CN114804076A - Composite material of metal oxide coated multi-walled carbon nanotube and preparation method and application thereof - Google Patents
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Abstract
Description
技术领域technical field
本发明公开涉及复合电极材料技术领域，尤其涉及一种金属氧化物包覆多壁碳纳米管的复合材料及其制备方法、应用。The present invention relates to the technical field of composite electrode materials, in particular to a composite material of metal oxide-coated multi-walled carbon nanotubes, a preparation method and application thereof.
背景技术Background technique
超级电容器具有超高的功率密度、优异的循环性能和快速充电能力，在许多领域都受到了广泛的关注。电极材料作为超级电容器的组成部分之一，对超级电容器的发展起着至关重要的作用。Supercapacitors have received extensive attention in many fields due to their ultra-high power density, excellent cycling performance, and fast charging capability. As one of the components of supercapacitors, electrode materials play a crucial role in the development of supercapacitors.
在电极材料中，多孔金属氧化物基纳米材料在不同形貌和尺寸的纳米材料中表现出更大的优势，其理论电容高、氧化还原可逆性好、环境友好等优点被广泛应用于超级电容器中。但是电解液与电极材料之间的传输效率较低在电化学反应过程中限制了金属氧化物的电化学性能。因此，金属氧化物与碳质载体复合材料的研究日益深入，这是利用电极材料的开放空间、高比表面积和结构变异性提高电极材料的电化学性能的途径之一。Among electrode materials, porous metal oxide-based nanomaterials show greater advantages in nanomaterials with different morphologies and sizes, and are widely used in supercapacitors due to their high theoretical capacitance, good redox reversibility, and environmental friendliness. middle. However, the low transport efficiency between electrolyte and electrode materials limits the electrochemical performance of metal oxides during electrochemical reactions. Therefore, the research on composite materials of metal oxides and carbonaceous supports has been deepened, which is one of the ways to improve the electrochemical performance of electrode materials by utilizing the open space, high specific surface area and structural variability of electrode materials.
所以提供一种金属氧化物与碳质载体的新型复合材料及制备工艺是人们亟待解决的问题。Therefore, it is an urgent problem to provide a new type of composite material of metal oxide and carbonaceous carrier and its preparation process.
发明内容SUMMARY OF THE INVENTION
鉴于此，本发明公开提供了一种金属氧化物包覆多壁碳纳米管的复合材料及其制备方法、应用，以解决现有的金属氧化物自身导电性能差等一系列的缺点。In view of this, the present disclosure provides a metal oxide-coated multi-walled carbon nanotube composite material, a preparation method and an application thereof, so as to solve a series of shortcomings such as poor electrical conductivity of the existing metal oxide itself.
本发明提供的技术方案，具体为，第一方面，本发明提供了一种金属氧化物包覆多壁碳纳米管的复合材料，所述复合材料为珠状结构的金属氧化物包覆链状结构的多壁碳纳米管从而构成的核壳结构。The technical solutions provided by the present invention, specifically, in the first aspect, the present invention provides a composite material of metal oxide-coated multi-walled carbon nanotubes, the composite material is a metal oxide-coated chain-shaped bead-like structure The structure of multi-walled carbon nanotubes thus constitutes a core-shell structure.
优选地，所述金属氧化物为CeO2。Preferably, the metal oxide is CeO 2 .
第二方面，本发明提供了一种金属氧化物包覆多壁碳纳米管的复合材料的制备方法，包括如下步骤：In a second aspect, the present invention provides a method for preparing a composite material of metal oxide-coated multi-walled carbon nanotubes, comprising the following steps:
1)将金属铈盐、尿素及多壁碳纳米管、加入到溶剂中，制备得到前驱体；1) adding metal cerium salt, urea and multi-walled carbon nanotubes into a solvent to prepare a precursor;
2)升温加热步骤1)中所得的前驱体，将得到的产物依次进行洗涤、冷冻干燥，最终得到金属氧化物包覆多壁碳纳米管的珠链状复合材料。2) heating the precursor obtained in step 1) by heating, and washing the obtained product and freeze-drying it in sequence to finally obtain a metal oxide-coated multi-walled carbon nanotube bead-chain composite material.
