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1.
J Am Chem Soc ; 146(3): 1992-2004, 2024 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-38221743

RESUMEN

Solid polymer electrolytes (SPEs) have emerged as promising candidates for sodium-based batteries due to their cost-effectiveness and excellent flexibility. However, achieving high ionic conductivity and desirable mechanical properties in SPEs remains a challenge. In this study, we investigated an AB diblock copolymer, PS-PEA(BuImTFSI), as a potential SPE for sodium batteries. We explored binary and ternary electrolyte systems by combining the polymer with salt and [C3mpyr][FSI] ionic liquid (IL) and analyzed their thermal and electrochemical properties. Differential scanning calorimetry revealed phase separation in the polymer systems. The addition of salt exhibited a plasticizing effect localized to the polyionic liquid (PIL) phase, resulting in an increased ionic conductivity in the binary electrolytes. Introducing the IL further enhanced the plasticizing effect, elevating the ionic conductivity in the ternary system. Spectroscopic analysis, for the first time, revealed that the incorporation of NaFSI and IL influences the conformation of TFSI- and weakens the interaction between TFSI- and the polymer. This establishes correlations between anions and Na+, ultimately enhancing the diffusivity of Na ions. The electrochemical properties of an optimized SPE in Na/Na symmetrical cells were investigated, showcasing stable Na plating/stripping at high current densities up to 0.7 mA cm-2, maintaining its integrity at 70 °C. Furthermore, we evaluated the performance of a Na|NaFePO4 cell cycled at different rates (C/10 and C/5) and temperatures (50 and 70 °C), revealing remarkable high-capacity retention and Coulombic efficiency. This study highlights the potential of solvent-free diblock copolymer electrolytes for high-performance sodium-based energy storage systems, contributing to advanced electrolyte materials.

2.
Thorax ; 79(10): 934-942, 2024 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-39107111

RESUMEN

BACKGROUND: Silicosis, a chronic respiratory disease caused by crystalline silica exposure, is a persistent global lung health issue. No systematic review of the relationship between cumulative respirable crystalline silica (RCS) exposure and silicosis exists. UK exposure limits are currently under review. We therefore performed a systematic review and dose-response meta-analysis of this relationship. METHODS: Web of Science, Medline and Embase were searched on 24 February 2023. Studies of radiographic, autopsy or death certificate silicosis, with an estimated average follow-up of over 20 years since first employment, were included. Cumulative silicosis risk methods were compared. The relative risks (RR) of silicosis at increasing cumulative exposures were calculated and used to estimate the absolute risk reduction (ARR). RESULTS: Eight eligible studies, including 10 cohorts, contributed 8792 cases of silicosis among 65 977 participants. Substantial differences in cumulative risk estimates between methodologies exist. Using the same method, we observed higher cumulative silicosis risks among mining compared with non-mining cohorts. A reduction from 4 to 2 mg/m³-years in cumulative RCS exposure corresponded to substantial risk reductions among miners (RR 0.23 (95% CI 0.18 to 0.29, I2=92.9%) with an ARR of 323 (95% CI 298 to 344) per 1000) and non-miners (RR 0.55 (95% CI 0.36 to 0.83, I2=77.0%) with an ARR of 23 (95% CI 9 to 33) per 1000). CONCLUSION: Despite significant heterogeneity, our findings support a reduction in permissible exposure limits from 0.1 mg/m3 to 0.05 mg/m³, particularly among mining populations. Further research is needed among non-miners as only two studies were eligible.


Asunto(s)
Exposición Profesional , Dióxido de Silicio , Silicosis , Silicosis/etiología , Humanos , Dióxido de Silicio/efectos adversos , Exposición Profesional/efectos adversos
3.
Small ; 20(1): e2304844, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37653594

