In this report, we present a simple and generic concept involving metal nanoclusters supported on metal oxide nanowires as stable and high capacity anode materials for Li-ion batteries. Specifically, SnO(2) nanowires covered with Sn nanoclusters exhibited an exceptional capacity of >800 mAhg(-1) over hundred cycles with a low capacity fading of less than 1% per cycle. Post lithiation analyses after 100 cycles show little morphological degradation of the hybrid nanowires. The observed, enhanced stability with high capacity retention is explained with the following: (a) the spacing between Sn nanoclusters on SnO(2) nanowires allowed the volume expansion during Li alloying and dealloying; (b) high available surface area of Sn nanoclusters for Li alloying and dealloying; and (c) the presence of Sn nanoclusters on SnO(2) allowed reversible reaction between Sn and Li(2)O to produce both Sn and SnO phases.
In this study, vertical nanowire arrays of MoO(3-x) grown on metallic substrates with diameters of ~90 nm show high-capacity retention of ~630 mAhg(-1) for up to 20 cycles at 50 mAg(-1) current density. Particularly, they exhibit a capacity retention of ~500 mAhg(-1) in the voltage window of 0.7-0.1 V, much higher than the theoretical capacity of graphite. In addition, 10 nm Si-coated MoO(3-x) nanowire arrays have shown a capacity retention of ~780 mAhg(-1), indicating that hybrid materials are the next generation materials for lithium ion batteries.
Hollow core-shell structured porous Si-C nanocomposites with void space up to tens of nanometres are designed to accommodate the volume expansion during lithiation for high-performance Li-ion battery anodes. An initial capacity of $760 mA h g À1 after formation cycles (based on the entire electrode weight) with $86% capacity retention over 100 cycles is achieved at a current density of 1 A g À1 . Good rate performance is also demonstrated.
Li-S batteries are a complicated system with many challenges existing before their final market penetration. While most of the reported work for Li-S batteries is focused on the cathode design, we demonstrate in this work that the anode consumption accelerated by corrosive polysulfide solution also critically determines the Li-S cell performance. To validate this hypothesis, ionic liquid (IL) N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Py 14 TFSI) has been employed to modify the properties of the SEI layer formed on the Li metal surface in Li-S batteries. It is found that the IL-enhanced passivation film on the lithium anode surface exhibits very different morphology and chemical composition, effectively protecting lithium metal from continuous attack by soluble polysulfides. Therefore, both the cell impedance and the irreversible consumption of polysulfides on lithium metal are reduced. As a result, the Coulombic efficiency and the cycling stability of Li-S batteries have been greatly improved. After 120 cycles, the Li-S battery cycled in the electrolyte containing 75% IL demonstrates a high capacity retention of 94.3% at 0.1 C rate. These results reveal one of the main failure mechanisms in Li-S batteries and shine the light on new approaches to improve the reversible capacity and cyclability of Li-S batteries. This work provides important clues for the understanding and thus the improvement of Li-S battery systems through a different point of view.
Since the first report of using micromechanical cleavage method to produce graphene sheets in 2004, graphene/graphene‐based nanocomposites have attracted wide attention both for fundamental aspects as well as applications in advanced energy storage and conversion systems. In comparison to other materials, graphene‐based nanostructured materials have unique 2D structure, high electronic mobility, exceptional electronic and thermal conductivities, excellent optical transmittance, good mechanical strength, and ultrahigh surface area. Therefore, they are considered as attractive materials for hydrogen (H2) storage and high‐performance electrochemical energy storage devices, such as supercapacitors, rechargeable lithium (Li)‐ion batteries, Li–sulfur batteries, Li–air batteries, sodium (Na)‐ion batteries, Na–air batteries, zinc (Zn)–air batteries, and vanadium redox flow batteries (VRFB), etc., as they can improve the efficiency, capacity, gravimetric energy/power densities, and cycle life of these energy storage devices. In this article, recent progress reported on the synthesis and fabrication of graphene nanocomposite materials for applications in these aforementioned various energy storage systems is reviewed. Importantly, the prospects and future challenges in both scalable manufacturing and more energy storage‐related applications are discussed.
A hierarchically structured nitrogen-doped porous carbon is prepared from a nitrogen-containing isoreticular metal-organic framework (IRMOF-3) using a self-sacrificial templating method. IRMOF-3 itself provides the carbon and nitrogen content as well as the porous structure. For high carbonization temperatures (950 °C), the carbonized MOF required no further purification steps, thus eliminating the need for solvents or acid. Nitrogen content and surface area are easily controlled by the carbonization temperature. The nitrogen content decreases from 7 to 3.3 at % as carbonization temperature increases from 600 to 950 °C. There is a distinct trade-off between nitrogen content, porosity, and defects in the carbon structure. Carbonized IRMOFs are evaluated as supercapacitor electrodes. For a carbonization temperature of 950 °C, the nitrogen-doped porous carbon has an exceptionally high capacitance of 239 F g(-1). In comparison, an analogous nitrogen-free carbon bears a low capacitance of 24 F g(-1), demonstrating the importance of nitrogen dopants in the charge storage process. The route is scalable in that multi-gram quantities of nitrogen-doped porous carbons are easily produced.
A cost-effective and scalable method is developed to prepare a core-shell structured Si/B(4)C composite with graphite coating with high efficiency, exceptional rate performance, and long-term stability. In this material, conductive B(4)C with a high Mohs hardness serves not only as micro/nano-millers in the ball-milling process to break down micron-sized Si but also as the conductive rigid skeleton to support the in situ formed sub-10 nm Si particles to alleviate the volume expansion during charge/discharge. The Si/B(4)C composite is coated with a few graphitic layers to further improve the conductivity and stability of the composite. The Si/B(4)C/graphite (SBG) composite anode shows excellent cyclability with a specific capacity of ∼822 mAh·g(-1) (based on the weight of the entire electrode, including binder and conductive carbon) and ∼94% capacity retention over 100 cycles at 0.3 C rate. This new structure has the potential to provide adequate storage capacity and stability for practical applications and a good opportunity for large-scale manufacturing using commercially available materials and technologies.
The synthesis of transition metal nitride nanoparticles is challenging, in part because the unreactive nature of the most common nitrogen reagents necessitates high-temperature and/or high-pressure reaction conditions. Here we report the solution-phase synthesis and characterization of antiperovskite-type Cu3PdN nanocrystals that are multifaceted, uniform, and highly dispersible as colloidal solutions. Colloidal Cu3PdN nanocrystals were synthesized by reacting copper(II) nitrate and palladium(II) acetylacetonate in 1-octadecene with oleylamine at 240 °C. The Cu3PdN nanocrystals were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) under alkaline conditions, where both Cu3N and Pd nanocrystals are known to be active. The ORR activity of the Cu3PdN nanocrystals appears to be superior to that of Cu3N and comparable to that of Pd synthesized using similar methods, but with significantly improved mass activity than Pd control samples. The Cu3PdN nanocrystals also show greater stability than comparably synthesized Pd nanocrystals during repeated cycling under alkaline conditions.
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