KLiSO_4(C_6~6)结构中Li原子位置的测定

Bradley在1925年所定出KLiSO_4室温相的结构为C_6~6,但其中的Li原子位置并非测定的,而是推断为在三次轴上有较大的空隙处。这一位置与晶体学一般成键理论的认识是有矛眉的,因而最近有人提出了异议。我们重新测定了这一晶体结构,特别是实测了Li原子的位置。 新定出的KLiSO_4晶体结构中的Li原子位置是:x=1/3,y=2/3,z=0.1797(16)。而Bradley所推断的Li原子位置是:x=1/3,y=2/3,z=0.3488。前者与文献[8]中估算值相接近。新定出的Li原子位置与近邻O原子构成了键长约在1.9A左右的Li—O四面体。     

室温下KLiSO4晶体的中子衍射结构分析

用中子衍射方法研究了室温下KLiSO₄的晶体结构,进一步确定了Li原子的位置,所得到的结果与近年采用X射线分析的结果在z/c上的差异小于1％。 关键词：     

Bi2Sr2CaCu2O8的晶体结构与超导性能

本文研究了Bi-Sr-Ca-Cu-O体系中理想成份为Bi₂Sr₂CaCu₂O₈化合物的超导性能和晶体结构。名义成份为BiSrCaCu₂O_5.5零电阻超导转变温度T_c(0)=81.5K。用X射线粉末衍射方法测定了Bi₂Sr₂CaCu₂O₈的晶体结构,其基本结构属体心四方晶系,空间群为D_4h¹⁷-l4/mmm,点阵常数a=3.825?,c=30.82?。每单胞化合式单位为2.2Ca占据2(a)等效点系,4Sr,4Bi和4Cu占据三组4(e)位置,其原子参数z分别为0.110,0.302和0.445,16O分别占据8(g),z=0.445和二组4(e),z=0.210和0.380。Bi₂Sr₂CaCu₂O₈晶体结构可认为是阳离子沿z轴的(00z)和((1/2)(1/2)z)交错排列,由Aurivillius相导生出来的。讨论了在Bi-Sr-Ca-Cu-O体系中可能存在的其它沿z轴不同堆垛层数的超导相。 关键词：     

石墨/Li（Ni1/3Co1/3Mn1/3）O2电池充放电过程中电极材料的XRD研究

利用XRD系统地研究了石墨/Li（Ni_1/3Co_1/3Mn_1/3）O₂ 18650型锂离子电池充放电过程中正负极活性材料的晶体结构和微结构的变化.已观测到,由于Li原子的脱嵌,使得LiMO₂点阵参数a缩小,c增大,微应变增大,衍射强度比I₁₀₄/I₁₀₁和I₀₁₂/I₁₀₁降低;此外,由于Li原子的嵌入,2H-石墨的点阵参数a和c,以及微应变ε和堆垛无序度P都增加.同时,讨论了活性材料Li（Ni_1/3Co_1/3Mn_1/3）O₂和石墨在电池充放电过程中的嵌脱锂的物理机理.在充电时,正极Li（Ni_1/3Co_1/3Mn_1/3）O₂中处于（000）位的Li原子优先脱离晶体点阵,继后才是位于（2/3 1/3 1/3）和（1/3 2/3 2/3）位的Li原子离开点阵.锂嵌入石墨,优先进入碳原子六方网格面间的间隙位置,当负极的堆垛无序度达到一定值后,3R相逐渐析出.当电池满充或过充时,在六方石墨中形成LiC₁₂和LiC₆相.放电时,与上述过程相反,但并非是完全可逆的. 关键词： 锂离子电池 微结构 X射线衍射 嵌脱锂物理机理     

LiErP4O12的晶体结构

对于盐熔法合成的LiErP₄O₁₂单晶进行了X射线衍射分析。该晶体属于单斜晶系,空间群为C2/c,z=4,晶胞参数为:a=16.229?,b=7.009?,c=9.524?,β=125.92°。包括把二次消光作为晶体结构参数的全矩阵最小二乘法修正给出1282个独立反射的R=0.058。基本的结构单位为(PO₃)_n的螺旋带,它们由共角的四面体构成。十二面体ErO₈不共有任何O原子,从这意义来说是相互分立的。 关键词：     

