Small Changes,Big Impact: Tungsten Bronzes with Extremely Large Second Harmonic Generation Achieved by the Transition Metal Doping on the B-Site

Two novel transition metal-doped tungsten bronze oxides, Pb_2.15Li_0.85Nb_4.85Ti_0.15O₁₅ (PLNT) and Pb_2.15Li_0.55Nb_4.85W_0.15O₁₅ (PLNW), are synthesized by high-temperature solid-state reactions. The Rietveld method using the high-resolution synchrotron radiation indicates that PLNT and PLNW crystallize in the orthorhombic polar noncentrosymmetric space group, Pmn2₁ (no. 31). As a class of tungsten bronze oxide, PLNT and PLNW retain a unique rigid framework composed of d⁰ transition metal cation (Ti⁴⁺ or W⁶⁺)-doped highly distorted NbO₆ octahedra along with the subsequently generated Pb/LiO₁₂ and PbO₁₅ polyhedra. Interestingly, the d⁰ transition metal-doped tungsten bronzes, PLNT and PLNW, exhibit extremely large second-harmonic generation (SHG) responses of 56 and 67 × KH₂PO₄, respectively. The observed immeasurably strong SHG is mainly attributed to a net polarization originating from the alignment of highly distorted NbO₆ octahedra with doped transition metals in the frameworks. It is believed that doping transition metal cations at the B-site of the tungsten bronze structures should be an innovative strategy to develop novel high-performance nonlinear optical materials.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Regulation of Ionic Distribution and Desolvation Activation Energy Enabled by In Situ Zinc Phosphate Protective Layer toward Highly Reversible Zinc Metal Anodes

Despite the merits of high specific capacity, low cost, and high safety, the practical application of aqueous Zn metal batteries (AZMBs) is plagued by the dendritic growth and corrosion reaction of Zn metal anodes. To solve these issues, a Zn₃(PO₄)₂·4H₂O protective layer is in-situ constructed on Zn foil (Zn@ZnPO) by a simple hydrothermal method, avoiding the traditional slurry-casting process. The insulating and conformable ZnPO layer improves the wettability of Zn@ZnPO and aqueous electrolyte via decreasing the contact angle to 11.7^o. Compared with bare Zn, the Zn@ZnPO possesses a lower desolvation activation energy of 35.25 kJ mol^-1, indicating that the ZnPO fasters the desolvation of hydrated Zn²⁺ ions and thereby ameliorates their transport dynamics. Micro-morphology and structural characterization show that there are no dendrites forming on the post-cycling Zn@ZnPO anodes, and the interfacial ZnPO layer remains almost identical before and after cycles. It can be explained that the electrochemically stable ZnPO layer acts as an ionic modulator to enable the homogeneous distribution of Zn²⁺ ions, inhibiting the growth of Zn dendrites. Benefiting from these advantages, the Zn@ZnPO based symmetric and full cells deliver highly reversible Zn plating/stripping behavior and long cycling lifespans.     

Recent Progress of Bismuth Effect on All-Inorganic Lead-Free Metal Halide Derivatives: Crystals Structure,Luminescence Properties,and Applications

Bismuth (Bi³⁺)-included lead-free metal halide (LFMH) materials attract much attention in lighting, display, photodetectors, X-ray detectors, and photovoltaic fields, due to the tunable luminescence and optoelectronic performance in response to crystal and electronic structure, morphology, and particle sizes. This review summarizes Bi³⁺-included LFMH materials about their preparation approach, crystal and electronic structure properties, luminescence performance, and emerging applications. Notably, Bi³⁺ ions not only can act as framework cation to construct stable LFMH structure, but can also incorporate into LFMH materials as activators or sensitizers to generate remarkable luminescence tuning and band engineering. The Bi³⁺ effect on the luminescence and optoelectronic properties of LFMH materials, including, promotion of exciton localization, enhancement of light absorption in near-ultraviolet region, action as sensitizer ions to transfer energy to rare earth or transition metal ions and emission of highly-efficient light is systematically summarized. The proposed structure-luminescence relationship offers guidance for the optimization of current Bi³⁺-included LFMH materials and the exploitation of new LFMH derivatives.     

