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1.
Nano Lett ; 23(12): 5555-5561, 2023 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-37315026

RESUMEN

Ion adsorption within nanopores is involved in numerous applications. However, a comprehensive understanding of the fundamental relationship between in-pore ion concentration and pore size, particularly in the sub-2 nm range, is scarce. This study investigates the ion-species-dependent concentration in multilayered graphene membranes (MGMs) with tunable nanoslit sizes (0.5-1.6 nm) using nuclear magnetic resonance and computational simulations. For Na+-based electrolytes in MGMs, the concentration of anions in graphene nanoslits increases in correlation with their chaotropic properties. As the nanoslit size decreases, the concentration of chaotropic ion (BF4-) increases, whereas the concentration of kosmotropic ions (Cit3-, PO43-) and other ions (Ac-, F-) decreases or changes slightly. Notably, anions remain more concentrated than counter Na+ ions, leading to electroneutrality breakdown and unipolar anion packing in MGMs. A continuum modeling approach, integrating molecular dynamic simulation with the Poisson-Boltzmann model, elucidates these observations by considering water-mediated ion-graphene non-electrostatic interactions and charge screening from graphene walls.

2.
Zhongguo Dang Dai Er Ke Za Zhi ; 25(4): 357-361, 2023 Apr 15.
Artículo en Chino | MEDLINE | ID: mdl-37073839

RESUMEN

OBJECTIVES: To study the changes in cell free-DNA (cf-DNA), a marker of neutrophil extracellular traps (NETs), in neonates with acute respiratory distress syndrome (ARDS), and to evaluate its relationship with the severity and early diagnosis of ARDS. METHODS: The neonates diagnosed with ARDS in the Affiliated Hospital of Jiangsu University from January 2021 to June 2022 were enrolled in the prospective study. The neonates were divided into mild, moderate, and severe ARDS groups based on the oxygen index (OI) (4≤OI<8, 8≤OI<16, and OI≥16, respectively). The control group was selected from jaundice neonates who were observed in the neonatal department of the hospital during the same period, and they had no pathological factors causing neonatal jaundice. Peripheral blood samples were collected on day 1, day 3, and day 7 after admission for the ARDS group, and on the day of admission for the control group. Serum cf-DNA levels were measured using a fluorescence enzyme-linked immunosorbent assay. Serum interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) levels were measured using enzyme-linked immunosorbent assay. A Pearson correlation analysis was used to evaluate the correlation of serum cf-DNA levels with serum IL-6 and TNF-α levels. RESULTS: A total of 50 neonates were enrolled in the ARDS group, including 15 neonates with mild ARDS, 25 with moderate ARDS, and 10 with severe ARDS. Twenty-five neonates were enrolled in the control group. Compared with the control group, the serum levels of cf-DNA, IL-6, and TNF-α in all ARDS groups were significantly increased (P<0.05). Compared with the mild ARDS group, the serum levels of cf-DNA, IL-6, and TNF-α in the moderate and severe ARDS groups were significantly increased (P<0.05), and the increase was more significant in the severe ARDS group (P<0.05). The serum levels of cf-DNA, IL-6, and TNF-α in all ARDS groups were significantly increased on day 3 after admission and significantly decreased on day 7 after admission compared with those on day 1 after admission (P<0.05). The Pearson correlation analysis showed that there was a positive correlation between serum cf-DNA levels and IL-6 levels as well as TNF-α levels in 50 neonates with ARDS (P<0.05). CONCLUSIONS: There is an excessive expression of NETs in neonates with ARDS, and dynamic monitoring of serum cf-DNA levels has certain clinical value in evaluating the severity and early diagnosis of ARDS in neonates.


