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CN105712316B - A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material - Google Patents

A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material Download PDF

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CN105712316B
CN105712316B CN201510607850.2A CN201510607850A CN105712316B CN 105712316 B CN105712316 B CN 105712316B CN 201510607850 A CN201510607850 A CN 201510607850A CN 105712316 B CN105712316 B CN 105712316B
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zinc oxide
solution
composite material
seed layer
carbon nanofiber
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CN105712316A (en
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岳红彦
林轩宇
张虹
高鑫
姚龙辉
王宝
郭二军
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Harbin University of Science and Technology
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Abstract

一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备,涉及一种纳米复合材料的制备方法。本发明是要解决现有碳纳米纤维表面积小,在应用中与溶液接触面积有限的问题。本发明制备方法如下:一、静电纺丝法;二、水热合成法。一种氧化锌纳米线阵列/碳纳米纤维复合材料具有表面积大和电导性能优良等特点。本发明主要用于制备一种氧化锌纳米线阵列/碳纳米纤维复合材料。The invention relates to the preparation of a zinc oxide nanowire array/carbon nanofiber composite material, relating to a preparation method of the nanocomposite material. The invention aims to solve the problem that the existing carbon nanofiber has a small surface area and a limited contact area with a solution in application. The preparation method of the present invention is as follows: 1. electrostatic spinning method; 2. hydrothermal synthesis method. A zinc oxide nanowire array/carbon nanofiber composite material has the characteristics of large surface area, excellent electrical conductivity, and the like. The invention is mainly used for preparing a zinc oxide nanowire array/carbon nanofiber composite material.

Description

一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备Preparation of a ZnO nanowire array/carbon nanofiber composite material

技术领域technical field

本发明涉及一种新型纳米复合材料的制备方法。The invention relates to a preparation method of a novel nanocomposite material.

背景技术Background technique

碳纳米纤维是由多层石墨片卷曲而成的纤维状纳米碳材料,具有优异的物理、力学性能和化学稳定性,如良好的导电导热性能和出色的机械性能。碳纳米纤维一般来源于静电纺丝聚合物纳米纤维,如用聚丙烯腈和沥青等。聚丙烯腈是制备纳米碳纳米纤维的主要前驱体,因为可以通过控制后期碳化和稳定化温度来灵活控制碳纳米纤维的强度和弹性模量。Carbon nanofibers are fibrous nanocarbon materials rolled from multilayer graphite sheets, which have excellent physical and mechanical properties and chemical stability, such as good electrical and thermal conductivity and excellent mechanical properties. Carbon nanofibers are generally derived from electrospun polymer nanofibers, such as polyacrylonitrile and pitch. Polyacrylonitrile is the main precursor for preparing nano-carbon nanofibers, because the strength and elastic modulus of carbon nanofibers can be flexibly controlled by controlling the later carbonization and stabilization temperature.

纳米氧化锌是指晶粒尺寸介于1nm~100nm之间的纳米材料,由于晶粒尺寸的急剧减小,纳米氧化锌表现出许多块体材料所不具备的特殊性质,如非迁移性、荧光性、压电性、吸收和散射紫外线能力等。其中一维氧化锌纳米线阵列,由于形貌可控且表面积大成为目前纳米材料领域最重要的研究对象之一。一维氧化锌纳米线阵列的合成方法通常有化学气相沉积、物理气相沉积和水热合成等方法。其中水热合成方法具有合成温度低,成本低廉且可以大规模化生产,因此备受关注。Nano-zinc oxide refers to nano-materials with a grain size between 1nm and 100nm. Due to the sharp decrease in grain size, nano-zinc oxide exhibits many special properties that bulk materials do not have, such as non-migration, fluorescence properties, piezoelectricity, ability to absorb and scatter ultraviolet rays, etc. Among them, the one-dimensional ZnO nanowire array has become one of the most important research objects in the field of nanomaterials due to its controllable shape and large surface area. The synthesis methods of one-dimensional ZnO nanowire arrays usually include chemical vapor deposition, physical vapor deposition, and hydrothermal synthesis. Among them, the hydrothermal synthesis method has low synthesis temperature, low cost and large-scale production, so it has attracted much attention.

发明内容Contents of the invention

本发明是要解决碳纳米纤维表面积小,在应用中与溶液接触面积有限的问题,开发一种新型的氧化锌纳米线阵列/碳纳米纤维复合材料,从而提供一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法。The present invention aims to solve the problem of small surface area of carbon nanofibers and limited contact area with solution in application, and develops a novel zinc oxide nanowire array/carbon nanofiber composite material, thereby providing a zinc oxide nanowire array/carbon nanofiber composite material. Preparation method of nanofiber composite material.

