Fluorinated Nonflammable In Situ Gel Polymer Electrolyte for High-Voltage Lithium Metal Batteries.

Rechargeable lithium metal batteries (LMBs) offer excellent opportunities for applications requiring high-energy-density battery systems. So far, it has received a lot of interest in pairing higher-energy-density high-voltage nickel-rich cathodes. Here, fluorinated solvents were used instead of the usual carbonate solvents to prepare gel polymer electrolytes (FGPE) by in situ polymerization of polymers introducing the fluorine-containing groups. Theoretically and experimentally, FGPE has proven to be ultra-compatible with the lithium metal anode and LiNi0.8Co0.1Mn0.1O2 cathode. A stable plating/stripping process of over 2000 h can be achieved for symmetrical lithium cells using FGPE. The Li||FGPE||NCM811 cell has a longer cycle life at a high voltage (4.5 V). In addition, the zero self-extinguishing time indicates that the FGPE has sufficient safety. In summary, the design of this electrolyte provides ideas to improve the safety and energy density of LMBs.

Self-powered, ultraviolet-to-near infrared broadband photodetector based on Ag-doped CsPbI3/PEDOT:PSS heterojunction.

Metal halide perovskites are studied for photodetection applications because of their outstanding optical and electrical properties. A self-powered ultraviolet-to-near infrared broadband photodetector based on a Ag-doped CsPbI3/PEDOT:PSS heterojunction was investigated. The photodetector using a CsPbI3:Ag/PEDOT:PSS heterostructure with a planar photoconductive structure operated over a broad 355-1560 nm wavelength range in self-powered mode. A terahertz signal was modulated with the CsPbI3:Ag/PEDOT:PSS structure at low optical excitation intensity to investigate its photodetection mechanism. The experimentally designed detector can present images of the letters "C", "N" and "U" in the visible and near-infrared wavelengths, indicating a potential broadband imaging application.

Rational prediction of multifunctional bilayer single atom catalysts for the hydrogen evolution, oxygen evolution and oxygen reduction reactions.

Bimetallic atom catalysts (BACs), which can exhibit remarkable catalytic performance compared with single atom catalysts (SACs) due to their higher metal loading and the synergy between two metal atoms, have attracted great attention in research. Herein, by means of density functional theory calculations, novel BACs with a bilayer structure composed of monolayers FeN4 (Fe and nitrogen co-doped graphene) and MN4 (Fe/M, M represents transition metal atoms) as electrocatalysts for the hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and oxygen evolution reaction (OER) are investigated. Among these bilayer SACs, a series of highly efficient monofunctional, bifunctional, and even trifunctional electrocatalysts have been screened. For example, the overpotentials for the HER, ORR, and OER can reach -0.02 (Fe/Cu), 0.31 (Fe/Hg), and 0.27 V (Fe/Hf), respectively; Fe/Hf and Ir/Fe can serve as promising bifunctional catalysts for the ORR/OER and HER/OER, respectively and Fe/Rh is considered as an excellent trifunctional catalyst for the HER, OER, and ORR. This work not only provides a new idea for understanding and optimizing the active sites of BACs, but also proposes a new strategy for designing high-performance multifunctional electrocatalysts for fuel cells and metal-air batteries.

Bimetallic Pairs Supported on Graphene as Efficient Electrocatalysts for Nitrogen Fixation: Search for the Optimal Coordination Atoms.