优选地，所述步骤1)制备前驱体的方法为：将金属铈盐、尿素及多壁碳纳米管依次加入到溶剂中，搅拌1小时后得到均匀的混合溶液，然后将混合溶液转移至聚四氟乙烯内胆的不锈钢高压反应釜中，密封后放入鼓风干燥箱中，升温至100-150℃，反应5-15h，缓慢冷却到室温，静置至少1天后，过滤，洗涤后，干燥得到前驱体。Preferably, the method for preparing the precursor in step 1) is as follows: adding metal cerium salt, urea and multi-walled carbon nanotubes to the solvent in sequence, stirring for 1 hour to obtain a uniform mixed solution, and then transferring the mixed solution to a polymer In a stainless steel autoclave with a tetrafluoroethylene liner, sealed and placed in a blast drying oven, heated to 100-150°C, reacted for 5-15h, slowly cooled to room temperature, left standing for at least 1 day, filtered, washed, The precursor is obtained by drying.
优选地，所述步骤2)中加热前驱体的具体步骤为：将所得前驱体转移至到瓷舟中，瓷舟置于管式炉中，惰性气体保护下，升温至400-600℃，煅烧1-2h后，降至室温，得金属氧化物包覆多壁碳纳米管的珠链状复合材料。Preferably, the specific step of heating the precursor in the step 2) is: transferring the obtained precursor to a porcelain boat, placing the porcelain boat in a tube furnace, under the protection of an inert gas, heating up to 400-600 ° C, calcining After 1-2 hours, the temperature is lowered to room temperature to obtain a bead-chain composite material of metal oxide-coated multi-walled carbon nanotubes.
优选地，所述金属铈盐为六水合硝酸铈。Preferably, the metal cerium salt is cerium nitrate hexahydrate.
优选地，所述多壁碳纳米管未经任何氧化处理。Preferably, the multi-walled carbon nanotubes are not subjected to any oxidation treatment.
优选地，步骤1)中得到前驱体前的干燥为冷冻干燥。Preferably, the drying before obtaining the precursor in step 1) is freeze-drying.
最后，本发明提供了一种金属氧化物包覆多壁碳纳米管的复合材料的应用，所述复合材料应用于超级电容器电极材料中。Finally, the present invention provides the application of a metal oxide-coated multi-walled carbon nanotube composite material, which is used in supercapacitor electrode materials.
本发明提供的一种金属氧化物包覆多壁碳纳米管的复合材料的制备方法，该方法中的用料价格低廉、产物纯度高、分散性好且孔径可控制、工艺步骤简单，易于操作。所制得的由二氧化铈包覆多壁碳纳米管的珠链状复合材料，可直接作为超级电容器的电极材料，具有优异的电化学行为，可应用在高稳定性，电化学能源存储器件等场合。The invention provides a method for preparing a composite material of metal oxide-coated multi-walled carbon nanotubes. The method has the advantages of low cost of materials, high product purity, good dispersibility, controllable pore size, simple process steps and easy operation. . The prepared bead-chain composite material coated with multi-walled carbon nanotubes by ceria can be directly used as an electrode material for supercapacitors, has excellent electrochemical behavior, and can be applied in high stability, electrochemical energy storage devices and other occasions.
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本发明的公开。It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the disclosure of the present invention.
附图说明Description of drawings
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本发明的实施例，并与说明书一起用于解释本发明的原理。The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description serve to explain the principles of the invention.
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，对于本领域普通技术人员而言，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. In other words, other drawings can also be obtained based on these drawings without creative labor.
