定向凝固条件下Al-35%La过共晶合金的组织演变

在常规凝固条件下,Al-35%La过共晶合金可形成周期性双相枝晶组织,这种组织类似于带状组织,即其中枝晶的成分沿生长方向是周期性变化的。为了研究这种组织的形成条件,采用定向凝固技术研究了凝固速度对Al-35%La合金形貌特征的影响。结果表明:在不同凝固速度条件下,Al-35%La合金均形成周期性双相枝晶组织;同时发现:随着凝固速度的提高,初生相Al11La3呈现从周期性双相胞晶→周期性双相枝晶→周期性双相细胞晶的演变规律。在此基础上,讨论了这些组织形态的形成机理。     

面向可充电电池的锂金属负极的枝晶生长:理论基础、影响因素和抑制方法

在全球能源与环境问题日趋紧迫的大背景下,可再生能源的获取与利用途径及高效安全的储能技术的研发一直是工业界和科学界关注的热点之一。锂离子二次电池作为能量存储器件,拥有高比能量、长循环寿命等优点,近十几年来其研究取得了长足进展,并在各类便携式电子设备和电动交通工具中获得了广泛应用。然而,随着各种高性能设备的不断涌现,商业化的锂离子电池越来越难以满足其在能量密度、循环稳定性和安全性等方面的要求。为了进一步提高锂离子电池的能量密度,需要开发出高比容量的负极材料(硅、锡和锂等)以取代传统石墨负极。硅、锡等新式负极材料通过与锂离子反应形成含锂化合物的原理来存储与释放锂离子,完成电池的一个充放电过程。这个过程往往伴随着负极材料体积的剧烈变化,经历较长时间循环使用后会导致负极材料的粉化甚至从集流体上剥离,引起电池容量迅速衰减甚至失效。而锂负极通过锂在负极上的溶解和沉积来完成电池的充放电过程,该过程不存在反应相变所导致的体积变化。另外,锂金属负极材料具有极高的质量比容量(3 860mAh/g)、低密度(0.59g/cm3)和低的还原电位(-3.04V,相比于氢标准电极),被认为是一种理想的可充电电池负极材料。然而,锂的枝晶生长、锂金属电池低的库伦效率和锂的无主体沉积引起的体积膨胀等一些关键问题长期以来制约着锂负极的商业应用。锂的每次沉积都会产生枝晶,在充放电循环中,锂枝晶会导致电池内部短路甚至发生爆炸,带来严重的安全问题。除此之外,锂枝晶还会增加负极表面积,新暴露的锂金属会与电解液反应生成固态电解质膜(Solid electrolyte interface,SEI),这会损耗活性材料以及降低电池的库伦效率。为了解决以上问题,研究者们对锂金属电极进行了许多探索,尤其是在锂枝晶生长的机理及其抑制方法方面。一些理论模型如扩散模型、SEI保护模型、电荷诱导生长模型和薄膜生长模型等,以及与这些模型相对应的一些抑制方法如均匀锂离子流法、SEI膜保护法、稳定沉积主体法和静电屏蔽保护法等被提出。这些抑制方法能够在一定程度上缓解锂枝晶的生长问题,但都未能达到商业化应用的要求。本文总结了近几年研究人员针对锂离子电池锂金属负极的一些重要研究,系统地介绍了业内较为认同的枝晶生长模型和影响因素,并着重叙述了抑制枝晶生长的方法及成效,最后就锂金属负极将来的研究方向给出一些建议。     

Hydrothermal synthesis of CdSe hierarchical dendrites using ionic liquid as template

Well-defined CdSe hierarchical dendrites have been synthesized through a facile and effective hydrothermal method. The as-formed CdSe dendrites possess good dispersity and have an average length of about 1 μm along the trunk. Most importantly, it is found that long-chain ionic liquid [C₁₆mim]Cl (1-hexadecyl-3-methylimidazolium chloride), which can adsorb on the (002) plane of wurtize CdSe driven by the coulomb force, serves as an effective template and plays a critical role for the morphology of the product. Furthermore, the UV-vis spectrum of the CdSe dendrites displays absorption maxima at 296 nm; therefore, the obtained CdSe dendrites might have promising application in blue emitters, gas sensors, and light-emitting devices.     

