Crystal plane induced in-situ electrochemical activation of manganese-based cathode enable long-term aqueous zinc-ion batteries

Rapid capacity decay and sluggish reaction kinetics are major barriers hindering the applications of manganese-based cathode materials for aqueous zinc-ion batteries.Herein,the effects of crystal plane on the in-situ transformation behavior and electrochemical performance of manganese-based cathode is discussed.A comprehensive discussion manifests that the exposed(100)crystal plane is beneficial to the phase transformation from tunnel-structured MnO_(2) to layer-structured ZnMn_(3)O_(7)·3H_(2)O,which plays a critical role for the high reactivity,high capacity,fast diffusion kinetics and long cycling stability.Additionally,a two-stage zinc storage mechanism can be demonstrated,involving continuous activation reaction and phase transition reaction.As expected,it exhibits a high capacity of 275 mAh g^(-1)at 100 mA g^(-1),a superior durability over 1000 cycles and good rate capability.This study may open new windows toward developing advanced cathodes for ZIBs,and facilitate the applications of ZIBs in large-scale energy storage system.

Anti-Corrosion and Reconstruction of Surface Crystal Plane for Zn Anodes by an Advanced Metal Passivation Technique

For the aqueous Zn-ion battery,dendrite formation,corrosion,and interfacial parasitic reactions are major issues,which greatly inhibits their practical application.How to develop a method of Zn construction or treatment to solve these issues for Zn anodes are still great challenges.Herein,a simple and cheap metal passivation technique is proposed for Zn anodes from a corrosion science perspective.Similar to the metal anticorrosion engineering,the formed interfacial protective layer in a chemical way can sufficiently solve the corrosion issues.Furthermore,the proposed passivity approach can reconstruct Zn surface-preferred crystal planes,exposing more(002)planes and improving surface hydrophilicity,which inhibits the formation of Zn dendrites and hydrogen evolution effectively.As expected,the passivated Zn achieves outstanding cycling life(1914 h)with low voltage polarization(<40 mV).Even at 6 mA cm^(−2) and 3 mA h cm^(−2),it can achieve stable Zn deposition over 460 h.The treated Zn anode coupled with MnO_(2) cathode shows prominently reinforced full batteries service life,making it a potential Zn anode candidate for excellent performance aqueous Zn-ion batteries.The proposed passivation approach provides a guideline for other metal electrodes preparation in various batteries and establishes the connections between corrosion science and batteries.

Deciphering the degradation discrepancy in Ni-rich cathodes with a diverse proportion of[003]crystallographic textures

The crystal plane plays a very important role in the properties of Ni-rich cathodes.[003]crystallographic texture regulation has been proven to improve structural stability,and yet,the discrepancy of particles with different exposed ratios of[003]in structural attenuation has not been clarified.Herein,we have unraveled comprehensively the structural decay difference for Ni-rich cathodes’primary particles with the different percentages of exposed[003]by regulating the precursor coprecipitation process.The findings based on structural characterization,first-principles calculations,finite element analysis,and electrochemical test reveal that the length and width of particles represent[110]and[003]directions,respectively,and show that cathode particles with a higher[110]/[003]ratio can effectively inhibit structure degradation and intergranular/intragranular crack formation owing to the low oxygen vacancy formation energy on(003)planes and the small local stress on secondary/primary particles.This study may provide guidance for the structural design of layered cathodes.

Influence of cellulose crystal plane on cellulose hydrolysis

Cellulose polymerization degree and crystal plane changing are both considered to affect acid hydrolysis,however,it is uncertain to identify which one is more important.In this study,the filter paper was treated with dilute hydrochloric acid to investigate the cellulose polymerization degree changing,and cotton linter was treated with NaOH for the purpose of changing its crystal plane.Both the treated and untreated samples were hydrolyzed under the condition of 1.0 wt%dilute hydrochloric acid with solid-liquid ratio 1:40 at 140℃for 30 min to compare the hydrolysis effects.It was found that the glucose yield increased from 9.5%to 19.7%when treated with 15%NaOH at 50℃for 30 min,and new crystal planes(1-10)(1-20)appeared after alkali treatment.According to the experimental results,it is concluded that crystal plane plays a vital role in cellulose acid hydrolysis.