Asunto(s)
Trampas Extracelulares , Síndrome de Dificultad Respiratoria , Recién Nacido , Humanos , Estudios Prospectivos , Factor de Necrosis Tumoral alfa , Interleucina-6 , Pronóstico , Curva ROC , ADN
3.
Sci Adv ; 9(4): eabq1369, 2023 Jan 27.
Artículo en Inglés | MEDLINE | ID: mdl-36706186

RESUMEN

Single-ion selectivity with high precision has long been pursued for fundamental bioinspired engineering and applications such as in ion separation and energy conversion. However, it remains a challenge to develop artificial ion channels to achieve single-ion selectivity comparable to their biological analogs, especially for high Na+/K+ selectivity. Here, we report an artificial sodium channel by subnanoconfinement of 4'-aminobenzo-15-crown-5 ethers (15C5s) into ~6-Å-sized metal-organic framework subnanochannel (MOFSNC). The resulting 15C5-MOFSNC shows an unprecedented Na+/K+ selectivity of tens to 102 and Na+/Li+ selectivity of 103 under multicomponent permeation conditions, comparable to biological sodium channels. A co-ion-responsive single-file transport mechanism in 15C-MOFSNC is proposed for the preferential transport of Na+ over K+ due to the synergetic effects of size exclusion, charge selectivity, local hydrophobicity, and preferential binding with functional groups. This study provides an alternative strategy for developing potential single-ion selective channels and membranes for many applications.

4.
Front Oncol ; 12: 929092, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35847876

RESUMEN

Background: Accumulating data support that regular physical activity potentially inhibits chronic colitis, a risk factor for colitis-associated cancer (CAC). However, possible effects of physical activity on CAC and the underlying mechanisms remain poorly understood. Methods: A pretreatment of swimming on azoxymethane/dextran sodium sulfate (AOM/DSS)-induced CAC mice was implemented to determine its protective effect. Inflammation and tumorigenesis were assessed using colorectums from C57BL/6 mice. In order to determine how swimming alters colonic lipid metabolism and gene expression, a comparative analysis was conducted. Meanwhile, alterations in intestinal microbiota and short-chain fatty acids (SCFAs) were detected and analyzed. Finally, an integration analysis of colonic lipid metabolism with gene expression and intestinal microbiota was performed respectively. Result: Swimming pretreatment relieved bowel inflammation and minimized tumor formation. We demonstrated that prostaglandin E2 (PGE2)/PGE2 receptor 2 subtype (EP2) signaling as a potential regulatory target for swimming induces colonic lipid metabolites. Swimming-induced genera, Erysipelatoclostridium, Parabacteroides, Bacteroides, and Rikenellaceae_RC9_gut_group, induced intestinal SCFAs and affected the function of colonic lipid metabolites enriched in glycerophospholipid metabolism and choline metabolism in cancer. Conclusion: According to our experiments, swimming pretreatment can protect mice from CAC by intervention in the possible link between colonic lipid metabolites and PGE2/EP2 signaling. Further, swimming-induced genera and probiotics promoted glycerophospholipid metabolism and choline metabolism in cancer, the major constituents of colonic lipid metabolites, and increased SCFAs, which were also important mechanisms for the anti-inflammatory and anti-tumorigenic effects of swimming.

5.
Phys Chem Chem Phys ; 24(27): 16712-16723, 2022 Jul 13.
Artículo en Inglés | MEDLINE | ID: mdl-35770687

RESUMEN

Hexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) has recently been shown to be a promising solid state organic ionic plastic crystal with potential application in advanced alkali metal batteries. This study provides a detailed exploration of the structural and dynamic behavior of [HMG][FSI] mixtures with the sodium salt NaFSI across the whole composition range from 0 to 100 mol%. All mixtures are solids at room temperature. A combination of differential scanning calorimetry (DSC), synchrotron X-ray diffraction (SXRD) and multinuclear solid state NMR spectroscopy is employed to identify a partial phase diagram. The 25 mol% NaFSI/75 mol% [HMG][FSI] composition presents as the eutectic composition with the eutectic transition temperature at 44 °C. Both DSC and SXRD strongly support the formation of a new compound near 50 mol% NaFSI. Interestingly, the 53 mol% NaFSI [HMG][FSI] composition was consistently found to display features of a pure compound whereas the 50 mol% materials always showed a second phase. Many of the compositions examined showed unusual metastable behaviour. Moreover, the ion dynamics as determined by NMR, indicate that the Na+ and FSI- anions are signifcantly more mobile than the HMG cation in the liquid state (including the metastable state) for these materials.