Photothermal Fabric Based on In Situ Growth of CuO@Cu Fractal Dendrite Fiber for Personal Thermal Management

Advanced personal thermal management fabrics are being developed to realize improved human body thermal comfort and effectively regulate heat exchange between the human body and surroundings. Fiber-based thermal management fabrics are directly worn on soft and curved multiple curvature human body. Herein, a flexible photothermal fiber based on copper fractal dendrites with abundant CuO nanowires is designed. Well-aligned Cu fractal dendrite fiber is electrodeposited template freely via a low-cost and scalable process in an aqueous solution. Then, flexible CuO@Cu fractal dendritic photothermal fiber is fabricated by direct in situ oxidation and calcination of Cu fractal dendrites. Furthermore, the CuO@Cu fractal dendritic photothermal fiber can be woven into photothermal fabric by the traditional jacquard embroidery process. The temperature of photothermal fabric can be adjusted within the range of 35–65 °C by adjusting the number of photothermal fibers, which can be achieved with comfortable wearing of human thermal management and hot compress of hyperthermia to relieve local pain. Therefore, the Cu fractal dendrites have shown considerable potential for promoting the photothermal conversion of flexible personal thermal management.     

Dendritic Deposition of NH_4CI Crystals with Free Surface as Simulations of Surface Solidification of Materials

As a simulation of surface solidification of materials,quasi-two dimensional dendritic deposition ofammonium chloride(NH_4Cl)crystals from an aqueous solution film with free surface byvapourization was investigated by the in- situ observation technique.The depositing morphologiesof NH_4Cl crystals are faceted and of growth laws differing from the three-dimensional case.Underlow supersaturation,faceted dendrites formed,whereas the anisotropy in growth kinetics decreaseswith the increase of supersaturation.When vapourizing rate(supersaturation)is not very low,oscillations of growth rate.tip-radius and second arm spacing of the dendrites were observed.It issuggested that this dynamic phenomenon is attributed to the correlation between theconvection-transfer effect induced by the surface tension gradient of solution film.and the drivingforce for deposition.     

Draining Over Blocking: Nano-Composite Janus Separators for Mitigating Internal Shorting of Lithium Batteries

Catastrophic battery failure due to internal short is extremely difficult to detect and mitigate. In order to enable the next-generation lithium-metal batteries, a “fail safe” mechanism for internal short is highly desirable. Here, a novel separator design and approach is introduced to mitigate the effects of an internal short circuit by limiting the self-discharge current to prevent cell temperature rise. A nano-composite Janus separator—with a fully electronically insulating side contacting the anode and a partially electronically conductive (PEC) coating with tunable conductivity contacting the cathode—is implemented to intercept dendrites, control internal short circuit resistance, and slowly drain cell capacity. Galvanostatic cycling experiments demonstrate Li-metal batteries with the Janus separator perform normally before shorting, which then results in a gradual increase of internal self-discharge over >25 cycles due to PEC-mitigated shorting. This is contrasted by a sudden voltage drop and complete failure seen with a single layer separator. Potentiostatic charging abuse tests of Li-metal pouch cells result in dendrites completely penetrating the single-layer separator causing high short circuit current and large cell temperature increase; conversely, negligible current and temperature rise occurs with the Janus separator where post mortem electron microscopy shows the PEC layer successfully intercepts dendrites.     

