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1.
Angew Chem Int Ed Engl ; 62(44): e202310132, 2023 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-37713281

RESUMEN

Coupled electron/ion transport is a decisive feature of Li plating/stripping, wherein the compatibility of electron/ion transport rates determines the morphology of deposited Li. Local Li+ hotspots form due to inhomogeneous interfacial charge transfer and lead to uncontrolled Li deposition, which decreases the Li utilization rate and safety of Li metal anodes. Herein, we report a method to obtain dendrite-free Li metal anodes by driving electron pumping and accumulating and boosting Li ion diffusion by tuning the work function of a carbon host using cobalt-containing catalysts. The results reveal that increasing the work function provides an electron deviation from C to Co, and electron-rich Co shows favorable binding to Li+ . The Co catalysts boost Li+ diffusion on the carbon fiber scaffolds without local aggregation by reducing the Li+ migration barrier. The as-obtained dendrite-free Li metal anode exhibits a Coulombic efficiency of 99.0 %, a cycle life of over 2000 h, a Li utilization rate of 50 %, and a capacity retention of 83.4 % after 130 cycles in pouch cells at a negative/positive capacity ratio of 2.5. These findings provide a novel strategy to stabilize Li metal by regulating the work function of materials using electrocatalysts.

2.
Adv Mater ; 35(49): e2303550, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37528474

RESUMEN

Aqueous zinc batteries have emerged as promising energy storage devices; however, severe parasitic reactions lead to the exacerbated production of Zn dendrites that decrease the utilization rate of Zn anodes. Decreasing the electrolyte content and regulating the water activity are efficient means to address these issues. Herein, this work shows that limiting the aqueous electrolyte and bonding water to bacterial cellulose (BC) can suppress side reactions and regulate stable Zn plating/stripping. This approach makes it possible to use less electrolyte and limited Zn foil. A symmetric Zn cell assembles with the hydrogel electrolyte with limited electrolyte (electrolyte-to-capacity ratio E/C = 1.0 g (Ah)-1 ) cycled stably at a current density of 6.5 mA cm-2 and achieved a capacity of 6.5 mA h cm-2 and depth of discharge of 85%. Full cells with the BC hydrogel electrolyte delivers a discharge capacity of 212 mA h cm-2 and shows a capacity retention of 83% after 1000 cycles at 5 A g-1 . This work offers new fundamental insights into the effect of restricting water to reshape the Zn plating/stripping process and provides a route for designing novel hydrogel electrolytes to better stabilize and efficiently utilize the Zn anodes.

3.
Angew Chem Int Ed Engl ; 60(48): 25508-25513, 2021 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-34580988

RESUMEN

The plating/stripping of Li dendrites can fracture the static solid electrolyte interphase (SEI) and cause significant dynamic volume variations in the Li anode, which give rise to poor cyclability and severe safety hazards. Herein, a tough polymer with a slide-ring structure was designed as a self-adaptive interfacial layer for Li anodes. The slide-ring polymer with a dynamically crosslinked network moves freely while maintaining its toughness and fracture resistance, which allows it can to dissipate the tension induced by Li dendrites on the interphase layer. Moreover, the slide-ring polymer is highly stretchable, elastic, and displays an ultrafast self-healing ability, which allows even pulverized Li to remain coalesced without disintegrating upon consecutive cycling. The Li anodes demonstrate greatly improved suppression of Li dendrite formation, as evidenced by the high critical current density (6 mA cm-2 ) and stable cycling for the full cells with high-areal capacity LiFePO4 , high-voltage NCM, and S cathodes.

4.
Adv Sci (Weinh) ; 7(22): 2002212, 2020 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-33240768

RESUMEN

Lithium (Li) is a promising battery anode because of its high theoretical capacity and low reduction potential, but safety hazards that arise from its continuous dendrite growth and huge volume changes limit its practical applications. Li can be hosted in a framework material to address these key issues, but methods to encage Li inside scaffolds remain challenging. The melt infusion of molten Li into substrates has attracted enormous attention in both academia and industry because it provides an industrially adoptable technology capable of fabricating composite Li anodes. In this review, the wetting mechanism driving the spread of liquefied Li toward a substrate is discussed. Following this, various strategies are proposed to engineer stable Li metal composite anodes that are suitable for liquid and solid-state electrolytes. A general conclusion and a perspective on the current limitations and possible future research directions for constructing composite Li anodes for high-energy lithium metal batteries are presented.

5.
Dalton Trans ; 44(10): 4594-600, 2015 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-25655996

RESUMEN

A Fe/Fe3O4/N-carbon composite consisting of a porous carbon matrix containing a highly conductive N-doped graphene-like network and Fe/Fe3O4 nanoparticles was prepared. The porous carbon has a hierarchical structure which is inherited from rice husk and the N-doped graphene-like network formed in situ. When used as an anode material for lithium batteries, the composite delivered a reversible capacity of approximately 610 mA h g(-1) at a current density of 200 mA g(-1) even after 100 cycles, due to the synergism between the unique hierarchical porous structures, highly electrically conductive N-doped graphene-like networks and nanosized particles of Fe/Fe3O4. This work provides a simple approach to prepare N-doped porous carbon activated nanoparticle composites which could be used to improve the electrochemical performance of lithium ion batteries.

6.
Nano Lett ; 13(3): 1230-6, 2013 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-23379626

RESUMEN

GeO2/Ge/C anode material synthesized using a simple method involving simultaneous carbon coating and reduction by acetylene gas is composed of nanosized GeO2/Ge particles coated by a thin layer of carbon, which is also interconnected between neighboring particles to form clusters of up to 30 µm. The GeO2/Ge/C composite shows a high capacity of up to 1860 mAh/g and 1680 mAh/g at 1 C (2.1 A/g) and 10 C rates, respectively. This good electrochemical performance is related to the fact that the elemental germanium nanoparticles present in the composite increases the reversibility of the conversion reaction of GeO2. These factors have been found through investigating and comparing GeO2/Ge/C, GeO2/C, nanosized GeO2, and bulk GeO2.

8.
J Phys Chem A ; 112(24): 5390-4, 2008 Jun 19.
Artículo en Inglés | MEDLINE | ID: mdl-18491876

RESUMEN

Traditionally, chemical reaction between solids has been considered to typically occur on a geological time scale without the benefit of high temperature, due to diffusion block in the solids. However, recent advancements have revealed that many solvent-free reactions between molecular crystals can quickly occur at room or near-room temperature. These reactions have raised a novel scientific question as to how the reactive species can overcome the diffusion-controlled kinetic limitations under such moderate conditions. From time-resolved powder UV-vis reflection spectra and optical micrographs with the reaction between dimethylglyoxime and Ni(Ac) 2.4H 2O and the reaction between hexamethylenetetramine and CoCl 2.6H 2O as models, we found that the solvent-free reaction really occurs at an intermediate state between the solid state and the liquid state. Formation of the liquid phase provides a convenient approach to diffusion of reactive species, whereas formation of a solid product layer hampered the transfer of reactive species. Both factors led to a broad reactive rate band in the long reaction region. The results have explained the diffusion mechanism of the fast reaction between the molecular crystals under moderate conditions.

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