Search

Electrochemical technologies add a unique dimension for ore refinement, representing tunable methods that can integrate with renewable energy sources and existing downstream process flows. However, the development of electrochemical extraction technologies has been impeded by the technological maturity of hydro- and pyro-metallurgy, as well as the electrical insulating properties of many metal oxide ores. The fabrication and use of carbon/insulating material composite electrodes has been a longstanding method to enable electrochemical activation. Here, using real hectorite ore, we employ this technical approach to fabricate hectorite-carbon black composite electrodes (HCCEs) and achieve electrochemical activation of hectorite. Anodic polarization results in lithium-ion release through a multi-step chemical and electrochemical mechanism that results in 50.7 ± 4.4% removal of lithium from HCCE, alongside other alkaline ions. This technical proof-of-concept study underscores that electrochemical activation of ores can facilitate lattice deterioration and ion removal from ores. Electrochemical technologies for ore refinement provide a unique opportunity to integrate with renewable energy sources but are impeded by the insulating properties of many ores. Here, the authors take inspiration from the lithium-ion battery field and fabricate hectorite–carbon black composite electrodes to enhance electron percolation into hectorite enabling lithium-ion release through a multi-step (electro)chemical mechanism. [ABSTRACT FROM AUTHOR]

Researchers from a broad spectrum of scientific and engineering disciplines are increasingly using scattering‐type near‐field infrared spectroscopic techniques to characterize materials non‐destructively with nanoscale spatial resolution. However, a sub‐optimal understanding of a technique's implementation can complicate data interpretation and act as a barrier to entering the field. Here the key detection and processing steps involved in producing scattering‐type near‐field nanoscale Fourier transform infrared spectra (nano‐FTIR) are outlined. The self‐contained mathematical and experimental work derives and explains: i) how normalized complex‐valued nano‐FTIR spectra are generated, ii) why the real and imaginary components of spectra qualitatively relate to dispersion and absorption respectively, iii) a new and generally valid equation for spectra which can be used as a springboard for additional modeling of the scattering processes, and iv) an algebraic expression that can be used to extract an approximation to the sample's local extinction coefficient from nano‐FTIR. The algebraic model for weak oscillators is validated with nano‐FTIR and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectra on samples of polystyrene and Kapton and further provides a pedagogical pathway to cementing some of the technique's key qualitative attributes. [ABSTRACT FROM AUTHOR]

C–H bond activation enables the facile synthesis of new chemicals. While C–H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C–H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C–C coupling mediated by 2D TMDCs to promote C–H activation and carbon dots synthesis. Our results shed light on 2D materials for C–H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials. C–H activation in long-chain organic molecules remains largely unexplored. Here, the authors report light-driven C–H activation mediated by 2D TMDCs and the resultant synthesis of luminescent carbon dots. [ABSTRACT FROM AUTHOR]

Demand for lithium for batteries and other green technologies is exploding. The industry must develop sustainable methods to remove and process the element from ores and brines to avoid environmental damage. [ABSTRACT FROM AUTHOR]

A series of low‐temperature studies on LiNi0.80Co0.15Al0.05O2 18650‐type batteries of high‐energy type with different stabilized states of fatigue is carried out using spatially resolved neutron powder diffraction, infrared/thermal imaging, and quasi‐adiabatic calorimetry. In‐plane distribution of lithium in the graphite anode and frozen electrolyte in fully charged state is determined non‐destructively with neutron diffraction and correlated to the introduced state of fatigue. An independent electrolyte characterization is performed via calorimetry studies on variously aged 18650‐type lithium‐ion batteries, where the shape of the thermodynamic signal is evolving with the state of fatigue of the cells. Analyzing the liquid electrolyte extracted/harvested from the studied cells reveals the decomposition of conducting salt to be the main driving factor for fatigue in the electrolyte degradation. [ABSTRACT FROM AUTHOR]