Crystal plane engineering of MAPbI_(3) in epoxy-based materials for superior gamma-ray shielding performance

The rapid development of the aerospace and nuclear industries is accompanied by increased exposure to high-energy ionising radiation.Thus,the performance of radiation shielding materials needs to be improved to extend the service life of detectors and ensure the safety of personnel.The development of novel lightweight materials with high electron density has therefore become urgent to alleviate radiation risks.In this work,new MAPbI_(3)/epoxy(CH 3NH 3PbI 3/epoxy)composites were prepared via a crystal plane engineering strategy.These composites delivered excellent radiation shielding performance against 59.5 keV gamma rays.A high linear attenuation coefficient(1.887 cm−1)and mass attenuation coefficient(1.352 cm2 g−1)were achieved for a representative MAPbI_(3)/epoxy composite,which was 10 times higher than that of the epoxy.Theoretical calculations indicate that the electron density of MAPbI_(3)/epoxy composites significantly increases when the content ratio of the(110)plane in MAPbI_(3) increases.As a result,the chances of collision between the incident gamma rays and electrons in the MAPbI_(3)/epoxy composites were enhanced.The present work provides a novel strategy for designing and developing high-efficiency radiation shielding materials.

Band structures analysis of one-dimensional photonic crystals using plane wave expansion

A theoretical analysis is made, using plane wave expansion, on how the width of the first three band gaps is influenced by filling ratio, dielectric constant ratio, and periodic width in one-dimensional photonic crystals （PhCs）. From simulation and analysis, there are one, two, and three peak points on the first, second and third band gaps respectively with the changes of filling ratio un- der fixed dielectric constant ratio. When filling ratio is fixed, the bandwidth of the first band gap consistently increases with dielectric constant ratio. However, no similar trend is observed in the second and the third band gaps. Because of scaling properties, varying periodic width does not alter the relative bandwidth.

Investigation of a silicon-based one-dimensional phononic crystal plate via the super-cell plane wave expansion method

The super-cell plane wave expansion method is employed to calculate band structures for the design of a siliconbased one-dimensional phononic crystal plate with large absolute forbidden bands. In this method, a low impedance medium is introduced to replace the free stress boundary, which largely reduces the computational complexity. The dependence of band gaps on structural parameters is investigated in detail. To prove the validity of the super-cell plane wave expansion, the transmitted power spectra of the Lamb wave are calculated by using a finite element method. With the detailed computation, the band-gap of a one-dimensional plate can be designed as required with appropriate structural parameters, which provides a guide to the fabrication of a Lamb wave phononic crystal.

Optical simulation of in-plane-switching blue phase liquid crystal display using the finite-difference time-domain method

The finite-difference time-domain method is used to simulate the optical characteristics of an in-plane switching blue phase liquid crystal display.Compared with the matrix optic methods and the refractive method,the finite-difference timedomain method,which is used to directly solve Maxwell＇s equations,can consider the lateral variation of the refractive index and obtain an accurate convergence effect.The simulation results show that e-rays and o-rays bend in different directions when the in-plane switching blue phase liquid crystal display is driven by the operating voltage.The finitedifference time-domain method should be used when the distribution of the liquid crystal in the liquid crystal display has a large lateral change.

黄铁矿晶体断裂机制与表面反应性研究

通过密度泛函理论、断裂键参数和晶体结构分析,本文研究了黄铁矿晶体各向异性、晶体断裂规律及表面反应性。研究结果表明,黄铁矿晶体中存在Fe—S和S—S两种化学键,且Fe—S键的键能高于S—S键。Fe—S键与S—S键强度不等导致晶面断裂键密度与表面能关系不显著。通过引入化学键能量参数,本文得出晶面断裂能密度更适合分析黄铁矿晶体断裂机制和预测表面能,进而从晶体化学的角度解释了黄铁矿(100)、(111)、(210)、(110)面的表面能及其在晶体断裂时出现的困难程度依次增加的趋势,同时明确了黄铁矿常见暴露面的位点配位性质。基于此,研究得出黄铁矿表面低配位数的位点活性相对较强,从晶体化学的角度阐述了含金黄铁矿具有良好可浮性以及黄铁矿不同晶面氧化性差异的机理。

蓝宝石晶体纳米压入本构方程

应用有限元方法(FEM)结合神经网络优化及无量纲模型,建立了可统一描述蓝宝石不同晶面纳米压入行为的本构方程。采用纳米压痕方法对蓝宝石晶体的四个典型晶面(C、A、R、M)的表面微力学行为进行了研究,本构方程计算结果与实测结果对比表明:加载、卸载曲线均可由压入深度h的二次函数表达;加载曲线是压入面弹性模量E、屈服应力Y和加工硬化指数n的函数,卸载曲线则除此三个因素之外还与卸载位置(最大深度)h_(max)有关;对同一晶面而言,残余深度hr正比于h_(max),塑性功正比于h_(max)的三次方。结果还表明,对蓝宝石晶体这类难以应用常规力学性能试验研究手段的超硬高脆材料,利用本构方程结合纳米压痕试验,可以比较有效地获得其基本力学性能。

