非晶态锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3

木文研究了Al₂O₃对B₂O₃-0.7Li₂O-0.7LiCl非晶态的形成和电学性能的影响,我们发现:加入适量的Al₂O₃后,无需借助液氮骤冷技术,直接将熔体倾倒在室温下的紫铜板上就很容易形成大块非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃。Al₂O₃的加入使B₂O₃-0.7Li₂O-0.7LiCl的电导率有所降低,但在高温下不太明显,电导激活能略微升高,实验发现:Al₂O₃含量x=0.03是较合适的剂量,较容易形成大块非晶态,对电导率的影响也不大。 关键词：     

非晶态锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3-0.1V2O5的电学性质和电子自旋共振研究

对两种非晶态B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15),用差热分析、电导率测量、X射线衍射和电子自旋共振进行研究,发现:1)V₂O₅不仅作非晶网络形成剂,而且改变了晶化过程;2)对B₂O₃-Li_{2关键词：}     

非晶锂离子导体P2O5-0.7Li2O-0.4LiCl-0.1Al2O3的离子导电性与结构研究

本文研究了非晶锂离子导体P₂O₅-0.7Li₂O-0.4LiCl-0.1Al₂O₃的60目、120目、200目粉末、粉末压片和整片非晶在60至380℃的离子电导率和激活能。发现颗粒度减小能使离子电导率提高四倍以上,但不影响激活能,它归因于同一非晶相的界面效应。各样品在380℃等温热处理76h内的离子电导率和X射线衍射研究表明:颗粒度越小,晶化就越容易。整片非晶比粉末压片不仅电导率提高两个数量级,激 关键词：     

非晶态离子导体Li2B2O4的核磁共振研究

本文报道了非晶态离子导体Li₂B₂O₄的⁷Li核磁共振研究。测量了⁷Li核磁共振谱与温度的关系。实验中发现,Li₂B₂O₄的晶态、非晶态和部分晶化样品的⁷Li核磁共振谱有很大的不同,且在部分晶化样品的⁷Li核磁共振谱上有附加的小峰,它与LiCl(Al₂O₃)的⁷Li核磁共振谱上附加的小峰相类似。我们也对非晶态离子导体B₂O₃-0.7Li₂O-0.7LiCl进行了⁷Li核磁共振研究,其结果与上面的类似。研究结果表明,它们都起因于非晶母体与微晶的界面效应。 关键词：     

非晶锂离子导体B2O3-0.7Li2O—0.7LiCl-xAl2O3晶化过程的正电子湮没一维角关联辐射研究

本文用中国第一台正电子湮没辐射一维角关联实验装置,测量了非晶锂离子导体B₂O-0.7Li₂O-0.7LiCl-xAl₂O₃(x=0.15;0.10;0.05)晶化过程中各条正电子湮没辐射的一维角关联曲线,并对归一化的电子动量分布进行了线形参数的计算,从其S参数同样能推测出该离子导体在晶化过程中缺陷浓度的变化。非晶离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃的实验结果表明,Al₂O₃组分不同,对非晶态样品在室温下一维角关联曲线的S参数亦无较大影响。完全晶化后,一维角关联曲线的S参数均有很大下降。在晶化过程最初期,无论Al₂O₃含量多少,S参数都明显略增;到晶化温度附近,仅对Al₂O₃含量较多的非晶,S参数反常增高。这些结果验证和补充了测正电子平均寿命得出的结论。由此初步证实了界面层有大量缺陷的物理图象。 关键词：     

非晶锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3晶化初期的核磁共振研究

通过真空密封热处理、避免了样品晶化后吸水引起的误差,采用脉冲法在293K和77K测量了晶化过程初期三种非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃(x=0.15,0.10和0.05)的⁷Li核磁共振谱。发现在低温(77K)只有固相锂离子对应的自旋-自旋弛豫时间T₂=87μs,严格按高斯函数衰减。在室温下固相锂离子对应的T_2s=127μs,仍是高斯型;但液相锂离子对应的T₂却按洛仑兹函数衰减。这反映出锂离子导体的固-液二相性。三种非晶B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃(x=0.15,0.10和0.05)分别在热处理温度401,388和381℃附近,其液相锂离子对应的T_2l都剧增,其吸收谱线宽都变窄。由此再次验证了非晶母体与微晶之间的两相界面效应的物理图象。 关键词：     

Li2SO4—Li2B2O4,Li2SO4—(NH4)2SO4赝二元系相图及离子导电性研究

本文用差热分析和X射线衍射方法对Li₂SO₄-Li₂B₂O₄和Li₂SO₄-[NH₄]₂SO₄两个赝二元系相图进行了研究。Li₂SO₄-Li₂B₂O₄是共晶体系,共晶温度为720℃ 关键词：     

非晶离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3晶化过程的正电子湮没寿命谱和扫描电子显微镜研究

传统的粉末压片样品严重影响了正电子湮没寿命谱及电子显微镜测量的准确性和重复性。本文克服了以上困难,制出大片非晶离子导体样品,得到了晶化过程正电子湮没寿命谱及扫描电子显微镜研究的新结果。非晶离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃的实验结果发现:Al₂O₃组分不同对非晶态样品在室温下的正电子平均寿命无较大影响。完全晶化后,正电子平均寿 关键词：     