6.
J Am Chem Soc ; 144(22): 9806-9816, 2022 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-35638261

RESUMEN

Polymer electrolytes (PEs) with excellent flexibility, processability, and good contact with lithium metal (Li°) anodes have attracted substantial attention in both academic and industrial settings. However, conventional poly(ethylene oxide) (PEO)-based PEs suffer from a low lithium-ion transference number (TLi+), leading to a notorious concentration gradient and internal cell polarization. Here, we report two kinds of highly lithium-ion conductive and solvent-free PEs using the benzene-based lithium salts, lithium (benzenesulfonyl)(trifluoromethanesulfonyl)imide (LiBTFSI) and lithium (2,4,6-triisopropylbenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiTPBTFSI), which show significantly improved TLi+ and selective lithium-ion conductivity. Using molecular dynamics simulations, we pinpoint the strong π-π stacking interaction between pairs of benzene-based anions as the cause of this improvement. In addition, we show that Li°âˆ¥Li° and Li°âˆ¥LiFePO4 cells with the LiBTFSI/PEO electrolytes present enhanced cycling performance. By considering π-π stacking interactions as a new molecular-level design route of salts for electrolyte, this work provides an efficient and facile novel strategy for attaining highly selective lithium-ion conductive PEs.

7.
ACS Appl Mater Interfaces ; 14(3): 4022-4034, 2022 Jan 26.
Artículo en Inglés | MEDLINE | ID: mdl-35019264

RESUMEN

A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na-O2 batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na-O2 cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na+ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 µm) sodium superoxide (NaO2) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na-O2 batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm-2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm-2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm-2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.

8.
ACS Appl Mater Interfaces ; 13(45): 54354-54362, 2021 Nov 17.
Artículo en Inglés | MEDLINE | ID: mdl-34730327

RESUMEN

Composite solid electrolytes including inorganic nanoparticles or nanofibers which improve the performance of polymer electrolytes due to their superior mechanical, ionic conductivity, or lithium transference number are actively being researched for applications in lithium metal batteries. However, inorganic nanoparticles present limitations such as tedious surface functionalization and agglomeration issues and poor homogeneity at high concentrations in polymer matrixes. In this work, we report on polymer nanoparticles with a lithium sulfonamide surface functionality (LiPNP) for application as electrolytes in lithium metal batteries. The particles are prepared by semibatch emulsion polymerization, an easily up-scalable technique. LiPNPs are used to prepare two different families of particle-reinforced solid electrolytes. When mixed with poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide (LiTFSI/PEO), the particles invoke a significant stiffening effect (E' > 106 Pa vs 105 Pa at 80 °C) while the membranes retain high ionic conductivity (σ = 6.6 × 10-4 S cm-1). Preliminary testing in LiFePO4 lithium metal cells showed promising performance of the PEO nanocomposite electrolytes. By mixing the particles with propylene carbonate without any additional salt, we obtain true single-ion conducting gel electrolytes, as the lithium sulfonamide surface functionalities are the only sources of lithium ions in the system. The gel electrolytes are mechanically robust (up to G' = 106 Pa) and show ionic conductivity up to 10-4 S cm-1. Finally, the PC nanocomposite electrolytes were tested in symmetrical lithium cells. Our findings suggest that all-polymer nanoparticles could represent a new building block material for solid-state lithium metal battery applications.

9.
J Inflamm Res ; 14: 5305-5318, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-34703270

RESUMEN

PURPOSE: Helminths and their products can regulate immune response and offer new strategies to control and alleviate inflammation, including asthma. We previously found that a peptide named as SJMHE1 from Schistosoma japonicum can suppress asthma in mice. This study mainly investigated the molecular mechanism of SJMHE1 in inhibiting asthma inflammation. METHODS: SJMHE1 was administered to mice with OVA-induced asthma via subcutaneous injection, and its effects were detected by testing the airway inflammation of mice. The Th cell distribution was analyzed by flow cytometry. Th-related transcription factor and cytokine expression in the lungs of mice were analyzed using quantitative real-time PCR (qRT-PCR). The expression of miR-155 and levels of phosphorylated STAT3 and STAT5 were also determined after SJMHE1 treatment in mice by qRT-PCR and Western blot analysis. The in vitro mouse CD4+ T cells were transfected with lentivirus containing overexpressed or inhibited miR-155, and the proportion of Th17, Treg cells, CD4+p-STAT3+, and CD4+p-STAT5+ cells were analyzed by flow cytometry. RESULTS: SJMHE1 ameliorated the airway inflammation of asthmatic mice, upregulated the proportion of Th1 and Treg cells, and the expression of Th1 and Treg-related transcription factor and cytokines. Simultaneously, SJMHE1 treatment reduced the percentage of Th2 and Th17 cells and the expression of Th2 and Th17-related transcription factor and cytokines. SJMHE1 treatment decreased the expression of miR-155 and p-STAT3 but increased p-STAT5 expression. In vitro, the percentage of Th17 and CD4+p-STAT3+ cells increased in CD4+ T cells transfected over-expression of miR-155, but SJMHE1 inhibited the miR-155-mediated increase of Th17 cells. Furthermore, SJMHE1 increased the proportion of Treg and CD4+p-STAT5+ cells after transfected over-expression or inhibition of miR-155. CONCLUSION: SJMHE1 regulated the balance of Th17 and Treg cells by modulating the activation of STAT3 and STAT5 via miR-155 in asthma. SJMHE1 might be a promising treatment for asthma.