RESUMEN

Fabricating highly efficient and long-life redox bifunctional electrocatalysts is vital for oxygen-related renewable energy devices. To boost the bifunctional catalytic activity of Fe-N-C single-atom catalysts, it is imperative to fine-tune the coordination microenvironment of the Fe sites to optimize the adsorption/desorption energies of intermediates during oxygen reduction/evolution reactions (ORR/OER) and simultaneously avoid the aggregation of atomically dispersed metal sites. Herein, a strategy is developed for fabricating a free-standing electrocatalyst with atomically dispersed Fe sites (≈0.89 wt.%) supported on N, F, and S ternary-doped hollow carbon nanofibers (FeN4 -NFS-CNF). Both experimental and theoretical findings suggest that the incorporation of ternary heteroatoms modifies the charge distribution of Fe active centers and enhances defect density, thereby optimizing the bifunctional catalytic activities. The efficient regulation isolated Fe centers come from the dual confinement of zeolitic imidazole framework-8 (ZIF-8) and polymerized ionic liquid (PIL), while the precise formation of distinct hierarchical three-dimensional porous structure maximizes the exposure of low-doping Fe active sites and enriched heteroatoms. FeN4 -NFS-CNF achieves remarkable electrocatalytic activity with a high ORR half-wave potential (0.90 V) and a low OER overpotential (270 mV) in alkaline electrolyte, revealing the benefit of optimizing the microenvironment of low-doping iron single atoms in directing bifunctional catalytic activity.

4.
Nat Mater ; 21(9): 1057-1065, 2022 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-35788569

RESUMEN

Rechargeable batteries paired with sodium metal anodes are considered to be one of the most promising high-energy and low-cost energy-storage systems. However, the use of highly reactive sodium metal and the formation of sodium dendrites during battery operation have caused safety concerns, especially when highly flammable liquid electrolytes are used. Here we design and develop solvent-free solid polymer electrolytes (SPEs) based on a perfluoropolyether-terminated polyethylene oxide (PEO)-based block copolymer for safe and stable all-solid-state sodium metal batteries. Compared with traditional PEO SPEs, our results suggest that block copolymer design allows for the formation of self-assembled nanostructures leading to high storage modulus at elevated temperatures with the PEO domains providing transport channels even at high salt concentration (ethylene oxide/sodium = 8/2). Moreover, it is demonstrated that the incorporation of perfluoropolyether segments enhances the Na+ transference number of the electrolyte to 0.46 at 80 °C and enables a stable solid electrolyte interface. The new SPE exhibits highly stable symmetric cell-cycling performance at high current density (0.5 mA cm-2 and 1.0 mAh cm-2, up to 1,000 h). Finally, the assembled all-solid-state sodium metal batteries demonstrate outstanding capacity retention, long-term charge/discharge stability (Coulombic efficiency, 99.91%; >900 cycles with Na3V2(PO4)3 cathode) and good capability with high loading NaFePO4 cathode (>1 mAh cm-2).

5.
Nat Mater ; 19(10): 1096-1101, 2020 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-32367080

RESUMEN

Non-uniform metal deposition and dendrite formation in high-density energy storage devices reduces the efficiency, safety and life of batteries with metal anodes. Superconcentrated ionic-liquid electrolytes (for example 1:1 ionic liquid:alkali ion) coupled with anode preconditioning at more negative potentials can completely mitigate these issues, and therefore revolutionize high-density energy storage devices. However, the mechanisms by which very high salt concentration and preconditioning potential enable uniform metal deposition and prevent dendrite formation at the metal anode during cycling are poorly understood, and therefore not optimized. Here, we use atomic force microscopy and molecular dynamics simulations to unravel the influence of these factors on the interface chemistry in a sodium electrolyte, demonstrating how a molten-salt-like structure at the electrode surface results in dendrite-free metal cycling at higher rates. Such a structure will support the formation of a more favourable solid electrolyte interphase, accepted as being a critical factor in stable battery cycling. This new understanding will enable engineering of efficient anode electrodes by tuning the interfacial nanostructure via salt concentration and high-voltage preconditioning.

