Mesoporous Germanium Anode Materials for Lithium‐Ion Battery with Exceptional Cycling Stability in Wide Temperature Range

Porous structured materials have unique architectures and are promising for lithium‐ion batteries to enhance performances. In particular, mesoporous materials have many advantages including a high surface area and large void spaces which can increase reactivity and accessibility of lithium ions. This study reports a synthesis of newly developed mesoporous germanium (Ge) particles prepared by a zincothermic reduction at a mild temperature for high performance lithium‐ion batteries which can operate in a wide temperature range. The optimized Ge battery anodes with the mesoporous structure exhibit outstanding electrochemical properties in a wide temperature ranging from ?20 to 60 °C. Ge anodes exhibit a stable cycling retention at various temperatures (capacity retention of 99% after 100 cycles at 25 °C, 84% after 300 cycles at 60 °C, and 50% after 50 cycles at ?20 °C). Furthermore, full cells consisting of the mesoporous Ge anode and an LiFePO₄ cathode show an excellent cyclability at ?20 and 25 °C. Mesoporous Ge materials synthesized by the zincothermic reduction can be potentially applied as high performance anode materials for practical lithium‐ion batteries.     

Rational Design and Synthesis of Extremely Efficient Macroporous CoSe2–CNT Composite Microspheres for Hydrogen Evolution Reaction

Uniquely structured CoSe₂–carbon nanotube (CNT) composite microspheres with optimized morphology for the hydrogen‐evolution reaction (HER) are prepared by spray pyrolysis and subsequent selenization. The ultrafine CoSe₂ nanocrystals uniformly decorate the entire macroporous CNT backbone in CoSe₂–CNT composite microspheres. The macroporous CNT backbone strongly improves the electrocatalytic activity of CoSe₂ by improving the electrical conductivity and minimizing the growth of CoSe₂ nanocrystals during the synthesis process. In addition, the macroporous structure resulting from the CNT backbone improves the electrocatalytic activity of the CoSe₂–CNT microspheres by increasing the removal rate of generated H₂ and minimizing the polarization of the electrode during HER. The CoSe₂–CNT composite microspheres demonstrate excellent catalytic activity for HER in an acidic medium (10 mA cm^?2 at an overpotential of ≈174 mV). The bare CoSe₂ powders exhibit moderate HER activity, with an overpotential of 226 mV at 10 mA cm^?2. The Tafel slopes for the CoSe₂–CNT composite and bare CoSe₂ powders are 37.8 and 58.9 mV dec^?1, respectively. The CoSe₂–CNT composite microspheres have a slightly larger Tafel slope than that of commercial carbon‐supported platinum nanoparticles, which is 30.2 mV dec^–1.     

Trimetallic PtCoFe Alloy Monolayer Superlattices as Bifunctional Oxygen‐Reduction and Ethanol‐Oxidation Electrocatalysts

A synthesis strategy for the preparation of trimetallic PtCoFe alloy nanoparticle superlattices is reported. Trimetallic PtCoFe alloy monolayer array of nanoparticle superlattices with a large density of high index facets and platinum‐rich surface are successfully prepared by coreduction of metal precursors in formamide solvent. The concentration of cetyl trimethyl ammonium bromide plays a vital role for the formation of a monolayer array of nanoparticle superlattices, while the size of nanoparticles is determined by NaI. The prepared monolayer array of nanoparticle superlattices is the superior catalyst for oxygen reduction reaction as well as for ethanol oxidation owing to their specific structural and compositional characteristics.     