金属镍枝晶电沉积的二维生长

将分形几何与电化学原理相结合,编程模拟了点阴极和点阳极电沉积中枝晶的分形生长。采用圆形电解池点阴极电沉积和点阳极射流电沉积的方法分别制备了不同浓度下的金属镍枝晶,并与模拟结果进行比较,结果表明,点阴极电沉积和点阳极射流电沉积中的枝晶均是分形生长的;电解质浓度的变化对枝晶生长形态的影响与模拟的结果具有极好的相似性,模拟结果是可以对点阴极和点阳极电沉积中枝晶的生长机理进行正确表述的,同时发现,气泡对枝晶的生长形貌影响显著。     

Dendrite Deformation in the Rejoined Platforms of Ni-Based Single-Crystal Superalloys

Dendrite deformation often occurs during the preparation of single-crystal superalloy blades by directional solidification and can cause solidification defects, such as low-angle boundaries (LABs), slivers, and orientation deviations. Continuous dendritic deformation is uncommon and its mechanisms and influencing factors are poorly understood. However, this can lead to significant orientation deviation and performance degradation. Herein, a model with rejoined platforms is designed to study the dendrite growth and orientation evolution in a rejoined platform of Ni-based single-crystal superalloys. It is indicated in the results that, under certain conditions, the developed secondary dendrites deform continuously near the mold wall of the rejoined platforms and the resulting disorientation has a cumulative effect. Finally, LABs and dendritic fragments appear on the rejoined platforms. Thus, the integrity of the single crystal is destroyed. This can be the result of the local shrinkage stress on the long secondary dendrites within a sufficient growth space.     

Homeomorphisms of the Sierpinski curve with periodic properties

In this paper, we study the three following types of homeomorphisms of the Sierpinski curve of the two sphere : pointwise periodic, periodic, and almost periodic, and we prove that they are equivalent. We show that a subgroup of homeomorphisms whose orbits are all finite, is a finite subgroup.     

金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积

锂金属具有高理论比容量和低电化学电位,是发展高能量密度电池最有吸引力的负极材料之一。然而,锂金属负极在反复的沉积/剥离过程中,不可避免地会出现不规则的锂枝晶生长,这将严重影响锂金属电池的循环寿命和使用安全性。本研究发展了一种简单温和的策略,在碳纳米管上原位修饰铋纳米颗粒,并涂覆在商业铜箔表面用作锂金属负极的集流体。研究表明,原位修饰的铋纳米颗粒可显著促进锂均匀沉积,抑制锂枝晶生长,从而提高锂金属电池的电化学性能。在电流密度为1 mA·cm^–2的条件下,基于Bi@CNT/Cu集流体的锂铜电池循环300圈后库仑效率可稳定在98%。基于Li@Bi@CNT/Cu负极的对称电池可稳定循环1000 h。基于Bi@CNT/Cu集流体的磷酸铁锂(LFP)全电池也获得了优异的电化学性能,在1C(170m A·g^–1)倍率下可稳定循环700圈。本研究为抑制锂金属负极枝晶生长提供了新的思路。     

Crystal Nucleation and Growth of Al-based Alloys Produced by Electrolysis

The nucleation and growth of grains in a series of Al-based alloys produced by electrolysis are observed under SEM. The atomic Ti/Al ratios of the nuclei and the distribution of Ti at certain points are analyzed by point EDS. The particles in different atomic Ti/Al ratios might act as the nuclei of α-Al. At the early stage of growth, the spherical Ti-enriched regions might form around these particles within very limited temperature ranges in which the reactions such as the peritectic reactions etc occur.At the latter stage of growth, the dendrites freely develop in the radial orientations, and the concentration of Ti decreases linearly along the dendrite arm and becomes negligible in the region near the periphery of the dendrite. It is believed that the nucleation is closely related with the number and dispersion of primary spherical areas in the melts, and the segregation of Ti leads to the free growth of dendrite, which is necessary for the formation of equiaxial grains.     

晶态颗粒、枝晶增韧非晶基复合材料的研究进展

综述了晶态颗粒、枝晶增韧非晶基复合材料的种类与形成机理.分别介绍了这种材料的微观组织与力学性能,并对其变形(增强韧)机理进行了分析,在此基础上展望了今后的研究方向.     