6.
Curr Cardiol Rep ; 22(1): 2, 2020 01 15.
Artículo en Inglés | MEDLINE | ID: mdl-31940097

RESUMEN

PURPOSE OF REVIEW: This review provides an update on the immunopathogenesis of tuberculous pericarditis (TBP), investigations to confirm tuberculous etiology, the limitations of anti-tuberculous therapy (ATT), and recent efficacy trials. RECENT FINDINGS: A profibrotic immune response characterizes TBP, with low levels of AcSDKP, high levels of γ-interferon and IL-10 in the pericardium, and high levels of TGF-ß and IL-10 in the blood. These findings may have implications for future therapeutic targets. Despite advances in nucleic acid amplification approaches, these tests remain disappointing for TBP. Trials of corticosteroids and colchicine have had mixed results, with no impact on mortality, evidence of a reduction in rates of constrictive pericarditis and potential harm in those with advanced HIV. Small studies suggest that ATT penetrates the pericardium poorly. Given that there is a close association between high bacillary burden and mortality, a rethink about the optimal drug doses and duration may be required. The high mortality and morbidity from TBP despite use of anti-tuberculous drugs call for researches targeting host-directed immunological determinants of treatment outcome. There is also a need for the identification of steps in clinical management where interventions are needed to improve outcomes.


Asunto(s)
Antituberculosos/uso terapéutico , Pericarditis Tuberculosa/diagnóstico , Pericarditis Tuberculosa/tratamiento farmacológico , Manejo de la Enfermedad , Humanos , Derrame Pericárdico/diagnóstico , Derrame Pericárdico/tratamiento farmacológico , Pericarditis Constrictiva/diagnóstico , Pericarditis Constrictiva/tratamiento farmacológico , Pericarditis Tuberculosa/etiología , Pericardio
7.
Emerg Infect Dis ; 24(8): 1412-1421, 2018 08.
Artículo en Inglés | MEDLINE | ID: mdl-30014839

RESUMEN

We describe a case series of 35 Ebola virus disease (EVD) survivors during the epidemic in West Africa who had neurologic and accompanying psychiatric sequelae. Survivors meeting neurologic criteria were invited from a cohort of 361 EVD survivors to attend a preliminary clinic. Those whose severe neurologic features were documented in the preliminary clinic were referred for specialist neurologic evaluation, ophthalmologic examination, and psychiatric assessment. Of 35 survivors with neurologic sequelae, 13 had migraine headache, 2 stroke, 2 peripheral sensory neuropathy, and 2 peripheral nerve lesions. Of brain computed tomography scans of 17 patients, 3 showed cerebral and/or cerebellar atrophy and 2 confirmed strokes. Sixteen patients required mental health followup; psychiatric disorders were diagnosed in 5. The 10 patients who experienced greatest disability had co-existing physical and mental health conditions. EVD survivors may have ongoing central and peripheral nervous system disorders, including previously unrecognized migraine headaches and stroke.


Asunto(s)
Epidemias , Fiebre Hemorrágica Ebola/complicaciones , Fiebre Hemorrágica Ebola/epidemiología , Trastornos Migrañosos/etiología , Enfermedades del Sistema Nervioso Periférico/etiología , Accidente Cerebrovascular/etiología , Adulto , Estudios de Cohortes , Femenino , Humanos , Masculino , Sierra Leona/epidemiología , Adulto Joven
8.
Phys Chem Chem Phys ; 20(6): 4579-4586, 2018 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-29376537

RESUMEN

Proton conductors are widely used in different electrochemical devices including fuel cells and redox flow batteries. Compared to conventional proton conducting polymer membranes, protic organic ionic plastic crystal (POIPC) is a novel solid-state proton conductor with high proton conductivity even under anhydrous conditions. In this work, different organic protic salts based on the same parent di-functional cation with different anions were synthesized and characterized. It is found that the di-protonated cation plays an important role in defining the thermal properties, leading to stronger plastic crystal behavior and a higher melting point. Static solid-state NMR and the synchrotron XRD results show that the di-protonated cation allows greater dynamics in the crystal in contrast to the mono-protonated counterparts. The 1-(N,N-dimethylammonium)-2-(ammonium)ethane triflate ([DMEDAH2][Tf]2) has the highest ionic conductivity of 1.1 × 10-4 S cm-1 at 50 °C, whereas the bis(trifluoromethanesulfonyl)amide counterpart [DMEDAH2][TFSA]2 has the lowest ionic conductivity (2.8 × 10-7 S cm-1 at 50 °C) with no measureable mobile ion component at this temperature. The fraction of mobile species is significantly suppressed in the TFSA containing salts as against the Tf systems.