The electrocatalytic nitrogen reduction reaction (NRR) is a most attractive approach to ammonia synthesis, and the development of catalysts with excellent activity, high NRR selectivity, and long-term durability is crucial but remains a great challenge. Herein, by means of density functional theory calculations, the stability and catalytic performance of anchored bimetals was systematically investigated by pairing different transition-metal atoms (Mo, Cr, Ti, V, Ru, and W) on graphene with different coordination atoms (C, N, O, P, and S) for N2 fixation. By screening the stability, limiting potential, and selectivity of 105 candidates, carbon was found to be the optimal coordination atom for bimetallic pairs, whereas the other four coordination atoms were unsatisfactory owing to either thermodynamically unstable anchor sites for bimetallic pairs (O, P, and S atoms) or relatively low catalytic activity (N atom). Notably, the bimetallic compound of Mo and Ti supported on C-coordinated graphene (MoTi-CG) and TiV-CG were predicted as effective NRR catalysts with the attractive limiting potentials of -0.34 and -0.30 V. Furthermore, the volcano curve between the limiting potential and the adsorption free energy of NH2 * [ΔG(NH2 *)] was revealed, in which a moderate ΔG(NH2 *) was required for high-activity NRR catalysts. This study not only provides a theoretical basis for the rational design of bimetallic compounds anchored on graphene as effective NRR catalysts under ambient conditions but also opens up a new way to accelerate the screening of NRR catalysts.

Investigation of the Microstructures of Graphene Quantum Dots (GQDs) by Surface-Enhanced Raman Spectroscopy.

Photoluminescence (PL) is the most significant feature of graphene quantum dots (GQDs). However, the PL mechanism in GQDs has been debated due to the fact that the microstructures, such as edge and in-plane defects that are critical for PL emission, have not been convincingly identified due to the lack of effective detection methods. Conventional measures such as high-resolution transmission electron microscopy and infrared spectroscopy only show some localized lattice fringes of GQDs and the structures of some substituents, which have little significance in terms of thoroughly understanding the PL effect. Here, surface-enhanced Raman spectroscopy (SERS) was introduced as a highly sensitive surface technique to study the microstructures of GQDs. Pure GQDs were prepared by laser ablating and cutting highly oriented pyrolytic graphite (HOPG) parallel to the graphite layers. Consequently, abundant SERS signals of the GQDs were obtained on an Ag electrode in an electrochemical environment for the first time. The results convincingly and experimentally characterized the typical and detailed features of GQDs, such as the crystallinity of sp² hexagons, the quantum confinement effect, various defects on the edges, sp³-like defects and disorders on the basal planes, and passivated structures on the periphery and surface of the GQDs. This work demonstrates that SERS is thus by far the most effective technique for probing the microstructures of GQDs.

The Relationship between the Hydrophilicity and Surface Chemical Composition Microphase Separation Structure of Multicomponent Silicone Hydrogels.

Three series of multicomponent silicone hydrogels were prepared by the copolymerization of two hydrophobic silicon monomers bis(trimethylsilyloxy) methylsilylpropyl glycerol methacrylate (SiMA) and tris(trimethylsiloxy) 3-methacryloxypropylsilane (TRIS) with three hydrophilic monomers. The surface hydrophilicity of the silicone hydrogels was characterized by contact angle measurements, and an interesting phenomenon was found that the silicone hydrogels made from less hydrophobic monomer SiMA possess more hydrophobic surfaces than those made from TRIS. The surface properties such as morphology and elemental composition of the silicone hydrogels were explored by scanning electron microscopy (SEM) imaging and energy dispersive spectrometry (EDS) analysis, and their relationships with the surface hydrophilicity were investigated in details. The results show neither the surface morphology nor the elemental composition has obvious impact on the surface hydrophilicity. Atomic force microscopy (AFM) imaging revealed that SiMA hydrogel had a more significant phase separation structure, which also made its surface uneven: a lot of tiny holes were observed on the surface. This surface phase separation structure made SiMA hydrogel more difficult to be wetted by water or PBS buffer, i.e., more hydrophobic than TRIS hydrogel. On the basis of these results, we propose that the phase separation structure as well as the nature of silicon monomers might be the fundamental reasons of surface hydrophilicity. These results could help to design a silicone hydrogel with better surface properties and wider application.

Effect of pump depletion on second harmonic generation in multiple quasi-phase-matching gratings.

