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All solid-state lithium-ion batteries (lithium ASSBs) are promising candidates for their use in high energy density applications like electric vehicles (EVs). With the current global projections of over 130 million EVs on road by 2030, there soon will be a need for lithium ASSBs waste management. For lithium ASSBs, various combinations of solid electrolytes and electrode materials could be imagined, e.g., with garnet electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZTO) and the use of a solid electrolyte might shift focus on recycling strategies. Not only the transition metals of the electrode materials will then be an important target, but also the recovery of La/Zr/Ta. In this work, we present a recycling approach based on a two-step leaching process with citric acid to separate and recover the individual components of a full model cell comprising of Li4Ti5O12 (LTO) anode, Li6.5La3Zr1.5Ta0.5O12 (LLZTO) garnet electrolyte and LiNi1/3Mn1/3Co1/3O2 (NMC) cathode. By treating the complex mixture of LTO/LLZTO/NMC in this process, we manage to separate the materials from each other without strong mixing of elements between the individual phases. We show that the battery components can maintain their principle performance characteristics, demonstrating that the developed process can serve as a basis to recover functional battery materials. Thus, the process developed has a potential for upscaling and can guide towards considering separation capability for battery components in the development of lithium ASSBs.

Within this article, it is shown that an electrochemical defluorination and additional fluorination of Ruddlesden–Popper-type La2NiO3F2 is possible within all-solid-state fluoride-ion batteries. St...

BackgroundThe extent of inappropriate prescribing observed in geriatric medicine has not been thoroughly evaluated in people ageing with HIV. We determined the prevalence of and risk factors for inappropriate prescribing in individuals aged ≥75 years enrolled in the Swiss HIV Cohort Study.MethodsRetrospective review of medical records was performed to gain more insights into non-HIV comorbidities. Inappropriate prescribing was screened using the Beers criteria, the STOPP/START criteria and the Liverpool drug–drug interactions (DDIs) database.ResultsFor 175 included individuals, the median age was 78 years (IQR 76–81) and 71% were male. The median number of non-HIV comorbidities was 7 (IQR 5–10). The prevalence of polypharmacy and inappropriate prescribing was 66% and 67%, respectively. Overall, 40% of prescribing issues could have deleterious consequences. Prescribing issues occurred mainly with non-HIV drugs and included: incorrect dosage (26%); lack of indication (21%); prescription omission (drug not prescribed although indicated) (17%); drug not appropriate in elderly individuals (18%) and deleterious DDIs (17%). In the multivariable logistic regression, risk factors for prescribing issues were polypharmacy (OR: 2.5; 95% CI: 1.3–4.7), renal impairment (OR: 2.7; 95% CI: 1.4–5.1), treatment with CNS-active drugs (OR: 2.1; 95% CI: 1.1–3.8) and female sex (OR: 8.3; 95% CI: 2.4–28.1).ConclusionsPolypharmacy and inappropriate prescribing are highly prevalent in elderly people living with HIV. Women are at higher risk than men, partly explained by sex differences in the occurrence of non-HIV comorbidities and medical care. Medication reconciliation and periodic review of prescriptions by experienced physicians could help reduce polypharmacy and inappropriate prescribing in this vulnerable, growing population.

In this paper, we report on a non-oxidative topochemical route for the synthesis of a novel indate-based oxyfluoride, LaBaInO3F2 using a low-temperature reaction of Ruddlesden-Popper-type LaBaInO4 with polyvinylidene difluoride as a fluorinating agent. The reaction involves the insertion and substitution of oxide ions by fluoride ions. From the characterization via powder X-ray diffraction and Rietveld analysis as well as attenuated electron diffraction tomography it could be followed that the fluorination results in a symmetry lowering from I4/mmm (139) to monoclinic C2/c (15) with an expansion perpendicular to the perovskite layers and a strong tilting of the octahedra along the ab plane. While an ordering of vacancies on the interstitial sites is observed, disorder of anions on the three anion sites seems be favored. The most stable configuration for the anion ordering is estimated based on an evaluation of bond distances from ADT measurements via bond valence sums. The observed disordering of the anions in the oxyfluoride consequently resulted in changes of the bandgap, interestingly leading to an enhanced photocatalytic activity for the hydrogen (H2) evolution as compared to the pure oxide. Thus, we show that topochemical anion modification can present a viable route to obtain improved photocatalysts.