图1为本发明提供的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的XRD测试图谱；Fig. 1 is the XRD test pattern of the core-shell structure composite material formed by the bead structure metal cerium oxide coating chain structure multi-wall carbon nanotube provided by the present invention;
图2为本发明提供的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的SEM图；Fig. 2 is the SEM image of the core-shell structure composite material formed by the bead structure metal cerium oxide coated chain structure multi-wall carbon nanotube provided by the present invention;
图3为本发明提供的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料热解后的EDS能谱；Fig. 3 is the EDS energy spectrum of the core-shell structure composite material formed by the bead structure metal cerium oxide coated chain structure multi-wall carbon nanotube provided by the present invention after pyrolysis;
图4为本发明提供的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的循环伏安曲线；Fig. 4 is the cyclic voltammetry curve of the core-shell structure composite material formed by the bead structure metal cerium oxide coated chain structure multi-wall carbon nanotube provided by the present invention;
图5为本发明提供的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的恒流充放电曲线；Fig. 5 is the constant current charge-discharge curve of the core-shell structure composite material composed of the bead structure metal cerium oxide coated chain structure multi-wall carbon nanotube provided by the present invention;
图6为本发明提供的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的阻抗性能测试的尼奎斯特图。FIG. 6 is a Nyquist diagram of the impedance performance test of the core-shell structure composite material provided by the present invention, which is composed of a bead structure metal cerium oxide coated with a chain structure multi-walled carbon nanotube.
图7是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料制备流程图；7 is a flow chart of the preparation of the core-shell structure composite material composed of the pearl-shaped structure metal cerium oxide coated chain structure multi-walled carbon nanotubes of the present invention;
图8是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料反应时间延长后的形貌对比。FIG. 8 is a comparison of the morphology of the core-shell structure composite material composed of the pearl-shaped structure metal cerium oxide coated with chain structure multi-walled carbon nanotubes of the present invention after the reaction time is prolonged.
其中，a：12h；b：24h；c：36h；d：48h；Among them, a: 12h; b: 24h; c: 36h; d: 48h;
图9是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料反应增加反应温度的形貌对比。FIG. 9 is a morphological comparison of the core-shell structure composite material composed of the pearl-like structure metal cerium oxide coated with chain-like structure multi-walled carbon nanotubes in the present invention, and the reaction temperature is increased.
其中，a：100℃；b：120℃；c：140℃；d：160℃；Among them, a: 100°C; b: 120°C; c: 140°C; d: 160°C;
具体实施方式Detailed ways
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本发明相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本发明的一些方面相一致的***的例子。Exemplary embodiments will be described in detail herein, examples of which are illustrated in the accompanying drawings. When the following description refers to the drawings, the same numerals in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the illustrative examples below are not intended to represent all implementations consistent with the present invention. Rather, they are merely examples of systems consistent with some aspects of the invention as recited in the appended claims.
为解决现有技术中，金属氧化物自身导电性能差等一系列的缺点，本实施方案首先提供了一种金属氧化物包覆多壁碳纳米管的复合材料，该复合材料为珠状结构的金属氧化物包覆链状结构的多壁碳纳米管从而构成的核壳结构。In order to solve a series of shortcomings in the prior art, such as the poor electrical conductivity of metal oxide itself, this embodiment first provides a composite material of metal oxide-coated multi-walled carbon nanotubes, the composite material is a bead structure. The metal oxide coats the chain-like structure of multi-walled carbon nanotubes to form a core-shell structure.
上述金属氧化物优选为CeO2。金属氧化物CeO2具有较高的理论比电容，结合碳纳米管本身为链状结构，及碳管自身的大π键，有利于电荷的积累和电解液离子的传输，从而有利于比电容的提高。即本实施方案中的珠状结构金属氧化物包覆链状结构多壁碳纳米管结构，可有利于电子的传输。The above-mentioned metal oxide is preferably CeO 2 . The metal oxide CeO 2 has a high theoretical specific capacitance, combined with the carbon nanotube itself as a chain structure, and the large π bond of the carbon tube itself, which is conducive to the accumulation of charges and the transport of electrolyte ions, which is beneficial to the specific capacitance. improve. That is, the bead-like structure metal oxide in this embodiment coats the chain-like structure multi-walled carbon nanotube structure, which can be beneficial to the transport of electrons.
