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1.
Proc Natl Acad Sci U S A ; 121(5): e2309981121, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38252819

RESUMO

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing-structure-property relationships of metal electrodes.

2.
J Am Chem Soc ; 145(40): 22184-22193, 2023 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-37768698

RESUMO

Current lithium-ion batteries degrade under high rates and low temperatures due to the use of carbonate electrolytes with restricted Li+ conduction and sluggish Li+ desolvation. Herein, a strong solvent with dual lithium salts surmounts the thermodynamic limitations by regulating interactions among Li+ ions, anions, and solvents at the molecular level. Highly dissociated lithium bis(fluorosulfonyl)imide (LiFSI) in dimethyl sulfite (DMS) solvent with a favorable dielectric constant and melting point ensures rapid Li+ conduction while the high affinity between difluoro(oxalato)borate anions (DFOB-) and Li+ ions guarantees smooth Li+ desolvation within a wide temperature range. In the meantime, the ultrathin self-limited electrode/electrolyte interface and the electric double layer induced by DFOB- result in enhanced electrode compatibility. The as-formulated electrolyte enables stable cycles at high currents (41.3 mA cm-2) and a wide temperature range from -78 to 60 °C. The 1 Ah graphite||LiCoO2 (2 mAh cm-2) pouch cell achieves 80% reversible capacity at 2 C rate under -20 °C and 86% reversible capacity at 0.1 C rate under -50 °C. This work sheds new light on the electrolyte design with strong solvent and dual lithium salts and further facilitates the development of high-performance lithium-ion batteries operating under extreme conditions.

3.
Small ; 19(28): e2301737, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37191324

RESUMO

Prelithiating cathode is considered as one of the most promising lithium compensation strategies for practical high energy density batteries. Whereas most of reported cathode lithium compensation agents are deficient owing to their poor air-stability, residual insulating solid, or formidable Li-extracting barrier. Here, this work proposes molecularly engineered 4-Fluoro-1,2-dihydroxybenzene Li salt (LiDF) with high specific capacity (382.7 mAh g-1 ) and appropriate delithiation potential (3.6-4.2 V) as an air-stable cathode Li compensation agent. More importantly, the charged residue 4-Fluoro-1,2-benzoquinone (BQF) can synergistically work as an electrode/electrolyte interface forming additive to build uniform and robust LiF-riched cathode/anode electrolyte interfaces (CEI/SEI). Consequently, less Li loss and retrained electrolyte decomposition are achieved. With 2 wt% 4-Fluoro-1,2-dihydroxybenzene Li salt initially blended within the cathode, 1.3 Ah pouch cells with NCM (Ni92) cathode and SiO/C (550 mAh g-1 ) anode can keep 91% capacity retention after 350 cycles at 1 C rate. Moreover, the anode free of NCM622+LiDF||Cu cell achieves 78% capacity retention after 100 cycles with the addition of 15 wt% LiDF. This work provides a feasible sight for the rational designing Li compensation agent at molecular level to realize high energy density batteries.

4.
Small ; 19(36): e2301166, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37140076

RESUMO

Li metal anode has been recognized as the most promising anode for its high theoretical capacity and low reduction potential. But its large-scale commercialization is hampered because of the infinite volume expansion, severe side reactions, and uncontrollable dendrite formation. Herein, the self-supporting porous lithium foam anode is obtained by a melt foaming method. The adjustable interpenetrating pore structure and dense Li3 N protective layer coating on the inner surface enable the lithium foam anode with great tolerance to electrode volume variation, parasitic reaction, and dendritic growth during cycling. Full cell using high areal capacity (4.0 mAh cm-2 ) LiNi0.8Co0.1Mn0.1 (NCM811) cathode with the N/P ratio of 2 and E/C ratio of 3 g Ah-1 can stably operate for 200 times with 80% capacity retention. The corresponding pouch cell has <3% pressure fluctuation per cycle and almost zero pressure accumulation.

