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1.
ACS Nano ; 16(11): 18058-18070, 2022 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-36259968

RESUMO

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na+ diffusion channels and complicated phase evolution during Na+ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi0.5Mn0.5-xSbxO2 (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na+ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na+ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g-1 at 0.2 C and 74.5 mAh g-1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

2.
ACS Appl Mater Interfaces ; 11(46): 43056-43065, 2019 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-31660726

RESUMO

Solid-state rechargeable batteries using polymer electrolytes have been considered, which can avoid safety issues and enhance energy density. However, commercial application of the polymer electrolyte solid-state battery is still significantly limited by the low room-temperature ionic conductivity, poor mechanical properties, and weak interfacial compatibility between the electrolyte and electrode, especially for the room-temperature solid-state rechargeable battery. In this work, a poly(vinylene carbonate)-based composite polymer electrolyte (PVC-CPE) is reported for the first time to realize room-temperature solid-state sodium batteries with high performances. This in situ solidified PVC-CPE possesses superior ionic conductivity (0.12 mS cm-1 at 25 °C), high Na+ transference number (tNa+ = 0.60), as well as enhanced electrode/electrolyte interfacial stability. Notably, the composite cathode NaNi1/3Fe1/3Mn1/3O2 (c-NFM) is designed through the in situ growth of the polymer electrolyte inside the electrode to decrease interfacial resistance and facilitate effective ion transport in electrode/electrolyte interfaces. It is demonstrated that the solid-state c-NFM/PVC-CPE/Na battery assembled by a one-step in situ solidification method exhibits remarkably enhanced cell performances at room temperature compared with a reference NFM/PVC-CPE/Na assembled through a conventional ex situ method. The battery presents a high initial specific capacity of 104.2 mA h g-1 at 0.2 C with a capacity retention of 86.8% over 250 cycles and ∼80.2 mA h g-1 at 1 C. This study suggests that PVC-CPE is a very promising electrolyte for solid-state sodium batteries. This study also suggests a new method to design high-performance polymer electrolytes for other solid-state rechargeable batteries to realize high safety and considerable electrochemical performance at room temperature.

3.
J Am Chem Soc ; 139(23): 7893-7903, 2017 06 14.
Artigo em Inglês | MEDLINE | ID: mdl-28535684

RESUMO

Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbOx/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nb in unsaturated NbOx owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbOx, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt-Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt-O interactions improve the ORR activity by shortening the Pt-Pt bond distance. Pt donates electrons to NbOx in both Pt-Nb and Pt-O cases. The resultant electron eficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.


Assuntos
Carbono/química , Nióbio/química , Óxidos/química , Oxigênio/química , Platina/química , Catálise , Técnicas Eletroquímicas , Oxirredução , Tamanho da Partícula , Propriedades de Superfície
4.
Nanoscale ; 8(7): 4121-6, 2016 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-26866581

RESUMO

Hierarchically structured carbon coated SnO2 nanoparticles well-anchored on the surface of a CNT (C-SnO2/CNT) material were synthesized by a facile hydrothermal process and subsequent carbonization. The as-obtained C-SnO2/CNT hybrid, when applied as an anode material for lithium ion batteries (LIBs), showed a high reversible capacity up to 1572 mA h g(-1) at 200 mA g(-1) with a superior rate capability (685 mA h g(-1) at 4000 mA g(-1)). Even after 100 charge/discharge cycles at 1000 mA g(-1), a specific capacity of 1100 mA h g(-1) can still be maintained. Such impressive electrochemical performance can be mainly attributed to the hierarchical sandwiched structure and strong synergistic effects of the ultrafine SnO2 nanoparticles and the carbon coating, and thus presents this material a promising anode material for LIBs.

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