另外，本实施方案还提供了一种金属氧化物包覆多壁碳纳米管的复合材料的制备方法，即上述珠状结构金属氧化物包覆链状结构多壁碳纳米管构成的核壳结构复合材料的制备工艺流程为：依次将金属铈盐，尿素，多壁碳纳米管和无水乙醇溶液进行均匀混合，其次将混合均匀的溶液转移至聚四氟乙烯高压反应釜中进行溶剂热生长，最后煅烧制得产物。In addition, this embodiment also provides a method for preparing a composite material of metal oxide-coated multi-walled carbon nanotubes, that is, the core-shell structure composed of the above-mentioned bead-structured metal oxide-coated chain-like multi-walled carbon nanotubes The preparation process of the composite material is as follows: the metal cerium salt, urea, multi-walled carbon nanotubes and anhydrous ethanol solution are uniformly mixed in sequence, and then the uniformly mixed solution is transferred to a polytetrafluoroethylene autoclave for solvothermal growth. , and finally calcined to obtain the product.
具体包括如下步骤：Specifically include the following steps:
1)依次将金属铈盐、尿素和多壁碳纳米管、加入到溶剂中，制备得到前驱体；1) sequentially adding metal cerium salt, urea and multi-walled carbon nanotubes into a solvent to prepare a precursor;
2)升温加热步骤1)中所得的前驱体，将得到的产物依次进行洗涤、冷冻干燥，最终得到金属氧化物包覆多壁碳纳米管的珠链状复合材料。2) heating the precursor obtained in step 1) by heating, and washing the obtained product and freeze-drying it in sequence to finally obtain a metal oxide-coated multi-walled carbon nanotube bead-chain composite material.
本实施方案选用金属铈盐、尿素、多壁碳纳米管为原料，采用溶剂热法制备核壳结构复合材料。上述方法操作极为容易，原材料价格低廉，设备简单，制备过程无污染。In this embodiment, metal cerium salts, urea, and multi-wall carbon nanotubes are selected as raw materials, and a core-shell structure composite material is prepared by a solvothermal method. The above method is extremely easy to operate, the raw materials are cheap, the equipment is simple, and the preparation process is pollution-free.
溶剂优选为无水乙醇；The solvent is preferably absolute ethanol;
进一步地，步骤1)制备前驱体的方法为：将金属铈盐、尿素和多壁碳纳米管依次加入到无水乙醇中，搅拌1小时后得到均匀的混合溶液，然后将混合溶液转移至聚四氟乙烯内胆的不锈钢高压反应釜中，密封后放入鼓风干燥箱中，升温至100-160℃，反应5-15h，优选地，升温至120℃，反应12h；缓慢冷却到室温，静置至少1天后，过滤，洗涤后，干燥得到前驱体。优选的干燥方式为：将产物转移至冷冻干燥机中，干燥时长2d。Further, the method for preparing the precursor in step 1) is as follows: adding metal cerium salt, urea and multi-walled carbon nanotubes into absolute ethanol in sequence, stirring for 1 hour to obtain a uniform mixed solution, and then transferring the mixed solution to a polymer solution. In a stainless steel autoclave with a tetrafluoroethylene liner, sealed and placed in a blast drying oven, the temperature was raised to 100-160°C for 5-15h, preferably, the temperature was raised to 120°C and the reaction was performed for 12h; slowly cooled to room temperature, After standing for at least 1 day, the precursor is obtained by filtering, washing, and drying. The preferred drying method is: transfer the product to a freeze dryer, and the drying time is 2d.
优选地，上述金属铈盐为六水合硝酸铈，终浓度为0.011mol/L；尿素加入到无水乙醇溶液中后，浓度为0.03mol/L。多壁碳纳米管加入到无水乙醇溶液中后，浓度为0.014mol/L。Preferably, the above-mentioned metal cerium salt is cerium nitrate hexahydrate, and the final concentration is 0.011 mol/L; after the urea is added to the absolute ethanol solution, the concentration is 0.03 mol/L. After the multi-walled carbon nanotubes were added into anhydrous ethanol solution, the concentration was 0.014mol/L.