5.
Chem Commun (Camb) ; 56(37): 4998-5001, 2020 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-32239070

RESUMO

The limited discharge capacity of LiCoO2 can be improved by increasing its working potential, but it suffers from Co4+ dissolution and decomposition of the electrolyte. Nitriles have attracted great interest as high-voltage electrolytes due to their wide electrochemical window. However, the cathodic interfacial stability of nitrile electrolytes with a high-voltage LiCoO2 cathode has yet to be explored. Herein, we adopted an SN-based deep eutectic electrolyte with SN as the only solvent and found that Co4+ could be reduced by the SN solvent on the interface of the LiCoO2 electrode, causing a reverse phase change of LiCoO2 and severe self-discharge of the LiCoO2|Li and LiCoO2|Li4Ti5O12 batteries. When LiDFOB was introduced into the electrolyte, the self-discharge behavior of cells could be largely decelerated. The series of characterizations performed in our work revealed that the cathode/electrolyte interface generated from the LiDFOB salt could stabilize the interface of LiCoO2 and suppress the dissolution of the ions of the transition metal Co.

6.
Adv Sci (Weinh) ; 6(22): 1901036, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31763139

RESUMO

Low ionic conductivity at room temperature and limited electrochemical window of poly(ethylene oxide) (PEO) are the bottlenecks restricting its further application in high-energy density lithium metal battery. Herein, a differentiated salt designed multilayered PEO-based solid polymer electrolyte (DSM-SPE) is exploited to achieve excellent electrochemical performance toward both the high-voltage LiCoO2 cathode and the lithium metal anode. The LiCoO2/Li metal battery with DSM-SPE displays a capacity retention of 83.3% after 100 cycles at 60 °C with challenging voltage range of 2.5 to 4.3 V, which is the best cycling performance for high-voltage (≥4.3 V) LiCoO2/Li metal battery with PEO-based electrolytes up to now. Moreover, the Li/Li symmetrical cells present stable and low polarization plating/stripping behavior (less than 80 mV over 600 h) at current density of 0.25 mA cm-2 (0.25 mAh cm-2). Even under a high-area capacity of 2 mAh cm-2, the profiles still maintain stable. The pouch cell with DSM-SPE exhibits no volume expansion, voltage decline, ignition or explosion after being impaled and cut at a fully charged state, proving the excellent safety characteristic of the DSM-SPE-based lithium metal battery.

7.
Nat Commun ; 10(1): 5374, 2019 11 26.
Artigo em Inglês | MEDLINE | ID: mdl-31772177

RESUMO

The surface chemistry of solid electrolyte interphase is one of the critical factors that govern the cycling life of rechargeable batteries. However, this chemistry is less explored for zinc anodes, owing to their relatively high redox potential and limited choices in electrolyte. Here, we report the observation of a zinc fluoride-rich organic/inorganic hybrid solid electrolyte interphase on zinc anode, based on an acetamide-Zn(TFSI)2 eutectic electrolyte. A combination of experimental and modeling investigations reveals that the presence of anion-complexing zinc species with markedly lowered decomposition energies contributes to the in situ formation of an interphase. The as-protected anode enables reversible (~100% Coulombic efficiency) and dendrite-free zinc plating/stripping even at high areal capacities (>2.5 mAh cm‒2), endowed by the fast ion migration coupled with high mechanical strength of the protective interphase. With this interphasial design the assembled zinc batteries exhibit excellent cycling stability with negligible capacity loss at both low and high rates.

8.
Angew Chem Int Ed Engl ; 58(18): 5936-5940, 2019 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-30860309

RESUMO

The uncontrollable growth of Li dendrites and the accumulation of byproducts are two severe concerns for lithium metal batteries, which leads to safety hazards and a low Coulombic efficiency. To investigate the deterioration of the cell, it is important to figure out the distribution of active Li species on the anode surface and distinguish Li dendrites from byproducts. However, it is still challenging to identify these issues by conventional visual observation methods. In this work, we introduce a novel fluorescent probing strategy using 9,10-dimethylanthracene (DMA). By marking the cycled Li-anode surface, the active Li distribution can be visualized by the fluorescence quenching of DMA reacting with active Li. The method demonstrates validity for electrolyte selection and predictive detection of uneven Li deposition on Li metal anodes. Furthermore, the location of dendrites can be clearly identified after destructive utilization of the anode, which will contribute to the development of failure-analysis technology for Li metal batteries.

