Reconsidering Anode Materials for Fluoride-Ion Batteries-The Unexpected Roles of Carbide Formation.

Carbon is a ubiquitous additive to enhance the electrical conductivity of battery electrodes. Although carbon is generally assumed to be inert, the poor reversibility seen in some fluoride-ion battery electrodes has not been explained or systematically explored. Here, we utilize the Materials Project database to assess electrode deactivation reactions that result in the formation of a metal carbide. Specifically, we compare the theoretical potentials of MFy reduction to either the corresponding metal M or metal carbide MCx . We find that the formation of MCx is unlikely to be important in anodes that operate at modest reduction potentials, such as those made from electronegative metals like Zn, Sn, or Pb. However, in anodes that operate at extreme reduction potentials, such as alkaline earths or lanthanides, we find that formation of MCx is relevant and can emerge as a mechanism for capacity loss. Thus, side reactions of metals with carbon additives that form metal carbides possibly explain the poor reversibility of lanthanide or alkaline earth metal-based electrode materials. Finally, we highlight that the carbide formation process might be exploited for designing cheap anode systems with improved reversibility.

Recycling of All-Solid-State Li-ion Batteries: A Case Study of the Separation of Individual Components Within a System Composed of LTO, LLZTO and NMC.

With the current global projection of over 130 million electric vehicles (EVs), there soon will be a need for battery waste management. Especially for all-solid-state lithium-ion batteries (lithium ASSBs), aspects of waste management and circular economy have not been addressed so far. Within such ASSBs, the use of solid-electrolytes like garnet-type Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZTO) may shift focus on strategies to recover not only the transition metal elements but also elements like La/Zr/Ta. In this work, we present a two-step recycling approach using citric acid as the leaching agent to separate and recover the individual components of a model cell comprising of Li4 Ti5 O12 (LTO) anode, Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZTO) garnet electrolyte and LiNi1/3 Mn1/3 Co1/3 O2 (NMC) cathode. We observe that by adjusting the concentration of citric acid, it was possible to separate the materials from each other without strong mixing of individual phases and also to maintain their principle performance characteristics. Thus, the process developed has a potential for upscaling and can guide towards considering separation capability of battery components in the development of lithium ASSBs.

On the Surface Modification of LLZTO with LiF via a Gas-Phase Approach and the Characterization of the Interfaces of LiF with LLZTO as Well as PEO+LiTFSI.

In this study we present gas-phase fluorination as a method to create a thin LiF layer on Li6.5La3Zr1.5Ta0.5O12 (LLZTO). We compared these fluorinated films with LiF films produced by RF-magnetron sputtering, where we investigated the interface between the LLZTO and the deposited LiF showing no formation of a reaction layer. Furthermore, we investigated the ability of this LiF layer as a protection layer against Li2CO3 formation in ambient air. By this, we show that Li2CO3 formation is absent at the LLZTO surface after 24 h in ambient air, supporting the protective character of the formed LiF films, and hence potentially enhancing the handling of LLZTO in air for battery production. With respect to the use within hybrid electrolytes consisting of LLZTO and a mixture of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), we also investigated the interface between the formed LiF films and a mixture of PEO+LiTFSI by X-ray photoelectron spectroscopy (XPS), showing decomposition of the LiTFSI at the interface.

miR-497 and 219 in blood aid meningioma classification.

INTRODUCTION: The current WHO classification and methylation status help predict meningioma recurrence and prognosis. However, up to date, there is no circulating biomarker showing clinical value in meningioma diagnosis or classification. Circulating miRNAs showed the potential to be used as cancer biomarkers in various tumours. This research evaluated specific miRNAs, miR-497 and miR-219, as convenient and efficient predictors of meningioma grades. METHODS: We studied serum and exosomal levels of miR-497 in 74 meningioma samples (WHO grade I = 25, WHO grade II = 25, and WHO grade III = 24) and 53 healthy controls. The serum level of miR-219 was studied in 56 meningioma samples WHO grade I = 22, WHO grade II = 14, and WHO grade III = 20). We used qPCR for miRNA quantification. We also tested two different normalisers, endogenous and external, and evaluated their impact on the diagnostic value of miR-497. RESULTS: The serum and exosomal levels of miR-497 distinguished meningioma from the control samples. Moreover, miR-497 was a suitable identifier for meningioma grade. When we combined miR-497 and miR-219, the efficacy of the combined biomarker was higher than miR-497 or miR-219 when used individually in meningioma classification. Both miR-497 and miR-219 showed a noticeable change with the methylation class of meningioma. CONCLUSION: This study shows that serum miR-497 is an effective and easy-to-measure biomarker for meningioma diagnosis and classification. Moreover, when we combined miR-497 and miR-219, the combined biomarker showed enhanced accuracy in meningioma classification. Furthermore, this is the first study to evaluate the correlation between serum circulating miRNA and the methylation status in meningioma.