Second harmonic generation (SHG) from the aperiodic optical superlattice (AOS) in considering the pump depletion is investigated. It is found the domain configuration designed in undepleted pump approximation (UPA) can also be used to achieve multiple wavelength SHGs with high enough conversion efficiency for an exact solution. The applicable scope of UPA was estimated by a relative tolerance based on the related SHG conversion efficiency calculated in UPA and an exact solution. Results reveal that the relative tolerance is solely determined by the conversion efficiency, and unrelated to the sample configuration, pump intensity, incidental wavelength and nonlinear media. A model to evaluate an exact solution is proposed, and it is suggested that the SHG conversion efficiency can be easily assessed by the developed model. These results can be used to provide direct guidance for practical application, and can also make the estimation of practical samples more convenient.

Oxidation of the two-phase Nb/Nb5Si3 composite: the role of energetics, thermodynamics, segregation, and interfaces.

Oxidation behavior of the two-phase Nb/Nb(5)Si(3) composite is of significant importance for the potential applications of the composite at high-temperature conditions. We investigate the atomic-scale oxidation mechanism of the Nb/Nb(5)Si(3) composite with first-principles density-functional theory and thermodynamics analysis. In particular, the effects of energetics, thermodynamics, segregation, and interfaces are identified. The clean composite surface is found to be composed of both Nb(110) and Si-terminated Nb(5)Si(3)(001). Energetics and thermodynamics calculations show that, during the oxidation process, the Nb(110) surface is oxidized first, followed by the segregation of niobium of the Nb(5)Si(3)(001) surface and subsequent oxidation of the Nb element of Nb(5)Si(3). High coverage of oxygen results in dissolved oxygen in bulk Nb through the diffusion of oxygen in the surface and at the interface. The theoretical investigation also provides an explanation, at the atomic-scale, for the experimental observation that the oxidation layer is essentially composed of niobium oxide and almost free of silicon. Furthermore, the methodology of this work can be applied to investigations of the oxidation behavior of other two-phase and multi-phase composites.

Investigation of the wave behaviors inside a step-modulated subwavelength metal slit.

In this paper, we applied the modal expansion method (MEM) to investigate the wave behaviors inside a step-modulated subwavelength metal slit. The physical mechanism of the surface plasmon polariton (SPP) transmission is investigated in detail for slit structures with either dielectric or geometric modulation. The applicability of the effective index method is discussed. Moreover, as a special case of the geometric modulation, the evanescent-wave assisted transmission is demonstrated in a thin-modulated slit. We emphasize that a complete set is necessary in order to expand the wave functions in these kinds of structures. All the calculated results by the MEM are well retrieved by the finite-difference time-domain calculation.

Unexpected relationship between interlayer distances and surface/cleavage energies in γ-TiAl: density functional study.

Density functional calculations were performed to study the γ-TiAl (001), (100), (110) and (111) surfaces. The (100) surface is the most stable under Ti-rich conditions, while the Al-termination (110) surface becomes the most stable with the increase of Al chemical potential. We calculate that in γ-TiAl intermetallic compound the larger the interlayer distance, the larger the surface energy and cleavage energy. This is different from the situation in a pure metal. This phenomenon can be explained by the analysis of the bonding characteristics in γ-TiAl. In particular there are both metallic and covalent bonds in γ-TiAl, and the strongest covalent bonds mainly focus on the center of three Ti-Al-Ti atoms. It is the covalent bonds that affect greatly the cleavage energy, the surface energy and the surface stability.

Atomic structure and adhesion of the Nb(001)/α-Nb5Si3(001) interface: a first-principles study.