Background Leukocyte telomere length (TL) shortens with age and is associated with coronary artery disease (CAD) events in the general population. Persons living with human immunodeficiency virus (HIV; PLWH) may have accelerated atherosclerosis and shorter TL than the general population. It is unknown whether TL is associated with CAD in PLWH. Methods We measured TL by quantitative polymerase chain reaction (PCR) in white Swiss HIV Cohort Study participants. Cases had a first CAD event during 1 January 2000 to 31 December 2017. We matched 1–3 PLWH controls without CAD events on sex, age, and observation time. We obtained univariable and multivariable odds ratios (OR) for CAD from conditional logistic regression analyses. Results We included 333 cases (median age 54 years; 14% women; 83% with suppressed HIV RNA) and 745 controls. Median time (interquartile range) of TL measurement was 9.4 (5.9–13.8) years prior to CAD event. Compared to the 1st (shortest) TL quintile, participants in the 5th (longest) TL quintile had univariable and multivariable CAD event OR = 0.56 (95% confidence interval [CI], .35–.91) and OR = 0.54 (95% CI, .31–.96). Multivariable OR for current smoking was 1.93 (95% CI, 1.27–2.92), dyslipidemia OR = 1.92 (95% CI, 1.41–2.63), and for recent abacavir, cumulative lopinavir, indinavir, and darunavir exposure was OR = 1.82 (95% CI, 1.27–2.59), OR = 2.02 (95% CI, 1.34–3.04), OR = 3.42 (95% CI, 2.14–5.45), and OR = 1.66 (95% CI, 1.00–2.74), respectively. The TL-CAD association remained significant when adjusting only for Framingham risk score, when excluding TL outliers, and when adjusting for CMV-seropositivity, HCV-seropositivity, time spent with detectable HIV viremia, and injection drug use. Conclusions In PLWH, TL measured >9 years before, is independently associated with CAD events after adjusting for multiple traditional and HIV-related factors.

Within this study, we show that a broad range of reduced phases La2NiO3F2−Δ can be derived from Ruddlesden–Popper-type La2NiO3F2 using a reductive topochemical defluorination method based on reacti...

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 defluori...

Pneumococcal conjugate vaccines (PCVs) have lowered the incidence of invasive pneumococcal disease (IPD) worldwide. However, the influence of regional vaccine uptake differences on the changing epidemiology of IPD remains unclear. We aimed to examine the overall impact of both seven- and 13-valent PCVs (PCV7 and PCV13) on IPD in Switzerland. Three-year periods from 2005–2010 and 2011–2019 were considered, respectively, as (early and late) PCV7 eras and (early, mid and late) PCV13 eras. Vaccine coverage was estimated from a nationwide survey according to east (German-speaking) and west (French/Italian-speaking) regions for each period. Reported incidence rate ratios (IRRs) were compared between successive periods and regions using nationwide IPD surveillance data. Overall IPD incidence across all ages was only 16% lower in the late PCV13 era compared to the early PCV7 era (IRR 0.83, 95% CI 0.79–0.88), due to increasing incidence of non-PCV-type IPD (2.59, 2.37–2.83) in all age groups, except children &lt, 5 years. PCV uptake rates in swiss children were slightly higher in the west than the east (p &lt, 0.001), and were accompanied by lower IPD incidences across all age groups in the former region. Post-PCV13, non-PCV serotypes 8, 22F and 9N were the major cause of IPD in adults ≥65 years. Increased PCV coverage in both areas of Switzerland resulted in a decrease in vaccine-type and overall IPD incidence across all age groups, in a regionally dependent manner. However, the rising incidence of non-vaccine-type IPD, exclusive to older adults, may undermine indirect beneficial effects.

International audience; Fluoride-Ion Batteries (FIBs) have been recently proposed as a post-lithium-ion battery system. This review article presents recent progress of the synthesis and application aspects of the cathode, electrolyte, and anode materials for fluoride-ion batteries. In this respect, improvements in solid-state electrolytes for FIBs as well as liquid electrolytes will be discussed. Furthermore, the achievements regarding the development of cathode and anode materials will be considered. With the improvements made, the field is currently attracting a steady increase of interest, and we will discuss the potentials of this technology together with necessary future milestones to be achieved in order to develop FIBs for future energy storage.