Updated diagnostic criteria and nomenclature for neurofibromatosis type 2 and schwannomatosis: An international consensus recommendation.

PURPOSE: Neurofibromatosis type 2 (NF2) and schwannomatosis (SWN) are genetically distinct tumor predisposition syndromes with overlapping phenotypes. We sought to update the diagnostic criteria for NF2 and SWN by incorporating recent advances in genetics, ophthalmology, neuropathology, and neuroimaging. METHODS: We used a multistep process, beginning with a Delphi method involving global disease experts and subsequently involving non-neurofibromatosis clinical experts, patients, and foundations/patient advocacy groups. RESULTS: We reached consensus on the minimal clinical and genetic criteria for diagnosing NF2 and SWN. These criteria incorporate mosaic forms of these conditions. In addition, we recommend updated nomenclature for these disorders to emphasize their phenotypic overlap and to minimize misdiagnosis with neurofibromatosis type 1. CONCLUSION: The updated criteria for NF2 and SWN incorporate clinical features and genetic testing, with a focus on using molecular data to differentiate the 2 conditions. It is likely that continued refinement of these new criteria will be necessary as investigators study the diagnostic properties of the revised criteria and identify new genes associated with SWN. In the revised nomenclature, the term "neurofibromatosis 2" has been retired to improve diagnostic specificity.

One-Step Thermal Gradient- and Antisolvent-Free Crystallization of All-Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells.

All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat-sensitive hybrid organic-inorganic counterparts. In particular, CsPbI2 Br shows the highest potential for developing thermally-stable perovskite solar cells (PSCs) among all-inorganic compositions. However, controlling the crystallinity and morphology of all-inorganic compositions is a significant challenge. Here, a simple, thermal gradient- and antisolvent-free method is reported to control the crystallization of CsPbI2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin-coating and annealing to understand and optimize the evolving film properties. This leads to high-quality perovskite films with micrometer-scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open-circuit voltage (VOC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.

Towards Recycling of LLZO Solid Electrolyte Exemplarily Performed on LFP/LLZO/LTO Cells.

All-solid-state lithium ion batteries (ASS-LIBs) are promising due to their safety and higher energy density as compared to that of conventional LIBs. Over the next few decades, tremendous amounts of spent ASS-LIBs will reach the end of their cycle life and would require recycling in order to address the waste management issue along with reduced exploitation of rare elements. So far, only very limited studies have been conducted on recycling of ASS-LIBS. Herein, we investigate the recycling of the Li7 La3 Zr2 O12 (LLZO) solid-state electrolyte in a LiFePO4 /LLZO/Li4 Ti5 O12 system using a hydrometallurgical approach. Our results show that different concentration of the leaching solutions can significantly influence the final product of the recycling process. However, it was possible to recover relatively pure La2 O3 and ZrO2 to re-synthesize the cubic LLZO phase, whose high purity was confirmed by XRD measurements.

Pressure-Induced Structural Behavior of Orthorhombic Mn3(VO4)2: Raman Spectroscopic and X-ray Diffraction Investigations.

