高电导率金属磷化物电极材料的制备及储能特性研究
发布时间：2018-10-14 14:57
【摘要】：电极材料作为超级电容器最主要的因素之一已经受到研究者们的广泛关注。本文综述了超级电容器各类电极材料的研究进展,并在这些电极材料的基础上提出了金属磷化物这样一种具有高电导率的新型类金属型合金电极材料。对于充放电过程来说,材料具有高的导电性有利于大电流充放电过程中电子的快速转移,从而使得电极材料具有良好的倍率性能。本课题采用不同的制备方法合成了不同种类的金属磷化物电极材料并研究其储能特性。本课题遵循单金属磷化物-双金属磷化物-复合物材料为主线的研究路线,研究了电子导电性、材料本征结构、元素摩尔比等因素对电化学性能的影响规律。主要研究内容如下:一、采用液相合成法,以乙酰丙酮镍、十八烯为原料,在油胺和氮气环境中首先合成树枝状Ni_3C前躯体,在这个反应体系基础上加入一定量的三辛基膦制备了不同结晶态的磷化镍(Ni_2P、Ni_7P_3、Ni_(12)P_5)电极材料。Ni_2P继承了Ni_3C前躯体的树枝状结构,Ni_7P_3和Ni_(12)P_5则表现为均匀分散的团簇状结构,这种结构提供了大的比表面积有利于提高材料的比容量。通过线性扫描伏安曲线可以定性的分析材料的导电性,结果显示三种磷化镍的导电性远远高于氧化镍,甚至高于石墨。电化学性能结果显示Ni_2P具有最高的比容量(745 C g~(-1)),而Ni_(12)P_5具有最优异的倍率性能。为了考察磷化镍电极材料在实际应用中的储能特性,分别以磷化镍为正极,活性炭为负极组装了非对称电容器,其中AC//Ni_2P电容器具有最高的比容量(239.5 C g~(-1))和能量密度(53.2 Wh kg~(-1))。二、采用水热法合成了一系列具有不同Ni/Co理论摩尔比的磷化镍钴电极材料(Ni_xCo_(2-x)P),并对他们进行结构表征。研究表明:制备的磷化镍钴材料均为颗粒结构,其中NiCoP样品的颗粒结构分布较为均匀,并且颗粒与颗粒之间存在大量的空隙,这种结构便于电解液的穿梭,使得电荷存储较为容易。电化学结果显示,随着Ni/Co摩尔比的增加,磷化镍钴电极材料的比容量先增大后减小,当Ni/Co摩尔比为1:1时,即NiCo P样品达到最优异的电化学性能。将Ni CoP作为代表性样品进行研究,结果表明NiCoP具有很高的本征电导率,它的容量可达571 C g~(-1),具有比单品磷化钴(Co2P)和磷化镍(Ni_2P)更优异的电化学性能。为了考察NiCoP在实际应用中的储能特性,以NiCoP为正极活性炭为负极组装了非对称电容器,AC//NiCoP电容器的容量可达164 C g~(-1),同时具有优异的循环性能和高的能量密度。三、采用化学沉淀法合成了Ni_2P/Co_3V_2O_8复合材料。研究了Ni_2P:Co_3V_2O_8摩尔比对复合物电化学性能的影响。研究表明:制备的复合材料为纳米颗粒状结构,较小的Co_3V_2O_8颗粒包裹着较大的Ni_2P颗粒。这种结构不仅阻止了Co_3V_2O_8颗粒的团聚,而且形成了不同尺寸的空隙有利于电解液离子的浸润。电化学结果表明随着Ni_2P量的增多,复合材料的容量先增加后减小,当Ni_2P:Co_3V_2O_8摩尔比为0.8:0.2时材料具有最优异的电化学性能。由于Ni_2P作为导电添加剂存在,复合材料在一定程度上改善了Co_3V_2O_8的导电性,并且兼具了Ni_2P的高比容量与Co_3V_2O_8的优异的倍率性能和循环性能。为了考察Ni_2P/Co_3V_2O_8复合材料在实际应用中的储能特性,以Ni_2P/Co_3V_2O_8为正极活性炭为负极组装了非对称电容器,AC//Ni_2P/Co_3V_2O_8电容器实现了一个大的电位窗口(1.7 V),比容量可达206.5 C g~(-1),能量密度可达40.2 Wh kg~(-1)。
[Abstract]:As one of the most important factors in super capacitor, electrode materials have attracted much attention from researchers. In this paper, the research progress of all kinds of electrode materials of super capacitor is reviewed, and a new type of metal-type alloy electrode material with high electrical conductivity is proposed on the basis of these electrode materials. For the charging and discharging process, the material has high conductivity and is favorable for the rapid transfer of electrons in the process of large current charge and discharge, so that the electrode material has good rate performance. Different kinds of metal phosphide electrode materials were synthesized by different preparation methods and their energy storage characteristics were studied. Based on the study route of single metal phosphide-bimetal phosphide-composite material as the main line, the influence of the factors such as electron conductivity, intrinsic structure and molar ratio of element on the electrochemical performance was studied. The main research contents are as follows: firstly, a dendritic Ni _ 3C precursor is synthesized in an oil amine and a nitrogen environment by adopting a liquid phase synthesis method, and a dendritic Ni _ 3C precursor is first synthesized in an oil amine and a nitrogen environment, and a certain amount of trioctyl amine is added on the basis of the reaction system to prepare the nickel phosphide (Ni _ 2P) with different crystal states, Ni _ 7P _ 3, Ni _ (12) P _ 5) electrode materials. Ni _ 2P inherits the dendritic structure of the precursor of Ni _ 3C, and Ni _ 7P _ 3 and Ni _ (12) P _ 5 behave as uniformly dispersed clusters. This structure provides a large specific surface area which is helpful to improve the specific capacity of the material. The conductivity of the materials can be qualitatively analyzed by linear sweep voltammetry. The