本发明提供的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法是按以下步骤进行:The preparation method of a kind of zinc oxide nanowire array/carbon nanofiber composite material provided by the present invention is to carry out according to the following steps:

一、静电纺丝法1. Electrospinning method

1) 将1g聚丙烯腈粉末溶解于10mL二甲基甲酰胺溶液,并且在温度为100℃~150℃的条件下加热搅拌1h~2h,得到静电纺丝溶液。将该溶液转移到10mL的注射器中,再将注射器固定在注射泵上,控制静电纺丝电压为10KV~20KV,接收装置到纺丝针头的距离为5cm~15cm,溶液流速为1mL/h~2mL/h,于静电纺丝装置中进行静电纺丝得到聚丙烯腈纤维。1) Dissolve 1 g of polyacrylonitrile powder in 10 mL of dimethylformamide solution, and heat and stir for 1 h to 2 h at a temperature of 100 ° C to 150 ° C to obtain an electrospinning solution. Transfer the solution to a 10mL syringe, then fix the syringe on the syringe pump, control the electrospinning voltage to 10KV~20KV, the distance from the receiving device to the spinning needle is 5cm~15cm, and the solution flow rate is 1mL/h~2mL /h, electrospinning in an electrospinning device to obtain polyacrylonitrile fibers.

2) 将聚丙烯腈纤维置于鼓风干燥箱中,以1℃/min的速度升温到250℃~300℃,保温1h~1.5h进行稳定化处理。2) Put the polyacrylonitrile fiber in a blast drying oven, raise the temperature to 250°C~300°C at a rate of 1°C/min, and keep it warm for 1h~1.5h for stabilization.

3) 碳化过程在石英管式炉中进行。将步骤2)稳定化处理过后的聚丙烯腈纤维置于炉管中央,在氩气保护下从室温以3℃/min~8℃/min的速度升温到700℃~1000℃,并在温度700℃~1000℃的条件下保温60min~120min,然后随炉冷却到室温,得到碳纳米纤维。步骤一3)中所述的氩气的流速为380sccm~400sccm;3) The carbonization process is carried out in a quartz tube furnace. Place the stabilized polyacrylonitrile fiber in step 2) in the center of the furnace tube, and raise the temperature from room temperature to 700°C~1000°C at a rate of 3°C/min~8°C/min under the protection of argon, and heat it at a temperature of 700°C ℃~1000℃ under the condition of keeping warm for 60min~120min, then cooling down to room temperature with the furnace to obtain carbon nanofibers. The flow rate of argon described in step 13) is 380sccm~400sccm;

4) 将步骤3)得到的碳纳米纤维切割成面积为1cm2~2cm2的片,然后将切割好的碳纳米纤维固定到干净的玻璃上,再按每平方厘米有50μL~100μL的使用量,利用加样枪将氧化锌种子层溶液滴加到玻璃上的碳纳米纤维上,再置于温度为200℃~300℃的条件下保温60min~90min,得到预制有氧化锌种子层的碳纳米纤维/玻璃;步骤一4)中所述的氧化锌种子层溶液是按以下步骤制备的:将醋酸锌溶于甲醇中,然后以300r/min~500r/min的转速磁力搅拌3min~5min,得到氧化锌种子层溶液,其中所述的氧化锌种子层溶液中醋酸锌的浓度为0.005mol/L~0.05mol/L。4) Cut the carbon nanofibers obtained in step 3) into pieces with an area of 1cm 2 ~2cm 2 , then fix the cut carbon nanofibers on clean glass, and use 50μL~100μL per square centimeter , use a sample gun to drop the zinc oxide seed layer solution onto the carbon nanofibers on the glass, and then place it at a temperature of 200 ° C ~ 300 ° C for 60 min ~ 90 min to obtain prefabricated carbon nanofibers with a zinc oxide seed layer. Fiber/glass; the zinc oxide seed layer solution described in step 4) is prepared according to the following steps: dissolve zinc acetate in methanol, and then magnetically stir at a speed of 300r/min~500r/min for 3min~5min to obtain Zinc oxide seed layer solution, wherein the concentration of zinc acetate in the zinc oxide seed layer solution is 0.005mol/L-0.05mol/L.

