熔融盐法合成高密度锂离子电池正极材料LiNi_(0.8)Co_(0.15)Ti_(0.05)O_2

利用低共熔组成的0.38LiOH-0.62 LiNO3混合锂盐体系,与高密度前驱体掺杂Co的Ni(OH)2、TiO2粉末在低温下自混合,无需前期研磨和后续洗涤,直接制备出振实密度达3.17g/cm2的高密度锂离子电池正极材料LiNi0.8Co0.15Ti0.05O2.X射线衍射分析表明合成的LiNi0.8Co0.15Ti0.05O2具有规整的层状α-NaFeO2结构.扫描电镜显示产物颗粒均匀,电性能测试表明,在0.2C放电倍率和3.0～4.3V的电压范围内,LiNi0.8Co0.15Ti0.05O2良好首次放电比容量达169mAh/g,且具有良好的循环性能.     

几种高温钎料对C/C复合材料的润湿性研究

采用座滴法测试了10种钎料对C/C母材的润湿性.实验结果表明:随着活性元素Ti,Cr,V含量的提高,钎料润湿性逐渐改善.在Co-Ti和Ni-Ti钎料体系中,Ti元素的存在形式对钎料润湿性影响很大,Ti以固溶体形式存在,易于向C/C母材偏聚发生反应,从而提高润湿性,且润湿界面附近的Ti和C主要以TiC形式存在.采用PdNi-Cr-V-Si-B钎料的润湿界面中,活性元素Cr和V存在于扩散反应层中,推断Cr主要以Cr23C6形式存在,而V以V2C形式存在.当Cr和V同时加入钎料中,Cr向界面反应层扩散的倾向更明显.     

钴钛共掺杂对LiNiO2正极材料电化学性能的影响

本文采用溶胶-凝胶法制备了钴和钛共掺杂的层状LiNi_0.82Co_0.15Ti_0.03O₂正极材料,研究了离子掺杂对LiNiO₂材料电化学性能的影响。XRD和XPS分析显示,钴和钛共掺杂可以抑制Li+和Ni2+离子在Li层的混排现象。电化学测试结果表明,钴单元素掺杂可以显著提高LiNiO₂材料的倍率性能,而钛单掺杂则提高了材料的循环稳定性。进一步地,通过钴钛共掺杂的协同作用,可以使LiNiO₂材料的倍率性能和循环稳定性同时得到极大的提高。在200 mA/g的电流密度下循环200次,LiNi_0.82Co_0.15Ti_0.03O₂材料的容量保持率高达94.4%,而未掺杂的LiNiO₂材料容量保持率仅为57.1%;且在1000 mA/g的电流密度下,放电比容量仍能维持在100 mAh/g左右。     

硬质合金界面的实验观测与第一性原理计算研究进展

随着计算材料科学的发展,通过第一性原理计算加快硬质合金材料的研发速度,降低研发成本逐渐成为备受关注的研究课题。主要介绍了近年来基于密度泛函理论的第一性原理计算与高分辨透射电子显微术、三维原子探针等实验观测在硬质合金界面研究方面的进展。首先从界面强度评估方法、第一性原理界面能计算方法、晶界结构的理论模型等方面,结合硬质合金常见晶界计算,系统地对第一性原理计算界面的基本方法进行总结。然后结合最近的几个研究实例,展示了第一性原理计算在硬质合金研发中发挥的重要作用。最后,通过分析国内外学者的研究成果,阐述了硬质合金第一性原理计算领域存在的不足,以及这一领域可能需要进一步开展的工作。     

M型钡铁氧体掺杂Co-Ti改性研究

通过Co-Ti掺杂手段对M型钡铁氧体的磁电性能进行了改性,确定了较佳的掺杂量及配方工艺。在制备Co-Ti取代的BaM铁氧体时,采用取代量为1.0的BaM的铁氧体材料,起始磁导率从1.5提高至15,矫顽力H_C达到最小,而且介电常数随着频率的升高而减小。可用于制作高频片式电感。Co-Ti的引入,使材料的烧结温度降至1000℃。     

Liquid dynamics and glass formation of Gd55Co20Al25 metallic glass with minor Si addition

