CN102779986A - Preparation method of nanocomposite material with core shell structure - Google Patents

Abstract

The invention discloses a preparation method of a nanocomposite material with a core shell structure. According to the preparation method, alcoholic solution of copper-containing precursors is atomized and is then introduced into a burning reactor for carrying out hydrolysis reaction, and meanwhile, acetylene gas diluted by nitrogen gas is introduced into the burning reactor. In the flame, nano-copper particles are firstly generated, then, acetylene is resolved on the surfaces of the nano-copper particles to generate nanometer carbon tubes, and finally, the nanometer copper/nanometer carbon tube composite material with the core shell structure is obtained. The method has the advantages that the equipment and process are simple, the continuous production can be realized, the industrial implementation is easy, and the preparation method can be applied to fields of lithium ion batteries, conducting materials, field emission reinforcing material and the like.

Description

Translated fromChinese

一种具有核壳结构的纳米复合材料的制备方法A kind of preparation method of nanocomposite material with core-shell structure

技术领域technical field

本发明涉及一种具有核壳结构的纳米复合材料的制备方法，具体地，涉及铜/纳米碳管复合材料的制备方法，其可应用于锂离子电池、导电材料、场发射增强材料等领域。The invention relates to a method for preparing a nanocomposite material with a core-shell structure, in particular to a method for preparing a copper/carbon nanotube composite material, which can be applied to the fields of lithium ion batteries, conductive materials, field emission enhancement materials and the like.

背景技术Background technique

纳米铜颗粒因为其独特的物理和化学性质，被广泛的应用在催化、光学、电子学等领域。但是，由于为纳米尺寸，在空气不可避免地被氧化，从很大程度上限制了其进一步的发展。为了降低甚至阻止铜纳米颗粒在空气中的氧化，一条可行的途径是对其进行表面修饰，如进行碳或者二氧化硅的包覆，而碳包覆又是最佳之选。目前，制备碳包覆纳米铜颗粒的方法主要有液相化学法、电弧放电法、喷雾热解法、化学气相化学沉积法等。上述方法在一定程度上受到许多条件例如需要对产品的多步处理、高设备要求和高能耗，特别是间歇的操作方式严重制约了其工业化生产。喷雾燃烧法，具有简单快速而且产品纯度高等优点，同时反应本身由溶剂的燃烧为反应提供能量，有效地降低了能耗，是最具工业化前景的纳米材料制备方法之一。Copper nanoparticles are widely used in catalysis, optics, electronics and other fields because of their unique physical and chemical properties. However, due to the nanometer size, it is inevitably oxidized in the air, which greatly limits its further development. In order to reduce or even prevent the oxidation of copper nanoparticles in air, a feasible way is to modify their surface, such as coating with carbon or silicon dioxide, and carbon coating is the best choice. At present, the methods for preparing carbon-coated copper nanoparticles mainly include liquid phase chemical method, arc discharge method, spray pyrolysis method, chemical vapor phase chemical deposition method, etc. The above method is to a certain extent subject to many conditions such as the need for multi-step processing of the product, high equipment requirements and high energy consumption, especially the intermittent operation mode severely restricts its industrial production. The spray combustion method has the advantages of simplicity, speed and high product purity. At the same time, the reaction itself is powered by the combustion of the solvent, which effectively reduces energy consumption. It is one of the most industrialized nanomaterial preparation methods.

发明内容Contents of the invention

本发明的目的在于提供一种工艺简单、易于工业化实施的具有核壳结构的纳米铜/纳米碳管复合材料的制备方法The purpose of the present invention is to provide a method for preparing nano-copper/carbon nanotube composite materials with a core-shell structure that is simple in process and easy to implement industrially

本发明专利的构思如下：The design of the patent of the present invention is as follows:

本发明采用喷雾燃烧反应器，将含铜前驱体的醇溶液雾化后通入燃烧反应器进行水解反应，同时在反应器内通入氮气稀释的乙炔气体。纳米铜颗粒在火焰中首先生成，然后乙炔在纳米铜颗粒的表面分解生成纳米碳管，最终得到一种具有核壳结构的纳米铜/纳米碳管复合材料。该方法设备工艺简单，可连续化生产，易于工业化实施。The invention adopts a spray combustion reactor, atomizes the alcohol solution containing the copper precursor and passes it into the combustion reactor for hydrolysis reaction, and at the same time passes the acetylene gas diluted with nitrogen into the reactor. Nano-copper particles are first generated in the flame, and then acetylene decomposes on the surface of nano-copper particles to form carbon nanotubes, and finally a nano-copper/carbon nanotube composite material with a core-shell structure is obtained. The method has simple equipment and process, can be produced continuously, and is easy to implement industrially.