Communications materials 1(1), 27 (2020). doi:10.1038/s43246-020-0030-5, Fluoride ion batteries (FIBs) are a recent alternative all-solid-state battery technology. However, the FIB systems proposed so far suffer from poor cycling performance. In this work, we report La$_{2}$NiO$_{4.13}$ with a Ruddlesden-Popper type structure as an intercalation-based active cathode material in all solid-state FIB with excellent cycling performance. The critical charging conditions to maintain the conductivity of the cell were determined, which seems to be a major obstacle towards improving the cycling stability of FIBs. For optimized operating conditions, a cycle life of about 60 cycles and over 220 cycles for critical cut-off capacities of 50 mAh/g and 30 mAh/g, respectively, could be achieved, with average Coulombic efficiencies between 95 – 99%. Cycling of the cell is a result of fluorination/de-fluorination into and from the La$_{2}$NiO$_{4+d}$ cathode, and it is reve aled that La$_{2}$NiO$_{4.13}$ is a multivalent electrode material. Our findings suggest that La$_{2}$NiO$_{4.13}$ is a promising high energy cathode for FIBs., Published by Springer Nature, London

Within this study, we show that a sequence of substitutive topochemical fluorination of the

The Ruddlesden–Popper (K2NiF4) type phase La2NiO3F2 was prepared via a polymer-based fluorination of La2NiO4+d. The compound was found to crystallize in the orthorhombic space group Cccm (a = 12.8350(4) A, b = 5.7935(2) A, c = 5.4864(2) A). This structural distortion results from an ordered half occupation of the interstitial anion layers and has not been observed previously for K2NiF4-type oxyfluoride compounds. From a combination of neutron and X-ray powder diffraction and 19F magic-angle spinning NMR spectroscopy, it was found that the fluoride ions are only located on the apical anion sites, whereas the oxide ions are located on the interstitial sites. This ordering results in a weakening of the magnetic Ni–F–F–Ni superexchange interactions between the perovskite layers and a reduction of the antiferromagnetic ordering temperature to 49 K. Below 30 K, a small ferromagnetic component was found, which may be the result of a magnetic canting within the antiferromagnetic arrangement and will be the subjec...

Within this study, we demonstrate a newly developed reductive topochemical defluorination method which allows for a selective extraction/substitution of fluoride ions out of transition metal oxyfluorides using NaH as the reducing agent at temperatures as low as 300 °C, enabling the preparation and investigation of anode materials for fluoride-ion batteries in the charged state. A sequence of topochemical reactions, first substitutive fluorination of the K2NiF4 type precursor oxide Sr2TiO4 to Sr2TiO3F2 followed by the reductive defluorination/hydride-fluoride-substitution of Sr2TiO3F2, leads to the formation of compounds with approximate compositions of Sr2TiO3FH0.48 and Sr2TiO3H1.48. The evolution of the unit cell volumes upon extraction/substitution of fluoride ions has been monitored by an X-ray diffraction study. Strong structural changes were observed during the reaction, expressed by a decrease of the c-axis from ∼15.5 A in Sr2TiO3F2 to ∼13.0 A in Sr2TiO3FH0.48 and ∼12.7 A in Sr2TiO3H1.48, with additional symmetry lowering for Sr2TiO3FH0.48, and confirmed by neutron powder diffraction. Changes of the Ti oxidation states and coordination environment were examined and confirmed by means of X-ray absorption spectroscopy, electron paramagnetic resonance and magnetic measurements. Furthermore, we found that the surface chemistry of such compounds differs significantly from the bulk properties by means of an X-ray photoelectron spectroscopy study, showing that surface compositions of Sr2TiO3F and Sr2TiO3 with Ti3+ and Ti2+ species can be obtained on the reaction, respectively. We further highlight that a ‘direct’ reduction of the oxide precursor Sr2TiO4 to Sr2TiO3 is not possible using the same method. Therefore, the two-step modification of Sr2TiO4 allows for the preparation of compounds with low oxidation states at the lowest temperatures used so far for hydride based reductions of titanium containing oxides (300 °C compared to ∼600 °C used previously). The observed differences in the reactivity of oxyfluorides compared to oxides are well supported by DFT based calculations of formation energies. They show that the formation of NaF is a strong driving force, resulting in exergonic reductions/hydride-fluoride substitution reactions as compared to the endergonic formation of Na2O for pure oxide compounds.