一种用于长寿命水系锌锰电池的海藻酸钠/二氧化硅准凝胶复合电解质

锌锰(Zn-MnO₂)电池具有高安全性、高环保性、高性价比的优点, 适用于大规模储能电池。然而, 金属锌负极在充放电中会因为“尖端效应”而产生锌枝晶, 造成电池容量衰减甚至短路失效。本研究通过添加亲水性纳米二氧化硅(SiO₂)和海藻酸钠(SA)将电解质转化为准凝胶电解质, 有效抑制了锌负极表面的枝晶生长, 以及由之造成的Zn-MnO₂电池性能衰减。恒流充放电测试结果表明, 采用准凝胶电解质的Zn-MnO₂电池在1800次循环后容量保留率可达78%, 而使用普通电解质的Zn-MnO₂电池在1000次循环后容量已基本衰减为0。进一步探究准凝胶电解质对锌沉积行为的影响, 发现准凝胶电解质的三维网络结构可以提高锌离子分布的均匀性, 降低电池容量衰减速度与失效风险。     

Pointwise error estimation and adaptivity for the finite element method using fundamental solutions

In this paper, we present a goal-oriented a posteriori error estimation technique for the pointwise error of finite element approximations using fundamental solutions. The approach is based on an integral representation of the pointwise quantity of interest using the corresponding Green's function, which is decomposed into an unknown regular part and a fundamental solution. Since only the regular part must be approximated with finite elements, very accurate results are obtained. The approach also allows the derivation of error bounds for the pointwise quantity, which are expressed in terms of the primal problem and the regular part problem. The presented technique is applied to linear elastic test problems in two-dimensions, but it can be applied to any linear problem for which fundamental solutions exist.     

Effect of cooling rates on the dendritic morphology transition of Mg–6Gd alloy by in situ X-ray radiography

The effect of cooling rate on the transition of dendrite morphology of a Mg-6 Gd(wt%) alloy was semiquantitatively analyzed under a constant temperature gradient by using synchrotron X-ray radiographic technique. Results show that equiaxed dendrites, including exotic 'butterfly-shaped' dendrite morphology, dominate at high cooling rate(1 K/s). When the cooling rate decreases in the range of 0.5–1 K/s, the equiaxed-to-columnar transition takes place, and solute segregates at the center of two long dendrite arms(LDA) of the 'butterfly-shaped' dendrite. When the cooling rate is lower than 0.3 K/s, directional solidification occurs and the columnar dendritic growth direction gradually rotates from the crystalline axis to the thermal gradient direction with an increase in cooling rate. Meanwhile, interface moves faster but the dendrite arm spacing decreases. Floating, collision and rotation of dendrites under convection were also studied in this work.     

Microstructure evolution in equiaxed dendritic growth

Microstructure evolution in equiaxed dendritic solidification is investigated through the study of free dendritic growth in a supercooled melt. A detailed measurement of microstructural features (such as side-branch spacings, envelope shape, projection area, and contour length) of freely growing succinonitrile dendrites is performed using images from the microgravity experiment of Glicksman and co-workers. The measurements show that the microstructure evolution of an equiaxed dendrite is divided into two regimes: an initial linear regime and a subsequent non-linear coarsening regime. It is found that unique scaling relations exist between the measured geometry parameters and the primary tip radius or speed for both regimes. The underlying mechanisms involved in dendritic structure evolution are discussed. In addition, using the phase-field method, we perform numerical experiments to investigate the effects of melt convection on equiaxed dendritic growth. The dendrite tip operating state (i.e. the tip velocity and radius) is quantitatively evaluated as a function of the flow velocity and dendrite orientations and compared with Microscopic Solvability Theory. Other structural features (such as the side-branches) of an equiaxed dendrite in the presence of flow are also examined in order to show how convection influences microstructure evolution in equiaxed dendritic growth.     