二、水热合成法2. Hydrothermal Synthesis

1) 将硝酸锌、六亚甲基四胺和聚乙烯亚胺溶于去离子水中,加入氨水后以300r/min~500r/min的转速磁力搅拌3min~5min,得到水热反应溶液:步骤二1)所述的水热反应溶液中硝酸锌的浓度为0.01mol/L~0.1mol/L;六亚甲基四胺的浓度为0.01mol/L~0.1mol/L;聚乙烯亚胺的浓度为0.001mol/L~0.005mol/L;氨水的浓度为0.1mol/L~1mol/L。1) Dissolve zinc nitrate, hexamethylenetetramine and polyethyleneimine in deionized water, add ammonia and stir magnetically at a speed of 300r/min~500r/min for 3min~5min to obtain a hydrothermal reaction solution: Step 2 1) The concentration of zinc nitrate in the hydrothermal reaction solution is 0.01mol/L~0.1mol/L; the concentration of hexamethylenetetramine is 0.01mol/L~0.1mol/L; the concentration of polyethyleneimine 0.001mol/L~0.005mol/L; the concentration of ammonia water is 0.1mol/L~1mol/L.

2) 将步骤二1)得到的水热反应溶液倒入反应釜中,然后将步骤一4)预制有氧化锌种子层的碳纳米纤维/玻璃倒立放置于反应釜中的混合溶液中,盖上反应釜盖子,在80℃~120℃的温度条件下反应8h~15h,然后取出在空气中自然冷却到室温,得到纳米复合材料,打开反应釜用蒸馏水将该复合材料清洗干净,并于400℃~450℃下保温1h~1.5h,随炉冷却至室温,即得到氧化锌纳米线阵列/碳纳米纤维复合材料。2) Pour the hydrothermal reaction solution obtained in Step 2 1) into the reactor, then place the carbon nanofiber/glass prefabricated with the zinc oxide seed layer in Step 1 4) upside down in the mixed solution in the reactor, and cover React the lid of the reaction kettle for 8h~15h at a temperature of 80°C~120°C, then take it out and cool it to room temperature naturally in the air to obtain a nanocomposite material, open the reactor and clean the composite material with distilled water, and put Keep it warm at ~450°C for 1h~1.5h, and cool down to room temperature with the furnace to obtain the zinc oxide nanowire array/carbon nanofiber composite material.

本发明的优点:Advantages of the present invention:

(1)本发明方法通过静电纺丝方法制备碳纳米纤维,工艺简单,并且可以通过调节静电纺丝溶液的组成与静电纺丝参数来控制纤维的直径,得到直径分布均匀的碳纳米纤维。(1) The method of the present invention prepares carbon nanofibers by electrospinning. The process is simple, and the diameter of the fibers can be controlled by adjusting the composition of the electrospinning solution and the parameters of the electrospinning to obtain carbon nanofibers with uniform diameter distribution.

(2)本发明采用水热合成的方法在碳纳米纤维表面得到垂直生长的、直径分布均匀的氧化锌纳米线阵列。氧化锌纳米线阵列大大增加了碳纳米纤维的表面积,在碳纳米纤维的表面提供了无数活性点。(2) The present invention adopts a hydrothermal synthesis method to obtain zinc oxide nanowire arrays with vertical growth and uniform diameter distribution on the surface of carbon nanofibers. ZnO nanowire arrays greatly increase the surface area of carbon nanofibers and provide numerous active sites on the surface of carbon nanofibers.

附图说明Description of drawings

图1是静电纺丝制备的碳纳米纤维(CNF)的扫描电镜照片;Fig. 1 is the scanning electron micrograph of the carbon nanofiber (CNF) that electrospinning prepares;

图2是在氩气气氛下不同温度碳化得到的碳纳米纤维的直径;Fig. 2 is the diameter of carbon nanofibers obtained by carbonization at different temperatures under an argon atmosphere;

图3是不同温度下碳化得到的碳纳米纤维的电导性;Fig. 3 is the electrical conductivity of carbon nanofibers obtained by carbonization at different temperatures;

图4是合成的氧化锌纳米线阵列/碳纳米纤维复合材料的扫描电镜照片;Figure 4 is a scanning electron micrograph of the synthesized zinc oxide nanowire array/carbon nanofiber composite;

图5是合成的氧化锌纳米线阵列/碳纳米纤维复合材料截面的扫描电镜照片;Figure 5 is a scanning electron micrograph of the synthesized zinc oxide nanowire array/carbon nanofiber composite cross-section;

图6是静电纺丝制备的碳纳米纤维的拉曼图谱;Fig. 6 is the Raman spectrum of the carbon nanofiber prepared by electrospinning;

图7是制备的氧化锌纳米线阵列/碳纳米纤维复合材料的X射线衍射图谱,●碳纳米纤维的衍射峰,◆氧化锌的衍射峰。Fig. 7 is the X-ray diffraction spectrum of the prepared zinc oxide nanowire array/carbon nanofiber composite material, ●diffraction peaks of carbon nanofibers, ◆diffraction peaks of zinc oxide.