Liquid dynamics plays an essential role in glass formation.Here we observed a distinct change of liquid dynamics in Gd55Co20Al25 metallic glass induced by microalloying Si element.In the equilibrium melt,minor Si(0.5 at.％)addition leads to a more fragile liquid behavior and a smaller strength of liquid-liquid transition with the transition strength(ΔF)decreasing from 0.76 to 0.35.However,in the supercooled liquid,Si-doped liquid exhibits a remarkable enhanced fragile-to-strong transition(FST),and the value of FST factor f increases sharply from 1.63 to 3.84,resulting in a stronger liquid behavior and more sluggish crystallization kinetics for Gd55Co20Al24.5Si0.5 metallic glass.Moreover,minor Si addition promotes the formation of a crystal-like structure with a size of 1-2 nm.The interactions between the crystal-like structures and other local favored clusters frustrate the further growth of crystal-like phases,thus sta-bilizes the amorphous structure.As a result,the glass-forming ability(GFA)was largely improved.The critical diameter of Gd55Co20Al25 metallic glass increased from 2 to 7 mm with 0.5 at.％Si addition with-out deterioration of the magnetocaloric effect.This study provides valuable insight for understanding the distinct effect of microalloying on GFA of metallic glasses from the aspect of the evolution of the liquid.     

Transition of the magnetotransport in a Co-TbN system

Unexpected magnetism is investigated by measurements of the magnetic and magneto-transport properties in the two phase-separated thin films of nano-sized TbN clusters embedded in Co matrices. The spin-dependent transport depends strongly on the volume fraction of magnetic TbN clusters, especially on the continuity of the magnetic phase. With decreasing the TbN volume fraction, the giant magnetoresistance (GMR) is reduced and the anisotropic magnetoresistance (AMR) is enhanced. Unlike the GMR observed in Co68(TbN)32, the AMR is found in Co72(TbN)28. The room-temperature magnetization exhibits a typical ferromagnetic signal mainly due to the Co matrix, while the low-temperature magnetization shows an additional linear magnetic component. This is attributed to the magnetic moment of TbN at temperatures below the ferromagnetic transition temperature T(C) = 44 K, and the magnetic moments of TbN are coupled with those of Co. The topological and magnetic images support the magnetic exchange at the boundary between the TbN clusters and the Co matrix.     

Co—Ti,Ti—Zr—Cu高温钎料在Si3N4陶瓷上润湿性与界面连接

设计了Ｃｏ－Ｔｉ，Ｔｉ－Ｚｒ－Ｃｕ两种高温钎料，进行了它们与Ｓｉ３Ｎ４表面的润湿性实验，利用ＸＲＤ分析钎焊合金与陶瓷界面，结果表明Ｃｏ－Ｔｉ合金中Ｔｉ以化合形态形式存在时，钎料不润湿Ｓｉ３Ｎ４陶瓷，钎焊合金与陶瓷间的办面连接强度与基体材料及界面反应产物密切相关。     

First-principles approach to the calculation of electronic spectra in clusters

We discuss a method for first-principles calculations of photoemission spectra in small clusters, going well beyond a standard density functional theory-local density approximation (DFT-LDA) approach. Starting with a DFT-LDA calculation, we evaluate self-energy contributions to the quasiparticle energies of an electron or hole in the GW scheme, where the self-energy Σ = GW is constructed from the one-particle Green's function G and the RPA screened Coulomb interaction W. The contributions of structural relaxation are taken into account. We show the importance of these effects at the example of the photoemission spectrum of SiH₄. We also briefly discuss results for longer hydrogenated silicon chains, and address the problem of optical absorption.     