results show that the conductivity of the three kinds of nickel phosphide is much higher than that of nickel oxide, even higher than that of graphite. The electrochemical performance results show that Ni _ 2P has the highest specific capacity (745 C g ~ (-1)), while Ni _ (12) P _ 5 has the most excellent rate performance. In order to investigate the energy storage characteristics of the nickel phosphide electrode material in practical application, an asymmetric capacitor was assembled with nickel phosphide as the positive electrode and active carbon as the negative electrode. The AC/ Ni _ 2P capacitor had the highest specific capacity (239. 5 C g ~ (-1)) and the energy density (53. 2/ kg ~ (-1)). A series of nickel-cobalt electrode materials (Ni _ xCo _ (2-x) P) with different molar ratios of Ni/ Co were synthesized by hydrothermal method. The results show that the prepared cobalt-phosphide-cobalt material is a particle structure, in which the particle structure distribution of NiCoP sample is more uniform, and a large number of gaps exist between the particles and the particles. The structure is convenient for the shuttle of the electrolyte, so that the charge storage is easy. The electrochemical results show that, with the increase of Ni/ Co molar ratio, the specific capacity of the nickel phosphide-cobalt electrode material decreases, and when the molar ratio of Ni/ Co is 1: 1, that is, the NiCo P sample achieves the most excellent electrochemical performance. Ni CoP is used as a representative sample. The results show that NiCoP has a high intrinsic conductivity, and its capacity can reach 571 C g ~ (-1), and it has better electrochemical performance than single-product cobalt phosphide (Co2P) and nickel phosphide (Ni _ 2P). In order to investigate the energy storage characteristics of NiCoP in practical application, the capacity of AC/ NiCoP capacitor can reach 164 C g ~ (-1), while the capacity of AC/ NiCoP capacitor can reach 164 C g ~ (-1) with NiCoP as positive active carbon. Meanwhile, it has excellent cycle performance and high energy density. Ni _ 2P/ Co _ 3V _ 2O _ 8 composites were synthesized by chemical precipitation method. The effect of Ni _ 2P: Co _ 3V _ 2O _ 8 molar ratio on the electrochemical properties of composites was studied. The results show that the prepared composite is a nano-granular structure, and the smaller Co _ 3V _ 2O _ 8 particles are coated with larger Ni _ 2P particles. This structure not only prevents the agglomeration of Co _ 3V _ 2O _ 8 particles, but also forms pores with different sizes to facilitate the infiltration of electrolyte ions. The electrochemical results show that with the increase of the amount of Ni _ 2P, the capacity of the composites decreases, and when the molar ratio of Ni _ 2P: Co _ 3V _ 2O _ 8 is 0.8: 0.2, the material has the most excellent electrochemical properties. Because Ni _ 2P is present as conductive additive, the conductivity of Co _ 3V _ 2O _ 8 is improved to some extent, and the high specific capacity of Ni _ 2P and Co _ 3V _ 2O _ 8 have excellent multiplying power and cycle performance. In order to investigate the energy storage characteristics of Ni _ 2P/ Co _ 3V _ 2O _ 8 composites in practical applications, an asymmetric capacitor was assembled using Ni _ 2P/ Co _ 3V _ 2O _ 8 as negative electrode, and an AC/ Ni _ 2P/ Co _ 3V _ 2O _ 8 capacitor was used to realize a large potential window (1.7 V). The specific capacity can reach 206. 5 C g ~ (-1), and the energy density can reach 40. 2 kg ~ (-1).