3∶29型Gd3(Fe1-xCox)29-yCry化合物的成相与结构

通过X射线衍射分析和磁测量研究了Gd-Fe-Co-Cr四元系中对应于化学式Gd₃(Fe,Co,Cr)₂₉且Gd含量为一定值的截面内富Fe,Co区的相关系,重点探索了高Co含量3∶29型化合物合成的可能性,研究了3∶29型Gd₃(Fe_1-xCo_x)_29-yCr_y化合物的结构与磁性.研究结果表明,获得3∶29型单相Gd₃(Fe_1-xCo_x)_29-yCr_y化合物的范围为:y=5,0≤x≤0.7;y=5.5,0.7≤x≤0.8和y=6,0.8≤x≤0.9.基于对Gd₃(Fe_1-xCo_x)_29-yCr_y化合物成相条件的研究,成功地合成了纯Co基Gd₃Co_29-yCr_y化合物,其固溶范围为6.5≤y≤7.3.3∶29型单相Gd₃(Fe_1-xCo_x)_29-yCr_y化合物的晶体结构都属于单斜晶系,Nd₃(Fe,Ti)₂₉型结构,空间群为A2m.得到3∶29型单相Gd₃(Fe_1-xCo_x)_29-yCr_y化合物的固溶极限即Co含量的极大值与稳定元素Cr含量有关.Co原子的含量越高,所需稳定元素Cr的含量越大.值得注意的是,用Co原子替代Fe原子会导致Gd₃(Fe_1-xCo_x)_29-yCr_y化合物磁晶各向异性的显著改变.当x≥0.4时,化合物的磁晶各向异性从易面型转变为易轴型 关键词： 3(Fe_1-xCo_x)_29-yCr_y化合物')" href="#">Gd₃(Fe_1-xCo_x)_29-yCr_y化合物 相关系和相结构 X射线衍射 磁晶各向异性     

PrBa2Cu3O6+x(x=1,0.3)中Pr价态随氧含量的变化

报道了陶瓷和c轴取向薄膜 PrBa₂Cu₃O_6+x(x=1,0.3)材料的红外反射光谱，通过比较区分出该材料的沿着c轴振动和沿着a-b平面振动的声子模，PrBa₂Cu₃O_6+x和RBa₂Cu₃O_6+x(x=1-0,R=Y和稀土元素)有类似的晶体结构，分析和比较它们的声子谱，其中尤其是Pr和Y,Pr和其它稀土元素 关键词：     

第一原理研究Mn掺杂LiNbO3晶体的磁性和光吸收性质

采用基于密度泛函理论和局域密度近似的第一性原理分析了Mn掺杂LiNbO₃晶体的结构, 磁性, 电子特性和光吸收特性. 文中计算了Mn占据Li位和Nb位体系的形成焓, 对应的形成焓分别为-8.340 eV/atom和-8.0062 eV/atom, 也就意味着Mn 原子优先占据Li位. 这也就意味着Mn原子占据Li位的掺杂LiNbO₃晶体结构更稳定. 磁性分析的结果显示, 其对应磁矩也比占据Nb位的高. 进一步分析磁性的来源, 自旋态密度结果显示: Mn掺杂LiNbO₃晶体的磁性主要源于掺杂原子Mn, Mn原子携带的磁矩高达 4.3 μ_B, 显示出高自旋结构. 由于Mn-3d与近邻O-2p及次近邻Nb-4d 轨道的杂化作用, 计算表明: 诱导近邻O原子及次近邻Nb原子产生的磁矩对总磁矩的贡献较小. 通过光学吸收谱的分析, 得出在可见光区Li位被Mn原子替代以后显示出更好的光吸收响应相比于Nb位. 本文还分析了O空位对于LiNbO₃晶体磁性与电子性质的影响, 结果显示O空位的存在可以增加Mn掺杂LiNbO₃体系的磁性.     