10.
J Phys Chem Lett ; 12(40): 9853-9858, 2021 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-34606277

RESUMEN

Organic ionic plastic crystals (OIPCs) are an emerging family of materials with demonstrated applications in electrochemical devices such as lithium/sodium ion batteries, dye-sensitized solar cells, and hydrogen fuel cells. Herein, we present direct evidence of anion diffusion through a relatively static background of a cation lattice in an ionic plastic crystal compound, [P122i4][PF6], in an elevated temperature solid phase. We found all anions are diffusive, whereas only a small population of cations is diffusive. Two anion populations were identified with diffusion coefficients differing by 2 orders of magnitude. The slow-diffusing anion is attributed to the plastic crystal region where the cation forms a relative static background, allowing anions to diffuse possibly through a defect-assisted hopping mechanism.

11.
J Phys Chem B ; 125(39): 11005-11016, 2021 10 07.
Artículo en Inglés | MEDLINE | ID: mdl-34570507

RESUMEN

The study highlights the effect of acid- and base-rich conditions on the proton dynamics of diethylmethylammonium poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide, [DEMA][PSTFSI], a polymerized protic ionic liquid designed as a polymer electrolyte for nonhumidified polymer electrolyte membrane fuel cells. Different proportions of triflic acid (HTf) and diethylmethylamine (DEMA) were added to the pristine polymer. The thermal analysis of the mixtures revealed that the addition of the base increases the glassy/amorphous nature of the polymer; however, HTf plasticizes the polymer and lowers the Tg value, so that it falls outside of the differential scanning calorimetry-studied temperature range. 50 mol % doping of the HTf contents increases the conductivity upto 0.952 mS cm-1, and 50 mol % DEMA mixture has a conductivity of 0.169 mS cm-1 at 100 °C. Vogel-Tamman-Fulcher fitting of the ionic conductivities of the doped systems suggested that the ionic conductivities are completely decoupled from segmental motion of the polymer. A combination of Fourier transform infrared and static NMR studies demonstrated that HTf-added polymer composites show conduction via Grotthuss and vehicular mechanisms, while DEMA-added polymer composites show predominantly a Grotthuss mechanism by developing the aggregates of proton and added base.


Asunto(s)
Imidas , Líquidos Iónicos , Dietilaminas , Mesilatos , Protones
12.
J Phys Chem Lett ; 12(23): 5552-5557, 2021 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-34101470

RESUMEN

Herein, we demonstrate that the potential difference of proton reduction and hydrogen gas oxidation of protic ionic liquids is closely related to the proton exchange rate in the electrolyte. Through a careful design of anion chemistry, the proton exchange rate can be boosted by several orders of magnitude, reaching 200 kHz at 100 °C. It is found that the enhanced proton exchange rate can effectively decrease the potential loss at the electrode, most likely through alleviating the H+ concentration gradient incurred by electrochemical reactions at the electrode surfaces. This research therefore highlights the strategy of using anions of medium-strength acids, such as H2PO4-, for protic ionic liquids with enhanced proton exchange capability.

13.
Chem Commun (Camb) ; 57(46): 5609-5625, 2021 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-34048516

RESUMEN

Ionic liquids, and their solid-state equivalents organic ionic plastic crystals, show many useful and tailorable properties that make them interesting for a wide range of applications including as electrolytes for energy storage devices. Nuclear magnetic resonance spectroscopy and related techniques offer a powerful and versatile toolkit for the characterisation of structure, interactions and dynamics in these materials. This article summarises both commonly used methods and some recent advances in this area, including solution- and solid-state methods, dynamic nuclear polarisation, imaging, diffusion and relaxation measurements, and example applications of some less commonly studied nuclei.