【学位授予单位】：兰州理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM53;TB33
本文编号：2270813
[Abstract]:As one of the most important factors in super capacitor, electrode materials have attracted much attention from researchers. In this paper, the research progress of all kinds of electrode materials of super capacitor is reviewed, and a new type of metal-type alloy electrode material with high electrical conductivity is proposed on the basis of these electrode materials. For the charging and discharging process, the material has high conductivity and is favorable for the rapid transfer of electrons in the process of large current charge and discharge, so that the electrode material has good rate performance. Different kinds of metal phosphide electrode materials were synthesized by different preparation methods and their energy storage characteristics were studied. Based on the study route of single metal phosphide-bimetal phosphide-composite material as the main line, the influence of the factors such as electron conductivity, intrinsic structure and molar ratio of element on the electrochemical performance was studied. The main research contents are as follows: firstly, a dendritic Ni _ 3C precursor is synthesized in an oil amine and a nitrogen environment by adopting a liquid phase synthesis method, and a dendritic Ni _ 3C precursor is first synthesized in an oil amine and a nitrogen environment, and a certain amount of trioctyl amine is added on the basis of the reaction system to prepare the nickel phosphide (Ni _ 2P) with different crystal states, Ni _ 7P _ 3, Ni _ (12) P _ 5) electrode materials. Ni _ 2P inherits the dendritic structure of the precursor of Ni _ 3C, and Ni _ 7P _ 3 and Ni _ (12) P _ 5 behave as uniformly dispersed clusters. This structure provides a large specific surface area which is helpful to improve the specific capacity of the material. The conductivity of the materials can be qualitatively analyzed by linear sweep voltammetry. The results show that the conductivity of the three kinds of nickel phosphide is much higher than that of nickel oxide, even higher than that of graphite. The electrochemical performance results show that Ni _ 2P has the highest specific capacity (745 C g ~ (-1)), while Ni _ (12) P _ 5 has the most excellent rate performance. In order to investigate the energy storage characteristics of the nickel phosphide electrode material in practical application, an asymmetric capacitor was assembled with nickel phosphide as the positive electrode and active carbon as the negative electrode. The AC/ Ni _ 2P capacitor had the highest specific capacity (239. 5 C g ~ (-1)) and the energy density (53. 2/ kg ~ (-1)). A series of nickel-cobalt electrode materials (Ni _ xCo _ (2-x) P) with different molar ratios of Ni/ Co were synthesized by hydrothermal method. The results show that the prepared cobalt-phosphide-cobalt material is a particle structure, in which the particle structure distribution of NiCoP sample is more uniform, and a large number of gaps exist between the particles and the particles. The structure is convenient for the shuttle of the electrolyte, so that the charge storage is easy. The electrochemical results show that, with the increase of Ni/ Co molar ratio, the specific capacity of the nickel phosphide-cobalt electrode material decreases, and when the molar ratio of Ni/ Co is 1: 1, that is, the NiCo P sample achieves the most excellent electrochemical performance. Ni CoP is used as a representative sample. The results show that NiCoP has a high intrinsic conductivity, and its capacity can reach 571 C g ~ (-1), and it has better electrochemical performance than single-product cobalt phosphide (Co2P) and nickel phosphide (Ni _ 2P). In order to investigate the energy storage characteristics of NiCoP in practical application, the capacity of AC/ NiCoP capacitor can reach 164 C g ~ (-1), while the capacity of AC/ NiCoP capacitor can reach 164 C g ~ (-1) with NiCoP as positive active carbon. Meanwhile, it has excellent cycle performance and high energy density. Ni _ 2P/ Co _ 3V _ 2O _ 8 composites were synthesized by chemical precipitation method. The effect of Ni _ 2P: Co _ 3V _ 2O _ 8 molar ratio on the electrochemical properties of composites was studied. The results show that the prepared composite is a nano-granular structure, and the smaller Co _ 3V _ 2O _ 8 particles are coated with larger Ni _ 2P particles. This structure not only prevents the agglomeration of Co _ 3V _ 2O _ 8 particles, but also forms pores with different sizes to facilitate the infiltration of electrolyte ions. The electrochemical results show that with the increase of the amount of Ni _ 2P, the capacity of the composites decreases, and when the molar ratio of Ni _ 2P: Co _ 3V _ 2O _ 8 is 0.8: 0.2, the material has the most excellent electrochemical properties. Because Ni _ 2P is present as conductive additive, the conductivity of Co _ 3V _ 2O _ 8 is improved to some extent, and the high specific capacity of Ni _ 2P and Co _ 3V _ 2O _ 8 have excellent multiplying power and cycle performance. In order to investigate the energy storage characteristics of Ni _ 2P/ Co _ 3V _ 2O _ 8 composites in practical applications, an asymmetric capacitor was assembled using Ni _ 2P/ Co _ 3V _ 2O _ 8 as negative electrode, and an AC/ Ni _ 2P/ Co _ 3V _ 2O _ 8 capacitor was used to realize a large potential window (1.7 V). The specific capacity can reach 206. 5 C g ~ (-1), and the energy density can reach 40. 2 kg ~ (-1).
【学位授予单位】：兰州理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM53;TB33
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