透明吸波体综述北大核心CSCD

吸波体是一种带有损耗特性的周期结构,能够吸收电磁波,将电磁能转化为热能,降低反射的电磁波能量。随着应用场景的特殊化,吸波体朝着特殊领域、特定功能、更具针对性的方向发展。由于各类含有光学窗口的应用环境对抗电磁干扰需求的不断提高,吸波体光学透明化成为研究的重点方向。为了对透明吸波体的发展状况有系统的认识,文章以制造材料为脉络梳理了近年来可见光透明吸波体的研究现状,包括氧化铟锡(ITO)、金属网栅、石墨烯等,综述了以它们为材料制备的透明吸波体优缺点以及发展趋势,最后对透明吸波体的未来发展进行了展望。     

Metal Micropatterning by Triboelectric Spark Discharge

Metal micropatterns play critical roles in flexible electronics. However, the lack of versatile strategies for micropatterning of diverse metal materials on various thin, flexible or stretchable substrates has limited the rapid development of flexible electronics. Here, a metal micropatterning method by triboelectric spark discharge under atmospheric environment is developed, where a triboelectric nanogenerator (TENG) is employed to precisely and safely control the voltage, current, and frequency of the spark discharges. Micropatterns of metal films like gold, silver, copper, aluminum and platinum are successfully fabricated on substrates of polyimide, polyethylene terephthalate, polyvinyl chloride, polydimethylsiloxane, paper or latex, even on ultrathin substrates (5 μm thick) without damage, where the feature sizes of metal patterns are controllable from 20 μm to 1 mm. Experimental insights into the triboelectric spark discharge behaviors and the pattern feature sizes control are discussed. A straightforward fabrication of metal patterns on the balloon surface or human skin through “handwriting” by a pencil as discharge electrode is realized. Besides metals, extended processibility of conductive materials like carbon nanotubes, graphene, MXene, graphite, carbon fibers, and conductive polymers are also demonstrated. This work proves the possibility of microfabrication by TENG, which is of simplicity and attractiveness for flexible electronics.     

Effects of material combination on laser beam drilling of a metal foil using a cover plate

This research investigated the microdrilling characteristics of metal foils depending on the materials of the cover plates and metal foils in the cover plate-laser beam machining (c-LBM) process, which is a method to achieve better quality in metal foil machining with a given piece of equipment. Laser beam drilling using a nanosecond pulsed laser was carried out on 10-µm-thick stainless steel 304 (STS304), nickel, and copper foils with 100-µm-thick cover plates of each material. Consequently, STS304 was found to be an effective cover plate material for reducing the hole diameter and spatter deposition on metal foils. Compared to the results without using a cover plate, the average hole diameter and the area of spatter deposition decreased by up to 77% and 96%, respectively, by using the STS304 cover plate. Meanwhile, the thermal deformation of the STS304 and nickel foils was prevented by using a cover plate, while the copper foil was barely deformed even without a cover plate. Lastly, it was remarkable that the copper foil was drilled with approximately 67% lower pulse energy than the effective minimum pulse energy required to drill it by using the STS304 cover plate, resulting in a smaller hole with little spatter.     

Optical properties of carbon-containing titanium oxide nanocomposites obtained by the pulsed plasma chemical method

This paper presents the results of an experimental investigation on the optical properties of the TiO₂ and Ti_xC_yO_z nanopowders, produced by the pulsed plasma chemical method. Pulsed plasma chemical synthesis is realized on the laboratory stand, including a plasma chemical reactor (6 l) and TEA-500 electron accelerator. The parameters of the electron beam are as follows: 400–450 keV electron energy, 60 ns half-amplitude pulse duration, up to 200 J pulse energy, and 5 cm beam diameter. In TiO₂ sample, obtained using the pulsed plasma chemical method, the particles can be divided into two groups: 100–500 nm large spherical particles and tiny complex particles (sized less than 100 nm). For TixCyOz sample, the morphology of the particles is mainly presented with irregular fragment shape. The average size of the particles is ranged from 200 to 300 nm. The band gap for all synthesized samples is within 2.94–3.35 eV.