Li2O-(LiCl)2-B2O3-Al2O3系统玻璃的声学性质

本工作测量了Li₂O-(LiCl)₂-B₂O₃-Al₂O₃系统玻璃的密度、超声速,计算了玻璃的绝热压缩系数,从声学性质分析了玻璃骨架结构随组成的变化,为研究玻璃的离子导电性提供了方法和分析的依据。 关键词：     

BaO-Li2O-B2O3三元系中BaB2O4-Li2B2O4和BaB2O4-Li2O截面相平衡关系的研究

本文用X射线和差热分析方法对BaO-Li₂O-B₂O₃三元系中的两个截面:BaB₂O₄-Li₂B₂O₄和BaB₂O₄-Li₂O作了研究。在BaB₂O₄-Li₂B₂O₄赝二元系中发现了一个新的化合物4BaB₂O₄·Li₂B₂O₄。化合物在930±3℃由包晶反应形成,并与Li₂B₂O₄形成共晶反应。共晶温度为797±3℃,共晶点组分为79mol％Li₂B₂O₄。在BaB₂O₄-Li₂O截面中也存在化合物4BaB₂O₄·Li₂B₂O₄,其包晶反应温度从930±3℃随Li₂O含量增加下降到908±3℃。在组分60mol％Li₂O处形成另一个新的化合物2BaB₂O₄·3Li₂O。该化合物在630±3℃也是由包晶反应形成,并与Li₂O和Li₂CO₃分别形成共晶反应,共晶温度分别为400±3℃和612±3℃。在BaB₂O₄-Li₂B₂O₄和BaB₂O₄-Li₂O体系中都没有观察到固溶体。用计算机程序分别对化合物4BaB₂O₄·Li₂B₂O₄和2BaB₂O₄·3Li₂O的X射线粉末衍射图案进行了指标化,其结果:4BaB₂O₄·Li₂B₂O₄的空间群为Pmma,a=13.033?,b=14.630?,c=4.247?,每个单胞包含两个化合式单位;2BaB₂O₄·3Li₂O的空间群为Pmmm,a=4.814?,b=9.897?,c=11.523?,每个单胞也含有两个化合式单位。 关键词：     

Molecular dynamics simulation of ternary glasses Li2O-P2O5-LiCl

Molecular dynamics simulation of binary glass 52Li₂O-48P₂O₅ and ternary glasses 45Li₂O-42P₂O₅-13LiCl and 39Li₂O-36P₂O₅-25LiCl was undertaken to study the effects of the addition of LiCl to the binary phosphate glass. The results show that addition of LiCl in the glass creates more non-bridging oxygens and reduces P-O-P chain lengths and branches in these chains, leading to a weakening of the glass matrix and consequent lowering of T_g. Interchain linkages mediated by Li in the binary structure diminish, and consequently better channels are created for Li⁺ movement, enhancing the ionic conductivity σ. Structure parameters also indicate the absence of LiCl clusters in the glass matrix.     

Lithium ion conduction in lithium metaphosphate based systems

A comparative investigation on Li⁺ ion transport has been carried out in various phases of lithium metaphosphate such as (i) crystalline LiPO₃, (ii) glassy form as mol % 50Li₂O-50P₂O₅, synthesized by melt-quenching process, (iii) single phase glass-ceramic LiPO₃ obtained through controlled heat treatment of mol % 50Li₂O-50P₂O₅ and (iv) newly identified polymer-metal salt complex (PEO)₆: LiPO₃. All of the above materials have been characterized through XRD, DSC, optical microscopy and impedance spectroscopy techniques. The Li⁺ ions, migrating with an activation energy value of 1.4 eV through “interstitial mechanism” in polycrystalline LiPO₃, exhibited a dc conductivity value of 2.5×10^-8 Scm^-1 at 280 °C. The above conductivity value was enhanced by four orders of magnitude in Li₂O-P₂O₅ glass, with an activation energy value of 0.72 eV. The glass subjected to controlled heat treatment devitrified into single phase glass-ceramic, as revealed by XRD and optical microscopy studies. The glass-ceramic exhibited better conduction characteristics compared to polycrystalline LiPO₃. Polycrystalline LiPO₃, complexed with polymer PEO has exhibited a conductivity value of 3.1×10^-7 Scm^-1 at 78 °C with activation energies of 0.21 and 0.88 eV for Li⁺ ion migration above and below the softening point of the polymer, respectively. PACS 66.10.Ed; 71.55.Jv; 81.30.Hd; 82.45.Gj; 82.45.Wx     

The effect of TiO2 addition on the crystallization and phase formation in lithium aluminum silicate (LAS) glasses nucleated by P2O5

