Optical excitation at terahertz frequencies has emerged as an effective means to dynamically manipulate complex materials. In the molecular solid K3C60, short mid-infrared pulses transform the high-temperature metal into a non-equilibrium state with the optical properties of a superconductor. Here we tune this effect with hydrostatic pressure and find that the superconducting-like features gradually disappear at around 0.3 GPa. Reduction with pressure underscores the similarity with the equilibrium superconducting phase of K3C60, in which a larger electronic bandwidth induced by pressure is also detrimental for pairing. Crucially, our observation excludes alternative interpretations based on a high-mobility metallic phase. The pressure dependence also suggests that transient, incipient superconductivity occurs far above the 150 K hypothesized previously, and rather extends all the way to room temperature.
We report on the ability of fullerene C60 and hydrogenated fullerene C60Hx (x∼39) to operate as negative electrodes in novel Na-ion batteries. Building upon the known solubility of C60 in common organic electrolytes used in batteries, we developed a suitably optimized solid-state Na-(polyethylene oxide) electrolyte for this application. Electrochemical and structural properties of the fullerene electrodes were investigated through cyclic voltammetry, fixed-current charge/discharge of the electrodes, impedance spectroscopy and powder X-ray diffraction. Both C60 and hydrogenated C60 have been electrochemically intercalated with sodium. Specific capacities after the first cycle are 250 mAh g−1 and 230 mAh g−1 for C60 and C60Hx respectively. However, C60 electrode shows a strong irreversible character after the first discharge, probably due to the formation of stable polymeric NaxC60 phases, where Na+ ions diffusion is hindered. On the contrary, C60Hx displays better reversibility, suggesting that hydrogenation of the buckyball could be effective to preserve sufficiently large interstitial pathways for Na+ diffusion upon intercalation.
Modification of graphene has been undertaken in many research contexts in order to improve its properties. In this study, we examine Ni-nanoparticles decoration on graphene and its effect on sodiumion battery performance. A definite trend is observed on the relationship between Ni-nanoparticles concentration (and hence size) and battery performance. Comparable capacities on the order of 420 mAhg1 after 20 cycles at 100 mAg1 is observed for the 3 relatively high Ni-concentration samples NiC10, NiC40, and NiC80. As the Ni:C ratio decreases, a decreasing trend is observed in the measured capacity, with NiC200, NiC500, and NiC1000 producing capacities of 350 mAhg1, 380 mAhg1, and 300 mAhg1 respectively after 20 cycles at the same rate. Ex situ energy dispersive X-ray spectroscopy, scanning, and transmission electron microscopy shows the morphology of the Ni-nanoparticles decorated graphene and assists in quantifing their sodium content, emphasizing the increasing sodium content with increasing Ni-nanoparticles concentration. This systematic study details how Ninanoparticles concentration on graphene surfaces can be manipulated to enhance electrochemical performance, and that higher concentrations up to NiC10 favour better performance. For a compromise between performance and cost (Ni cost), the best composition is NiC500 which favors best performance with the least Ni decoration.
Single-walled carbon nanotubes (SWCNTs) possessing a confined inner space protected by chemically resistant shells are promising for delivery, storage, and desorption of various compounds, as well as carrying out specific reactions. Here, we show that SWCNTs interact with molten mercury dichloride (HgCl2) and guide its transformation into dimercury dichloride (Hg2Cl2) in the cavity. The chemical state of host SWCNTs remains almost unchanged except for a small p-doping from the guest Hg2Cl2 nanocrystals. The density functional theory calculations reveal that the encapsulated HgCl2 molecules become negatively charged and start interacting via chlorine bridges when local concentration increases. This reduces the bonding strength in HgCl2, which facilitates removal of chlorine, finally leading to formation of Hg2Cl2 species. The present work demonstrates that SWCNTs not only serve as a template for growing nanocrystals but also behave as an electron-transfer catalyst in the spatially confined redox reaction by donation of electron density for temporary use by the guests.
We present a detailed NMR study of the insulator-to-metal transition induced by an applied pressure p in the A15 phase of Cs3C60. We evidence that the insulating antiferromagnetic (AFM) and superconducting (SC) phases coexist only in a narrow p range. At fixed p, in the metallic state above the SC transition Tc, the 133Cs and 13C NMR spin-lattice relaxation data are seemingly governed by a pseudogaplike feature. We prove that this feature, also seen in the 133Cs NMR shift data, is rather a signature of the Mott transition which broadens and smears out progressively for increasing (p, T). The analysis of the variation of the quadrupole splitting νQ of the 133Cs NMR spectrum precludes any cell symmetry change at the Mott transition and only monitors a weak variation of the lattice parameter. These results open an opportunity to consider theoretically the Mott transition in a multiorbital three-dimensional system well beyond its critical point.
Li6C60 has been chosen as the most representative system to study the hydrogenation mechanism in alkali-cluster intercalated fullerides. We present a muon spin relaxation (μSR) experiment that hints the chance to achieve a higher storage capacity on fullerene with respect to the values suggested in literature. Moreover, a linear relationship between the muonium adduct radical hyperfine frequency and the level of C60 hydrogenation was found and it can be exploited to probe the C60 hydrogenation level, giving more credit to this technique in the field of hydrogen storage materials.
We report on the C60, Na, and Li dynamics in NaxLi6−xC60 fullerides (x = 0, 1, 5, and 6) in the temperature range 80−550 K by using 13C, 23Na, and 7Li solid state NMR. The results show that the C60 reorientation dynamics is hindered at room temperature for the Li-enriched fullerides, but it is active for the Na rich ones with a rate of the order of few kilohertz. 23Na and 7Li NMR measurements show the presence of two dominant thermally activated dynamics that can be associated with Li/Na ionic motions within the octahedral sites (intrasite motion) and between the octahedral and tetrahedral sites (intersite motion). The substitution of one Na or one Li ion in the end members Li6C60 and Na6C60, respectively, yields to an increase of the hopping rate of the intersite motion, which is necessary for the ionic diffusion in possible fulleride-based ionic conductors.
Two chemically synthesized defective graphene materials with distinctly contrasting extended structures and surface chemistry are used to prepare sodium-ion battery electrodes. The difference in electrode performance between the chemically prepared graphene materials is qualified based on correlations with intrinsic structural and chemical dissimilarities. The overall effects of the materials physical and chemical discrepancies are quantified by measuring the electrode capacities after repeated charge/discharge cycles. Solvothermal synthesized graphene (STSG) electrodes produce capacities of 92 mAh/g in sodium-ion batteries after 50 cycles at 10 mA/g, while thermally exfoliated graphite oxide (TEGO) electrodes produce capacities of 248 mAh/g after 50 cycles at 100 mA/g. Solid-state 23Na nuclear magnetic resonance spectroscopy is employed to locally probe distinct sodium environments on and between the surface of the graphene layers after charge/discharge cycles that are responsible for the variations in electrode capacities. Multiple distinct sodium environments of which at least 3 are mobile during the charge–discharge cycle are found in both cases, but the majority of Na is predominantly located in an immobile site, assigned to the solid electrolyte interface (SEI) layer. Mechanisms of sodium insertion and extraction on and between the defective graphene surfaces are proposed and discussed in relation to electrode performance. This work provides a direct account of the chemical and structural environments on the surface of graphene that govern the feasibility of graphene materials for use as sodium-ion battery electrodes.
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Understanding the mobility of H at the surface of carbon nanostructures is one of the essential ingredients for a deep comprehension of the catalytic formation of H2 in interstellar clouds. We combined neutron vibrational spectroscopy with DFT molecular dynamics simulations to … Continue reading