The success of rechargeable lithium-ion batteries has brought indisputable convenience to human society for the past two decades. However, unlike commercialized intercalation cathodes, high-energy-density sulphur cathodes are still in the stage of research because of the unsatisfactory capacity retention and long-term cyclability. The capacity degradation over extended cycles originates from the soluble polysulphides gradually diffusing out of the cathode region. Here we report an applicable way to recharge lithium-sulphur cells by a simple charge operation control that offers tremendous improvement with various lithiumsulphur battery systems. Adjusting the charging condition leads to long cycle life (over 500 cycles) with excellent capacity retention (499%) by inhibiting electrochemical reactions along with severe polysulphide dissolution. This charging strategy and understanding of the reactions in different discharge steps will advance progress in the development of lithiumsulphur batteries.
Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.
A series of carbon-supported core-shell nanoparticles with Pd(x)Cu(y)-rich cores and Pt-rich shells (Pt@Pd(x)Cu(y)/C) has been synthesized by a polyol reduction of the precursors followed by heat treatment to obtain the Pd(x)Cu(y)/C (1 ≤ x ≤ 3 and 0 ≤ y ≤ 5) cores and the galvanic displacement of Pd(x)Cu(y) with [PtCl(4)](2-) to form the Pt shell. The nanoparticles have also been investigated with respect to the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells (PEMFCs). X-ray diffraction (XRD) analysis suggests that the cores are highly alloyed and that the galvanic displacement results in a certain amount of alloying between Pt and the underlying Pd(x)Cu(y) alloy core. Transmission electron microscopy (TEM) images show that the Pt@Pd(x)Cu(y)/C catalysts (where y > 0) have mean particle sizes of <8 nm. Compositional analysis by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) clearly shows Pt enrichment in the near-surface region of the nanoparticles. Cyclic voltammograms show a positive shift of as much as 40 mV for the onset of Pt-OH formation in the Pt@Pd(x)Cu(y)/C electrocatalysts compared to that in Pt/C. Rotating disk electrode (RDE) measurements of Pt@PdCu(5)/C show an increase in the Pt mass activity by 3.5-fold and noble metal activity by 2.5-fold compared to that of Pt/C. The activity enhancements in RDE and PEMFC measurements are believed to be a result of the delay in the onset of Pt-OH formation.
Metallic aluminum (Al) is of interest as a reducing agent because of its low standard reduction potential. However, its surface is invariably covered with a dense aluminum oxide film, which prevents its effective use as a reducing agent in wet-chemical synthesis. Pitting corrosion, known as an undesired reaction destroying Al and is enhanced by anions such as F−, Cl−, and Br− in aqueous solutions, is applied here for the first time to activate Al as a reducing agent for wet-chemical synthesis of a diverse array of metals and alloys. Specifically, we demonstrate the synthesis of highly dispersed palladium nanoparticles on carbon black with stabilizers and the intermetallic Cu2Sb/C, which are promising candidates, respectively, for fuel cell catalysts and lithium-ion battery anodes. Atomic hydrogen, an intermediate during the pitting corrosion of Al in protonic solvents (e.g., water and ethylene glycol), is validated as the actual reducing agent.
Boron doping into carbon nanotubes improves the CO tolerance and increases the utilization efficiency of the supported Pt nanoparticles. Boron doping leads to a uniform deposition of Pt nanoparticles and also facilitates the removal of CO from the Pt surface, resulting in an increase in the electrocatalytic activity for methanol oxidation.
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