阅读说明：本技术 一种燃料电池负极催化剂纳米粒子复合材料的制备方法 (Preparation method of fuel cell cathode catalyst nano particle composite material ) 是由 崔大祥 李梦飞 刘鹏飞 周霖 李天昊 葛美英 张芳 于 2020-12-01 设计创作，主要内容包括：本发明公开一种燃料电池负极催化剂纳米粒子复合材料的制备方法,该方法在水热条件下,利用碳纳米管作为前驱体,在合成过程中NiFe_2O_4纳米粒子直接成核,均匀地生长和锚定在碳纳米管上,同时在碳纳米管框架结构中掺入氮元素,实现了NiFe_2O_4纳米粒子在氮掺杂碳纳米管(CNT)上的均匀负载,制得了NiFe_2O_4/CNT纳米复合材料。本发明的优点在于水热法制备方法简单,反应温度低,无需后续处理条件且该复合材料对氧气还原反应具有优良的催化活性和稳定性,该发明制备的NiFe_2O_4/CNT纳米复合材料不仅可用于燃料电池阴极催化剂,同时还可应用于传感器和超级电容器等领域。(The invention discloses a preparation method of a fuel cell cathode catalyst nano particle composite material, which utilizes a carbon nano tube as a precursor under the hydrothermal condition and NiFe in the synthesis process 2 O 4 Nano particles are directly nucleated, uniformly grow and are anchored on the carbon nano tube, and simultaneously nitrogen is doped into the carbon nano tube framework structure, so that NiFe is realized 2 O 4 The uniform load of the nano particles on the nitrogen-doped Carbon Nano Tube (CNT) is adopted to prepare the NiFe 2 O 4 A/CNT nanocomposite material. The invention has the advantages that the hydrothermal method has simple preparation method, low reaction temperature and no need of subsequent treatment conditions, and the composite material has the function of oxygen reduction reactionExcellent catalytic activity and stability, NiFe prepared by said invention 2 O 4 the/CNT nano composite material can be used for a fuel cell cathode catalyst, and can also be applied to the fields of sensors, supercapacitors and the like.)

1. A process for preparing the nm-particle composite material of negative electrode catalyst of fuel cell features that under hydrothermal condition, the carbon nanotubes are used as the precursor of NiFe₂O₄Nano particles are directly nucleated, uniformly grow and are anchored on the carbon nano tube, and simultaneously nitrogen is doped into the carbon nano tube framework structure, so that NiFe is realized₂O₄The NiFe is prepared by uniformly loading the nano particles on the nitrogen-doped Carbon Nano Tube (CNT)₂O₄the/CNT nanocomposite material comprises the following steps:

(1) respectively weighing 0.1-0.5 g of iron salt and nickel salt, and placing the iron salt and the nickel salt in a beaker so that the molar ratio of the iron salt to the nickel salt is 2: 1; then weighing 0.02 g-0.1 g of graphene carbon nanotubes and placing the graphene carbon nanotubes in another beaker;

(2) adding 20mL of ethanol into the two beakers, firstly carrying out ultrasonic treatment on the beaker solution filled with the graphene carbon nanotubes for 1 hour, then mixing the two beaker solutions, carrying out magnetic stirring at the speed of 600 r/min for 2 hours, and dropwise adding 0.5 mL of 28% ammonia water solution while stirring;

(3) stirring the solution in a water bath at 80 ℃ for 10 hours, and drying the solution at 80 ℃ for 5 hours to obtain a reactant;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3-5 h at 160-180 ℃, and cooling to room temperature to obtain a product;

(5) centrifugally cleaning the product obtained in the step (4) by using deionized water at the speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the NiFe₂O₄A/CNT nanocomposite material.

2. The method for preparing the fuel cell anode catalyst nanoparticle composite material according to claim 1, wherein the method comprises the following steps: the ferric salt and the nickel salt in the step (1) are at least one of ferric chloride, ferric nitrate and ferric sulfate; the nickel salt is at least one of nickel chloride, nickel nitrate and nickel sulfate.

Technical Field

The invention relates to a preparation method of a fuel cell cathode catalyst nano particle composite material, in particular to a preparation method of a carbon-based transition metal doped non-metal nano particle composite material under a spinel structure.

Background

The fuel cell technology is considered as a clean new energy technology which can occupy an important position in the future due to the advantages of high energy conversion efficiency, zero emission or low emission, abundant fuel sources and the like, and is one of important technical means for solving the problems of energy shortage and environmental pollution in the future. The biggest obstacle hindering the large-scale commercial application of fuel cells is the cost problem caused by using Pt as a catalyst, so research and development of a non-platinum cathode catalyst with wide raw material source, low cost and high ORR catalytic activity to replace an expensive Pt catalyst is the most key technology for reducing the cost of fuel cells and promoting the large-scale commercial application of fuel cells.