Bi2Pb2V2O10的晶体结构

使用X射线单晶衍射法测定了Bi₂Pb₂V₂O₁₀的结构。该晶体属三斜晶系,空间群为C₁¹-P1,单位晶胞内化学式数Z=1,晶胞参数为:a=7.084(4)?,b=7.278(3)?,c=5.587(3)?,α=111.91(5)°,β=95.01(6)°,γ=108.86(4)°,V=245.70?³,D_x=7.35g/cm³,μ(MoK_α)=678,94cm^-1,F(000)=456。用Patterson函数分析及Forier技术测定了结构,对原子坐标、各向同性及各向异性热参数进行了最小二乘方修正,R=0.079。结构分析表明,Bi₂Pb₂V₂O₁₀的Pb原子与O原子形成八角十二面体,Bi原子与O原子形成六角多面体。两个共棱的Pb—O多面体与两个共棱的Bi—O多面体相连,并沿bc平面无限延伸。讨论了吸收的影响。最后,将Bi₂Pb₂VO₁₀的结构与Pb₂SO₅的结构进行了比较。 关键词：     

基于形变势理论的掺杂计算Sb2Se3空穴迁移率

硒化锑(Sb₂Se₃)是一种元素丰富、经济且无毒的太阳电池吸收层材料.太阳电池的性能在很大程度上取决于载流子的传输特性,然而在Sb₂Se₃中,这些特性尚未得到很好的理解.通过密度泛函理论和形变势理论,本文对纯Sb₂Se₃以及掺杂了As, Bi的Sb₂Se₃的空穴传输特性进行研究,计算并分析了影响迁移率的3个关键参数:有效质量、形变势和弹性常数.结果显示,有效质量对迁移率具有最大影响,掺杂Bi的Sb₂Se₃表现出最高的平均迁移率.同时发现, Sb₂Se₃的空穴迁移率呈现出明显的各向异性,其中x方向的迁移率远高于y,z方向,这应该与x方向的原子主要以较强的共价键连接,而y, z方向以较弱的范德瓦耳斯力连接有关.载流子传输能力强的方向有助于有效传输和收集光生载流子,本研究从理论上强调了控制Sb₂Se_3...     

Remarks on the measurement of polarization of6Li-ions

The determination of the polarization of⁶Li-ions is discussed. It is shown, that independent of the reaction mechanism the following relations between the analysing powers for polarized deuterons and polarized⁶Li-ions hold for the⁶Li(d, α)⁴He-reaction: for all scattering angles \(\vartheta : A_{y y}^{(d)} (E, \vartheta ) = A_{y y}^{(Li)} (E, \vartheta )\) for the scattering angle \(\vartheta = \pi /2\) only: $$A_{z z}^{(d)} (E, \vartheta = \pi /2) = A_{z z}^{(Li)} (E, \vartheta = \pi /2)$$ and $$A_{x x - y y}^{(d)} (E, \vartheta = \pi /2) = A_{x x - y y}^{(Li)} (E, \vartheta = \pi /2)$$ . Using these identities the determination of the polarization of⁶Li-beams is reduced to the experimentally well established determination of the polarization of deuterons.     

Structure and lithium ionic conduction mechanism in La4/3−yLi3yTi2O6

The solid solutions La_4/3−yLi_3yTi₂O₆ (y=0.09∼0.33) have been studied by complex impedance spectroscopy, X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) methods. The ionic conductivity shows a maximum value at around y=0.21, and keeps high values at high y concentrations. The XRD patterns show a single phase for all concentration. The crystal structure is orthorhombic with space groupPmmm for y=0.09∼0.15 and tetragonal with space groupP4/mmm for y=0.17∼0.33. The⁷Li static NMR spectra show a main central peak with a Lorenzian shape for y=0.09∼0.21. The central peak is divided into two parts for y=0.23∼0.33. The narrow intense peak is a mobile component due to mobile ions, and a small broad central peak is due to less mobile lithium ions which contribute to immobile component. The⁷Li MAS NMR spectra show negative chemical shifts which decrease with increasing y concentration. In this paper, we discuss the conduction mechanism and the structure from the analysis of conductivity, lattice parameters, occupation, atomic positions and the⁷Li static/MAS NMR spectra.     