9.
Infect Genet Evol ; 43: 86-93, 2016 09.
Artigo em Inglês | MEDLINE | ID: mdl-27174089

RESUMO

Sepsis is a whole-body inflammatory response to infection with high mortality and is treated in intensive care units (ICUs). In the present study, to identify metabolic biomarkers that can differentiate sepsis models induced by caecal ligation puncture (CLP) or Staphylococcus aureus (S. aureus), small molecular metabolites in the serum were measured by liquid chromatography quadruple time-of-flight mass spectrometry (LC-QTOF-MS) and analysed using the multivariate statistical analysis (MVA) of partial least square-discrimination analysis (PLS-DA) method. The results demonstrated that the body showed obvious metabolic disorders in the sepsis groups compared with the control group. A total of 8 potential biomarkers were identified in the CLP group, and 10 potential biomarkers were identified in the S. aureus group. These potential biomarkers primarily reflected an energy metabolism disorder, inflammatory response, oxidative stress and tissue damage, which occur during sepsis, and these markers might potentially be used to differentiate CLP from Staphylococcus aureus sepsis.


Assuntos
Biomarcadores/sangue , Metabolômica/métodos , Sepse/sangue , Sepse/diagnóstico , Infecções Estafilocócicas/sangue , Infecções Estafilocócicas/diagnóstico , Animais , Ceco/cirurgia , Cromatografia Líquida/métodos , Diagnóstico Diferencial , Modelos Animais de Doenças , Ligadura , Masculino , Espectrometria de Massas/métodos , Punções , Ratos , Ratos Sprague-Dawley , Sepse/etiologia , Organismos Livres de Patógenos Específicos
10.
Arch Dermatol Res ; 305(7): 629-36, 2013 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-23589093

RESUMO

Atopic dermatitis (AD) is an inflammatory, chronically relapsing, pruritic skin disease and lesions associated with AD are frequently colonized with Staphylococcus aureus (S. aureus). Activation of T cells by staphylococcal enterotoxins (SE) plays a crucial role in the pathogenesis of AD. Previous studies have demonstrated that lidocaine could attenuate allergen-induced T cell proliferation and cytokine production in peripheral blood mononuclear cells (PBMCs) from asthma patients. The purpose of this study was to investigate the effects of lidocaine on SE-stimulated activation of PBMCs from AD patients. PBMCs were isolated from ten AD patients and stimulated by staphylococcal enterotoxin A (SEA) or staphylococcal enterotoxin B (SEB) in the presence or absence of lidocaine in various concentrations. Cellular proliferation and the release of representative TH1- and TH2-type cytokines were measured. The effect of lidocaine on filaggrin (FLG) expression in HaCaT cells co-cultured with SE-activated PBMCs was also examined. Our results demonstrated that lidocaine dose-dependently inhibited the proliferative response and the release of IL-4, IL-5, IL-13, TNF-α, and IFN-γ from SEA- and SEB-stimulated PBMCs and also blocked the down-regulation of FLG expression in HaCaT cells co-cultured with SEA- and SEB-activated PBMCs. These results indicate that lidocaine inhibited SEA- and SEB-stimulated activation of PBMCs from patients with AD. Our findings encourage the use of lidocaine in the treatment of AD.


Assuntos
Dermatite Atópica/imunologia , Lidocaína/farmacologia , Staphylococcus aureus/metabolismo , Células Th1/imunologia , Células Th2/imunologia , Linhagem Celular , Proliferação de Células/efeitos dos fármacos , Técnicas de Cocultura , Citocinas/metabolismo , Dermatite Atópica/patologia , Regulação para Baixo/efeitos dos fármacos , Enterotoxinas/imunologia , Feminino , Proteínas Filagrinas , Humanos , Proteínas de Filamentos Intermediários/genética , Proteínas de Filamentos Intermediários/metabolismo , Queratinócitos/efeitos dos fármacos , Ativação Linfocitária/efeitos dos fármacos , Masculino , Células Th1/efeitos dos fármacos , Células Th2/efeitos dos fármacos
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