Are Operando Measurements of Rechargeable Batteries Always Reliable? An Example of Beam Effect with a Mg Battery.

Operando and in situ techniques are becoming mandatory to study Li-ion, post Li-ion, and solid-state batteries. They are essential for monitoring the (electro)chemical and dynamic processes in the battery environment and for providing understanding at different spatial and temporal scales. While operando measurements are becoming more and more routine, scientists have to keep in mind that such experiments are not always harmless for the battery operation, especially when using synchrotron techniques. This is the case in the example described herein with Mg batteries. We show that the electrode reactivity in a InSb/organohaluminate electrolyte/Mg cell is strongly retarded during operando synchrotron X-ray absorption acquisition. Through comparison of ex situ, operando, and in situ data, we demonstrate that this effect occurred only on the samples' volumes exposed to the X-ray radiation. This study illustrates how incorrect conclusions might be drawn from operando measurements, especially when looking at new battery chemistries, and calls for extreme caution when designing and interpreting operando data.

Nanoscale Secondary Ion Mass Spectrometry determination of the water content of staurolite.

RATIONALE: Staurolite is an important mineral that can reveal much about metamorphic processes. For instance, it dominates the Fe-Mg exchange reactions in amphibolite-facies rocks between about 550 and 700°C, and can be also found at suprasolidus conditions. Staurolite contains a variable amount of OH in its structure, whose determination is a key petrological parameter. However, staurolite is often compositionally zoned, fine-grained, and may contain abundant inclusions. This makes conventional water analysis (e.g., Fourier transform infrared (FTIR) spectroscopy or by chemical titration) unsuitable. With its high sensitivity at high spatial resolution, Nanoscale Secondary Ion Mass Spectrometry (NanoSIMS) is potentially a valuable tool for determining water contents in staurolite. However a calibration with relevant standards covering a large range of water content is required to obtain accurate and reliable analyses, because matrix effects typically prevent direct quantification of water content by SIMS techniques. METHODS: In this study, a calibration for NanoSIMS analyses of water content by using minerals with crystallographic structures comparable to that of staurolite (i.e., amphibole and kyanite, an inosilicate and a nesosilicate, respectively) has been developed. RESULTS: Water measurements in an inclusion-free crystal from Pizzo Forno, Ticino, Switzerland, by FTIR spectroscopy (1.56 ± 0.14 wt% H2 O) and by Elastic Recoil Detection Analysis (ERDA) (1.58 ± 0.15 wt% H2 O) are consistent with NanoSIMS results (1.56 ± 0.04 wt% H2 O). CONCLUSIONS: This implies that our approach can accurately account for NanoSIMS matrix effects in the case of staurolite. With this calibration, it is now possible to investigate variations in water content at the microscale in metamorphic minerals exhibiting high spatial variability and/or very small size (few micrometers).

Influence of Electrolyte on the Electrode/Electrolyte Interface Formation on InSb Electrode in Mg-Ion Batteries.

Achieving the full potential of magnesium-ion batteries (MIBs) is still a challenge due to the lack of adequate electrodes or electrolytes. Grignard-based electrolytes show excellent Mg plating/stripping, but their incompatibility with oxide cathodes restricts their use. Conventional electrolytes like bis(trifluoromethanesulfonyl)imide ((Mg(TFSI)2) solutions are incompatible with Mg metal, which hinders their application in high-energy Mg batteries. In this regard, alloys can be game changers. The insertion/extraction of Mg2+ in alloys is possible in conventional electrolytes, suggesting the absence of a passivation layer or the formation of a conductive surface layer. Yet, the role and influence of this layer on the alloys performance have been studied only scarcely. To evaluate the reactivity of alloys, we studied InSb as a model material. Ex situ X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy were used to investigate the surface behavior of InSb in both Grignard and conventional Mg(TFSI)2/DME electrolytes. For the Grignard electrolyte, we discovered an intrinsic instability of both solvent and salt against InSb. XPS showed the formation of a thick surface layer consisting of hydrocarbon species and degradation products from the solvent (THF) and salt (C2H5MgCl-(C2H5)2AlCl). On the contrary, this study highlighted the stability of InSb in Mg(TFSI)2 electrolyte.

MIL-53 Metal-Organic Framework as a Flexible Cathode for Lithium-Oxygen Batteries.

