模板法制备新型超级电容器电极材料及其电化学性能研究

发布时间：2018-05-19 12:39

本文选题：超级电容器 + 金属氧化物　；参考：《常州大学》2011年硕士论文

【摘要】：超级电容器是20世纪70年代发展起来的一种新型储能元件，其具有较高能量密度和功率密度以及较好的循环使用寿命，受到国内外学者的广泛关注。目前对超级电容器的研究主要集中于对电极材料的研究上。电化学比电容是衡量电极材料储能性能的重要手段。电极材料的比电容与纳米材料的孔径大小和孔容有密切的关系。本论文分别采用“软、硬”模板法合成了具有不同形貌结构和孔径分布的电极材料，并利用TGA、XRD、SEM、TEM和BET等技术对电极材料的微观结构和形貌进行表征，采用循环伏安(CV)、恒电流充放电和电化学阻抗(EIS)等测试技术对材料的电化学电容性能进行表征。主要研究内容如下： 1、分别以CoCl_2·6H_2O、NiCl_2·6H_2O和MnCl_2·4H_2O为原料，NH_3·H_2O为沉淀剂，，AAO为“硬”模板，采用简单的化学沉淀法，通过考察原料的浓度及浸入时间，沉淀剂的浓度及浸入时间制备了Co(OH)2、Ni(OH)2和Mn(OH)2前躯体，经热处理得到Co_3O_4、NiO和MnO_2纳米管。Co_3O_4纳米管的孔径分布在40～100nm，比表面积为218m~2/g，将其应用于超级电容器具有较好的超电容性能和较好的循环稳定性，比电容可以达到574F/g，循环充放电1000圈后的比电容仍然可以达到552F/g，具有较长的循环使用寿命；NiO纳米管的比表面积为239m~2/g，电化学比电容最大可以达到266F/g；MnO_2纳米管的比表面积为179m~2/g，电化学比电容最大可以达到566F/g，循环充放电1000圈后比电容维持在90%以上。 2、以P123(聚环氧乙烯醚-聚环氧丙烯醚-聚环氧乙烯醚三嵌段共聚物，即EO_20PO70EO_20，平均分子量5800)为“软”模板，采用简单的化学沉淀法制备了Co_3O_4纳米材料。研究结果表明，电极材料具有较好的超电容性能，P123浓度从0g/L增加到50g/L时，材料的比电容增加明显，从263F/g增加到325F/g。P123浓度从50g/L增加到75g/L，比电容增加缓慢，从325F/g增加到326.7F/g。 3、以P123为“软”模板，采用溶胶-凝胶法制备NiO纳米材料及NiO/Co_3O_4复合纳米材料。通过考察热处理温度对比电容的影响，确定了制备NiO的最佳热处理温度为350°C。在最佳煅烧温度条件下，NiO的比电容比非模板法制备的NiO提高了110%，从273F/g增加到583F/g。采用该方法制备的NiO/Co_3O_4复合材料的比电容明显高于模板法制备的纯NiO和纯Co_3O_4的比电容，最大比电容达到671F/g。 4、以CTAB(十六烷基三甲基溴化铵)为“软”模板，采用水热法制备了直径为500nm，长度为2μm的纳米棒状α-MnO_2，电化学测试结果显示，其最大比电容达到140F/g。
[Abstract]:Supercapacitor is a new type of energy storage element developed in the 1970s. It has high energy density, power density and good cycle life, and has been widely concerned by scholars at home and abroad. At present, the research on supercapacitors is mainly focused on electrode materials. Electrochemical capacitance is an important method to measure the energy storage performance of electrode materials. The specific capacitance of electrode materials is closely related to the pore size and pore volume of nanomaterials. In this thesis, the electrode materials with different morphology and pore size distribution were synthesized by "soft and hard" template method, and the microstructure and morphology of the electrode materials were characterized by TGA XRDX Sem TEM and BET. The electrochemical capacitance properties of the materials were characterized by cyclic voltammetry (CV), constant current charge-discharge and electrochemical impedance spectroscopy (EIS). The main contents of the study are as follows: 1. Using CoCl_2 6H _ 2O NiCl _ 2 6H_2O and MnCl_2 4H_2O as raw materials, NH _ 3H _ 2O was used as precipitator and AAO as "hard" template. By means of simple chemical precipitation method, CoH2NiOH2 and Mn(OH)2 were prepared by investigating the concentration of raw material and immersion time, the concentration of precipitant and the time of immersion. Co3O4NiO and MnO_2 nanotubes are obtained by heat treatment. The pore size distribution of Co3O4NiO nanotubes is 40 ~ 100nm, and the specific surface area is 218mnm / g. The application of Co3O4NiO nanotubes to supercapacitors has better supercapacitor performance and better cyclic stability. The specific capacitance can reach 574 F / g, the specific capacitance can still reach 552 F / g after 1000 cycles, the specific surface area of nio nanotubes with long cycle life is 239mg / g, and the maximum electrochemical specific capacitance can reach 266F / g / g MNO _ 2 nanotube's specific surface area. The maximum specific capacitance is 566F / g for 179mg / g, and the specific capacitance is over 90% after 1000 cycles of cyclic charge and discharge. (2) Co_3O_4 nanomaterials were prepared by a simple chemical precipitation method using P123 (poly (cyclooxyethylene ether-polyepoxypropylene ether) -polycyclic oxyethylene ether triblock copolymers, i.e. EOs 20PO70EO20, average molecular weight 5800) as the "soft" template. The results show that when the P123 concentration of electrode material increases from 0g/L to 50g/L, the specific capacitance increases obviously, from 263F/g to 325F/g.P123 concentration increases from 50g/L to 75 g / L, and the specific capacitance increases slowly from 325F/g to 326.7 F / g. 3. Using P123 as a "soft" template, NiO nanomaterials and NiO/Co_3O_4 composite nanomaterials were prepared by sol-gel method. By investigating the effect of heat treatment temperature on capacitance, the optimum heat treatment temperature of NiO was determined to be 350 掳C. At the optimum calcination temperature, the specific capacitance of nio is 110% higher than that of NiO prepared by non-template method, from 273F/g to 583 F / g. The specific capacitance of NiO/Co_3O_4 composite prepared by this method is obviously higher than that of pure NiO and pure Co_3O_4 prepared by template method, and the maximum specific capacitance is 671F / g. 4. Using CTAB (cetyltrimethylammonium bromide) as "soft" template, nanorods with diameter of 500 nm and length of 2 渭 m were prepared by hydrothermal method. The electrochemical test results showed that the maximum specific capacitance was 140 Fr / g.
【学位授予单位】：常州大学
【学位级别】：硕士
【学位授予年份】：2011
【分类号】：TM53

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