The effect of high pressure on the structure of orthorhombic Mn3(VO4)2 is investigated using in situ Raman spectroscopy and X-ray powder diffraction up to high pressures of 26.2 and 23.4 GPa, respectively. The study demonstrates a pressure-induced structural phase transition starting at 10 GPa, with the coexistence of phases in the range of 10-20 GPa. The sluggish first-order phase transition is complete by 20 GPa. Importantly, the new phase could be recovered at ambient conditions. Raman spectra of the recovered new phase indicate increased distortion and as a consequence the lowering of the local symmetry of the VO4 tetrahedra. This behavior is different from that reported for isostructural compounds Zn3(VO4)2 and Ni3(VO4)2 where both show stable structures, although almost similar anisotropic compression of the unit cell is observed. The transition observed in orthorhombic Mn3(VO4)2 could be due to the internal charge transfer between the cations, which favors the structural transition at lower pressures and the eventual recovery of the new phase even upon pressure release in comparison to other isostructural compounds. The experimental equation of state parameters obtained for orthorhombic Mn3(VO4)2 match excellently with empirically calculated values reported earlier.

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy.

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21 c) to the cubic polymorph (ß, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

Structural and Magnetic Properties of BaFeO2.667 Synthesized by Oxidizing BaFeO2.5 Obtained via Nebulized Spray Pyrolysis.

A vacancy-ordered perovskite-type compound Ba3Fe3O8 (BaFeO2.667) was prepared by oxidizing BaFeO2.5 (P21/c) with the latter compound obtained by a spray pyrolysis technique. The structure of Ba3Fe3O8 was found to be isotypic to Ba3Fe3O7F (P21/m) and can be written as Ba3Fe3+2Fe4+1O8. Mössbauer spectroscopy and ab initio calculations were used to confirm mixed iron oxidation states, showing allocation of the tetravalent iron species on the tetrahedral site, and octahedral as well as square pyramidal coordination for the trivalent species within a G-type antiferromagnetic ordering. The uptake and release of oxygen were investigated over a broad temperature range from room temperature to 1100 °C under pure oxygen and ambient atmosphere via a combination of DTA/TG and variable temperature diffraction measurements. The compound exhibited a strong lattice enthalpy driven reduction to monoclinic and cubic BaFeO2.5 at elevated temperatures.

Compositional Dependence of Li-Ion Conductivity in Garnet-Rich Composite Electrolytes for All-Solid-State Lithium-Ion Batteries-Toward Understanding the Drawbacks of Ceramic-Rich Composites.

Composite electrolytes comprising a polymer plus Li salt matrix and embedded fillers have the potential of realizing high lithium-ion conductivity, good mechanical properties, wide electrochemical operational window, and stability against metallic lithium, all of which are essential for the development of high-energy-density all-solid-state lithium-ion batteries. In this study, a solvent-free approach has been used to prepare composite electrolytes with tetragonal and cubic phase garnets synthesized via nebulized spray pyrolysis with polyethylene oxide (PEO) being the polymer component. Electrochemical impedance spectroscopy (EIS) is used to examine a series of composites with different garnets and weight fractions. The results show that with the increase in the ceramic weight fraction in the composites, ionic conductivity is reduced and alternative Li-ion transport pathways become accessible for composites as compared to the filler-free electrolytes. An attempt is made to understand the ion transport mechanism within the composites. The role of the chemical and morphological properties of the ceramic filler in polymer-rich and ceramic-rich composite electrolytes is explained by studying the blends of nonconducting ceramics with the Li-conducting polymer, indicating that the intrinsic conductivity of the ceramic filler significantly contributes to the overall conductive process in the ceramic-rich systems. Further, the stability of the garnet/PEO interface is studied via X-ray photoelectron spectroscopy, and its impact on the lithium-ion transport is studied using EIS.

Structural, Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67.

A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO2.67 (Ba3 Co3 O8 □1 ) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10-4  S cm-1 is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-y , confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts.

Investigation of the thermal removal steps of capping agents in the synthesis of bimetallic iridium-based catalysts for the ethanol oxidation reaction.