9.
Phys Chem Chem Phys ; 19(3): 2225-2234, 2017 Jan 18.
Artículo en Inglés | MEDLINE | ID: mdl-28054060

RESUMEN

Using the organic ionic plastic crystal N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C2mpyr][FSI]) with electrospun nanofibers, LiFSI doped [C2mpyr][FSI]-PVdF composites were developed as solid state, self-standing electrolyte membranes. Different lithium salt concentration were investigated, with 10 mol% LiFSI found to be optimal amongst those assessed. Composites with different weight ratios of plastic crystal and polymer were prepared and 10 wt% polymer gave the highest conductivity. In addition, the effects of PVdF incorporation on the morphological, thermal, and structural properties of the organic ionic plastic crystal were investigated. Ion mobilities were also studied using solid-state nuclear magnetic resonance techniques. The electrolytes were then assembled into lithium symmetric cells and cycled galvanostatically at 0.13 mA cm-2 at both ambient temperature and at 50 °C, for more than 500 cycles.

10.
Phys Chem Chem Phys ; 18(42): 29337-29347, 2016 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-27734040

RESUMEN

The electrochemical systems containing zinc dicyanamide salt (Zn(dca)2) in both 1-ethyl-3-methylimidazolium dicyanamide ([C2mim][dca]) and N-butyl-N-methylpyrrolidinium dicyanamide ([C4mpyr][dca]) ionic liquids (ILs) have been studied by atomic force microscopy (AFM) on a highly oriented pyrolytic graphite (HOPG) surface under different conditions and applied potentials. The results reveal the following: (1) interfacial layers exist in both ILs, even after the addition of 3 wt% water and 9 mol% Zn(dca)2 salt. (2) The number of layers is different for the different ILs, with the [C2mim][dca]-based samples exhibiting a much more limited interfacial structure compared to the [C4mpyr][dca] at almost all of the tested conditions. (3) For the [C4mpyr][dca]-based samples, without added zinc salt, the number of detected interfacial layers increases with negative potential. With added zinc, the [C4mpyr][dca] sample shows about the same number of layers independent of the applied potentials, namely between 5-7. Likewise, for the [C2mim][dca] samples, with the zinc added the sample shows the same number of layers at the applied potentials, but for this system only 1-2 layers are detected. And (4) the addition of Zn(dca)2 into the [C2mim][dca] IL does not cause a large change in the interfacial ordering, whereas the addition of the same salt into the [C4mpyr][dca] samples is marked by a stark increase in both the number and the consistency of the perceived interfacial layers. These results are significant because they show a marked difference in the interfacial nanostructure between two zinc-based electrochemical systems that were previously shown to have distinctly different electrochemical behaviour, despite their chemical similarity.

11.
Phys Chem Chem Phys ; 18(9): 6541-7, 2016 Mar 07.
Artículo en Inglés | MEDLINE | ID: mdl-26865399

RESUMEN

The efficacy of ionic liquids (ILs) as lubricant additives to a model base oil has been probed at the nanoscale and macroscale as a function of IL concentration using the same materials. Silica surfaces lubricated with mixtures of the IL trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate and hexadecane are probed using atomic force microscopy (AFM) (nanoscale) and ball-on-disc tribometer (macroscale). At both length scales the pure IL is a much more effective lubricant than hexadecane. At the nanoscale, 2.0 mol% IL (and above) in hexadecane lubricates the silica as well as the pure IL due to the formation of a robust IL boundary layer that separates the sliding surfaces. At the macroscale the lubrication is highly load dependent; at low loads all the mixtures lubricate as effectively as the pure IL, whereas at higher loads rather high concentrations are required to provide IL like lubrication. Wear is also pronounced at high loads, for all cases except the pure IL, and a tribofilm is formed. Together, the nano- and macroscales results reveal that the IL is an effective lubricant additive - it reduces friction - in both the boundary regime at the nanoscale and mixed regime at the macroscale.