具体技术方案如下：The specific technical scheme is as follows:

一种具有核壳结构的纳米复合材料的制备方法，包括如下步骤：A method for preparing a nanocomposite with a core-shell structure, comprising the steps of:

将含铜前驱体和溶剂配制成溶液，所述溶液雾化后通入燃烧反应器进行水解反应，同时在所述燃烧反应器内通入氮气稀释的乙炔气体；在所述燃烧反应器的火焰中首先生成纳米铜颗粒，所述乙炔气体在所述纳米铜颗粒的表面分解生成纳米碳管，最终得到一种具有核壳结构的纳米铜/纳米碳管复合材料；The copper-containing precursor and the solvent are prepared into a solution, and the solution is atomized and passed into a combustion reactor for hydrolysis reaction, and at the same time, acetylene gas diluted with nitrogen is passed into the combustion reactor; the flame in the combustion reactor First generate nano-copper particles, the acetylene gas decomposes on the surface of the nano-copper particles to generate carbon nanotubes, and finally obtains a nano-copper/carbon nanotube composite material with a core-shell structure;

其中，in,

所述含铜前驱体溶液的摩尔浓度在0.1～0.5 mol/L，进料量为3～10 ml/min；The molar concentration of the copper-containing precursor solution is 0.1-0.5 mol/L, and the feed rate is 3-10 ml/min;

所述燃烧反应器中空气的进料量为1.0～3.0 m³/h；The feed rate of air in the combustion reactor is 1.0-3.0 m³ /h;

所述乙炔气体的流量为0.02～0.1 m³/h，所述氮气的流量为0.3～1.0 m³/h；The flow rate of the acetylene gas is 0.02-0.1 m³ /h, and the flow rate of the nitrogen gas is 0.3-1.0 m³ /h;

所述水解反应的反应温度为1200～1800℃。The reaction temperature of the hydrolysis reaction is 1200-1800°C.

所述含铜前驱体是铜的无机盐类化合物，所述溶剂为可燃性液态醇类。The copper-containing precursor is an inorganic salt compound of copper, and the solvent is a flammable liquid alcohol.

所述含铜前驱体氯化铜、硝酸铜或硫酸铜，所述溶剂为甲醇或乙醇。The copper-containing precursor is copper chloride, copper nitrate or copper sulfate, and the solvent is methanol or ethanol.

所述核壳结构的纳米铜/纳米碳管复合材料中纳米铜颗粒的粒径为20～50nm，纳米碳管的长度为200～500nm。纳米碳管包覆在纳米铜颗粒的表面。The particle size of the nano-copper particle in the nano-copper/carbon nanotube composite material with core-shell structure is 20-50 nm, and the length of the carbon nano-tube is 200-500 nm. Carbon nanotubes are coated on the surface of copper nanoparticles.

本发明的具有核壳结构的纳米铜/纳米碳管复合材料的制备方法工艺简单，容易操作，无需后处理，且材料结构稳定，可应用在锂离子电池、导电材料、场发射增强材料等领域。The preparation method of the nano-copper/carbon nanotube composite material with a core-shell structure of the present invention is simple in process, easy to operate, does not require post-processing, and has a stable material structure, and can be applied in the fields of lithium-ion batteries, conductive materials, field emission enhancement materials, etc. .

附图说明Description of drawings

图1是实施例1产物的透射电镜照片；Fig. 1 is the transmission electron micrograph of embodiment 1 product;

图2是实施例2产物的透射电镜照片；Fig. 2 is the transmission electron micrograph ofembodiment 2 product;

图3是实施例1产物的XRD谱图。Fig. 3 is the XRD spectrogram of the product of embodiment 1.

具体实施方式Detailed ways

下面通过实施举例对本发明进行具体描述。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据本发明的内容作出的一些非本质的改进和调整，仍属于本发明的保护范围。The present invention will be specifically described below by implementing examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention, and cannot be interpreted as limiting the protection scope of the present invention, some non-essential improvements and adjustments made by those skilled in the art according to the contents of the present invention , still belong to the protection scope of the present invention.