Organic multiferroic tunnel junctions with ferroelectric poly(vinylidene fluoride) barriers

Organic materials are promising for applications in spintronics due to their long spin-relaxation times in addition to their chemical flexibility and relatively low production costs. Most studies of organic materials for spintronics focus on nonpolar dielectrics or semiconductors, serving as passive elements in spin transport devices. Here, we demonstrate that employing organic ferroelectrics, such as poly(vinylidene fluoride) (PVDF), as barriers in magnetic tunnel junctions (MTJs) allows new functionality in controlling the tunneling spin polarization via the ferroelectric polarization of the barrier. Using first-principles methods based on density functional theory we investigate the spin-resolved conductance of Co/PVDF/Co and Co/PVDF/Fe/Co MTJs as model systems. We show that these tunnel junctions exhibit multiple resistance states associated with different magnetization configurations of the electrodes and ferroelectric polarization orientations of the barrier. Our results indicate that organic ferroelectrics may open a new and promising route in organic spintronics with implications for low-power electronics and nonvolatile data storage.     

Dependence of exchange coupling on interfacial conditions in SmCo5/Co system: a first-principles study

We have performed first-principles calculations to study the interfacial exchange coupling in a SmCo5/Co multilayer model system. The hard phase hcp SmCo5 and the soft phase hcp Co (or Co(1-x)Fe(x)) stacking along (1010) direction are structurally well matched. The atomic structure, including the alignment and the separation between layers, were optimized first. Then the non-collinear magnetic structures were calculated to explore the exchange coupling dependence on the variation of the atomic composition across the interface. We found that the inter-phase exchange coupling strength is strongly dependent on the interface condition between the hard and soft phase by comparing the exchange coupling strengths in different interface conditions. The findings were further confirmed by the calculated site-to-site exchange parameters across the interface.     

超高强度马氏体时效钢的力学行为与微观组织演化的关系

用高分辨透射电镜(HRTEM)和原子探针层析技术(APT)等手段研究了2.4 GPa级超高强度马氏体时效钢在时效过程中析出相的演化规律及其与材料力学性能的关系。对组织观察的结果表明,马氏体时效钢在时效过程中析出相的演化规律分为三个阶段：时效初期富Ni和富Ti团簇的形成、峰时效期金属间化合物Ni₃Ti及其界面处富Mo相的形成、过时效阶段Ni₃Ti的粗化和富Mo相过渡为Ni₃Mo。力学性能的实验结果表明,随着时效时间的延长抗拉强度呈现先提高后降低的趋势,时效时间为4 h时抗拉强度达到最大值2560 MPa。断裂韧性呈现与抗拉强度相反的变化趋势,时效时间为4 h时的断裂韧性值最低,仅为20 MPa·m^1/2。根据不同时效阶段材料中析出相的演化规律,探讨了马氏体时效钢的力学行为与析出相的关系。     

Dependence on temperature and energy of the heteroepitaxy of small metallic nanoclusters

Deposition at different energies and temperatures of small metallic nanoclusters on metallic substrates is studied by molecular-dynamics simulations. Small-, Co/Cu(001), and large-misfit, Cu/Au(001) and Au/Cu(001), systems are considered. The rise in temperature improves the epitaxial order, although its effect is smaller in large-misfit systems. Thus, by increasing this parameter, non-epitaxial clusters can turn their structure into epitaxial in the case of Co/Cu(001), into aligned in Cu/Au(001), and into layered in Au/Cu(001). Therefore, the characteristics of the alignment are determined by the properties of the material. In addition, the influence of the initial structure is more marked in Co and Cu clusters, since they can reproduce locally other phases. Epitaxy can also be improved if the deposition energy is increased, although the deposited cluster loses its original shape progressively. Its effect is different depending mainly on the degree of misfit. An increase in energy (of up to 0.75 eV/atom) produces similar effects, but more noticeable, as a rise in temperature.     

La2BO4(B:B位元素)系列混合导体掺杂成份优化规律研究

基于材料基因组计划(MGI)研究方式, 利用密度泛函理论(DFT)的第一性原理的总能量计算方法, 以K₂NiF₄型La₂BO₄(B:B位元素)相关的几种相结构为计算模型, 针对4~6周期48种B位金属元素替换, 进行几何优化的总能量计算, 得到这些相关虚拟相结构的结合能随元素的变化规律。通过层状相La₂BO₄与立方相LaBO₃的比较, 着重讨论了一些重要B位元素(Fe、Co、Ni、Cu、Zn、Se)对稳定La₂BO₄复合氧化物相稳定性的影响作用和趋势。结合相关的实验数据, 进一步讨论了掺杂B位元素的优化稳定区域。本定量分析方法为此类材料的合成和成份优化设计提供了一种行之有效的分析方法。     