The capacity of lithium transition‐metal (TM) oxide cathodes is directly linked to the magnitude and accessibility of the redox reservoir associated with TM cations and/or oxygen anions, which traditionally decreases with cycling as a result of chemical, structural, or mechanical fatigue. Here, it is shown that a capacity increase over 125% can be achieved upon cycling of high‐energy Mn‐ and F‐rich cation‐disordered rocksalt oxyfluoride cathodes. This study reveals that in Li1.2Mn0.7Nb0.1O1.8F0.2, repeated Li extraction/reinsertion utilizing Mn3+/Mn4+ redox along with some degree of O‐redox participation leads to local structural rearrangements and formation of domains with off‐stoichiometry spinel‐like features. The effective integration of these local "structure‐domains" within the cubic disordered rocksalt framework promotes better Li diffusion and improves material utilization, consequently increased capacity upon cycling. This study provides important new insights into materials design strategies to further exploit the rich compositional and structural space of Mn chemistry for developing sustainable, high‐energy cathode materials. [ABSTRACT FROM AUTHOR]

Solid-state batteries possess the potential to significantly impact energy storage industries by enabling diverse benefits, such as increased safety and energy density. However, challenges persist with physicochemical properties and processes at electrode/electrolyte interfaces. Thus, there is great need to characterize such interfaces in situ, and unveil scientific understanding that catalyzes engineering solutions. To address this, we conduct multiscale in situ microscopies (optical, atomic force, and infrared near-field) and Fourier transform infrared spectroscopies (near-field nanospectroscopy and attenuated total reflection) of intact and electrochemically operational graphene/solid polymer electrolyte interfaces. We find nanoscale structural and chemical heterogeneities intrinsic to the solid polymer electrolyte initiate a cascade of additional interfacial nanoscale heterogeneities during Li plating and stripping; including Li-ion conductivity, electrolyte decomposition, and interphase formation. Moreover, our methodology to nondestructively characterize buried interfaces and interphases in their native environment with nanoscale resolution is readily adaptable to a number of other electrochemical systems and battery chemistries. Solid-state batteries remain promising but essential insights into electrode-electrolyte interface are required. Here, the authors report in situ infrared nanospectroscopy of the lithium-polymer-electrolyte interface to reveal its intrinsic molecular, structural, and chemical heterogeneities. [ABSTRACT FROM AUTHOR]

The application of lithium rich disordered rock salts (DRX) as cathode materials has greatly expanded the materials space for high energy density cathodes. These materials are able to consistently achieve capacities higher than 250mAhg-1via a complex percolation based intercalation mechanism. Most current DRX materials face significant capacity fade when cycled over an extended period. One of the factors responsible for this could be deleterious side effect of interface reactions between the electrode and electrolyte at high voltage. We aim to focus on one aspect of this interaction, i.e the effect of exposure to electrolyte on the surface and its effect on the electrochemical properties of Li1.2Mn0.625Nb0.175O1.95F0.05 (LMNOF) powder. LMNOF was systematically treated in an electrolyte solution for varying periods of time at an elevated temperature. Treated samples exhibit surface layer modification (removal of F rich surface layer), leading to a 10 % improvement in the capacity retention behavior of LMNOF. Surface and bulk based measurements indicate an increase in disorder and gradual removal of F and Li. All of these processes mimic an aging process similar to cycling. This a priori formed interface allows for increased stability with respect to retention of capacity and oxygen loss.Cathode/electrolyte interface stabilization in disordered rock salts was achieved by a priori modification of the surface layer by electrolyte pre‐treatment. The exposure to electrolyte removes an amorphous layer on the surface exposing fresh crystalline facets for Li (de)intercalation. It also acts as a trigger to reduce cation short range order and form a more permeable 0‐TM network. The resulting modified material indicates a 10 % improvement in capacity retention. [ABSTRACT FROM AUTHOR]