Two iridium-based catalysts (namely IrSn and IrNi) are synthesised via a polyol route involving capping agents. The capping agents are removed according to a time-consuming multistep heat-treatment protocol described in the literature (N2 → N2/O2 → H2). In this work the effect of each of these steps on the structural composition and catalytic activity is investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and electrochemistry. It is shown that heating in nitrogen is not required, whereas air is the most effective for the removal of the capping agents. Besides FT-IR, the analysis of sp3 carbon (from XPS) turned out to give reasonable insights into capping agent removal. Induced by hydrogen treatment no further change of the surface occurs, while particles tend to grow and become more crystalline. While structural changes are similar for both catalysts, the impact of each of the steps on the catalysis is different: the activity per gram of iridium becomes even lower for IrSn (an electrochemical cleaning agent that was used as reference measurements, seems best suited) while the activity is doubled for the IrNi case. Our results illustrate that the selection of the cleaning procedure strongly depends on the investigated system and should be optimised individually.

On the Impact of the Degree of Fluorination on the ORR Limiting Processes within Iron Based Catalysts: A Model Study on Symmetrical Films of Barium Ferrate.

In this study, symmetrical films of BaFeO2.67, BaFeO2.33F0.33 and BaFeO2F were synthesized and the oxygen uptake and conduction was investigated by high temperature impedance spectroscopy under an oxygen atmosphere. The data were analyzed on the basis of an impedance model designed for highly porous mixed ionic electronic conducting (MIEC) electrodes. Variable temperature X-ray diffraction experiments were utilized to estimate the stability window of the oxyfluoride compounds, which yielded a degradation temperature for BaFeO2.33F0.33 of 590 °C and a decomposition temperature for BaFeO2F of 710 °C. The impedance study revealed a significant change of the catalytic behavior in dependency of the fluorine content. BaFeO2.67 revealed a bulk-diffusion limited process, while BaFeO2.33F0.33 appeared to exhibit a fast bulk diffusion and a utilization region δ larger than the electrode thickness L (8 µm). In contrast, BaFeO2F showed very area specific resistances due to the lack of oxygen vacancies. The activation energy for the uptake and conduction process of oxygen was found to be 0.07/0.29 eV (temperature range-dependent), 0.33 eV and 0.67 eV for BaFeO2.67, BaFeO2.33F0.33 and BaFeO2F, respectively.

Topochemical Fluorination of n = 2 Ruddlesden-Popper Type Sr3Ti2O7 to Sr3Ti2O5F4 and Its Reductive Defluorination.

Within this study, we show that a sequence of substitutive topochemical fluorination of the n = 2 Ruddlesden-Popper type compounds Sr3Ti2O7 to Sr3Ti2O5F4 followed by reductive topochemical defluorination reactions between the oxyfluoride and the reducing agent sodium hydride allows for a substantial reduction of the oxidation state of Ti due to selective extraction and hydride substitution of fluoride ions. The oxyfluoride Sr3Ti2O5F4 has been synthesized and characterized structurally for the first time. The defluorination experiments have been conducted at temperatures as low as 300 °C, enabling also the reduction of this metastable compound. The evolution of phase fractions and unit cell volumes of various reduced phases as well as of side products has been monitored by an X-ray diffraction study as a function of the amount of sodium hydride used. Strong structural changes within the reduced phases, involving considerable decreases in the c lattice parameters partly accompanied by symmetry, lowering have been observed. To gain a deeper understanding of the structural changes, selected reduction reaction products have been further investigated by coupled analysis of X-ray and neutron powder diffraction data. Moreover, changes in the oxidation state of Ti have been studied using magnetic measurements and X-ray photoelectron spectroscopy examining differences between the bulk and the surface properties. Additionally, similarities and differences between previously published results on the topochemical defluorination of the n = 1 Ruddlesden-Popper type compound Sr2TiO3F2 are discussed.

BaCoO2+δ: a new highly oxygen deficient perovskite-related phase with unusual Co coordination obtained by high temperature reaction with short reaction times.

A new highly oxygen deficient metastable modification of perovskite-related BaCoO2+δ (δ ∼ 0.01-0.02) has been prepared using high temperature reactions with short heating times. This defect rich compound has at least partially square planar coordination of the Co2+ ions, a highly unusual coordination environment for Co. Low temperature neutron powder diffraction showed a G-type antiferromagnetic ordering, confirmed by SQUID magnetic measurements, which indicate a high Néel temperature of 220 K. This work shows how novel defective phases can be synthesized by exploiting short reaction times in solid state synthesis, thus offering an alternative route for new materials synthesis.