优选地，上述多壁碳纳米管未经任何氧化处理；Preferably, the above-mentioned multi-walled carbon nanotubes are not subjected to any oxidation treatment;
步骤2)中加热前驱体的具体步骤为：将所得前驱体转移至到瓷舟中，瓷舟置于管式炉中，惰性气体保护下，升温至400-600℃，煅烧1-2h后，降至室温，得金属氧化物包覆多壁碳纳米管的珠链状复合材料。The specific steps of heating the precursor in step 2) are as follows: transferring the obtained precursor to a porcelain boat, placing the porcelain boat in a tube furnace, under the protection of an inert gas, heating up to 400-600 ° C, and calcining for 1-2 h, The temperature is lowered to room temperature to obtain a bead-chain composite material of metal oxide-coated multi-walled carbon nanotubes.
优选的，上述管式炉的温度为500℃，煅烧2h。惰性保护气体为氩气。管式炉的升温速度为5℃ min-1，降温速率为5℃ min-1。Preferably, the temperature of the above-mentioned tubular furnace is 500° C., and the calcination is performed for 2 hours. The inert protective gas is argon. The heating rate of the tube furnace was 5°C min -1 , and the cooling rate was 5°C min -1 .
本实施方案采用溶剂热法制备的珠状结构金属氧化物包覆链状结构多壁碳纳米管构成的核壳结构复合材料，工艺步骤简单，价格低廉，易于操作，制得的复合电极材料具有高的比表面积，多级孔结构，并且其具有优异的电容性能，可应用在高稳定性，高功率密度电源的场合。In this embodiment, the core-shell structure composite material composed of multi-walled carbon nanotubes with bead-like structure coated with chain-like structure metal oxides prepared by solvothermal method is adopted. The process steps are simple, the price is low, and the operation is easy. The obtained composite electrode material has High specific surface area, multi-level porous structure, and excellent capacitance performance, can be used in high stability, high power density power supply occasions.
上述的珠状结构金属氧化物包覆链状结构多壁碳纳米管构成的核壳结构复合材料作为电极材料在超级电容器中的应用。The application of the core-shell structure composite material composed of the above-mentioned bead structure metal oxide coating chain structure multi-wall carbon nanotubes as an electrode material in a super capacitor.
下面结合具体的实施例对本发明进行更近一步的解释说明，但是并不用于限制本发明的保护范围。The present invention will be further explained below in conjunction with specific embodiments, but it is not intended to limit the protection scope of the present invention.
实施例1Example 1
珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料Core-shell structure composite composed of bead-like structure metal cerium oxide coated chain-like structure multi-walled carbon nanotubes
(1)珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的制备：(1) Preparation of core-shell structure composite material composed of bead structure metal cerium oxide coated chain structure multi-wall carbon nanotubes:
将0.3mmol的六水合硝酸铈，1mmol尿素加入到30mL的无水乙醇溶液中，搅拌混合均匀得混合溶液，再将多壁碳纳米管添加到混合溶液中，然后将最后的均匀的混合溶液共同转移至体积为50mL的聚四氟乙烯高压反应釜中。将反应釜密封好放入鼓风干燥箱中，加热使鼓风干燥箱的温度从室温达到120℃，升温速率为2℃ min-1，并保持温度在此条件下保温12小时。缓慢冷却到室温，静置至少1天，得到沉淀；过滤，依次用水和乙醇洗涤各三次，并在冷冻干燥机中干燥2d，所得产物转移至管式炉中，在氩气气氛中升温至500℃，升温速率为5℃ min-1，煅烧2h，降至室温，得珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料。Add 0.3 mmol of cerium nitrate hexahydrate and 1 mmol of urea to 30 mL of anhydrous ethanol solution, stir and mix evenly to obtain a mixed solution, then add multi-walled carbon nanotubes into the mixed solution, and then combine the final uniform mixed solution together. Transfer to a Teflon autoclave with a volume of 50 mL. The reaction kettle was sealed and placed in a blast drying oven, heated to make the temperature of the blast drying oven reach 120°C from room temperature, and the heating rate was 2°C min -1 , and the temperature was maintained under this condition for 12 hours. Slowly cooled to room temperature, let stand for at least 1 day to obtain a precipitate; filtered, washed with water and ethanol three times in turn, and dried in a freeze dryer for 2d, the obtained product was transferred to a tube furnace, and heated to 500 in an argon atmosphere ℃, the heating rate was 5 ℃ min -1 , calcined for 2 h, and then lowered to room temperature to obtain a core-shell composite material composed of bead-like structure metal ceria coated with chain-like structure multi-walled carbon nanotubes.