Li-air batteries possess higher specific energies than the current Li-ion batteries. Major drawbacks of the air cathode include the sluggish kinetics of the oxygen reduction (OER), high overpotentials and pore clogging during discharge processes. Metal-Organic Frameworks (MOFs) appear as promising materials because of their high surface areas, tailorable pore sizes and catalytic centers. In this work, we propose to use, for the first time, aluminum terephthalate (well known as MIL-53) as a flexible air cathode for Li-O2 batteries. This compound was synthetized through hydrothermal and microwave-assisted routes, leading to different particle sizes with different aspect ratios. The electrochemical properties of both materials seem to be equivalent. Several behaviors are observed depending on the initial value of the first discharge capacity. When the first discharge capacity is higher, no OER occurs, leading to a fast decrease in the capacity during cycling. The nature and the morphology of the discharge products are investigated using ex situ analysis (XRD, SEM and XPS). For both MIL-53 materials, lithium peroxide Li2O2 is found as the main discharge product. A morphological evolution of the Li2O2 particles occurs upon cycling (stacked thin plates, toroids or pseudo-spheres).

NanoSIMS Imaging of D/H Ratios on FIB Sections.

The D/H ratio imaging of weakly hydrated minerals prepared as focused ion beam (FIB) sections is developed in order to combine isotopic imaging by nanoscale secondary ion mass spectrometry (NanoSIMS) of micrometer-sized grains with other nanoscale imaging techniques, such as transmission electron microscopy. In order to maximize the accuracy, sensitivity, precision, and reproducibility of D/H ratios at the micrometer size, while minimizing the surface contamination at the same time, we explored all instrumental parameters known to influence the measurement of D/H ratios in situ. Optimal conditions were found to be obtained with the use of (i) a Cs+ ion source and detection of H- and D- at low mass resolving power, (ii) a primary beam intensity of 100 pA, and (iii) raster sizes in the range of 8-15 µm. Nominally anhydrous minerals were used to evaluate the detection limits and indicate a surface contamination level of ∼200 ppm equivalent H2O under these conditions. With the high primary intensity used here, the dwell time is not a parameter as critical as found in previous studies and a dwell time of 1 ms/px is used to minimize dynamic contamination during analysis. Analysis of FIB sections was found to reduce significantly static contamination due to sample preparation and improved accuracy compared to using polished sections embedded not only in epoxy but in indium as well. On amphiboles, the typical overall uncertainty including reproducibility is ∼20 ‰ on bulk FIB sections and ∼50 ‰ at the 1.5 µm scale using image processing (1σ).

Low hydrogen contents in the cores of terrestrial planets.

Hydrogen has been thought to be an important light element in Earth's core due to possible siderophile behavior during core-mantle segregation. We reproduced planetary differentiation conditions using hydrogen contents of 450 to 1500 parts per million (ppm) in the silicate phase, pressures of 5 to 20 GPa, oxygen fugacity varying within IW-3.7 and IW-0.2 (0.2 to 3.7 log units lower than iron-wüstite buffer), and Fe alloys typical of planetary cores. We report hydrogen metal-silicate partition coefficients of ~2 × 10-1, up to two orders of magnitude lower than reported previously, and indicative of lithophile behavior. Our results imply H contents of ~60 ppm in the Earth and Martian cores. A simple water budget suggests that 90% of the water initially present in planetary building blocks was lost during planetary accretion. The retained water segregated preferentially into planetary mantles.

Using µPIXE for quantitative mapping of metal concentration in Arabidopsis thaliana seeds.

Seeds are a crucial stage in plant life. They contain the nutrients necessary to initiate the development of a new organism. Seeds also represent an important source of nutrient for human beings. Iron (Fe) and zinc (Zn) deficiencies affect over a billion people worldwide. It is therefore important to understand how these essential metals are stored in seeds. In this work, Particle-Induced X-ray Emission with the use of a focused ion beam (µPIXE) has been used to map and quantify essential metals in Arabidopsis seeds. In agreement with Synchrotron radiation X-ray fluorescence (SXRF) imaging and Perls/DAB staining, µPIXE maps confirmed the specific pattern of Fe and Mn localization in the endodermal and subepidermal cell layers in dry seeds, respectively. Moreover, µPIXE allows absolute quantification revealing that the Fe concentration in the endodermal cell layer reaches ~800 µg·g(-1) dry weight. Nevertheless, this cell layer accounts only for about half of Fe stores in dry seeds. Comparison between Arabidopsis wild type (WT) and mutant seeds impaired in Fe vacuolar storage (vit1-1) or release (nramp3nramp4) confirmed the strongly altered Fe localization pattern in vit1-1, whereas no alteration could be detected in nramp3nramp4 dry seeds. Imaging of imbibed seeds indicates a dynamic localization of metals as Fe and Zn concentrations increase in the subepidermal cell layer of cotyledons after imbibition. The complementarities between µPIXE and other approaches as well as the importance of being able to quantify the patterns for the interpretation of mutant phenotypes are discussed.

Accumulation, translocation and impact of TiO2 nanoparticles in wheat (Triticum aestivum spp.): influence of diameter and crystal phase.