The density functional calculations have been performed to study the Nb(001) and α-Nb5Si3(001) surfaces as well as the interface properties of Nb(001)/α-Nb5Si3(001). The surface energy of the Nb(001) surface is about 2.25 J m (- 2). The calculated cleavage energies of bulk Nb5Si3 are 5.103 J m (- 2) and 5.787 J m (- 2) along (001) planes with the breaking of Nb-Si and Nb-NbSi bonds, respectively. For the Nb(001)/α-Nb5Si3(001) models, the Nb atoms in the interface region initially belonging to body centered cubic metal Nb are twisted to the position of the Nb atom layer in Nb5Si3 and the interlayer distance is similar to that of bulk Nb5Si3 after being fully relaxed. The ideal work of adhesion of the Nb(001)/Nb5Si3(001) interface is calculated and compared to those of bulk Nb and Nb5Si3. The results show that the bulk Nb5Si3 has the largest work of adhesion, the bcc Nb ranks second and the interface ranks last. Moreover, the Nb-Si bond is weaker than Nb-NbSi and Nb-Nb bonds in the interface, which means that the Nb-Si bond in the interface is the most possible site for the micro-crack generation when the stress is applied quasi-statically along the [001] direction. The densities of states, Mulliken population and overlap population of the Nb(001)/α-Nb5Si3(001) interface are also analyzed.

Surface segregation of Si and its effect on oxygen adsorption on a γ-TiAl(111) surface from first principles.

We perform first-principles calculations based on the density-functional theory to study the surface segregation of Si and its effect on the oxygen adsorption on a γ-TiAl(111) surface for a range of oxygen coverage 0<Θ≤1.0 monolayer (ML). The calculated results show that the alloying Si atoms prefer occupying surface Ti sites to the sites in the bulk of γ-TiAl, which suggests the occurrence of Si surface segregation. When oxygen atoms adsorb on a pure γ-TiAl(111) surface, the most favorable sites are the adsorption sites with more Ti atoms as their nearest neighbors in the surface layer at all the calculated coverages and the interactions between adsorbed oxygen atoms are repulsive. However, when oxygen atoms adsorb on an Si-alloyed γ-TiAl(111) surface, the interactions between the adsorbed oxygen atoms are attractive at oxygen coverage 0<Θ≤1.0 ML. Meanwhile, the interactions between O and Al atoms become stronger whereas those between O and Ti atoms become weaker relative to oxygen adsorbed on a pure γ-TiAl(111) surface. The atomic geometry and density of state are analyzed. The results show that the surface ripple of the top metal layer for oxygen on a pure γ-TiAl(111) surface is Ti upwards, while that for oxygen on an Si-alloyed γ-TiAl(111) surface is Al upwards at high oxygen coverage (Θ≥0.50 ML). This effect of Si is of benefit to the nucleation of alumina, which is attributed to Si surface segregation and an increase of the surface Al:Ti ratio. This can help to explain why alloying the γ-TiAl(111) surface with Si could favor the formation of the Al(2)O(3) scale at the first stage and result in good oxidation resistance in experiments.

Switching control of spontaneous emission by polarized atoms in two-dimensional photonic crystals.

We calculate the lifetime distribution function of an assembly of polarized atoms in two-dimensional (2D) photonic crystals (PCs) at different polarization orientations of atomic dipole moments. We reveal a switching effect of atomic spontaneous emission (SE) and find a significant change of atomic lifetime, up to a factor of 33, by tuning the polarized orientation of the atoms. These observations suggest that the tuning of the polarized orientation of atoms provides a new way for the effective control of atomic SE processes in 2D PCs.

Photonic band gap effects on spontaneous emission lifetimes of an assembly of atoms in two-dimensional photonic crystals.

The lifetime distribution functions of the spontaneous emission (SE) of the excited atoms embedded in two-dimensional (2D) photonic crystals (PCs) with square lattice, consisting of square air rods in dielectric medium with different filling factors, are calculated by using the plane wave expansion method. The numerical results show that the SE in the 2D PCs cannot be prohibited completely but it can be inhibited intensively by the pseudo-PBG of the PCs. In the pseudoband edges, the SE is accelerated obviously. The reduced average lifetime of the excited atoms and the extension of the reduced lifetime distribution in the 2D PCs both are the same as those in the 3D PCs in the order of magnitude. Our results provide an available way to control the behavior of the SE by changing the structures of the 2D PCs.