14.
Macromolecules ; 54(13): 6214-6225, 2021 Jul 13.
Artículo en Inglés | MEDLINE | ID: mdl-35693113

RESUMEN

Polylactide (PLA) has emerged as one of the most promising bio-based alternatives to petroleum-based plastics, mainly because it can be produced from the fermentation of naturally occurring sugars and because it can be industrially compostable. In spite of these benefits, the industrial ring-opening polymerization (ROP) of l-lactide (L-LA) still requires the use of highly active and thermally stable metal-based catalysts, which have raised some environmental concerns. While the excellent balance between activity and functional group compatibility of organic acid catalysts makes them some of the most suitable catalysts for the metal-free ROP of L-LA, the majority of these acids are highly volatile and subject to decomposition at high temperature, which limits their use under industrially relevant conditions. In this work we exploit the use of a nonstoichiometric acid-base organocatalyst to promote the solvent-free and metal-free ROP of L-LA at elevated temperatures in the absence of epimerization and transesterification. To do so, a stable acidic complex was prepared by mixing 4-(dimethylamino)pyridine (DMAP) with 2 equiv of methanesulfonic acid (MSA). Both experimental and computational results indicate that DMAP:MSA (1:2) not only is highly thermally stable but also promotes the retention of stereoregularity during the polymerization of L-LA, leading to PLLA with a molar mass of up to 40 kg mol-1 and a chiral purity in excess of 98%. This result provides a new feature to exploit in organocatalyzed polymerization and in the design of new catalysts to facilitate the path to market.

15.
Polymers (Basel) ; 12(3)2020 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-32150967

RESUMEN

In the present article, we report on the chemical modifications of some carbohydrate-based substrates, such as potato starch, dextran, ß-cyclodextrin, agar agar and tamarind, by reacting with diethylchlorophosphate (DECP), in dispersions in dichloromethane (DCM), in the presence of triethylamine (TEA) as the base. The modified substrates, after recovery and purification, were analyzed for their chemical constitutions, thermal stabilities and calorimetric properties using a variety of analytical techniques. These included: solid-state 31P NMR, inductively coupled plasma-optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC). The unmodified counterparts were also subjected to the same set of analyses with a view to serving as controls. Phosphorus analyses, primarily through ICP-OES on the recovered samples, showed different degrees of incorporation. Such observations were optionally verified through solid-state 31P NMR spectroscopy. The thermograms of the modified substrates were noticeably different from the unmodified counterparts, both in terms of the general profiles and the amounts of char residues produced. Such observations correlated well with the relevant parameters obtained through PCFC runs. Overall, the modified systems containing phosphorus were found to be less combustible than the parent substrates, and thus can be considered as promising matrices for environmentally benign fire-resistant coatings.

16.
J Phys Chem Lett ; 11(2): 510-515, 2020 Jan 16.
Artículo en Inglés | MEDLINE | ID: mdl-31896255

RESUMEN

Organic ionic plastic crystals (OIPCs) are an important family of materials that have shown exciting possibilities as solid electrolytes for lithium ion batteries and other electrochemical devices. In this study we demonstrate for the first time that, although the X-ray shows sharp diffraction peaks, both cation and anion clearly exhibit significant ion diffusion in solid phase I. Two phases with ion diffusivities differing by 2 orders of magnitude can be identified. The populations of the cation and anion in both phases are found to be unequal, hinting at the existence of (negatively charged) cation vacancies in the plastic crystal phase and a positively charged grain boundary phase. These interesting properties of ion vacancies and unequal populations of cation and anion are likely to be ubiquitous in other OIPCs, and it is of paramount importance to be aware of these features to correctly understand the structure-property relationships of this important material family.