(二)检测(2) Detection
1)性能指标如表11) The performance indicators are shown in Table 1
表1Table 1
由表1可见，纳米颗粒构成的珠状CeO2与MWCNTs复合，构成核壳结构的CeO2@MWCNTs，经退火处理，比表面积增加，孔体积增大，说明复合之后，其比表面积显著增加。It can be seen from Table 1 that the beaded CeO 2 composed of nanoparticles is composited with MWCNTs, and the CeO 2 @MWCNTs composed of core-shell structure, after annealing treatment, the specific surface area and pore volume increase, indicating that the specific surface area increases significantly after composite.
2)图1为本实施方案制备的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的XRD图。由图1可见，本发明中的珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料被成功制备。2) FIG. 1 is an XRD pattern of the core-shell structure composite material composed of the bead structure metal cerium oxide coated chain structure multi-walled carbon nanotubes prepared in the present embodiment. It can be seen from FIG. 1 that the core-shell structure composite material composed of the bead-structured metal ceria coated with chain-like structure multi-walled carbon nanotubes in the present invention has been successfully prepared.
3)图2为珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的扫描电子显微镜照片(SEM)。由图2可见，本发明制备的金属氧化铈包覆多壁碳纳米管构成的核壳结构复合材料呈现珠链状结构。由图2a可见，得到的金属氧化铈呈现出珠状结构，单个珠状结构CeO2的直径30-60nm，多壁碳纳米管的直径约为15-20nm。由图2b可见，CeO2@MWCNTs成核壳结构，珠状结构CeO2均匀生长在多壁碳纳米管表面，经高温煅烧后CeO2@MWCNTs保持了完好的核壳结构。3) FIG. 2 is a scanning electron microscope photograph (SEM) of a core-shell structure composite material composed of a bead structure metal cerium oxide coated with a chain structure multi-walled carbon nanotube. It can be seen from FIG. 2 that the core-shell structure composite material composed of metal cerium oxide-coated multi-walled carbon nanotubes prepared by the present invention exhibits a bead-chain structure. It can be seen from Figure 2a that the obtained metal cerium oxide exhibits a bead-like structure, the diameter of a single bead - like structure CeO2 is 30-60 nm, and the diameter of multi-walled carbon nanotubes is about 15-20 nm. It can be seen from Figure 2b that CeO 2 @MWCNTs forms a core-shell structure, and the bead-like CeO 2 grows uniformly on the surface of multi-walled carbon nanotubes. After high temperature calcination, CeO 2 @MWCNTs maintains an intact core-shell structure.
4)图3是本发明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料煅烧后的EDS能谱。由图3分析可得，本发明所得珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料由C、O、Ce三种元素组成。4) FIG. 3 is the EDS energy spectrum of the core-shell structure composite material composed of the bead structure metal ceria coated with chain structure multi-wall carbon nanotubes of the present invention after calcination. It can be seen from the analysis in FIG. 3 that the core-shell structure composite material obtained by the present invention, which is composed of bead-structured metal cerium oxide coated with chain-like structure multi-walled carbon nanotubes, is composed of three elements: C, O, and Ce.
5)图4是本发明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的循环伏安曲线。由图4分析可得，本发明所得珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料在不同扫速下，呈现出镜像电流响应，并具有氧化还原峰，说明其既具有双电层电容特征，又具有赝电容特征。且在不同扫速下，表现出良好的循环性能。5) FIG. 4 is the cyclic voltammetry curve of the core-shell structure composite material composed of the bead structure metal cerium oxide coated chain structure multi-wall carbon nanotubes of the present invention. It can be seen from the analysis of FIG. 4 that the core-shell structure composite material obtained by the present invention, which is composed of bead structure metal cerium oxide coated chain structure multi-wall carbon nanotubes, exhibits mirror current response and has redox peaks at different scan speeds. , indicating that it has both electric double-layer capacitance characteristics and pseudo-capacitance characteristics. And at different scan speeds, it showed good cycle performance.
