金属有机配位聚合物的制备及电性能研究

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Major: Materials Process Engineering
College of Materials Engineering Shanghai University of Engineering Science Shanghai, P.R. China December, 2011
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III
Electrochemical characterization were carried out using cyclic voltammetry, Galvanostatic charge-discharge test, electrochemical impedance spectroscopy and cycle life test. The main results and innovations are as follows: 1. Cobalt-based MOF Co(bdc)(ted)0.5 (bdc=1,4-benzenedicarboxylate; ted= triethylenediamine ) with BET surface area of 1244 m2/g and 3D pore size of 7.3 Å was prepared using cobalt nitrate as metal precursor, terephthalic acid and triethylenediamine as organic ligands via solvothermal method. Structural analysis and electrochemical test were carried out; Influence of reaction temperature, reaction time and molar ratio of the reactants on the electrochemical performance of the electrode material was also investigated. The highest specific capacitance reached 937 F· g -1 in 6M KOH electrolyte at the scan rate of 5mv/s; 2. Nickel-based MOF [Ni3(HCOO)6]· DMF with BET surface area of 304 m2/g and 1D pore size of 5.0 Å was prepared using nickel nitrate as metal precursor, formic acid as organic ligand via solvothermal method. Structural analysis and electrochemical test were carried out; Influence of reaction condition on the electrochemical performance of the electrode material was also investigated. The highest specific capacitance reached 1217 F· g-1 in 6M KOH electrolyte at the scan rate of 5mv/s; 3. Single crystal of zinc-based ionic metal-organic frameworks was prepared using zinc nitrate as metal precursor and N,N`-diacetic acid imidazole as organic ligand via solvothermal method. Single-crystal XRD was carried out to analyze the crystal structure; Electrochemical activities of the sample under different scan rates were studied and promising capacitive performance under high scan rates was observed. KEY WORDS ： suprecapacitor ， metal-organic frameworks ， solvothermal method ， electrochemical performance
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金属-有机配位聚合物的制备及电性能研究 摘 要
超级电容器是一种性能卓越的新型储能元件，因具有高能量密度、高功率密度、 循环寿命长、污染小等特点, 成为近年来电化学领域研究的热点。超级电容器在功率 密度上高于其他二次电池，而在能量密度上则远高于传统物理电容，使其在工业、电 力、运输、绿色能源、军事、航空航天领域等领域具有广阔的应用价值。目前，超级 电容器的研究重点主要围绕在开发高性能电极材料， 使其在保持高功率密度的同时获 得更高的能量密度。从储能机理上看，超级电容器可分为双电层电容和赝电容两类， 常用的电极材料主要有炭材料、金属化合物和导电聚合物 (Electrically Conducting Polymer，ECP)以及炭/氧化物，炭/ECP，氧化物/导电聚合物等一系列复合材料。 金属有机配位聚合物化合物（ MOF）材料，由于在多个领域具有广阔的应用前 景，因此被认为是现今最具前景的材料之一。MOF 材料的应用范围涉及催化、氢气 存储、离子交换、传感器、药物中间体、光学材料等等相关领域。相比传统的多孔材 料，MOF 灵活多变的孔道结构也成为其被关注的原因之一。金属-有机配位聚合物 （MOF）作为新型多孔材料，具有高比表面积的同时在结构中包含活性金属离子或 原子簇， 这一显著特征使其具备了成为高性能超级电容器电极材料的潜力。但目前国 内外学术界对 MOF 材料的电化学方面的研究不多，尤其是对其在超级电容器当中的 应用研究则更少，有待进一步深入研究。本论文以溶剂热法制备了系列含钴、镍、锌 的 MOF 材料作为超级电容器正极材料，通过 XRD, N2 等温吸附脱附曲线进行结构表 征，并在水系电解液中以循环伏安，直流充放电、交流阻抗和循环寿命等手段进行了 电化学表征。论文的主要研究内容如下： (1) 以硝酸钴为金属源，对苯二甲酸为配体，三乙二胺为第二配体，通过溶剂热 法制备了 BET 比表面为 1244 m2/g, 平均孔径为 7.3 Å、具有三维孔道结构的 MOF 材 料 Co(bdc)(ted)0.5 (bdc=1,4-benzenedicarboxylate; ted= triethylenediamine )并进行了结 构表征及电化学测试；在此基础上，研究了不同制备温度、时间及反应物比例对其电 化学性能的影响；在 6M KOH 水溶液中 5mv/s 扫描速率下，最优制备条件下的比电
关键词：超级电容器，金属有机配位聚合物，水热法，电化学性能
II
STUDIES ON PREPARATION AND ELECTROCHEMICAL PROPERTIES OF METAL-ORGANIC FRAMEWORKS
ABSTRACT
The supercapacitor is a new type of electrochemical energy storage device which has attracted considerable attention due to its high energy density, high power density, long cycle life and less pollution. Supercapacitors can provide higher power density than traditional secondary batteries as well as much higher energy density than physical capacitors, which achieved much attention in many fields, such as mobile telecommunication, information technology, consumer electronics, aerospace, military force, and so on. Recently, studies on supercapacitors have been mainly focused on the preparation of high performance electrode materials with both high power density and energy density. According to the principle of energy-storage there are two types of supercapacitors: electric double-layer capacitor and faradaic pseudocapacitor. Electrode materials mainly include carbon materials，metal oxides and conducting polymers (ECP). Metal-organic frameworks (MOF) has been considered as one of the most promising materials for their extensive applications in many fields such as catalysis, hydrogen storage, ion exchange, sensor, medicine intermediate as well as optical materials. Comparing with traditional porous materials, the flexible and various pore structures of MOFs have been the main reason for the particular attention. As a new type of porous material, MOFs not only have high specific surface area but also contain active metal ions or clusters within their structures, which makes MOFs a promising candidate for electrode materials of electrochemical capacitors. However, studies on electrochemistry of MOFs, particularly on their application in electrochemical capacitors are rare at present and further research is needed. In the present paper, a series of MOF materials containing cobalt, nickel and zinc ions were successfully synthesized via solvothermal method; Structural analysis were carried out using single-crystal/powder XRD and N2 adsorption-desorption studies;