水热法合成超细斜发沸石试验研究

斜发沸石具有较强的吸附和离子交换能力,在重金属和油污废水去除、制糖、造纸净化、抗菌抗癌药物助剂制备、石油化工催化裂化、国防以及CO_(2)脱除等领域应用广泛。为了获得纯度较高的斜发沸石,以NaOH、KOH、Al(OH)_(3)、Na_(2)O·nSiO_(2)、H_(2)O为原料,采用水热法制备了斜发沸石,并通过XRD和晶面分析,研究了斜发沸石的合成条件,结果表明:合成斜发沸石的最佳条件为n(SiO_(2))/n(Al_(2)O_(3))=11、n(OH-)/n(SiO_(2))=0.55、n(H_(2)O)/n(SiO_(2))=25~55、温度150℃、时间6 d,合成的斜发沸石呈片状结构,特征峰完整,纯度较高,其晶胞组成为Na_(0.36)K_(6.58)[(AlO_(2))6(SiO_(2))_(25.26)]·6.71H_(2)O,n(SiO_(2))/n(Al_(2)O_(3))约为8.5,属中硅铝比沸石。SEM分析结果显示,其粒径在1.3μm以下,表明粒度非常细;其静态水吸附量为34.3%,达到了HG/T 2690-2012《13X分子筛》中的一等品指标要求。研究成果可为高纯度细粒斜发沸石的精准合成提供借鉴。

载体晶面诱导的Pt-Sn合金及其丙烷脱氢研究

针对传统浸渍过程中Sn与氧化铝载体易于形成铝酸锡络合物,在反应过程中Pt-Sn合金结构易偏析的问题,利用Al_(2)O_(3)择优暴露晶面诱导效应构筑稳定的Pt-Sn/Al_(2)O_(3)有序合金催化剂。通过丙烷脱氢性能评价发现,棒状r-Al_(2)O_(3)负载的Pt-Sn催化剂形成了均匀且结构稳定的有序合金结构。在560℃时,丙烷初始转化率达68%,丙烯选择性大于97%,远高于其他氧化铝载体负载的Pt-Sn催化剂。利用SEM、STEM和CO-IR等对系列催化剂结构进行表征,结果表明,Pt-Sn/r-Al_(2)O_(3)中形成了隔离且电子富集的Pt物种,从而促进了C—H的活化及丙烯的脱附。

Morphology-dependent structures and catalytic performances of Au nanostructures on Cu_2O nanocrystals synthesized by galvanic replacement reaction

Au nanostructures were prepared on uniform Cu2O octahedra and rhombic dodecahedra via the galvanic replacement reaction between HAuCl 4 and Cu2O. The compositions and structures were studied by Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), High-Resolution Transmission Electron Microscope (HRTEM), X-Ray Diffraction (XRD), X-Ray Absorption Spectroscopy (XAS), X-ray Photoelectron Spectroscopy (XPS) and in-situ DRIFTS spectroscopy of CO adsorption. Different from the formation of Au-Cu alloys on Cu2O cubes by the galvanic replacement reaction (ChemNanoMat 2 (2016) 861-865), metallic Au particles and positively-charged Au clusters form on Cu2O octahedra and rhombic dodecahedra at very small Au loadings and only metallic Au particles form at large Au loadings. Metallic Au particles on Cu2O octahedra and rhombic dodecahedra are more active in catalyzing the liquid phase aerobic oxidation reaction of benzyl alcohol than positively-charged Au clusters. These results demonstrate an obvious morphology effect of Cu2O nanocrystals on the liquid-solid interfacial reactions and prove oxide morphology as an effective strategy to tune the surface reactivity and catalytic performance. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

金属有机框架晶体尺度形貌调控及其应用研究进展

金属有机框架(MOFs)是一类先进的有机无机杂化多孔材料。粒径与形貌的差异会影响其比表面积、活性位点种类与数量等,进而改变其催化活性、吸附能力或电化学性质等。首先讨论了调节剂、合成参数和外场强化对MOFs粒径的影响,随后,从MOFs材料维度出发,介绍了MOFs的形貌调控手段并分析了调控机理的差异。最后,介绍了MOFs材料粒径和形貌调控对其在分离、催化和电化学这3个领域应用中的积极效果。未来的研究应当从开发普适性强、成本低、稳定性强、节能环保的精确制备技术的角度推进。