Carbon nanotubes are an ideal electrocatalyst support material due to their small size, large surface area, low density, high electrical conductivity and high thermal conductivity. The carbon nano tube is used as a carbon carrier, and the design and preparation of an economic, efficient and stable oxygen reduction catalyst is used as a main research target, so that a novel carbon-based electrocatalyst synthesis method is developed. Due to N_iFe₂O₄Strong coupling and synergistic effect are generated between the nano particles and the graphene carbon nano tubes, N_iFe₂O₄the/CNT nanocomposite shows excellent catalytic activity and stability to ORR.

Disclosure of Invention

The invention aims to provide a preparation method of a fuel cell cathode catalyst nano particle composite material.

The purpose of the invention is realized by the following scheme: fuel cell cathode catalyst nano particleThe preparation method of the composite material utilizes the carbon nano tube as a precursor under the hydrothermal condition, and NiFe is generated in the synthesis process₂O₄Nano particles are directly nucleated, uniformly grow and are anchored on the carbon nano tube, and simultaneously nitrogen is doped into the carbon nano tube framework structure, so that NiFe is realized₂O₄The NiFe is prepared by uniformly loading the nano particles on the nitrogen-doped Carbon Nano Tube (CNT)₂O₄the/CNT nanocomposite material comprises the following steps:

(1) respectively weighing 0.1-0.5 g of iron salt and nickel salt, and placing the iron salt and the nickel salt in a beaker so that the molar ratio of the iron salt to the nickel salt is 2: 1; then weighing 0.02 g-0.1 g of graphene carbon nanotubes and placing the graphene carbon nanotubes in another beaker;

(2) adding 20mL of ethanol into the two beakers, firstly carrying out ultrasonic treatment on the beaker solution filled with the graphene carbon nanotubes for 1 hour, then mixing the two beaker solutions, carrying out magnetic stirring at the speed of 600 r/min for 2 hours, and dropwise adding 0.5 mL of 28% ammonia water solution while stirring;

(3) stirring the solution in a water bath at 80 ℃ for 10 hours, and drying the solution at 80 ℃ for 5 hours to obtain a reactant;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3-5 h at 160-180 ℃, and cooling to room temperature to obtain a product;

(5) centrifugally cleaning the product obtained in the step (4) by using deionized water at the speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the NiFe₂O₄A/CNT nanocomposite material.

Wherein, the ferric salt in the step (1) is at least one of ferric chloride, ferric nitrate and ferric sulfate; the nickel salt is at least one of nickel chloride, nickel nitrate and nickel sulfate.

The invention has the advantages that the hydrothermal method is simple in preparation method, low in reaction temperature and free of subsequent treatment conditions, the composite material has excellent catalytic activity and stability for oxygen reduction reaction, and the NiFe prepared by the invention₂O₄the/CNT nano composite material can be used for a fuel cell cathode catalyst, and can also be applied to the fields of sensors, supercapacitors and the like. The method for preparing NiFe by doping non-metallic nano particles with carbon-based transition metal under a spinel structure is relatively simple₂O₄A CNT nanocomposite, which has excellent catalytic activity and stability for oxygen reduction reaction. Therefore, the composite material can be used as a high-efficiency fuel cell cathode catalyst, and can also be applied to the fields of sensors, supercapacitors and the like. The method for preparing the catalyst can be further developed and applied in the field of preparation of other materials.

Drawings

FIG. 1 is NiFe₂O₄The SEM image of the/CNT nano material shows that the obtained material is nano particles, the size is 5-10nm, the size distribution is uniform, the smaller size has larger specific surface area, and the active sites of the material can be promoted when the material is used for catalyzing, so that the material has better catalytic property.

Detailed Description

Example 1:

a nano-particle composite material of fuel cell cathode catalyst features that under hydrothermal condition, the carbon nanotubes are used as precursor and NiFe is used in synthesizing process₂O₄Nano particles are directly nucleated, uniformly grow and are anchored on the carbon nano tube, and simultaneously nitrogen is doped into the carbon nano tube framework structure, so that NiFe is realized₂O₄The NiFe is prepared by uniformly loading the nano particles on the nitrogen-doped Carbon Nano Tube (CNT)₂O₄the/CNT nano composite material is prepared by the following steps:

(1) 0.1g of iron salt and nickel salt are weighed into a beaker respectively, so that the molar ratio of the iron salt to the nickel salt is 2: 1; then 0.02g of graphene carbon nanotubes are weighed and placed in another beaker;