We have prepared lithium aluminum silicate (LAS) glasses of compositions (wt%) 10.6Li₂O-71.7SiO₂-7.1Al₂O₃-4.9K₂O-3.2B₂O₃-2.5P₂O₅(LAS-P) and 10.6Li₂O-71.7SiO₂-7.1Al₂O₃-4.9K₂O-3.2B₂O₃-1.25P₂O₅-1.25TiO₂ (LAS-PT) by the conventional melt quench technique. P₂O₅ and TiO₂ are added as nucleating agents to transform them into glass ceramics. We have studied the interdependence of different phases formed, microstructure, thermal expansion coefficient (TEC), and microhardness (MH) using X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo-mechanical analysis (TMA), and MH (μ-hardness) measurements. The incorporation of TiO₂, in addition to P₂O₅, greatly affects phase evolution and morphology, thereby affecting the thermo-physical properties. Its presence resulted in the formation of only lithium disilicate phase in LAS-PT samples as compared to lithium disilicate and quartz in LAS-P samples on heat treatment at 820 °C. This produced low-aspect-ratio plate-like crystallites in LAS-PT vis-à-vis granular microstructure in LAS-P. Consequently due to the combined effect of both phase formation and morphology a single-phase glass ceramic with overall higher MH, TEC, and glass transition temperature (T_g) is produced.     

等温热处理过程中一种非晶态Li+导体电导行为的研究

本文在玻璃转变温度以下,采用交流伏安法连续自动观测了非晶态Li⁺导体B₂O₃-0.7Li₂O-0.7LiCl-0.1Al₂O₃在等温热处理条件下的电导行为。结果表明:材料的电导率先随时间升高,出现峰值后单调下降,并含有两个平台部分。与此相配合的DSC与XRD研究证实:形成电导率峰值的基本原因是由于发生了非晶态相分离,而电导率曲线下降部分的平台则是由于非晶态的晶化。最后,从相界 关键词：     

非晶态Li+导体分相和晶化过程中的相界效应

非晶态Li⁺导体B₂O₃-0.7Li₂O-0.7LiCl-0.1Al₂O₃在等温处理过程中,其电导率先随时间升高,出现峰值后下降,随后出现两个平台。这是由于材料的分相和晶化所致。本文据相界效应观点,认为不同相之间界面附近有一高电导率层,它对电导率的贡献补偿和超过了由于分相和晶化的体效应所引起的电导率下降。由此,对这种材料的电导率随时间变化曲线给出了解释。 关键词：     

Structure property correlation in lithium borophosphate glasses

To investigate the influence of cation mobility variation due to the mixed glass former effect, 0.45Li₂O-(0.55 − x) P₂O₅−x B₂O₃ glasses (0 ≤; x ≤ 0.55) are studied keeping the molar ratio of Li₂O/(P₂O₅ + B₂O₃) constant. Addition of B₂O₃ into lithium phosphate glasses increases the glass transition temperature (T _g) and number density, decreases the molar volume, and generally renders the glasses more fragile. The glass system has been characterised experimentally by XRD, XPS and impedance studies and studied computationally by constant volume molecular dynamics (MD) simulations and bond valence (BV) method to identify the structural variation with increasing the B₂O₃ content, its consequence for Li⁺ ion mobility, as well as the distribution of bridging and non-bridging oxygen atoms. These studies indicate the increase of P-O-B bonds (up to Y = [B₂O₃]/([B₂O₃] + [P₂O₅]) ≈ 0.5 and B-O-B bonds, as well as the decrease of P-O-P bonds and non-bridging oxygens (NBOs) with rising B₂O₃ content. The system with Y ≈ 0.5 exhibits maximum ionic conductivity, 1.0 × 10⁻⁷ S cm⁻¹, with activation energy 0.63 V. Findings are rationalised by a model of structure evolution with varying B₂O₃ content Y and an empirical model quantifying the effect of the various structural building blocks on the ionic conductivity in this mixed glass former system.     

The role of crystallization on microstructural and electrical studies of lithium germanium phosphate glass-ceramic electrolytes

The glass-ceramic samples with the general formula: (100???x) [0.4Li₂O-0.1GeO₂-0.6P₂O₅]?+?x 40-h ball-milled Al₂O₃ (where x?=?0, 2, 4, 6, 8, 10, and 12 mol%) were synthesized by high-energy ball milling technique. X-ray diffraction (XRD) analysis revealed that the phases such as LiGe₂(PO₄)₃, Li₄P₂O₇, GeO₂, and AlPO₄ were identified from major diffraction peaks of LGPA samples. The intensity and broadening of XRD peaks of LGPA glass-ceramic samples displayed that the LGPA₁₀ glass-ceramic possesses major crystalline phases namely sodium super ionic conductor (NASICON)-type phases of LiGe₂(PO₄)₃ and Li₄P₂O₇. Scanning electron micrograph (SEM) pictures further confirmed that the sample LGPA₁₀ has the presence of particles of varied sizes (20–30 nm) and also large clusters of less than 60 nm dispersed uniformly in a continuous glass matrix. The slight difference in the Z″ and M″ peaks for the LGPA samples suggests the presence of possibly more than one mechanism.