羟乙基纤维素对不同厚度电解铜箔性能的影响

[目的]研究镀液中羟乙基纤维素(HEC)质量浓度对不同厚度电解铜箔性能的影响。[方法]通过电镀制备了厚度分别为12、18和35μm的电解铜箔。研究了镀液中HEC质量浓度对不同厚度铜箔光泽度、粗糙度、组织结构及力学性能的影响。[结果]HEC质量浓度对35μm铜箔性能和组织结构的影响最大,对12μm铜箔的影响最小。电镀制备12、18和35μm铜箔时,宜将镀液的HEC质量浓度分别控制在5~10 mg/L、5~15 mg/L和5~10 mg/L范围内,以获得力学性能合格的铜箔。[结论]合理控制镀液添加剂浓度有利于获得力学性能优良的电解铜箔。

Photonic band structures of two-dimensional photonic crystals with deformed lattices

Using the plane-wave expansion method, we have calculated and analysed the changes of photonic band structures arising from two kinds of deformed lattices, including the stretching and shrinking of lattices. The square lattice with square air holes and the triangular lattice with circular air holes are both studied. Calculated results show that the change of lattice size in some special ranges can enlarge the band gap, which depends strongly on the filling factor of air holes in photonic crystals; and besides, the asymmetric band edges will appear with the broken symmetry of lattices.

Applications of Self-Collimated Properties of Photonic Crystal in 3D Imaging Lidar System

Photonic crystals （PCs） are increasingly attracting attention due to their ability to control light propagation.In this paper,the dispersion properties of a two-dimensional （2D） square lattice PCs with plane- wave expansion （PWE） method are presented,the equi-frequency contours and the band structure are analyzed,and the alignment transmission characteristics are simulated by using the finite difference time domain （FDTD） method.In addition,for the wavelength of 1.55 m,a kind of application structure with the lattice constant a=405 nm and the radius of air holes R=135 nm which can restrict the transmission of beams in photonic crystal without defect is proposed and simulated.The structure which can collimate the output beam and compress its divergence angle is easy to design.It has wide application prospects in optical communication and three-dimensional （3D） imaging lidar systems.

Tuning of band gaps for a two-dimensional piezoelectric phononic crystal with a rectangular lattice

In this paper, the elastic wave propagation in a two-dimensional piezoelectric phononic crystal is studied by considering the mechanic-electric coupling. The generalized eigenvalue equation is obtained by the relation of the mechanic and electric fields as well as the Bloch-Floquet theorem. The band structures of both the in-plane and anti-plane modes are calculated for a rectangular lattice by the planewave expansion method. The effects of the lattice constant ratio and the piezoelectricity with different filling fractions are analyzed. The results show that the largest gap width is not always obtained for a square lattice. In some situations, a rectangular lattice may generate larger gaps. The band gap characteristics are influenced obviously by the piezoelectricity with the larger lattice constant ratios and the filling fractions.

Dispersion characteristics of two-dimensional unmagnetized dielectric plasma photonic crystal

This paper studies dispersion characteristics of the transverse magnetic （TM） mode for two-dimensional unmagnetized dielectric plasma photonic crystal by a modified plane wave method. First, the cutoff behaviour is made clear by using the Maxwell-Garnett effective medium theory, and the influences of dielectric filling factor and dielectric constant on effective plasma frequency are analysed. Moreover, the occurence of large gaps in dielectric plasma photonic crystal is demonstrated by comparing the skin depth with the lattice constant, and the influence of plasma frequency on the first three gaps is also studied. Finally, by using the particle-in-cell simulation method, a transmission curve in the Г - X direction is obtained in dielectric plasma photonic crystal, which is in accordance with the dispersion curves calculated by the modified plane wave method, and the large gap between the transmission points of 27 GHz and 47 GHz is explained by comparing the electric field patterns in particle-in-cell simulation.

INFLUENCES OF ANISOTROPY ON BAND GAPS OF 2D PHONONIC CRYSTAL

Band gaps of 2D phononic crystal with orthotropic cylindrical fillers embedded in the isotropic host are studied in this paper. Two kinds of periodic structures, namely, the square lattice and the triangle lattice, are considered. For anisotropic phononic crystal, band gaps not only depend on the periodic lattice but also the angle between the symmetry axis of orthotropic material and that of the periodic structure. Rotating these cylindrical fillers makes the angle changing continuously; as a result, pass bands and forbidden bands of the phononic crystal are changed. The plane wave expansion method is used to reduce the band gap problem to an eigenvalue problem. The numerical example is given for YBCO/Epoxy composites. The location and the width of band gaps are estimated for different rotating angles. The influence of anisotropy on band gaps is discussed based on numerical results.