Molecular and translational advances in meningiomas.

Meningiomas are the most common primary intracranial neoplasm. The current World Health Organization (WHO) classification categorizes meningiomas based on histopathological features, but emerging molecular data demonstrate the importance of genomic and epigenomic factors in the clinical behavior of these tumors. Treatment options for symptomatic meningiomas are limited to surgical resection where possible and adjuvant radiation therapy for tumors with concerning histopathological features or recurrent disease. At present, alternative adjuvant treatment options are not available in part due to limited historical biological analysis and clinical trial investigation on meningiomas. With advances in molecular and genomic techniques in the last decade, we have witnessed a surge of interest in understanding the genomic and epigenomic landscape of meningiomas. The field is now at the stage to adopt this molecular knowledge to refine meningioma classification and introduce molecular algorithms that can guide prediction and therapeutics for this tumor type. Animal models that recapitulate meningiomas faithfully are in critical need to test new therapeutics to facilitate rapid-cycle translation to clinical trials. Here we review the most up-to-date knowledge of molecular alterations that provide insight into meningioma behavior and are ready for application to clinical trial investigation, and highlight the landscape of available preclinical models in meningiomas.

Microstrain and electrochemical performance of garnet solid electrolyte integrated in a hybrid battery cell.

Garnet type solid electrolytes are promising candidates for replacing the flammable liquid electrolytes conventionally used in Li-ion batteries. Al-doped Li7La3Zr2O12 (LLZO) is synthesized using nebulized spray pyrolysis and field assisted sintering technology (FAST), a novel synthesis route ensuring the preparation of samples with a homogeneous elemental distribution and dense ceramic electrolytes. Ceramic preparation utilizing field assisted sintering, in particular the applied pressure, has significant influence on the material structure, i.e. microstrain, and thereby its electrochemical performance. The phenomenon of microstrain enhancement of electrochemical performance might open a new route towards improved garnet solid electrolytes. A detailed mechanism is proposed for the lattice distortion and resulting microstrain during sintering. The charge transfer resistance of Li-ions at the interface between LLZO and Li is characterized using AC impedance spectroscopy and is amongst the best reported values to date. Additionally, the solid electrolyte is integrated in a full hybrid cell, a practical approach combining all the advantages of the solid electrolyte, while maintaining good contact with the cathode material.

Synthesis and characterisation of fluorinated epitaxial films of BaFeO2F: tailoring magnetic anisotropy via a lowering of tetragonal distortion.

In this article, we report on the synthesis and characterisation of fluorinated epitaxial films of BaFeO2F via low-temperature fluorination of thin films of BaFeO2.5+d grown by pulsed laser deposition. Diffraction measurements show that fluoride incorporation only results in a contraction of the film perpendicular to the film surface, where clamping by the substrate is prohibitive for strong in-plane changes. The fluorinated films were found to be homogenous regarding the fluorine content over the whole film thickness, and can be considered as single crystal equivalents to the bulk phase BaFeO2F. Surprisingly, fluorination resulted in the change of the tetragonal distortion to a nearly cubic symmetry, which results in a lowering of anisotropic orientation of the magnetic moments of the antiferromagnetically ordered compound, confirmed by Mössbauer spectroscopy and magnetic studies.

Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite-Type Structure.

Herein, we report the successful electrochemical fluorination and defluorination of schafarzikite-type compounds with the composition Fe0.5 m 0.5Sb2O4 (M=Mg or Co). We show that electrochemical methods can present a more controllable and less environmentally damaging route for fluorinating compounds in contrast to traditional methods that involve heating samples in F2-rich atmospheres. The reactivity of the host lattices with fluoride during electrochemical fluorination makes this material an interesting candidate for fluoride-ion battery applications. However, deleterious side reactions with the conductive carbon matrix during fluorination suggests to the contrary. Regardless of the side reactions, the schafarzikite structure was found to be an alternative reversible host lattice for fluoride incorporation and removal in addition to the previously reported Ruddlesden-Popper-type compounds.