Nucleation and growth of monodispersed cobalt nanoclusters on graphene moiré on Ru(0001)

Monodispersed Co nanoclusters have been grown on a graphene moiré on Ru(0001) at room temperature. Scanning tunneling microscopy measurements showed that the Co clusters nucleate at both the fcc and hcp regions. Co forms finely dispersed small three-dimensional (3D) clusters on graphene/Ru(0001), and a defined long-range ordering of Co nanoclusters with increasing coverage is not observed. The size distribution of the clusters is narrow and the size of the clusters is tunable. The absorbed Co begins to intercalate between the graphene layer and the Ru(0001) substrate when annealing the sample at temperatures up to about 473 K.     

The effect of spillover in the electronic and magnetic properties of Ni, Co, and Fe clusters

We calculate the electronic structure of 3d transition-metal clusters with a model Hamiltonian that takes into account electron spillover at the cluster surface and uses bulk parameter values for the interactions. We perform calculations for fcc and bcc clusters of up to 260 atoms making use of symmetry properties. We obtain magnetic moments per shell and ionization potentials for Ni, Co, and Fe clusters starting from an spd-bulk parametrization.     

Size-dependent dissociation of small cobalt clusters on ultrathin NaCl films

Mass-selected anionic cobalt clusters of two different sizes (Co2 and Co13) were deposited onto ultrathin NaC1 films grown on an Au(111) substrate.Using scanning tunneling microscopy experiments and density functional theory simulations,we show that the deposited Co2 cluster dissociates and that the resulting Co atoms dope the NaCl surface by substituting Na ions.In contrast,the larger Co13 cluster does not dissociate and remains stable on top of the NaC1 film.The sizedependent fragmentation of clusters is an important aspect in the understanding of the chemical interaction between size-selected small aggregates of atoms and supporting surfaces.     

First-principles study of small oxidized silver clusters

The structure and stability of clusters Ag(n)O+(m), Ag(n)O(m), and Ag(n)O(m)- (n = 1-6, m = 1-2) are studied by using the first-principles method. Calculated results show that the properties studied are strongly dependent on the size and charge state of the clusters, some of which show the odd-even alteration. Generally, the oxidation drives the transition of silver clusters from two-dimensional (2D) to three-dimensional (3D) structures. It is found that the structure with dissociated O2 is more stable if the silver cluster can provide oxygen with enough electrons.     

Texture development, microstructure and phase transformation characteristics of sputtered Ni-Ti Shape Memory Alloy films grown on TiN<111>

Near equiatomic Ni-Ti films have been deposited by magnetron co-sputtering on TiN films with a topmost layer formed by < 111> oriented grains (TiN/SiO₂/Si(100) substrate) in a chamber installed at a synchrotron radiation beamline. In-situ X-ray diffraction during Ni-Ti film growth and their complementary ex-situ characterization by Auger electron spectroscopy, scanning electron microscopy and electrical resistivity measurements during temperature cycling have allowed us to establish a relationship between the structure and processing parameters.A preferential development of < 110> oriented grains of the B2 phase since the beginning of the deposition has been observed (without and with the application of a substrate bias voltage of −45 and −90 V). The biaxial stress state is considerably influenced by the energy of the bombarding ions, which is dependent on the substrate bias voltage value applied during the growth of the Ni-Ti film. Furthermore, the present work reveals that the control of the energy of the bombarding ions is a promising tool to vary the transformation characteristics of Ni-Ti films, as shown by electrical resistivity measurements during temperature cycling.The in-situ study of the structural evolution of the growing Ni-Ti film as a consequence of changing the Ti:Ni ratio during deposition (on a TiN<111> layer) has also been performed. The preferential growth of < 110> oriented grains of the Ni-Ti B2 phase has been as well observed despite the precipitation of Ti₂Ni during the deposition of a Ti-rich Ni-Ti film fraction. Functionally graded Ni-Ti films should lead to an intrinsic “two-way” shape memory effect which is a plus for the miniaturization of Ni-Ti films based devices in the field of micro-electro-mechanical systems.