(2) adding 20mL of ethanol into the two beakers, firstly carrying out ultrasonic treatment on the beaker solution filled with the graphene carbon nanotubes for 1 hour, then mixing the two beaker solutions, carrying out magnetic stirring at the speed of 600 r/min for 2 hours, and dropwise adding 0.5 mL of 28% ammonia water solution while stirring;

(3) stirring the solution in a water bath at 80 ℃ for 10 hours, and drying the solution at 80 ℃ for 5 hours to obtain a reactant;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 h at 160 ℃, and cooling to room temperature to obtain a product;

(5) centrifugally cleaning the product obtained in the step (4) by using deionized water at the speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the NiFe₂O₄A/CNT nanocomposite material. NiFe₂O₄The SEM image of the/CNT nano material is shown in figure 1, and the obtained material is nano particles with the size of 5-10nm, the size distribution is uniform, and the smaller size has larger specific surface area, so that the active sites of the material can be promoted when the material is used as a catalytic material, and the material has better catalytic property.

Example 2:

the fuel cell anode catalyst nanoparticle composite material is prepared by the following steps, which are similar to the steps of the embodiment:

(1) 0.5g of iron salt and nickel salt are weighed into a beaker respectively, so that the molar ratio of the iron salt to the nickel salt is 2: 1; then 0.06g of graphene carbon nanotubes are weighed and placed in another beaker;

(2) adding 20mL of ethanol into the two beakers, firstly carrying out ultrasonic treatment on the beaker solution filled with the graphene carbon nanotubes for 1 hour, then mixing the two beaker solutions, carrying out magnetic stirring at the speed of 600 r/min for 2 hours, and dropwise adding 0.5 mL of 28% ammonia water solution while stirring;

(3) stirring the solution in a water bath at 80 ℃ for 10 hours, and drying the solution at 80 ℃ for 5 hours to obtain a reactant;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 h at 160 ℃, and cooling to room temperature to obtain a product;

(5) centrifugally cleaning the product obtained in the step (4) by using deionized water at the speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the NiFe₂O₄the/CNT nanocomposite material is used as a catalyst.

Example 3:

the fuel cell anode catalyst nanoparticle composite material is prepared by the following steps, which are similar to the steps of the embodiment:

(1) 0.3g of iron salt and nickel salt are weighed into a beaker respectively, so that the molar ratio of the iron salt to the nickel salt is 2: 1; then 0.05g of graphene carbon nanotubes are weighed and placed in another beaker;

(2) adding 20mL of ethanol into the two beakers, firstly carrying out ultrasonic treatment on the beaker solution filled with the graphene carbon nanotubes for 1 hour, then mixing the two beaker solutions, carrying out magnetic stirring at the speed of 600 r/min for 2 hours, and dropwise adding 0.5 mL of 28% ammonia water solution while stirring;

(3) stirring the solution in a water bath at 80 ℃ for 10 hours, and drying the solution at 80 ℃ for 5 hours to obtain a reactant;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 5 hours at 160 ℃, and cooling the reaction kettle to room temperature to obtain a product;

(5) centrifugally cleaning the product obtained in the step (4) by using deionized water at the speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the NiFe₂O₄the/CNT nanocomposite material is used as a catalyst.

Example 4:

the fuel cell anode catalyst nanoparticle composite material is prepared by the following steps, which are similar to the steps of the embodiment:

(1) 0.155g of iron salt and nickel salt was weighed into a beaker so that the molar ratio of iron salt to nickel salt was 2: 1; then 0.1g of graphene carbon nano tube is weighed and placed in another beaker;

(2) adding 20mL of ethanol into the two beakers, firstly carrying out ultrasonic treatment on the beaker solution filled with the graphene carbon nanotubes for 1 hour, then mixing the two beaker solutions, carrying out magnetic stirring at the speed of 600 r/min for 2 hours, and dropwise adding 0.5 mL of 28% ammonia water solution while stirring;

(3) stirring the solution in a water bath at 80 ℃ for 10 hours, and drying the solution at 80 ℃ for 5 hours to obtain a reactant;

(4) transferring the reactant into a 50 mL high-pressure reaction kettle, putting the reaction kettle into a forced air drying oven to react for 3 h at 180 ℃, and cooling to room temperature to obtain a product;

(5) centrifugally cleaning the product obtained in the step (4) by using deionized water at the speed of 10000 r/min for 5 min, and drying at 50 ℃ to obtain the NiFe₂O₄the/CNT nanocomposite material is used as a catalyst.

The embodiments described above are described to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.