各反应参数如下：The reaction parameters are as follows:

含铜前驱体溶液的摩尔浓度在0.1～0.5mol/L，进料量为3～10 ml/min；The molar concentration of the copper-containing precursor solution is 0.1-0.5mol/L, and the feed rate is 3-10 ml/min;

燃烧反应器中空气的进料量为1.0～3.0 m³/h；The feed rate of air in the combustion reactor is 1.0-3.0 m³ /h;

乙炔气体的流量为0.02～0.1 m³/h，氮气的流量为0.3～1.0 m³/h；The flow rate of acetylene gas is 0.02-0.1 m³ /h, and the flow rate of nitrogen gas is 0.3-1.0 m³ /h;

反应温度为1200～1800℃。The reaction temperature is 1200-1800°C.

实施例 1Example 1

利用喷雾燃烧反应器，将氯化铜和乙醇配制成溶液，雾化后通入燃烧反应器进行燃烧反应，其中，氯化铜的摩尔浓度为0.5mol/L，进料速率为3ml/min，燃烧用空气的进料量为3.0 m³/h，反应温度为1200℃。同时在反应器内通入氮气稀释的乙炔气体，用以稀释乙炔的氮气流量为1 m³/h，乙炔0.02 m³/h。纳米铜颗粒在火焰中先生成，乙炔在纳米铜的表面分解生成纳米碳管，最终得到一种具有核壳结构的纳米铜/纳米碳管复合材料，产物的电镜照片如图1所示、XRD照片如图3所示，其中，作为核的纳米铜颗粒粒径为50nm，包覆纳米铜颗粒的碳管长度为200nm。Utilize spray combustion reactor, cupric chloride and ethanol are mixed into solution, pass into combustion reactor after the atomization and carry out combustion reaction, wherein, the molar concentration of cupric chloride is 0.5mol/L, and feed rate is 3ml/min, The feed rate of combustion air is 3.0 m³ /h, and the reaction temperature is 1200°C. At the same time, nitrogen-diluted acetylene gas was fed into the reactor, the flow rate of nitrogen gas for diluting acetylene was 1 m³ /h, and the flow rate of acetylene was 0.02 m³ /h. Nano-copper particles are first formed in the flame, and acetylene decomposes on the surface of nano-copper to form carbon nanotubes, and finally a nano-copper/carbon nanotube composite material with a core-shell structure is obtained. The electron microscope photo of the product is shown in Figure 1, XRD The photo is shown in Figure 3, wherein the diameter of the nano-copper particle as the core is 50nm, and the length of the carbon tube covering the nano-copper particle is 200nm.

实施例 2Example 2

利用喷雾燃烧反应器，将硝酸铜和甲醇配制成溶液，雾化后通入燃烧反应器进行燃烧反应，其中，硝酸铜的摩尔浓度为0.1mol/L，进料速率为10 ml/min，燃烧用空气的进料量为1.0 m³/h，反应温度为1800℃。同时在反应器内通入氮气稀释的乙炔气体，用以稀释乙炔的氮气流量为0.3m³/h，乙炔0.1 m³/h。纳米铜颗粒在火焰中先生成，乙炔在纳米铜的表面分解生成纳米碳管，最终得到一种具有核壳结构的纳米铜/纳米碳管复合材料，产物的电镜照片如图2所示。其中，纳米铜颗粒粒径为20nm，碳管长度为500nm。Using a spray combustion reactor, copper nitrate and methanol are prepared into a solution, which is atomized and passed into the combustion reactor for combustion reaction. The molar concentration of copper nitrate is 0.1mol/L, and the feed rate is 10 ml/min. The feed rate of air is 1.0 m³ /h, and the reaction temperature is 1800°C. At the same time, nitrogen-diluted acetylene gas was introduced into the reactor, the flow rate of nitrogen gas for diluting acetylene was 0.3 m³ /h, and the flow rate of acetylene was 0.1 m³ /h. Nano-copper particles are first formed in the flame, and acetylene decomposes on the surface of nano-copper to form carbon nanotubes, and finally a nano-copper/carbon nanotube composite material with a core-shell structure is obtained. The electron microscope photo of the product is shown in Figure 2. Wherein, the diameter of the nano-copper particle is 20nm, and the length of the carbon tube is 500nm.

