intercalation exhibits a distinct preference, leading to non-uniform lithiation degrees across different electrode locations. The proposed methodology is not limited to the NMC cathode electrode but can be extended to study realistic dedicated electrodes with high active material (AM) density, facilitating exploration and quantification of heterogeneities and inhomogeneous lithiation within such electrodes. This multi-scale insight into the (de)lithiation process and lithiation heterogeneities within the electrodes is expected to provide valuable knowledge for optimizing electrode design and ultimately enhancing electrode performance in the context of material science and battery materials research.Comment: 6 figures (SI, 3 figures

Biogeochemistry of the Amazonian Floodplains: Insights from Six End-Member Mixing Models

International audienceThe influence of Amazonian floodplains on the hydrological, sedimentary, and biogeochemical river budget was investigated along the Vargem Grande–Óbidos reach, by applying six mixing models based on variable regional and/or variable hydrological sources. By comparing the output of many different models designed for different purposes, the nature and the magnitude of processes linking water and biogeochemical budgets of the Amazonian floodplains were clarified. This study reveals that most of the chemical baseline of the Amazon River basin is acquired before the studied 2000-km Amazonian reach. However, the tight connection between the hydrograph stage of the river and the chemical signals provides insightful information on the dynamics of its floodplains. The chemical expression of biotic and abiotic processes occurring in the Amazonian floodplains can be particularly perceived during falling waters. It appears delayed in time compared to the maximum extension of submerged area, because the alternating water circulation polarity (filling versus emptying) between the main channel and the adjacent floodplains determines delayed emptying of floodplains during falling waters. It results also in a longer time of residence in the hydrograph network, which strengthens the rate of transformation of transiting materials and solutes. Biotic and biologically mediated processes tend to accentuate changes in river water chemistry initiated upstream, in each subbasin, along river corridors, indicating that processes operating downstream prolong those from upstream (e.g., floodplains of the large tributaries). Conversely, the flood wave propagation tends to lessen the seasonal variability as a result of the water storage in the floodplains, which admixes waters of distinct origins (in time and space). The morphology of floodplains, determining the deposition and the diagenesis of the sediments as well as the variable extension of submerged areas or the chronology of floodplains storage/emptying, appears to be the main factor controlling the floodplains biogeodynamics. By coupling classical end-member mixing models (providing insight on hydrological source) with a variable regional contribution scheme, relevant information on the biogeochemical budget of the Amazonian floodplains can be achieved

Certification of a Maize NK603 Reference Material for its DNA Copy Number Ratio - Certified Reference Material ERM®-BF415e

This report describes the certification of the Certified Reference Material (CRM) ERM-BF415e for its DNA copy number ratio. This CRM is composed of genetically modified NK603 maize seed and conventional maize seed powders. The ERM-BF415e is part of a set of maize CRMs containing different mass fractions of genetically modified NK603 maize. The CRM was processed and originally certified for its mass fraction by the European Commission, Directorate General Joint Research Centre, Institute for Reference Materials and Measurements (IRMM), Geel, BE.JRC.DG.D.2-Reference material

Geometric and Electrochemical Characteristics of LiNi1/3Mn1/3Co1/3O2 Electrode with Different Calendering Conditions

The impact of calendering process on the geometric characteristics and electrochemical performance of LiNi1/3Mn1/3Co1/3O2 (NMC) electrode was investigated in this study. The geometric properties of NMC electrodes with different calendering conditions, such as porosity, pore size distribution, particle size distribution, specific surface area and tortuosity were calculated from the computed tomography data of the electrodes. A synchrotron transmission X-ray microscopy tomography system at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain the tomography data. The geometric and electrochemical analysis show that calendering can increase the electrochemically active area, which improves rate capability. However, more calendering will result in crushing of NMC particles, which can reduce the electrode capacity at relatively high C rates. This study shows that the optimum electrochemical performance of NMC electrode at 94:3:3 weight ratio of NMC:binder:carbon black can be achieved by calendering to 3.0 g/cm3 NMC density