Bi3+和四丁基溴化铵对碱性可充锌电极枝晶生长行为的影响*

采用电流－时间曲线、极化曲线和扫描电子显微镜等方法,研究了Bi^3 与四丁基溴化铵（TBAB）对可充锌电极在碱性锌酸盐溶液中枝晶生长行为的影响。实验结果表明,Bi^3 和TBAB对锌电极的枝晶生长均有一定的抑制作用,但在高阴极过电位下TBAB不能有效地抑制锌枝晶的生长。在实验过程中还发现,Bi^3 和TBAB对锌枝晶的抑制具有明显的协同作用,且对锌电极的放电行为几乎不产生影响。     

Regulating Li-Ion Transport through Ultrathin Molecular Membrane to Enable High-Performance All-Solid-State–Battery

Solid-state lithium metal batteries with garnet-type electrolyte provide several advantages over conventional lithium-ion batteries, especially for safety and energy density. However, a few grand challenges such as the propagation of Li dendrites, poor interfacial contact between the solid electrolyte and the electrodes, and formation of lithium carbonate during ambient exposure over the solid-state electrolyte prevent the viability of such batteries. Herein, an ultrathin sub-nanometer porous carbon nanomembrane (CNM) is employed on the surface of solid-state electrolyte (SSE) that increases the adhesion of SSE with electrodes, prevents lithium carbonate formation over the surface, regulates the flow of Li-ions, and blocks any electronic leakage. The sub-nanometer scale pores in CNM allow rapid permeation of Li-ions across the electrode–electrolyte interface without the presence of any liquid medium. Additionally, CNM suppresses the propagation of Li dendrites by over sevenfold up to a current density of 0.7 mA cm⁻² and enables the cycling of all-solid-state batteries at low stack pressure of 2 MPa using LiFePO₄ cathode and Li metal anode. The CNM provides chemical stability to the solid electrolyte for over 4 weeks of ambient exposure with less than a 4% increase in surface impurities.     

高温合金定向凝固过程中枝晶生长与溶质对流数值模拟

目的 针对高温合金叶片在定向凝固过程中容易出现雀斑缺陷,从而导致叶片报废的问题,对定向凝固枝晶生长与溶质对流进行模拟研究,以揭示雀斑缺陷的形成规律。方法 针对CM247LC合金定向凝固过程,采用相场模型模拟凝固过程枝晶生长,采用格子Boltzmann模型模拟溶质浓度差引起的自然对流。采用基于双重网格的GPU并行算法对相场-格子Boltzmann模型进行数值求解。研究在不同晶体取向角度与取向差条件下的枝晶形貌、对流速度及溶质羽流的演变规律。结果 当晶体取向角度不同时,在枝晶生长过程中,液相区域的平均对流速度均表现为周期性变化。当晶体取向角度较大时,随着晶体取向角度的变大,一次枝晶臂间距变大。当枝晶间存在晶体取向差时,溶质羽流倾向于在发散型晶界附近发起;随着晶体取向差的增大,溶质羽流发起时间提前。溶质羽流的形成阻碍了枝晶尖端及附近枝晶侧臂的生长。结论 晶体取向角度对溶质羽流形成的影响较小,较大的晶体取向差对溶质羽流的形成有促进作用。     

Spectrum analysis of motion parallax in a 3D cluttered scene and application to egomotion

Previous methods for estimating observer motion in a rigid 3D scene assume that image velocities can be measured at isolated points. When the observer is moving through a cluttered 3D scene such as a forest, however, pointwise measurements of image velocity are more challenging to obtain because multiple depths, and hence multiple velocities, are present in most local image regions. We introduce a method for estimating egomotion that avoids pointwise image velocity estimation as a first step. In its place, the direction of motion parallax in local image regions is estimated, using a spectrum-based method, and these directions are then combined to directly estimate 3D observer motion. There are two advantages to this approach. First, the method can be applied to a wide range of 3D cluttered scenes, including those for which pointwise image velocities cannot be measured because only normal velocity information is available. Second, the egomotion estimates can be used as a posterior constraint on estimating pointwise image velocities, since known egomotion parameters constrain the candidate image velocities at each point to a one-dimensional rather than a two-dimensional space.