Surface Energy and Surface Stability of Ag Nanocrystals at Elevated Temperatures and Their Dominance in Sublimation‐Induced Shape Evolution

The surface energy and surface stability of Ag nanocrystals (NCs) are under debate because the measurable values of the surface energy are very inconsistent, and the indices of the observed thermally stable surfaces are apparently in conflict. To clarify this issue, a transmission electron microscope is used to investigate these problems in situ with elaborately designed carbon‐shell‐capsulated Ag NCs. It is demonstrated that the {111} surfaces are still thermally stable at elevated temperatures, and the victory of the formation of {110} surfaces over {111} surfaces on the Ag NCs during sublimation is due to the special crystal geometry. It is found that the Ag NCs behave as quasiliquids during sublimation, and the cubic NCs represent a featured shape evolution, which is codetermined by both the wetting equilibrium at the Ag–C interface and the relaxation of the system surface energy. Small Ag NCs (≈10 nm) no longer maintain the wetting equilibrium observed in larger Ag NCs, and the crystal orientations of ultrafine Ag NCs (≈6 nm) can rotate to achieve further shape relaxation. Using sublimation kinetics, the mean surface energy of Ag NCs at 1073 K is calculated to be 1.1–1.3 J m^?2.     

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte

Nitrogen and sulfur‐codoped graphene composites with Co₉S₈ (NS/rGO‐Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO₂ catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only ?0.193 V to reach 10 mA cm^?2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half‐wave potential in ORR and the potential to reach 10 mA cm^?2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm^?2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S‐codoped rGO, and Co₉S₈ nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions.     

Defect‐Laden MoSe2 Quantum Dots Made by Turbulent Shear Mixing as Enhanced Electrocatalysts

A high density of edge sites and other defects can significantly improve the catalytic activity of layered 2D materials. Herein, this study demonstrates a novel top‐down strategy to maximize catalytic edge sites of MoSe₂ by breaking up bulk MoSe₂ into quantum dots (QDs) via “turbulent shear mixing” (TSM). The ultrasmall size of the MoSe₂ QDs provides a high fraction of atoms in reactive edge sites, thus significantly improving the catalytic activities. The violent TSM further introduces abundant defects as additional active sites for electrocatalytic reactions. These edge‐proliferated and defect‐laden MoSe₂ QDs are found to be efficient electrocatalysts for the hydrogen evolution reaction, and useful as counter electrodes in dye‐sensitized solar cells. The work provides a new paradigm for creating edge‐proliferated and defect‐rich QDs from bulk layered materials.     

Design of active and stable oxygen reduction reaction catalysts by embedding Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> nanoparticles into nitrogen-doped carbon

The oxygen reduction reaction (ORR) is essential in research pertaining to life science and energy. In applications, platinum-based catalysts give ideal reactivity, but, in practice, are often subject to high costs and poor stability. Some cost-efficient transition metal oxides have exhibited excellent ORR reactivity, but the stability and durability of such alternative catalyst materials pose serious challenges. Here, we present a facile method to fabricate uniform Co _x O _y nanoparticles and embed them into N-doped carbon, which results in a composite of extraordinary stability and durability, while maintaining its high reactivity. The half-wave potential shows a negative shift of only 21 mV after 10,000 cycles, only one third of that observed for Pt/C (63 mV). Furthermore, after 100,000 s testing at a constant potential, the current decreases by only 17%, significantly less than for Pt/C (35%). The exceptional stability and durability results from the system architecture, which comprises a thin carbon shell that prevents agglomeration of the Co _x O _y nanoparticles and their detaching from the substrate.

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Template-directed synthesis of nitrogen- and sulfur-codoped carbon nanowire aerogels with enhanced electrocatalytic performance for oxygen reduction

Heteroatom doping,precise composition control,and rational morphology design are efficient strategies for producing novel nanocatalysts for the oxygen reduction reaction (ORR) in fuel cells.Herein,a cost-effective approach to synthesize nitrogen-and sulfur-codoped carbon nanowire aerogels using a hard templating method is proposed.The aerogels prepared using a combination of hydrothermal treatment and carbonization exhibit good catalytic activity for the ORR in alkaline solution.At the optimal annealing temperature and mass ratio between the nitrogen and sulfur precursors,the resultant aerogels show comparable electrocatalytic activity to that of a commercial Pt/C catalyst for the ORR.Importantly,the optimized catalyst shows much better long-term stability and satisfactory tolerance for the methanol crossover effect.These codoped aerogels are expected to have potential applications in fuel cells.