硫酸铋碱金属复盐的合成及电化学性能研究

发布时间：2018-03-24 11:18

本文选题：硫酸铋碱金属复盐　切入点：固相法　出处：《上海工程技术大学》2015年硕士论文

【摘要】：探索新晶体材料是晶体领域研究中非常重要的一部分,也是促进新能源研发和实践工作的必然趋势。在众多晶体材料中,硫酸盐晶体是非常重要的一族。本论文采用中热固相法合成出了三种新型硫酸铋碱金属复盐晶体:Na Bi(SO4)2、KBi(SO4)2和Rb Bi(SO4)2,另外,采用水热合成法成功制得新型异双金属混合酸根复盐晶体Bi Cu2(Te O3)(SO4)(OH)3。晶体衍射数据都是在Bruker APEX-II CCD X-射线单晶衍射仪上收集的,运用SHELX-2013软件以直接法解析得到晶体结构。采用循环伏安法、交流阻抗法、充放电法来测试硫酸铋碱金属复盐的电化学性能,还采用了傅立叶红外光谱仪、紫外可见近红外光谱仪对它们的性质进行了表征和分析。本论文的主要研究内容如下:1.Na Bi(SO4)2晶体以单斜空间群P21/c结晶,晶胞参数:a=9.4340(18)?,b=7.0536(13)?,c=9.4489(18)?,β=95.839(3)°,Z=4。沿着[100]方向其晶体结构是由无数个SO4四面体和Bi O8双帽三棱柱连接构成的二维[Bi(SO4)2]-层状结构,Na+位于层与层之间。其中,每一个SO4四面体周围环绕着四个Bi O8双帽三棱柱,SO42-中的一个O同时连接两个Bi原子,其余三个O原子单独各自连接一个Bi原子。2.KBi(SO4)2晶体以单斜空间群C2/c结晶,晶胞参数:a=13.052(2)?,b=5.3577(10)?,c=9.4127(17)?,β=102.031(3)°,Z=4;Rb Bi(SO4)2晶体同样以单斜空间群C2/c结晶,晶胞参数:a=13.501(5)?,b=5.3688(19)?,c=9.467(3)?,β=102.697(6)°,Z=4。它们的结构可以描述为:沿着[100]方向相邻的Bi O8四方反棱柱通过两个SO4四面体连接形成无限的一维[Bi(SO3)2]3+链,平行的链与链之间通过SO4中的O3连接,在[001]方向形成二维的[Bi(SO4)2]-层状结构,层与层之间由K+或Rb+隔开。拉曼和红外光谱很好的证实了晶体结构中存在的S-O振动、O-Bi-O以及晶格振动。紫外可见漫反射光谱测得它们的禁带宽度分别为4.46e V、4.18 e V、4.15 e V。3.Bi Cu2(Te O3)(SO4)(OH)3晶体以单斜空间群P21/n结晶,晶胞参数:a=9.5513(15)?,b=6.3022(10)?,c=13.955(2)?,Z=4,其晶体结构是由两种Cu O6八面体形成的二维层状结构[Cu3O10]14-与扭曲Bi O帽三棱柱,Te O3三角锥,SO4四面体连接而形成的三维隧道框架结构。拉曼和红外光谱很好的证实了晶体结构中存在的Te O32-、SO42-、OH-等基团。紫外可见漫反射光谱测得化合物的禁带宽度为3.85 e V。4.论文首次尝试把硫酸铋碱金属复盐作为电极材料。高频区的交流阻抗图表明硫酸铋碱金属复盐作为电极材料是合适的。在6 M KOH溶液中扫描速率为5 m V/s下,Na Bi(SO4)2,KBi(SO4)2,Rb Bi(SO4)2的比电容分别为260,338,231 F/g。
[Abstract]:Exploring new crystal materials is a very important part of the research in crystal field, and is also an inevitable trend to promote the development and practice of new energy. Sulfate crystals are very important. In this paper, three new bismuth sulfate base metal double salt crystals of bismuth sulfate have been synthesized by medium thermal solid state method. A new type of double salt crystal Bi Cu2(Te O _ 3O _ 3O _ 4 so _ 4 O _ H _ 3 was successfully synthesized by hydrothermal synthesis. The diffraction data were collected on Bruker APEX-II CCD X-ray single crystal diffractometer. The crystal structure was obtained by direct analysis with SHELX-2013 software. The electrochemical properties of bismuth sulfate base metal compound salt were measured by cyclic voltammetry, AC impedance method and charge-discharge method, and Fourier transform infrared spectroscopy (FTIR) was used. Their properties were characterized and analyzed by UV-Vis near infrared spectrometer. The main contents of this thesis are as follows: 1. The crystal of Na Bi(SO4)2 is crystallized in monoclinic space group P21 / c. BX 7.0536? 9. 4489? The crystal structure is composed of numerous SO4 tetrahedrons and Bi O 8 double cap triangulated prisms. The two dimensional [Bi(SO4)2] -layered structure Na is located between layers. Each SO4 tetrahedron is surrounded by one of the four BiO8 double cap triprism columns so 42- and one of the other three O atoms is connected with two Bi atoms at the same time. The other three O atoms are individually connected to one Bi atom. 2. The crystal is crystallized in a monoclinic space group C _ 2 / P _ c, and the cell parameter is: a ~ (13. 0522)? 5. 3577? 10? 9. 4127? The crystal of Rb Bi(SO4)2 is also crystallized in monoclinic space group C _ 2 / c, the unit cell parameter is 1: a ~ (13.501)? 5. 3688? 9. 467? Their structures can be described as follows: bi O 8 tetragonal antiprism in the direction of [100] is joined by two SO4 tetrahedrons to form an infinite one dimensional [Bi(SO3)2] 3 chain, and parallel chains and chains are connected by O 3 in SO4. Forming a two-dimensional [Bi(SO4)2] -layered structure in the [001] direction, The layers are separated by K or RB. Raman and infrared spectra well confirm the existence of S-O vibration, O-Bi-O and lattice vibration in crystal structure. The band gap is 4.46 e V ~ (4) ~ (18) e V ~ (15) e measured by UV-Vis diffuse reflectance spectroscopy, respectively. V.3.Bi Cu2(Te O3)(SO4)(OH)3 crystals are crystallized in monoclinic space group P21 / n, Unit cell parameter: 9. 5513? 6. 3022? 10? C. C. 13.955? Its crystal structure is a three-dimensional tunneling frame structure formed by two kinds of CuO6 octahedron [Cu3O10] 14- and the twisted Bi O cap triangulated cone so 4 tetrahedron. Raman and infrared spectra show that the structure is very good. TeO32-OSO42-OH- groups were found in the crystal structure. The band gap of the compound was 3.85 e V. 4 measured by UV-Vis diffuse reflectance spectroscopy. The bismuth sulfate base metal compound was first used as electrode material in this paper. Ac impedance diagram of high frequency region. It is suitable to use bismuth sulfate alkali metal double salt as electrode material. The specific capacitance of Na ~ (2 +) ~ (so _ (4)) _ (2) K _ (B) _ (so _ (4)) ~ (2) R _ (b) Bi(SO4)2 is 260338231 F / g at a scanning rate of 5 MV / s in 6 M KOH solution.
【学位授予单位】：上海工程技术大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ135.32

【参考文献】