Foraminiferal assemblages were analyzed in a 620-cm long core retrieved from the central part of the Mecklenburg Bay (MB, south-western Baltic Sea) to aid in the reconstruction of environmental changes occurring in the area during the Holocene and to complement a set of previously investigated palaeoenvironmental proxies. A total of five foraminifera-based stratigraphic units were identified, including an initial 80-cm thick layer devoid of foraminifera. The next two units featured an increasing abundance of the foraminiferal assemblage dominated by the calcareous Ammonia group species. Nearly all the calcareous foraminifera found in the core were decalcified. Following the maximum abundance within the 470–410 cm layer, the foraminiferal abundance declined sharply and the assemblage's dominance structure changed to domination of the agglutinated foraminiferal species, Eggerelloides scaber, which continued up to the top of the core and marked a pronounced shift in environmental conditions (shallower depth, lower salinity, more dynamic sedimentation conditions). The foraminifera-based stratigraphy of the core proved to be complementary to that emerging from previous analyses of diatoms and sediment geochemistry. [ABSTRACT FROM AUTHOR]

Whether attempting to eliminate parasitic Li metal plating on graphite (and other Li‐ion anodes) or enabling stable, uniform Li metal formation in 'anode‐free' Li battery configurations, the detection and characterization (morphology, microstructure, chemistry) of Li that cannot be reversibly cycled is essential to understand the behavior and degradation of rechargeable batteries. In this review, various approaches used to detect and characterize the formation of Li in batteries are discussed. Each technique has its unique set of advantages and limitations, and works towards solving only part of the full puzzle of battery degradation. Going forward, multimodal characterization holds the most promise towards addressing two pressing concerns in the implementation of the next generation of batteries in the transportation sector (viz. reducing recharging times and increasing the available capacity per recharge without sacrificing cycle life). Such characterizations involve combining several techniques (experimental‐ and/or modeling‐based) in order to exploit their respective advantages and allow a more comprehensive view of cell degradation and the role of Li metal formation in it. It is also discussed which individual techniques, or combinations thereof, can be implemented in real‐world battery management systems on‐board electric vehicles for early detection of potential battery degradation that would lead to failure. [ABSTRACT FROM AUTHOR]

Single‐atom catalysts (SACs) are highly enviable to exploit the utmost utilization of metallic catalysts; their efficiency by utilizing nearly all atoms to often exhibit high catalytic performances. To architect the isolated single atom on an ideal solid support with strong coordination has remained a crucial trial. Herein, graphene functionalized with nitrile groups (cyanographene) as an ideal support to immobilize isolated copper atoms G(CN)‐Cu with strong coordination is reported. The precisely designed mixed‐valence single atom copper (G(CN)‐Cu) catalysts deliver exceptional conversions for electrochemical methanol oxidation (MOR) and CO2 reduction (CO2RR) targeting a "closed carbon cycle." An onset of MOR and CO2RR are obtained to be ≈0.4 V and ≈−0.7 versus Ag/AgCl, respectively, with single active sites located in an unsaturated coordination environment, it being the most active Cu sites for both studied reactions. Moreover, G(CN)‐Cu exhibited significantly lower resistivity and higher current density toward MOR and CO2RR than observed for reference catalysts. [ABSTRACT FROM AUTHOR]

We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N, and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excitedstate electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions. [ABSTRACT FROM AUTHOR]

Electrochemically deposited copper nanostructures were coated with silver to create a plasmonically active cathode for carbon dioxide (CO2) reduction. Illumination with 365 nm light, close to the peak plasmon resonance of silver, selectively enhanced 5 of the 14 typically observed copper CO2 reduction products while simultaneously suppressing hydrogen evolution. At low overpotentials, carbon monoxide was promoted in the light and at high overpotentials ethylene, methane, formate, and allyl alcohol were enhanced upon illumination; generally C1 products and C2/C3 products containing a double carbon bond were selectively promoted under illumination. Temperature-dependent product analysis in the dark showed that local heating is not the cause of these selectivity changes. While the exact plasmonic mechanism is still unknown, these results demonstrate the potential for enhancing CO2 reduction selectivity at copper electrodes using plasmonics. [ABSTRACT FROM AUTHOR]