实施例 3Example 3

利用喷雾燃烧反应器，将硫酸铜和乙醇配制成溶液，雾化后通入燃烧反应器进行燃烧反应，其中，硫酸铜的摩尔浓度为0.3mol/L，进料速率为7 ml/min，燃烧用空气的进料量为2.0m³/h，反应温度为1500℃。同时在反应器内通入氮气稀释的乙炔气体，用以稀释乙炔的氮气流量为0.5m³/h，乙炔0.05 m³/h。纳米铜颗粒在火焰中先生成，乙炔在纳米铜的表面分解生成纳米碳管，最终得到一种具有核壳结构的纳米铜/纳米碳管复合材料，其中，纳米铜颗粒粒径为30nm，碳管长度为400nm。Using a spray combustion reactor, copper sulfate and ethanol are prepared into a solution, which is atomized and passed into the combustion reactor for combustion reaction, wherein the molar concentration of copper sulfate is 0.3 mol/L, and the feed rate is 7 ml/min. The feed rate of air is 2.0 m³ /h, and the reaction temperature is 1500°C. At the same time, nitrogen-diluted acetylene gas is introduced into the reactor, the flow rate of nitrogen gas for diluting acetylene is 0.5 m³ /h, and the flow rate of acetylene is 0.05 m³ /h. Nano-copper particles are first generated in the flame, and acetylene decomposes on the surface of nano-copper to form carbon nanotubes, and finally a nano-copper/carbon nanotube composite material with a core-shell structure is obtained, wherein the nano-copper particles have a particle size of 30nm and carbon nanotubes. The tube length is 400 nm.

Claims (4)

Translated fromChinese

1.一种具有核壳结构的纳米复合材料的制备方法，其特征在于，包括如下步骤：1. a preparation method with a nanocomposite material of core-shell structure, is characterized in that, comprises the steps:将含铜前驱体和溶剂配制成溶液，所述溶液雾化后通入燃烧反应器进行水解反应，同时在所述燃烧反应器内通入氮气稀释的乙炔气体；在所述燃烧反应器的火焰中首先生成纳米铜颗粒，所述乙炔气体在所述纳米铜颗粒的表面分解生成纳米碳管，最终得到一种具有核壳结构的纳米铜/纳米碳管复合材料；The copper-containing precursor and the solvent are prepared into a solution, and the solution is atomized and passed into a combustion reactor for hydrolysis reaction, and at the same time, acetylene gas diluted with nitrogen is passed into the combustion reactor; the flame in the combustion reactor First generate nano-copper particles, the acetylene gas decomposes on the surface of the nano-copper particles to generate carbon nanotubes, and finally obtains a nano-copper/carbon nanotube composite material with a core-shell structure;其中，in,所述含铜前驱体溶液的摩尔浓度在0.1～0.5 mol/L，进料量为3～10 ml/min；The molar concentration of the copper-containing precursor solution is 0.1-0.5 mol/L, and the feed rate is 3-10 ml/min;所述燃烧反应器中空气的进料量为1.0～3.0 m³/h；The feed rate of air in the combustion reactor is 1.0-3.0 m³ /h;所述乙炔气体的流量为0.02～0.1 m³/h，所述氮气的流量为0.3～1.0 m³/h；The flow rate of the acetylene gas is 0.02-0.1 m³ /h, and the flow rate of the nitrogen gas is 0.3-1.0 m³ /h;所述水解反应的反应温度为1200～1800℃。The reaction temperature of the hydrolysis reaction is 1200-1800°C.2.根据权利要求1所述的制备方法，其特征在于，所述含铜前驱体是铜的无机盐类化合物，所述溶剂为可燃性液态醇类。2. The preparation method according to claim 1, wherein the copper-containing precursor is an inorganic salt compound of copper, and the solvent is a flammable liquid alcohol.3.根据权利要求2所述的制备方法，其特征在于，所述含铜前驱体为氯化铜、硝酸铜或硫酸铜，所述溶剂为甲醇或乙醇。3. The preparation method according to claim 2, wherein the copper-containing precursor is copper chloride, copper nitrate or copper sulfate, and the solvent is methanol or ethanol.4.根据权利要求1所述的制备方法，其特征在于，所述核壳结构的纳米铜/纳米碳管复合材料中纳米铜颗粒的粒径为20～50nm，纳米碳管的长度为200～500nm。4. The preparation method according to claim 1, characterized in that, the particle diameter of the nano-copper particles in the nano-copper/carbon nanotube composite material of the core-shell structure is 20-50 nm, and the length of the carbon nano-tubes is 200-50 nm. 500nm.

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