12.
Phys Chem Chem Phys ; 17(6): 4656-63, 2015 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-25587829

RESUMEN

Electrolytes based on bis(fluorosulfonyl)imide (FSI) with a range of LiFSI salt concentrations were characterized using physical property measurements, as well as NMR, FT-IR and Raman spectroscopy. Different from the behavior at lower concentrations, the FSI electrolyte containing 1 : 1 salt to IL mole ratio showed less deviation from the KCl line in the Walden plot, suggesting greater ionic dissociation. Diffusion measurements show higher mobility of lithium ions compared to the other ions, which suggests that the partial conductivity of Li(+) is higher at this higher composition. Changes in the FT-IR and Raman peaks indicate that the cis-FSI conformation is preferred with increasing Li salt concentration.

13.
Phys Chem Chem Phys ; 16(45): 25062-70, 2014 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-25330106

RESUMEN

New findings supporting the stability of the superoxide ion, O2˙(-), in the presence of the phosphonium cation, [P6,6,6,14](+), are presented. Extended electrochemical investigations of a series of neat phosphonium-based ILs with different anions, including chloride, bis(trifluoromethylsulfonyl)imide and dicyanamide, demonstrate the chemical reversibility of the oxygen reduction process. Quantum chemistry calculations show a short intermolecular distance (r = 3.128 Å) between the superoxide ion and the phosphonium cation. NMR experiments have been performed to assess the degree of long term degradation of [P6,6,6,14](+), in the presence of superoxide and peroxide species, showing no chemically distinct degradation products of importance in reversible air cathodes.

14.
Adv Mater ; 36(26): e2311272, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38377229

RESUMEN

The rational construction of highly active and durable oxygen-reactive electrocatalysts for oxygen reduction/evolution reaction (ORR/OER) plays a critical role in rechargeable metal-air batteries. It is pivotal to achieve optimal utilization of electrocatalytically active sites and valid control of the high specific internal surface area. Inspiration for designing electrocatalysts can come from nature, as it is full of precisely manipulated and highly efficient structures. Herein, inspired by earthworms fertilizing soil, a 3D carbon nanofibrous electrocatalyst with multiple interconnected nanoconfined channels, cobalt-based heterojunction active particles and enriched N, S heteroatoms (Co/Co3O4/CoF2@NSC with confined channels) is rationally designed, showing superior bifunctional electrocatalytic activity in alkaline electrolyte, even outperforming that of benchmark Pt/C-RuO2 catalyst. This work demonstrates a new method for porous structural regulation, in which the internal confined channels within the nanofibers are controllably formed by the spontaneous migration of cobalt-based nanoparticles under a CO2 atmosphere. Theoretical analysis reveals that constructing Co/Co3O4/CoF2@NSC electrocatalyst with confined channels can greatly adjust the electron distribution, effectively lower the reaction barrier of inter-mediate and reduce the OER/ORR overpotential. This work introduces a novel and nature-inspired strategy for designing efficient bifunctional electrocatalysts with well-designed architectures.