Rechargeable lithium-ion batteries with high energy density that can be safely charged and discharged at high rates are desirable for electrified transportation and other applications1–3. However, the sub-optimal intercalation potentials of current anodes result in a trade-off between energy density, power and safety. Here we report that disordered rock salt4,5 Li3+xV2O5 can be used as a fast-charging anode that can reversibly cycle two lithium ions at an average voltage of about 0.6 volts versus a Li/Li+ reference electrode. The increased potential compared to graphite6,7 reduces the likelihood of lithium metal plating if proper charging controls are used, alleviating a major safety concern (short-circuiting related to Li dendrite growth). In addition, a lithium-ion battery with a disordered rock salt Li3V2O5 anode yields a cell voltage much higher than does a battery using a commercial fast-charging lithium titanate anode or other intercalation anode candidates (Li3VO4 and LiV0.5Ti0.5S2)8,9. Further, disordered rock salt Li3V2O5 can perform over 1,000 charge–discharge cycles with negligible capacity decay and exhibits exceptional rate capability, delivering over 40 per cent of its capacity in 20 seconds. We attribute the low voltage and high rate capability of disordered rock salt Li3V2O5 to a redistributive lithium intercalation mechanism with low energy barriers revealed via ab initio calculations. This low-potential, high-rate intercalation reaction can be used to identify other metal oxide anodes for fast-charging, long-life lithium-ion batteries. A vanadium-based lithium-rich disordered rock salt oxide is shown to work as a low-potential anode with rapid intercalation kinetics for lithium-ion batteries. [ABSTRACT FROM AUTHOR]

Owing to the negative impact of the extensive utilization of batteries on the environment, sustainability of the cells needs to be included in the systemic research of batteries. Herein, a dissolvable ionic crosslinked polymer (DICP) is exploited as a binder for lithium–sulfur batteries by crosslinking the polyacrylic acid and polyethyleneimine through carboxy‐amino ionic interaction. This interaction is pH‐controlled, and therefore, the crosslinked binder network can be readily dissociated under basic conditions, providing a facile strategy enabling valuable components recycled through a convenient washing method. The sulfur cathode prepared using the recycled carbon–sulfur composite can deliver comparable capacity as that of fresh electrode. In addition, evidence from cell performance and characterizations, such as in situ X‐ray absorption spectroscopy, in situ UV–visible spectroscopy, X‐ray photoelectron spectroscopy, and density functional theory calculation, confirms that DICP is a more effective binder than its commercial counterpart on suppressing polysulfide dissolution in the electrolyte. Exploiting reversible crosslinked polymer binder for recyclable Li–S batteries with ameliorated electrochemical performance, this study illuminates sustainable development for large‐scale energy storage systems. [ABSTRACT FROM AUTHOR]

Herein, we present a scalable approach for the synthesis of a hydrogen-bonded organic–inorganic framework via coordination-driven supramolecular chemistry, for efficient remediation of trace heavy metal ions from water. In particular, using copper as our model ion of interest and inspired by nature's use of histidine residues within the active sites of various copper binding proteins, we design a framework featuring pendant imidazole rings and copper-chelating salicylaldoxime, known as zinc imidazole salicylaldoxime supramolecule. This material is water-stable and exhibits unprecedented adsorption kinetics, up to 50 times faster than state-of-the-art materials for selective copper ion capture from water. Furthermore, selective copper removal is achieved using this material in a pH range that was proven ineffective with previously reported metal–organic frameworks. Molecular dynamics simulations show that this supramolecule can reversibly breathe water through lattice expansion and contraction, and that water is initially transported into the lattice through hopping between hydrogen-bond sites. Heavy metals and metalloids pose major threats to health and environmental ecosystems, thus systems for low-cost remediation are needed. Here the authors report the scalable design of a hydrogen-bonded organic–inorganic framework for selective removal of trace heavy metal ions from water. [ABSTRACT FROM AUTHOR]