Perovskite oxides exhibiting mixed protonic and electronic conductivities have interesting applications in protonic ceramic fuel cells. In this work, we report on a hydrated phase of BaCoO1.80(OH)0.86 synthesized using nebulized spray pyrolysis. Structural analysis based on X-ray and neutron powder diffraction data showed that the compound is isotypic to BaFeO2.33(OH)0.33. The water loss behaviour was studied using simultaneous thermal analysis and high temperature X-ray diffraction, indicating that protons (respectively water) can be stabilized within the compound up to temperatures significantly above 673 K, confirmed by ex situ Fourier transform infrared spectroscopy studies. Impedance spectroscopy was used to determine the conductivity characteristics of BaCoO1.80(OH)0.86, finding and a total electrical conductivity in the order of 10−4 S cm−1 at ambient temperature with an activation energy of 0.28 eV.

Within this work, monodisperse porous silicon nanospheres have been derived from monodisperse silica nanospheres via two different magnesiothermic reduction routes, namely (i) magnesiothermic reduction using a two-chamber set-up, and (ii) magnesiothermic reduction using NaCl as heat scavenger. Both methods allow a size- and shape-preserving preparation of mesoporous silicon. Crystalline silicon with a particle size of 56 nm and a specific surface area of 198 m2 g− 1 and amorphous silicon with a particle size of 35 nm and a specific surface area of 623 m2 g− 1 are synthesized using the two chamber and salt assisted routes, respectively. TEM micrographs confirm enhanced porous character of silicon from NaCl assisted route. An unstable electrochemical performance of the crystalline silicon is found, whereas the amorphous Si presents a stable electrochemical behavior.

In this work, we present an easy and environmentally friendly approach to stabilize nanostructured, porous crystalline (Sitc) and amorphous (Sisa) silicon synthesized via magnesiothermic reduction. As matrix, fructose-derived carbon, polymer-derived SiOC ceramic or both, carbon and SiOC, are used. By means of X-ray diffraction and Raman spectroscopy it is found that the crystallinity of Sitc as well as the amorphous character of Sisa is preserved in the final composites. Embedding of crystalline silicon into carbon leads to high initial capacities of ~ 600–650 mAh·g− 1, but only the matrix consisting of carbon and SiOC results in a stable cycling behaviour over 50 cycles with a final capacity of 575 mAh·g− 1. All composites derived from amorphous Sisa show a stable cycling behaviour; the highest, stable capacity of ~ 500 mAh·g− 1 is observed when silicon is covered with carbon and SiOC.

Perovskite oxides exhibiting mixed protonic and electronic conductivities have interesting applications in protonic ceramic fuel cells. In this work, we report on a hydrated phase of BaCoO1.80(OH)0.86 synthesized using nebulized spray pyrolysis. Structural analysis based on X-ray and neutron powder diffraction data showed that the compound is isotypic to BaFeO2.33(OH)0.33. The water loss behaviour was studied using simultaneous thermal analysis and high temperature X-ray diffraction, indicating that protons (respectively water) can be stabilized within the compound up to temperatures significantly above 673 K, confirmed by ex situ Fourier transform infrared spectroscopy studies. Impedance spectroscopy was used to determine the conductivity characteristics of BaCoO1.80(OH)0.86, finding and a total electrical conductivity in the order of 10-4 S cm-1 at ambient temperature with an activation energy of 0.28 eV.

The Ruddlesden-Popper (K

This article reports on the investigation of LaSrMnO4 with K2NiF4 type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF2 based anodes and shows that fluoride intercalation proceeds stepwise to form LaSrMnO4F and LaSrMnO4F2–x. Ex-situ X-ray diffraction experiments were recorded for different cutoff voltages for a deeper understanding of the charging process, highlighting additional potential of the method to be used to adjust fluorine contents more easily than using conventional fluorination methods. A discharging capacity of approximately 20–25 mAh/g was found, which is ∼4–5 times higher compared to what was reported previously on the discharging of BaFeO2.5/BaFeO2.5F0.5, approaching discharge capacities for conversion based fluoride ion batteries. Density functional theory based calculations confirm the observed potential steps of approximately 1 and 2 V for the first (LaSrMnO4 → LaSrMnO4F) a...