15.
Ann Work Expo Health ; 68(1): 48-57, 2024 01 08.
Artículo en Inglés | MEDLINE | ID: mdl-37824745

RESUMEN

BACKGROUND: Globally, the number of small-scale miners (SSM) is estimated to be more than 25 million, but it supports the livelihoods of around 100 million individuals. In Tanzania, the number of SSM has increased from an estimated 150,000 in 1987 to ~1.5 million in 2017. The miners are at a high risk of occupational-related health challenges. The study aimed to assess the concentrations of respirable crystalline silica (RCS) and radon among the tanzanite mining communities in Simanjiro District, Tanzania. METHODS: We carried out a cross-sectional study involving the Mererani mines in Tanzania. These are underground mines comprised of informally employed miners, i.e. SSM. Concentrations of RCS and radon gas were measured in 44 study units, i.e. 22 mining pits and within 22 houses in the general community, e.g. shops in the peri-mining community. A total of 132 respirable personal dust exposure samples (PDS), 3 from each of the study units were taken, but only 66 PDS from the mining pits were analysed, as this was the main interest of this study. Radon concentration was measured by continuous monitoring throughout the working shift (and overnight for residences) using AlphaGuard monitor. The medians and comparison to the reference values, OSHA USA PEL and WHO/IARC references, were done for RCS and radon, respectively, using SPSS Ver. 27.0.0). RESULTS: The median time-weighted average (TWA) concentration of the RCS in the mining pits was 1.23 mg/m3. Of all 66 personal dust samples from the mining pits, 65 (98.5%) had concentrations of RCS above the Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) of 0.05 mg/m3. Mining pits had a median radon concentration of 169.50 bq/m3, which is above the World Health Organization (WHO)/International Commission on Radiation Protection (ICRP) recommended reference of 100.00 bq/m3 but not above the upper reference of 300.00 bq/m3, while the community buildings had a median radon concentration of 88.00 bq/m3. Overall, 9 (20.5%) and 17 (38.6%) radon measurements were above 300.00 bq/m3 and between 100.00 and 300.00 bq/m3 references, respectively. Specifically, in the mining pits, 9 (40.9%) test results were above 300.00 bq/m3, while none of the test results in the community was above 300.00 bq/m3. CONCLUSION: The tanzanite SSM in Mererani we highly exposed to RCS, which increases the risk of pulmonary diseases, including silicosis, tuberculosis, and pulmonary malignancies. Immediate action by OSHA Tanzania should be enforcement of wearing respirators by all miners throughout the working hours. Health education programmes to the SSM must be strengthened and OSHA Tanzania should adopt the 0.05 mg/m3 PEL, and enforce other occupational health and safety measures, including regular use of dust suppression mechanisms (water spray and wet drilling) and monitoring of RCS exposures among SSM. Monitoring of radon exposure both in the mining pits and community buildings should be conducted, and mitigation measures should be implemented in areas that exceed the reference level of 100.00 bq/m3.


Asunto(s)
Exposición Profesional , Radón , Humanos , Exposición Profesional/análisis , Radón/análisis , Tanzanía , Estudios Transversales , Dióxido de Silicio/análisis , Polvo/análisis
16.
ACS Nano ; 18(4): 3531-3541, 2024 Jan 30.
Artículo en Inglés | MEDLINE | ID: mdl-38236027

RESUMEN

Metallic lithium (Li) is the most attractive anode for Li batteries because it holds the highest theoretical specific capacity (3860 mA h g-1) and the lowest redox potential (-3.040 V vs SHE). However, the poor interface stability of the Li anode, which is caused by the high reactivity and dendrite formation of metallic Li upon cycling, leads to undesired electrochemical performance and safety issues. While two-dimensional boron nitride (BN) nanosheets have been utilized as an interfacial layer, the mechanism on how they stabilize the Li-electrolyte interface remains elusive. Here, we show how BN nanosheet interlayers suppress Li dendrite formation, enhance Li ion transport kinetics, facilitate Li deposition, and reduce electrolyte decomposition. We show through both simulation and experimental data that the desolvation process of a solvated Li ion within the interlayer nanochannels kinetically favors Li deposition. This process enables long cycling stability, reduced voltage polarization, improved interface stability, and negligible volume expansion. Their application as an interfacial layer in symmetric cells and full cells that display significantly improved electrochemical properties is also demonstrated. The knowledge gained in this study provides both critical insights and practical guidelines for designing a Li metal anode with significantly improved performance.

17.
Phys Chem Chem Phys ; 15(33): 13784-9, 2013 Sep 07.
Artículo en Inglés | MEDLINE | ID: mdl-23753038

RESUMEN

All solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes are described for the first time. The new composite materials exhibit enhanced conductivity, excellent thermal, mechanical and electrochemical stability and allow the production of optically transparent, free-standing, flexible, thin film electrolytes (10's µms thick) for application in electrochemical devices. Stable cycling of a lithium cell incorporating the new composite electrolyte is demonstrated, including cycling at lower temperatures than previously possible with the pure material.