Herein, we present a scalable approach for the synthesis of a hydrogen-bonded organic–inorganic framework via coordination-driven supramolecular chemistry, for efficient remediation of trace heavy metal ions from water. In particular, using copper as our model ion of interest and inspired by nature's use of histidine residues within the active sites of various copper binding proteins, we design a framework featuring pendant imidazole rings and copper-chelating salicylaldoxime, known as zinc imidazole salicylaldoxime supramolecule. This material is water-stable and exhibits unprecedented adsorption kinetics, up to 50 times faster than state-of-the-art materials for selective copper ion capture from water. Furthermore, selective copper removal is achieved using this material in a pH range that was proven ineffective with previously reported metal–organic frameworks. Molecular dynamics simulations show that this supramolecule can reversibly breathe water through lattice expansion and contraction, and that water is initially transported into the lattice through hopping between hydrogen-bond sites. Heavy metals and metalloids pose major threats to health and environmental ecosystems, thus systems for low-cost remediation are needed. Here the authors report the scalable design of a hydrogen-bonded organic–inorganic framework for selective removal of trace heavy metal ions from water. [ABSTRACT FROM AUTHOR]

The results of high-resolution records of pollen, plant macroremains and charred plant particles, diatoms, Cladocera and geochemistry from a 14C-dated core, and geomorphological studies enabled the reconstruction of landscape development at a site in western Poland which was occupied by Mesolithic hunter-gatherer groups. Special attention was paid to the evidence of human activities recorded in the sediments of the palaeolake located next to the archaeological site. The presence of pollen types from communities characteristic of openings in the forest, macroscopic/microscopic charcoal, and charred particles of herbaceous plants (mostly from between 5500 and 4600 bc, with clearly visible maxima ca 5300, 4900 and 4700 bc) evidence the changes related to these various kinds of activities. These analyses allowed us to reconstruct the fire events at and around the site as well as to consider whether they originated from natural or human induced fires. The increase in the biogenic sediments of elements such as Na, K and Mg indicate an intensive erosion of mineral soil between 5100 and 4600 bc, mirroring human activity in the vicinity of the Kopanica site. In addition, Cladocera analysis permitted a detailed recognition of palaeolake eutrophication ca 7200–4600 bc, also eutrophication induced by human impact between 5100 and 4600 bc. [ABSTRACT FROM AUTHOR]

Fluorescent species are formed during cycling of lithium ion batteries as a result of electrolyte decomposition due to the instability of the non-aqueous electrolytes and side reactions that occur at the electrode surface. The increase in the background fluorescence due to the presence of these components makes it harder to analyse data due to the spectroscopic overlap of Raman scattering and fluorescence. Herein, Kerr gated Raman spectroscopy was shown to be an effective technique for the isolation of the scattering effect from the fluorescence enabling the collection of the Raman spectra of LiPF6 salt and LiPF6-based organic carbonate electrolyte, without the interference of the fluorescence component. Kerr gated Raman was able to identify POF3 on the LiPF6 particle surface, after the addition of trace water. [ABSTRACT FROM AUTHOR]

The main aim of the study was to introduce a spatial database application for the estimation of changes in shoreline position. The open-source PostgreSQL database system with the PostGIS spatial extension was used as the data store for digitalised shorelines. The solution to calculations of the shoreline changes was based on the functions written in the PL/SQL language and geospatial functions provided by the PostGIS extension. The traditional baseline and transects method was used to quantify the distances and rate of shoreline movement. Outputs of the calculations were stored in the database table and simply visualised using graphical functions in the R software environment or in GIS Desktop software. The advantage of presented method is the application of SQL language in the analysis of the relation between the geometry of shorelines stored in the database table, which, compared to other similar solutions, gives the user fully open, simple analytical code and enable selecting custom parameters of analysis, modifying code and performing additional calculations. [ABSTRACT FROM AUTHOR]

Abstract: Electrochemical reduction of carbon dioxide (CO2) typically suffers from low selectivity and poor reaction rates that necessitate high overpotentials, which impede its possible application for CO2 capture, sequestration, or carbon‐based fuel production. New strategies to address these issues include the utilization of photoexcited charge carriers to overcome activation barriers for reactions that produce desirable products. This study demonstrates surface‐plasmon‐enhanced photoelectrochemical reduction of CO2 and nitrate (NO3−) on silver nanostructured electrodes. The observed photocurrent likely originates from a resonant charge transfer between the photogenerated plasmonic hot electrons and the lowest unoccupied molecular orbital (MO) acceptor energy levels of adsorbed CO2, NO3−, or their reductive intermediates. The observed differences in the resonant effects at the Ag electrode with respect to electrode potential and photon energy for CO2 versus NO3− reduction suggest that plasmonic hot‐carriers interact selectively with specific MO acceptor energy levels of adsorbed surface species such as CO2, NO3−, or their reductive intermediates. This unique plasmon‐assisted charge generation and transfer mechanism can be used to increase yield, efficiency, and selectivity of various photoelectrochemical processes. [ABSTRACT FROM AUTHOR]