Neutron-induced charged-particle reactions in 6Li and 9Be

Angular distributions of tritons from the ⁶Li(n, t)⁴He reaction were measured at E_n = 7.25, 6.77, 6.57, 5.24 and 4.71 MeV. Angular distributions of douterons from respectively, the ⁶Li(n, d)⁵He two-body breakup reaction were measured at E_n = 6.77 and 6.57 MeV, and of protons from the ⁶Li(n, p)⁶He reaction at E_n = 6.77, 5.24 and 4.71 MeV. All these reactions in ⁶Li were analyzed as direct interaction in the formalism of the distorted wave Born approximation. The optical model for the nuclear interaction was found to apply reasonably well to nuclei as light as ⁴He, ⁵He, ⁶He and ⁶Li. In addition, ⁶Li as an alpha-deuteron cluster gives the best bound-state wave function to describe the experimental angular distribution of tritons. The excitation functions at forward angles of the ⁶Li(n, t)⁴He, ⁶Li(n, d)⁵He and ⁶Li(n, p)⁶He reactions were measured for incident neutron energies between 4.4 and 7.3 MeV. It is found that the ⁶Li(n, d)⁵He two-body breakup reaction has a threshold at about E_n = 5.3 MeV. Angular distributions at E_n = 18.3 MeV for tritons and protons from the ⁹Be(n, t)⁷Li and ⁹Be(n, p)⁹Li, respectively, were also measured.     

KLiSO4单晶的电学性质

我们证实了KLiSO₄为Li离子导体。通过测定样品中的电位分布,确定其载流子为间隙Li离子和Li空位。其电流弛豫在一定时域内遵从负幂次衰减规律。与之对应,在一定频域内存在与频率成负幂次关系的介电色散。在相变温度附近,本底电流、直流电导率和表观介电常数除发生跃变外还出现一个尖锐的小峰。此峰只有在变温速率较慢时才能观察到,表明该相变具有弛豫过程。 关键词：     

钙钛矿（La1-yTby)0.67Sr0.33MnO3的磁致伸缩效应

采用固相反应烧结法制备了（La_1-yTb_y)_0.67Sr_0.33MnO₃系列样品（y=0,0.05,0.15,0.20,0.25,0.33,0.40,0.50,0.60,1.00).X射线衍射表明,随着y值增大钙钛矿型晶体结构从菱面对称性向正交对称性转变.180K时,μ₀H=7T条件下,在y=0.40样品的巨磁电阻可达900％.μ₀H=1.7T时,y=0.20样品的室温磁致伸缩为-50×10^-6.210K时,y=0.33样品的磁致伸缩可达-130×10^-6. 关键词：     

Coupled-channels study of projectile and target excitation in the scattering of 6Li from 12C and 16O

Coupled-channels calculations are presented tor elastic and inelastic ⁶Li + ¹²C scattering at E_c.m. = 16 MeV and 20 MeV, and for ⁶Li + ¹⁶O at 18.7 MeV. Excitation of states within ⁶Li, ¹²C and ¹⁶O are treated with rotational, rotation-vibration and vibrational models only. The 3⁺⁶Li and 2⁺¹²C states are strongly coupled to the elastic scattering and reduce the strengths of both the real and imaginary potentials. The 3^?16O state reduces only the strength of the imaginary potential. All other states are weakly coupled and have little effect on each other or the potential. The data are reasonably well described, with there being some preference for the 3^? state in ¹²C to be K = 0. Excitation of the 0₂⁺ state in ¹²C requires a combination of β-vibration and monopole breathing-mode form factors. The deformation lengths found are in poor agreement with those deduced from electron or proton scattering.     

A study of the 90Zr(6Li, 6He)90Nb reaction at E6Li = 93 MeV

The energy spectra of ⁶He nuclei from the ⁹⁰Zr(⁶Li, ⁶He) reaction at E_{⁶Li = 93 MeV} have been measured over the angular range of 7 ° ? θ_lab ? 20 °. The theoretical DWBA analysis of these spectra and angular distributions was performed employing transition densities of bound and resonance states obtained on the basis of the theory of finite Fermi systems. It is shown that up to excitation energies of E_x ≈ 10 MeV in ⁹⁰Nb a direct charge-exchange mechanism dominates in this reaction, while at higher E_x the contribution made by multistep processes increases significantly. It is also shown that the quasi-elastic cross section is determined by a sum of partial contributions of spin-isospin-flip transitions with multipolarities L=0 through L=6.     

Excitation cross sections of thulium atom transitions terminating at 4f13(2Fo)6s6p(3Po (7/2, J2) levels with J2 = 0, 1

The excitation of odd levels of the thulium atom, spontaneous transitions from which terminate at the 4f ¹³(² F ^o)6s6p(³ P ^o) (7/2, J ₂) levels with J ₂ = 0, 1, is studied by the method of extended crossing beams. Fifty four excitation cross sections are measured at an excitation electron energy of 50 eV. Seven optical excitation functions are recorded in the electron energy range of 0–200 eV.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.