17.
Angew Chem Int Ed Engl ; 58(47): 16928-16935, 2019 11 18.
Artículo en Inglés | MEDLINE | ID: mdl-31535784

RESUMEN

Homochiral metal-organic framework (MOF) membranes have been recently reported for chiral separations. However, only a few high-quality homochiral polycrystalline MOF membranes have been fabricated due to the difficulty in crystallization of a chiral MOF layer without defects on porous substrates. Alternatively, mixed matrix membranes (MMMs), which combine potential advantages of MOFs and polymers, have been widely demonstrated for gas separation and water purification. Here we report novel homochiral MOF-polymer MMMs for efficient chiral separation. Homochirality was successfully incorporated into achiral MIL-53-NH2 nanocrystals by post-synthetic modification with amino acids, such as l-histidine (l-His) and l-glutamic acid (l-Glu). The MIL-53-NH-l-His and MIL-53-NH-l-Glu nanocrystals were then embedded into polyethersulfone (PES) matrix to form homochiral MMMs, which exhibited excellent enantioselectivity for racemic 1-phenylethanol with the highest enantiomeric excess value up to 100 %. This work, as an example, demonstrates the feasibility of fabricating diverse large-scale homochiral MOF-based MMMs for chiral separation.

18.
Chemistry ; 25(53): 12281-12287, 2019 Sep 20.
Artículo en Inglés | MEDLINE | ID: mdl-31292996

RESUMEN

The conversion of renewable plant polyphenol to advanced materials with tailorable properties and various functions is desirable and challenging. In this work, monovalent cation-phenolic crystals contained K+ or Na+ ions were synthesized by using plant polyphenol as an organic source in alkaline solution. The crystal structure was resolved, showing a laminar crystal structure with M+ as connecting nodes. The morphologies (e.g., rod-like and spindle-shaped) and chemical compositions of crystals could be tuned by changing the cations. Interestingly, these polymer crystals exhibited a pH-driven reversible crystal transformation. They transformed into their protonated crystalline form under acidic conditions (e.g., pH 2) and went back to the cation-bound crystalline form in alkaline solutions. Furthermore, the crystals proved excellent antioxidants and heavy metal ion adsorbents.

19.
Angew Chem Int Ed Engl ; 58(35): 12070-12075, 2019 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-31259482

RESUMEN

Suppressing the mobility of anionic species in polymer electrolytes (PEs) is essential for mitigating the concentration gradient and internal cell polarization, and thereby improving the stability and cycle life of rechargeable alkali metal batteries. Now, an ether-functionalized anion (EFA) is used as a counter-charge in a lithium salt. As the salt component in PEs, it achieves low anionic diffusivity but sufficient Li-ion conductivity. The ethylene oxide unit in EFA endows nanosized self-agglomeration of anions and trapping interactions between the anions and its structurally homologous matrix, poly(ethylene oxide), thus suppressing the mobility of negative charges. In contrast to previous strategies of using anion traps or tethering anions to a polymer/inorganic backbone, this work offers a facile and elegant methodology on accessing selective and efficient Li-ion transport in PEs and related electrolyte materials (for example, composites and hybrid electrolytes).

20.
ChemSusChem ; 12(8): 1700-1711, 2019 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-30740908

RESUMEN

The effect of water on the properties of superconcentrated sodium salt solutions in ionic liquids (ILs) was investigated to design electrolytes for sodium battery applications with water as an additive. Water was added to a 50 mol % solution of NaFSI [FSI=bis(fluorosulfonyl)imide] in the ionic liquid N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C3 mpyrFSI). Although the thermal properties (e.g., glass transition temperature) showed little dependence on the water content, the viscosity and, in particular, the ionic conductivity were strongly affected. The Na|Na symmetrical cell cycling performance was strongly dependent on the applied current density as well as on the water content. At higher current densities (1.0 mA cm-2 ) the polarization profiles showed a water dependence, suggesting that water was actively involved in the formation of an improved solid electrolyte interface layer (SEI) for high-water-content samples (1000-5000 ppm), resulting in improved long-term cycling stability. The initial impedance of cells cycled at 1.0 mA cm-2 (measured after 20 cycles) was elevated after water addition, and large polarizations occured for the "wet" samples. However, with further cycling the wet cells began to exhibit lower polarization and improved stability compared to the "dry" sample. The Na|NaFePO4 cell cycling performance was also demonstrated with minimal effect on the cell capacity, further highlighting the negligible activity of water in these electrolyte systems. In fact, reduced cell polarization and a more clearly defined charge profile were evident after water addition. The work shown here suggests that water may be used as a convenient and inexpensive additive for superconcentrated sodium IL electrolytes for improved device performance.

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