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions. [ABSTRACT FROM AUTHOR]

The global demand for water and energy is projected to grow, but there likely will be significant constraints in our ability to keep meeting it. These constraints will be imposed partly by the interdependence between water, energy, and climate change. If left unchecked, these connections can exacerbate water and energy shortages and aggravate climate change impacts: Energy is used to supply and treat water; moreover, emissions from energy generation contribute to climate change, which affects water supplies and increases the demand for energy to sustain Earth's growing population and economy. The linkage between water and energy can offer opportunities for better meeting expected demand while minimizing damage from shortages of either. This article focuses on the technological and engineering aspects of various connections in the water-energy nexus where advancements can enable greater supply of one or both. It also outlines the benefits and challenges associated with each connection. [ABSTRACT FROM AUTHOR]

The paper presents the chronology of the Holocene evolution of the Baltic Sea based on the optically stimulated luminescence (OSL) and radiocarbon dating methods applied to a core taken from the Arkona Basin. The dating results were supplemented by grain size and geochemical analysis. The obtained results of OSL and radiocarbon dating enabled the construction of an age-depth model and confirmed the continuous sedimentation since 9900 cal yrs BP. One of the most interesting findings of this study is a clear relationship between the rate of sedimentation and fluctuations in the energy of depositional environment. The analyzed sediment core revealed two sections of different accumulation rates. The bottom section was deposited until 2700 cal yrs BP when the Ancylus Lake and the Littorina Sea were present, characterized by the accumulation rate estimated at around 0.46 mm year-1 and the dynamic sedimentation environment confirmed by grain size parameters. The accumulation rate at the top section deposited during the Post-Littorina Sea stage was estimated at around 1 mm year-1. This stage, characterized by more stable deposition and lower-energy environment conditions, was confirmed by small grain size, symmetric skewness and increasing content of organic matter. [ABSTRACT FROM AUTHOR]

Al-substituted LiLaZrO samples processed under argon show enhanced Li-ion transport and interfacial properties in symmetrical cells with lithium electrodes, compared to those prepared in air. In particular, the samples prepared under argon have higher ionic conductivities and lower interfacial impedances in symmetrical lithium cells, and show better DC cycling characteristics. The electronic conductivities are also somewhat higher. Pellets subjected to thermal treatment under the two types of atmospheres have different colors but exhibit similar microstructures. X-ray diffraction experiments suggest that there are slight structural differences between the two types of samples, but few dissimilarities were observed in elemental composition, distribution of ions, oxidation states, or bond lengths using laser-induced breakdown spectroscopy (LIBS), x-ray photoelectron spectroscopy (XPS), and extended x-ray absorption fine structure spectroscopy (EXAFS) to analyze the materials. Additionally, there was no evidence that La or Zr were reduced during the processing under Ar. Possible explanations for the improved electrochemical properties of the sample prepared under Ar compared to the one prepared in air include differences in grain boundary chemistries and conductivities and/or a small concentration of oxygen vacancies in the former. [ABSTRACT FROM AUTHOR]

Aging, conducting lithium salt, differential thermal analysis, electrolyte compositions, lithium-ion batteries, neutron powder diffraction Keywords: aging; conducting lithium salt; differential thermal analysis; electrolyte compositions; lithium-ion batteries; neutron powder diffraction EN aging conducting lithium salt differential thermal analysis electrolyte compositions lithium-ion batteries neutron powder diffraction 1 1 1 12/05/22 20221201 NES 221201 B Lithium-Ion Batteries b In article number 2201652, Anatoliy Senyshyn and co-workers investigate the degradation mechanisms of real life 18650-type lithium-ion batteries using a combination of neutron diffraction, calorimetry, infrared measurements, and chemical analytics of battery electrolytes. Aging-Driven Composition and Distribution Changes of Electrolyte and Graphite Anode in 18650-Type Li-Ion Batteries (Adv. [Extracted from the article]