18.
Phys Chem Chem Phys ; 15(45): 19570-4, 2013 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-24141563

RESUMEN

A molecular-level understanding of why the addition of lithium salts to Organic Ionic Plastic Crystals (OIPCs) produces excellent ionic conductivity is described for the first time. These materials are promising electrolytes for safe, robust lithium batteries, and have been experimentally characterised in some detail. Here, molecular dynamics simulations demonstrate the effects of lithium ion doping on both the structure and dynamics of an OIPC matrix (tetramethylammonium dicyanamide [TMA][DCA]) and illustrate a molecular-level transport model: in the plastic crystal phase lithium ions can form clusters with [DCA](-), and this clustering then in turn creates free volume or defect paths in the remainder of the lattice, which enhances ion conduction.

19.
PLOS Glob Public Health ; 3(9): e0002085, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37733799

RESUMEN

An estimated 44 million artisanal and small-scale miners (ASM), largely based in developing economies, face significant occupational risks for respiratory diseases which have not been reviewed. We therefore aimed to review studies that describe silicosis and tuberculosis prevalence and respirable crystalline silica (RCS) exposures among ASM and use background evidence to better understand the relationship between exposures and disease outcomes. We searched PubMed, Web of Science, Scopus and Embase for studies published before the 24th March 2023. Our primary outcome of interest was silicosis or tuberculosis among ASM. Secondary outcomes included measurements of respirable dust or silica, spirometry and prevalence of respiratory symptoms. A systematic review and narrative synthesis was performed and risk of bias assessed using the Joanna Briggs Prevalence Critical Appraisal Tool. Logistic and Poisson regression models with predefined parameters were used to estimate silicosis prevalence and tuberculosis incidence at different distributions of cumulative silica exposure. We identified 18 eligible studies that included 29,562 miners from 13 distinct populations in 10 countries. Silicosis prevalence ranged from 11 to 37%, despite four of five studies reporting an average median duration of mining of <6 years. Tuberculosis prevalence was high; microbiologically confirmed disease ranged from 1.8 to 6.1% and clinical disease 3.0 to 17%. Average RCS intensity was very high (range 0.19-89.5 mg/m3) and respiratory symptoms were common. Our modelling demonstrated decreases in cumulative RCS are associated with reductions in silicosis and tuberculosis, with greater reductions at higher mean exposures. Despite potential selection and measurement bias, prevalence of silicosis and tuberculosis were high in the studies identified in this review. Our modelling demonstrated the greatest respiratory health benefits of reducing RCS are in those with highest exposures. ASM face a high occupational respiratory disease burden which can be reduced by low-cost and effective reductions in RCS.

20.
Artículo en Inglés | MEDLINE | ID: mdl-38029333

RESUMEN

Organic ionic plastic crystals (OIPCs) are attractive solid electrolyte materials for advanced energy storage systems owing to their inherent advantages (e.g., high plasticity, thermal stability, and moderate ionic conductivity), which can be further improved/deteriorated by the addition of polymer or metal oxide nanoparticles. The role of the nanoparticle/OIPC combinations on the resultant interphase structure and transport properties, however, is still unclear due to the complexity within the composite structures. Herein, we demonstrate a systematic approach to specifically interrogating the interphase region by fabricating layered OIPC/polymer thin films via spin coating and correlating variation in the ionic conductivity of the OIPC with their microscopic structures. In-plane interdigitated electrodes have been employed to obtain electrochemical impedance spectroscopy (EIS) spectra on both OIPC and layered OIPC/polymer thin films. The thin-film EIS measurements were evaluated with conventional bulk EIS measurements on the OIPC pressed pellets and compared with EIS obtained from the OIPC-polymer composites. Interactions between the OIPC and polymer films as well as the morphology of the film surfaces have been characterized through multiple microscopic analysis tools, including scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and optical profilometry. The combination of EIS analysis with the microscopic visualization of these unique layered OIPC/polymer thin films has confirmed the impact of the OIPC-polymer interphase region on the overall ionic conductivity of bulk OIPC-polymer composites. By changing the chemistry of the polymer substrate (i.e., PMMA, PVDF, and PVDF-HFP), the importance of compatibility between the components in the interphase region is clearly observed. The methods developed here can be used to screen and further understand the interactions among composite components for enhanced compatibility and conductivity.

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