6)图5是本发明一种明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的恒流充放电曲线。由图5分析可得，本发明所得复合电极材料在1A g-1电流密度下，放电时间长，说明其具有优异的电荷储存特性。6) FIG. 5 is a constant current charge-discharge curve of a core-shell structure composite material composed of a pearl-shaped structure metal cerium oxide coated with a chain-shaped structure multi-walled carbon nanotube according to the present invention. It can be seen from the analysis in FIG. 5 that the composite electrode material obtained in the present invention has a long discharge time at a current density of 1 A g -1 , indicating that it has excellent charge storage characteristics.
7)图6是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料的阻抗能测试。由图6可知，明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料后等效串联内阻比未复合的氧化铈颗粒小很多，说明多壁碳纳米管的加入有效地提高了复合电极材料的导电性能。7) FIG. 6 is the impedance energy test of the core-shell structure composite material composed of the pearl-shaped structure metal cerium oxide coated chain structure multi-walled carbon nanotubes of the present invention. It can be seen from Figure 6 that the equivalent series internal resistance of the core-shell structure composite material composed of the pearl-like structure metal cerium oxide coated with the chain-like structure multi-wall carbon nanotubes is much smaller than that of the uncomplexed cerium oxide particles, indicating that the multi-wall carbon nanotubes The addition of ions effectively improves the electrical conductivity of the composite electrode material.
8)图7是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料制备流程图。8) FIG. 7 is a flow chart of the preparation of the core-shell structure composite material composed of the pearl-like structure metal cerium oxide covered with chain-like structure multi-walled carbon nanotubes of the present invention.
9)图8是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料反应时间延长后的形貌对比。由图8可知，在延长溶剂热的反应时间后明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料形貌逐渐改变，由珠链状转变为全包覆核壳结构，且粒径增大。9) FIG. 8 is a comparison of the morphology of the core-shell structure composite material composed of the pearl-like structure metal cerium oxide coated with chain-like structure multi-walled carbon nanotubes of the present invention after the reaction time is prolonged. It can be seen from Figure 8 that after prolonging the solvothermal reaction time, the morphology of the core-shell structure composite composed of bead-like structure metal ceria coated with chain-like structure multi-walled carbon nanotubes gradually changed, from bead-chain-like to fully coated core-shell structure and increased particle size.
10)图9是本发明明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料反应增加反应温度的形貌对比。由图9可知，随着溶剂热的反应温度的增加，明珠状结构金属氧化铈包覆链状结构多壁碳纳米管构成的核壳结构复合材料中明珠的直径逐渐增加。10) FIG. 9 is a morphological comparison of the core-shell structure composite material composed of the pearl-like structure metal cerium oxide coated with chain-like structure multi-walled carbon nanotubes in the present invention, and the reaction temperature is increased. It can be seen from Figure 9 that with the increase of the solvothermal reaction temperature, the diameter of the pearl in the core-shell composite material composed of the pearl-like structure metal cerium oxide coated chain-like structure multi-walled carbon nanotubes gradually increases.
本领域技术人员在考虑说明书及实践这里公开的发明后，将容易想到本发明的其它实施方案。本申请旨在涵盖本发明的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本发明的真正范围和精神由权利要求指出。Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses or adaptations of the invention which follow the general principles of the invention and which include common knowledge or conventional techniques in the art not disclosed by the invention . The specification and examples are to be regarded as exemplary only, with the true scope and spirit of the invention being indicated by the claims.
应当理解的是，本发明并不局限于上面已经描述并在附图中示出的精确结构，并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。It should be understood that the present invention is not limited to the precise structures described above and illustrated in the accompanying drawings, and that various modifications and changes may be made without departing from its scope. The scope of the present invention is limited only by the appended claims.
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