The energy density of current batteries is limited by the practical capacity of the positive electrode, which is determined by the properties of the active material and its concentration in the composite electrode architecture. The observation in dynamic conditions of electrochemical transformations creates the opportunity of identifying design rules toward reaching the theoretical limits of battery electrodes. But these observations must occur during operation and at multiple scales. They are particularly critical at the single-particle level, where incomplete reactions and failure are prone to occur. Here, operando full-field transmission X-ray microscopy is coupled with X-ray spectroscopy to follow the chemical and microstructural evolution at the nanoscale of single crystals of Li1+ xMn2- xO4, a technologically relevant Li-ion battery electrode material. The onset and crystallographic directionality of a series of complex phase transitions are followed and correlated with particle fracture. The dynamic character of this study reveals the existence of nonequilibrium pathways where phases at substantially different potentials can coexist at short length scales. The results can be used to inform the engineering of particle morphologies and electrode architectures that bypass the issues observed here and lead to optimized battery electrode properties. [ABSTRACT FROM AUTHOR]

Dense LLZO (Al-substituted Li7La3Zr2O12) pellets were processed in controlled atmospheres to investigate the relationships between the surface chemistry and interfacial behavior in lithium cells. Laser induced breakdown spectroscopy (LIBS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, synchrotron X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS) studies revealed that Li2CO3 was formed on the surface when LLZO pellets were exposed to air. The distribution and thickness of the Li2CO3 layer were estimated by a combination of bulk and surface sensitive techniques with various probing depths. First-principles thermodynamic calculations confirmed that LLZO has an energetic preference to form Li2CO3 in air. Exposure to air and the subsequent formation of Li2CO3 at the LLZO surface is the source of the high interfacial impedances observed in cells with lithium electrodes. Surface polishing can effectively remove Li2CO3 and dramatically improve the interfacial properties. Polished samples in lithium cells had an area specific resistance (ASR) of only 109 Ω cm2 for the LLZO/Li interface, the lowest reported value for Al-substituted LLZO. Galvanostatic cycling results obtained from lithium symmetrical cells also suggest that the quality of the LLZO/lithium interface has a significant impact on the device lifetime. [ABSTRACT FROM AUTHOR]

Four sediment cores from the southern part of the Arkona Basin were analyzed in terms of their geochemical composition, age and stratigraphy. The main stages of the Baltic Sea: the Baltic Ice Lake, the Ancylus Lake and the Littorina Sea were identified in all the analyzed cores. The data confirmed the high water fluctuation and significant environmental changes during the Baltic Sea evolution in the Late-Glacial and the Holocene. The signs of the second regression of the Baltic Ice Lake, dated at around 11 000 cal BP, were identified at a depth of 24 m b.s.l. Regression of the Ancylus Lake, dated at 9300 cal BP, was identified at a depth of 23 m b.s.l. The most pronounced period was the transition stage between the Ancylus Lake and the Littorina Sea. The record of the Littorina Sea onset in the sediments of the Arkona Basin is marked as a sudden increase in loss on ignition, biogenic silica, magnesium, calcium, iron and strontium. The age of the Littorina Sea in the Arkona Basin was estimated as younger than 8200 cal BP. [ABSTRACT FROM AUTHOR]

We demonstrate that electrocoagulation (EC) using iron electrodes can reduce arsenic below 10 μg/L in synthetic Bangladesh groundwater and in real groundwater from Bangladesh and Cambodia, while investigating the effect of operating parameters that are often overlooked, such as charge dosage rate. We measure arsenic removal performance over a larger range of current density than in any other single previous EC study (5000-fold: 0.02 – 100 mA/cm2) and over a wide range of charge dosage rates (0.060 – 18 Coulombs/L/min). We find that charge dosage rate has significant effects on both removal capacity (μg-As removed/Coulomb) and treatment time and is the appropriate parameter to maintain performance when scaling to different active areas and volumes. We estimate the operating costs of EC treatment in Bangladesh groundwater to be $0.22/m3. Waste sludge (∼ 80 – 120 mg/L), when tested with the Toxic Characteristic Leachate Protocol (TCLP), is characterized as non-hazardous. Although our focus is on developing a practical device, our results suggest that As[III] is mostly oxidized via a chemical pathway and does not rely on processes occurring at the anode. Supplementary materials are available for this article. Go to the publisher's online edition ofJournal of Environmental Science and Health, Part A,to view the free supplemental file. [ABSTRACT FROM AUTHOR]

