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.

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.

A general metrology of stress on crystalline silicon with random crystal plane by using micro-Raman spectroscopy

The requirement of stress analysis and measurement is increasing with the great development of heterogeneous structures and strain engineering in the field of semiconductors.Micro-Raman spectroscopy is an effective method for the measurement of intrinsic stress in semiconductor structures.However,most existing applications of Raman-stress measurement use the classical model established on the (001) crystal plane.A non-negligible error may be introduced when the Raman data are detected on surfaces/cross-sections of different crystal planes.Owing to crystal symmetry,the mechanical,physical and optical parameters of different crystal planes show obvious anisotropy,leading to the Raman-mechanical relationship dissimilarity on the different crystal planes.In this work,a general model of stress measurement on crystalline silicon with an arbitrary crystal plane was presented based on the elastic mechanics,the lattice dynamics and the Raman selection rule.The wavenumberstress factor that is determined by the proposed method is suitable for the measured crystal plane.Detailed examples for some specific crystal planes were provided and the theoretical results were verified by experiments.

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.

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.

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。

The internal COF features in Dome A of Antarctica revealed by multi-polarization-plane RES

The ice exceeding one million years old has significant meaning for verifying and interpreting the middle Pleistocene transition （MPT） and the relationship between greenhouse gas and climate change. The region near Dome A in Antarctica satisfies the conditions for obtaining million-years-old ice since it has low temperatures and low accumulation rates. We analyze the corresponding relation between radar wave features and the crystal orientation fabric （COF） types based on the results of multi-polarization plane radio echo sounding （RES）. The results show that, even in the summit of the ice sheet, the COF type is not perfect, but is an elongated single-pole COF. Principal-axis-orientation differences of the COF among the different periods exist and reveal that the ice flow orientations are not constant but deviate clockwise with the increasing depth. This may be related to the adjacent basal valley or both height and position changes of the summit during the glacial-interglacial periods.

Band Structure of Three-dimensional Phononic Crystals

By using the plane-wave-expansion method, the band structure of three-dimension phononic crystals was calculated, in which the cuboid scatterers were arranged in a host with a face-centered-cubic （FCC） structure.The influences of a few factors such as the component materials, the filling fraction of scatterers and the ratio （RHL） of the scatterer＇s height to its length on the band-gaps of phononic crystals were investigated.It is found that in the three-dimension solid phononic crystals with FCC structure, the optimum case to obtain band-gaps is to embed high-velocity and high-density scatterers in a low-velocity and low-density host. The maximum value of band-gap can be obtained when the filling fraction is in the middle value. It is also found that the symmetry of the scatterers strongly influences the band-gaps. For RHL＞1, the width of the band-gap decreases as RHL increases. On the contrary, the width of the band-gap increases with the increase of RHL when RHL is smaller than 1.

h‑MoO_(3)/SiO_(2)催化合成季戊四醇异辛酸酯

采用固相研磨法,制备了一系列h-MoO_(3)/SiO_(2)催化剂,这些催化剂用于季戊四醇(PER)和异辛酸(i-EHA)反应,合成季戊四醇异辛酸酯(POE),并采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、X射线光电子能谱(XPS)、N2吸附-脱附、扫描电镜(SEM)、透射电镜(TEM)对催化剂进行表征测试。结果表明,h-MoO_(3)负载量为15%的(200)晶面择优取向的h-MoO_(3)/SiO_(2)是合成POE的优良催化剂。适宜的反应工艺条件(ni-EHA/nPER=4.3,mh-MoO_(3)/SiO_(2)/mPER=0.003,T=220℃,t=4 h)下,酯化率可达90.83%,POE的选择性可达100%。

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。

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。

压电纳米声子晶体梁结构表面效应带隙特性研究

通过纳米尺寸下的纯弹性材料环氧树脂和压电材料PZT-4沿着轴向周期性交替排布,提出了压电纳米声子晶体梁结构的力学模型.将表面压电理论与Euler梁理论相结合,结合平面波展开法,建立了计算该模型能带结构的表面效应平面波展开法.进一步地,外加电压和外加轴力被用来研究机电耦合效应对带隙的影响,残余面应力和材料内禀长度被用来研究表面效应对带隙的影响,以及晶胞内PZT-4对环氧树脂的长度比和高宽比被用来研究几何参数对带隙的影响.研究结果和进一步的分析表明,影响规律对基于压电纳米声子晶体梁的纳米机电系统的设计过程和主动控制将起到积极的推动作用.

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.

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.

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.