The fundamental kinetics of the electrocatalytic sulfur reduction reaction (SRR), a complex 16-electron conversion process in lithium-sulfur batteries, is insufficiently explored to date. Herein, by directly profiling the activation energies in the multi-step SRR, we reveal that the initial reduction of sulfur to the soluble polysulfides is relatively easy with low activation energy, while the subsequent conversion of the polysulfides into the insoluble Li 2 S 2 /Li 2 S is more difficult with much higher activation energy, which contribute to the accumulation of polysulfides and exacerbate the polysulfide shuttling effect. We use heteroatom-doped graphene as a model system to explore electrocatalytic SRR. We show nitrogen and sulfur dual-doped graphene considerably reduces the activation energy to improve SRR kinetics. Density functional calculations confirm that the doping tunes the p-band center of the active carbons for an optimal adsorption strength of intermediates and electroactivity. This study establishes electrocatalysis as a promising pathway to high performance lithium-sulfur batteries. The sulfur reduction reaction (SRR) in lithium-sulfur (Li-S) chemistry undergoes a complex 16-electron conversion process, transforming S 8 ring molecules into a series of soluble lithium polysulfides (LiPSs) with variable chain lengths before fully converting them into 2 insoluble Li 2 S 2 /Li 2 S products. This 16-electron SRR process is of considerable interest for high-density energy storage with theoretical capacity of 1672 mAh g-1 , but the chemistry is plagued by sluggish sulfur reduction kinetics and polysulfide (PS) shuttling effect. In practical Li-S cells, these effects limit the rate capability and cycle life 1,2. These limitations are fundamentally associated with the slow and complex reduction reaction involving S 8 ring molecules. In general, the insulating nature of elemental sulfur and its reduced products, and the sluggish charge transfer kinetics lead to incomplete conversion of S 8 molecules to soluble LiPSs. These polysulfides may shuttle across the separator to react with and deposit on the lithium anode, resulting in rapid capacity fading 3. Considerable efforts have been devoted to combating the PS shuttling effect, typically by employing a passive strategy by using various sulfur host materials to physically or electrostatically trap the LiPSs in the cathode structure 4-13. These passive confinement/entrapping strategies have partly mitigated the PS shuttling
Ceramic aerogels are attractive for thermal insulation but plagued by poor mechanical stability and degradation under thermal shock. In this study, we designed and synthesized hyperbolic architectured ceramic aerogels with nanolayered double-pane walls with a negative Poisson’s ratio (−0.25) and a negative linear thermal expansion coefficient (−1.8 × 10−6 per °C). Our aerogels display robust mechanical and thermal stability and feature ultralow densities down to ~0.1 milligram per cubic centimeter, superelasticity up to 95%, and near-zero strength loss after sharp thermal shocks (275°C per second) or intense thermal stress at 1400°C, as well as ultralow thermal conductivity in vacuum [~2.4 milliwatts per meter-kelvin (mW/m·K)] and in air (~20 mW/m·K). This robust material system is ideal for thermal superinsulation under extreme conditions, such as those encountered by spacecraft.
A novel natural drying (ND) strategy for low-cost and simple fabrication of graphene aerogels (GAs) is highlighted. The as-formed NDGAs exhibit ultralarge reversible compressibility (99%) and tunable Poisson's ratio behaviors (-0.30 < ν < 0.46), which suggests promising applications in soft actuators, soft robots, sensors, deformable electronic devices, drug release, thermal insulator, and protective materials.
Graphene-supported single atomic metals (G-SAMs) have recently attracted considerable research interest for their intriguing catalytic, electronic, and magnetic properties. The development of effective synthetic methodologies toward G-SAMs with monodispersed metal atoms is vital for exploring their fundamental properties and potential applications. A convenient, rapid, and general strategy to synthesize a series of monodispersed atomic transition metals (for example, Co, Ni, Cu) embedded in nitrogen-doped graphene by two-second microwave (MW) heating the mixture of amine-functionalized graphene oxide and metal salts is reported here. The MW heating is able to simultaneously induce the reduction of graphene oxide, the doping of nitrogen, and the incorporation of metal atoms into the graphene lattices in one simple step. The rapid MW process minimizes metal diffusion and aggregation to ensure exclusive single metal atom dispersion in graphene lattices. Electrochemical studies demonstrate that graphene-supported Co atoms can function as highly active electrocatalysts toward the hydrogen evolution reaction. This MW-assisted method provides a rapid and efficient avenue to supported metal atoms for wide ranges of applications.
A hyperbolically patterned 3D graphene metamaterial (GM) with negative Poisson's ratio and superelasticity is highlighted. It is synthesized by a modified hydrothermal approach and subsequent oriented freeze-casting strategy. GM presents a tunable Poisson's ratio by adjusting the structural porosity, macroscopic aspect ratio (L/D), and freeze-casting conditions. Such a GM suggests promising applications as soft actuators, sensors, robust shock absorbers, and environmental remediation.
Three-dimensional (3D) graphene aerogels (GA) show promise for applications in supercapacitors, electrode materials, gas sensors, and oil absorption due to their high porosity, mechanical strength, and electrical conductivity. However, the control, actuation, and response properties of graphene aerogels have not been well studied. In this paper, we synthesized 3D graphene aerogels decorated with Fe3O4 nanoparticles (Fe3O4/GA) by self-assembly of graphene with simultaneous decoration by Fe3O4 nanoparticles using a modified hydrothermal reduction process. The aerogels exhibit up to 52% reversible magnetic field-induced strain and strain-dependent electrical resistance that can be used to monitor the degree of compression/stretching of the material. The density of Fe3O4/GA is only about 5.8 mg cm(-3), making it an ultralight magnetic elastomer with potential applications in self-sensing soft actuators, microsensors, microswitches, and environmental remediation.
This paper investigates the effect of varying the geometry of the die on the cell nucleation behavior of extruded PS foams blown with CO2. Three interchangeable groups of carefully calibrated filamentary dies have been used in the experimental study. The dies were deliberately designed to have either different pressure drop rates while having identical die pressures and flow rates, or different die pressures while having identical pressure drop rates and flow rates. The experimental results revealed that the geometry of the die governs the cell density of extruded PS foams, especially because of its significant effect on the pressure drop rate across the die. However, the effect of the die back pressure on the cell density was found to be marginal, whereas its effect on the cell morphology was found to be predominant. In addition, regardless of die geometry, the CO2 content proved to be a very sensitive parameter with respect to the cell nucleation behavior of extruded PS foams. On the other hand, the cell density was slightly improved by an increase of the tale content, especially at reduced concentrations of CO2.
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