Functional electrodes for batteries share a common design rule by which high electronic and ionic conductivity pathways must exist throughout the electrode in its pristine state. Notable amounts of conductive carbon additive in the composite electrode are usually included to form an electronically conductive matrix. However, excellent high rate cycling performance has been achieved in electrodes composed of the insulating Li4Ti5O12 without any conductive additives. This behavior opens the possibility of a new paradigm for designing functional electrodes by which high electronic conductivity in the pristine electrode is not required. The mechanism of operation that enables such unexpected electrochemical behavior is evaluated and discussed. Electronically conductive pathways due to the reduction of Ti4+ to Ti3+ form and percolate throughout the Li4Ti5O12 electrode in the early stage of Li insertion, eliminating the need for conductive additives. This work highlights the importance of the mass and charge transport properties of the intermediate states during cycling and of good interparticle ohmic contact in the electrode. This physical behavior can lead to novel system designs with improved battery utilization and energy density. [ABSTRACT FROM AUTHOR]

Over the past decades, there have been many projections on the future depletion of the fossil fuel reserves on earth as well as the rapid increase in green-house gas emissions. There is clearly an urgent need for the development of renewable energy technologies. On a different frontier, growth and manipulation of materials on the nanometer scale have progressed at a fast pace. Selected recent and significant advances in the development of nanomaterials for renewable energy applications are reviewed here, and special emphases are given to the studies of solar-driven photocatalytic hydrogen production, electricity generation with dye-sensitized solar cells, solid-state hydrogen storage, and electric energy storage with lithium ion rechargeable batteries. [ABSTRACT FROM AUTHOR]

Direct chemical analysis of electrode/electrolyte interfaces can provide critical information on surface phenomena that define and control the performance of Li-based battery systems. In this work, we introduce the use of ex situ femtosecond laser induced breakdown spectroscopy to probe compositional variations within the solid electrolyte interphase (SEI) layer. Nanometer-scale depth resolution was achieved for elemental and molecular depth profiling of SEI layers formed on highly oriented pyrolytic graphite electrodes in an organic carbonate-based electrolyte. This work demonstrates the unique ability of ultrafast laser spectroscopy as a highly versatile, light element-sensitive technique for direct chemical analysis of interfacial layers in electrochemical energy storage systems. [ABSTRACT FROM AUTHOR]

Ionic liquid (IL)-water mixtures can exhibit a lower critical solution temperature (LCST) transition, but changes in long-range order and local molecular environment during this transition are not comprehensively understood. Here we show that in IL-H2O LCST mixtures, the IL forms loosely held aggregate structures that grow in size leading up to a critical temperature, whereas the aggregation of a fully miscible aqueous mixture, obtained by minor chemical modification of the anion, decreases with increasing temperature. Radial distribution functions from molecular dynamics simulations support the observation of aggregation phenomena in the IL-H2O mixtures. A local molecular structure of the ions is derived from multi-dimensional NMR experiments in conjunction with reported molecular dynamics simulations. In addition to considerable shifts of water's hydrogen bonding network in the fully miscible phase, by NMR we observe the anion's protons response to the intermolecular thermal environment and the intramolecular environment and find that the responses are determined by the sulfonate ionic functional group. Aqueous solutions of ionic liquids can undergo thermally-controlled phase separation, but the microscopic processes driving this are not fully understood. Here a combination of experimental methods and molecular dynamics simulations are used to probe the influence of local structure on the formation of micron-scale clustering. [ABSTRACT FROM AUTHOR]