SummaryEndothelial dysfunction and enhanced platelet reactivity in congestive heart failure (CHF) contribute to poor prognosis. CHF patients display an impaired responsiveness to clopidogrel. Fractalkine activates platelets and elevated plasma levels of this chemokine are a feature of CHF. We here addressed the interrelation of fractalkine, platelet reactivity and clopidogrel efficacy in humans and rats with CHF. Fractalkine serum levels determined by ELISA were increased in CHF patients (CHF: 1548 ± 650 pg/ml; Control: 968 ± 575 pg/ml, p

The amorphisation of the lithiated crystalline silicon after the extraction of lithium in LiPF6/carbonates mixture based electrolyte has been demonstrated by the work of Obrovac and Christiansen [1] ten years ago. Within this work, we focus on the structural changes of the crystalline nanosilicon (nSi, 30-50nm) during electrochemical cycling in ionic liquid (IL) based electrolytes. By means of Raman Spectroscopy and X-Rays Diffraction we investigate the nSi electrodes after 1 cycle of lithium insertion/extraction in 0.8 M LiTFSI in 1-Methyl-1-propylpyrrolidiniumbis (trifluoromethylsulfonyl) imide (P13TFSI) and 1-Methyl-1-propylpiperidiniumbis (trifluoromethylsulfonyl) imide (PP13TFSI). For comparison, nSi electrode is also cycled in conventional LP30 electrolyte. The electrodes consist of 85 wt-% of nSi, 5 wt-% carbon black and 10 wt-% of CMC, the electrode is loading about 0.2 mg*cm-2, insertion/extraction current is 180 mA*g-1. During the first lithium insertion/extraction similar electrochemical behavior is observed in all electrolytes (Fig.1). Nevertheless, during extended cycling the capacity fade is much faster in ionic liquids with respect to LP30. The Raman spectra (Fig. 2) taken after lithium extraction in LP30 show clearly the broad band of amorphous silicon between 430 – 500 cm-1. In contrary no amorphous silicon is found after lithium extraction from nSi electrode in ionic liquids. Instead, the band located at ~ 506 cm-1 is registered in reproducible manner. The sample heating effect leading to the silicon phase transformation and peak of the shift can be excluded as low power of the laser was applied (less than 3 mW) and no significant difference was registered in three subsequent measurements. This shift has already been observed for lithiated silicon, however it has not been commented [2]. On the other hand, very detailed Raman spectroscopy investigation of the phase evolution of crystalline cubic silicon Si-I evolution under stress by means of Vickers indentation has been performed [3] [4]. In the center of the indent, amorphisation of the silicon leading to the broad Raman band at ~480 cm-1 was observed, while a pileup at the border of the indent was assigned to hexagonal silicon Si-IV, appearing as a band at 500-510 cm-1in Raman spectra. Direct phase transition of Si -I to Si-IV requires a high level of a shear deformation. Since the same shift of the Raman peak is observed in our electrochemical experiments of lithiation/delithiation of crystalline cubic nSi, it could be intuitively assumed that hexagonal silicon Si-IV is formed in ionic after cycling in ionic liquids. The XRD measurements confirm Raman Spectroscopy findings. The investigation, if the observed structural differences are the reason of the faster capacity fading of silicon electrode in ILs, is in progress. Is it possible that silicon is exposed to high shear deformation when cycled in ILs? Is it related to the insertion/reaction of TFSI anion which takes place at 0.8 – 1V? Within this work we try at least partially answer these questions. To our best knowledge the basic characteristic of silicon behavior in ILs has never been addressed in electrochemical setups in such context. Therefore, taking into account the interest of the scientific community towards application of silicon anodes as well as ionic liquids electrolytes, we consider this basic study of high importance. Fig. 1 Lithium insertion - extraction curves into nSi electrode recorded in LP30, P13TFSI and PP13TFSI, 180 mAg-1 Fig. 2 Raman Spectra of the nSi electrodes, pristine and after one cycle (Fig.1). [1] M.N. Obrovac, L. Christensen, Electrochemical and Solid-State Letters, 7 (2004) A93-A96. [2] H. Li, X. Huang, L. Chen, G. Zhou, Z. Zhang, D. Yu, Y.J. Mo, N. Pei, Solid State Ionics, 135 (2000) 181-191. [3] A. Kailer, Y.G. Gogotsi, K.G. Nickel, Journal of Applied Physics, 81 (1997) 3057-3063. [4] T. Wermelinger, R. Spolenak, Journal of Raman Spectroscopy, 40 (2009) 679-686.