Intensive production of TiO(2) nanoparticles (TiO(2)-NPs) would lead to their release in the environment. Their ecotoxicological impact is still poorly documented, while their use in commercial goods is constantly increasing. In this study we compare root accumulation and root-to-shoot translocation in wheat of anatase and rutile TiO(2)-NPs with diameters ranging from 14 nm to 655 nm, prepared in water. NP distribution in plant tissues was mapped by synchrotron-radiation micro-X-ray fluorescence, observed by transmission electron microscopy and quantified in the different compartments of plant roots by micro-particle-induced X-ray emission. Our results provide evidence that the smallest TiO(2)-NPs accumulate in roots and distribute through whole plant tissues without dissolution or crystal phase modification. We suggest a threshold diameter, 140 nm, above which NPs are no longer accumulated in wheat roots, as well as a threshold diameter, 36 nm, above which NPs are accumulated in wheat root parenchyma but do not reach the stele and consequently do not translocate to the shoot. This accumulation does not impact wheat seed germination, biomass and transpiration. It does not induce any modification of photosynthesis nor induce oxidative stress. However exposure of wheat plantlets to the smallest NPs during the first stages of development causes an increase of root elongation. Collectively, these data suggest that only the smallest TiO(2)-NPs may be accumulated in wheat plants, although in limited amounts and that their impact is moderate.

Uptake, localization, and speciation of cobalt in Triticum aestivum L. (wheat) and Lycopersicon esculentum M. (tomato).

The root-to-shoot transfer, localization, and chemical speciation of Co were investigated in a monocotyledon (Triticum aestivum L., wheat) and a dicotyledon (Lycopersicon esculentum M., tomato) plant species grown in nutrient solution at low (5 muM) and high (20 muM) Co(II) concentrations. Cobalt was measured in the roots and shoots by inductively coupled plasma-mass spectrometry. X-ray absorption spectroscopy measurements were used to identify the chemical structure of Co within the plants and Co distribution in the leaves was determined by micro-PIXE (particle induced X-ray emission). Although the root-to-shoot transport was higher for tomato plants exposed to excess Co, both plants appeared as excluders. The oxidation state of Co(II) was not transformed by either plant in the roots or shoots and Co appeared to be present as Co(II) in a complex with carboxylate containing organic acids. Cobalt was also essentially located in the vascular system of both plant species indicating that neither responded to Co toxicity via sequestration in epidermal or trichome tissues as has been observed for other metals in metal hyperaccumulating plants.

Membrane-dependent bystander effect contributes to amplification of the response to alpha-particle irradiation in targeted and nontargeted cells.

PURPOSE: Free radicals are believed to play an active role in the bystander response. This study investigated their origin as well as their temporal and spatial impacts in the bystander effect. METHODS AND MATERIALS: We employed a precise alpha-particle microbeam to target a small fraction of subconfluent osteoblastic cells (MC3T3-E1). gammaH2AX-53BP1 foci, oxidative metabolism changes, and micronuclei induction in targeted and bystander cells were assessed. RESULTS: Cellular membranes and mitochondria were identified as two distinct reactive oxygen species producers. The global oxidative stress observed after irradiation was significantly attenuated after cells were treated with filipin, evidence for the primal role of membrane in the bystander effect. To determine the membrane's impact at a cellular level, micronuclei yield was measured when various fractions of the cell population were individually targeted while the dose per cell remained constant. Induction of micronuclei increased in bystander cells as well as in targeted cells and was attenuated by filipin treatment, demonstrating a role for bystander signals between irradiated cells in an autocrine/paracrine manner. CONCLUSIONS: A complex interaction of direct irradiation and bystander signals leads to a membrane-dependent amplification of cell responses that could influence therapeutic outcomes in tissues exposed to low doses or to environmental exposure.

Elemental compositions of comet 81P/Wild 2 samples collected by Stardust.

We measured the elemental compositions of material from 23 particles in aerogel and from residue in seven craters in aluminum foil that was collected during passage of the Stardust spacecraft through the coma of comet 81P/Wild 2. These particles are chemically heterogeneous at the largest size scale analyzed ( approximately 180 ng). The mean elemental composition of this Wild 2 material is consistent with the CI meteorite composition, which is thought to represent the bulk composition of the solar system, for the elements Mg, Si, Mn, Fe, and Ni to 35%, and for Ca and Ti to 60%. The elements Cu, Zn, and Ga appear enriched in this Wild 2 material, which suggests that the CI meteorites may not represent the solar system composition for these moderately volatile minor elements.

Evidence of sequential lift in growth of aligned multiwalled carbon nanotube multilayers.

We synthesized aligned multiwalled carbon nanotube multilayers by aerosol-assisted catalytic chemical vapor deposition through sequential injections of aerosols containing both carbon and catalyst precursors. Each sequence was traced by a specific duration or precursor mixture, with the carbon source being possibly enriched in (13)C isotope labels. We discovered that any sequence involved the growth of a new layer on the substrate surface, under any pre-existing one by lifting it up, giving definitive evidence of a base-growth mechanism.