具体实施方式detailed description

具体实施方式一:本实施方式中一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,具体是按以下步骤进行的:Specific embodiment 1: In this embodiment, a method for preparing a zinc oxide nanowire array/carbon nanofiber composite material is specifically carried out according to the following steps:

一、静电纺丝法1. Electrospinning method

1) 将1g聚丙烯腈粉末溶解于10mL二甲基甲酰胺溶液,并且在温度为100℃~150℃的条件下加热搅拌1h~2h,得到静电纺丝溶液。将该溶液转移到10mL的注射器中,再将注射器固定在注射泵上,控制静电纺丝电压为10KV~20KV,接收装置到纺丝针头的距离为5cm~15cm,溶液流速为1mL/h~2mL/h,于静电纺丝装置中进行静电纺丝得到聚丙烯腈纤维。1) Dissolve 1 g of polyacrylonitrile powder in 10 mL of dimethylformamide solution, and heat and stir for 1 h to 2 h at a temperature of 100 ° C to 150 ° C to obtain an electrospinning solution. Transfer the solution to a 10mL syringe, then fix the syringe on the syringe pump, control the electrospinning voltage to 10KV~20KV, the distance from the receiving device to the spinning needle is 5cm~15cm, and the solution flow rate is 1mL/h~2mL /h, electrospinning in an electrospinning device to obtain polyacrylonitrile fibers.

2) 将聚丙烯腈纤维置于鼓风干燥箱中,以1℃/min的速度升温到250℃~300℃,保温1h~1.5h进行稳定化处理。2) Put the polyacrylonitrile fiber in a blast drying oven, raise the temperature to 250°C~300°C at a rate of 1°C/min, and keep it warm for 1h~1.5h for stabilization.

3) 碳化过程在石英管式炉中进行。将步骤2)稳定化处理过后的聚丙烯腈纤维置于炉管中央,在氩气保护下从室温以3℃/min~8℃/min的速度升温到700℃~1000℃,并在温度700℃~1000℃的条件下保温60min~120min,然后随炉冷却到室温,得到碳纳米纤维。步骤一3)中所述的氩气的流速为380sccm~400sccm。3) The carbonization process is carried out in a quartz tube furnace. Place the stabilized polyacrylonitrile fiber in step 2) in the center of the furnace tube, and raise the temperature from room temperature to 700°C~1000°C at a rate of 3°C/min~8°C/min under the protection of argon, and heat it at a temperature of 700°C ℃~1000℃ under the condition of keeping warm for 60min~120min, then cooling down to room temperature with the furnace to obtain carbon nanofibers. The flow rate of the argon gas described in step 13) is 380sccm~400sccm.

4) 将步骤3)得到的碳纳米纤维切割成面积为1cm2~2cm2的片,然后将切割好的碳纳米纤维固定到干净的玻璃上,再按每平方厘米有50μL~100μL的使用量利加样枪将氧化锌种子层溶液滴加到玻璃上的碳纳米纤维上,再置于温度为200℃~300℃的条件下保温60min~90min,得到预制有氧化锌种子层的碳纳米纤维/玻璃;步骤一4)中所述的干净的玻璃先后依次在丙酮中超声清洗15min~20min,乙醇中超声清洗15min~20min和去离子水中超声清洗15min~20min,在室温下自然干燥得到的;步骤一4)中所述的氧化锌种子层溶液是按以下步骤制备的:将醋酸锌溶于甲醇中,然后以300r/min~500r/min的转速磁力搅拌3min~5min,得到氧化锌种子层溶液,其中所述的氧化锌种子层溶液中醋酸锌的浓度为0.001mol/L~0.05mol/L。4) Cut the carbon nanofibers obtained in step 3) into pieces with an area of 1cm 2 ~2cm 2 , then fix the cut carbon nanofibers on clean glass, and use 50μL~100μL per square centimeter Use a sample gun to drop the zinc oxide seed layer solution onto the carbon nanofibers on the glass, and then place it at a temperature of 200°C~300°C for 60min~90min to obtain carbon nanofibers prefabricated with zinc oxide seed layers/ Glass; the clean glass described in step 14) is successively ultrasonically cleaned in acetone for 15min~20min, ultrasonically cleaned in ethanol for 15min~20min and deionized water for 15min~20min, and dried naturally at room temperature; step The zinc oxide seed layer solution described in 4) is prepared according to the following steps: dissolve zinc acetate in methanol, and then magnetically stir at a speed of 300r/min~500r/min for 3min~5min to obtain a zinc oxide seed layer solution , wherein the concentration of zinc acetate in the zinc oxide seed layer solution is 0.001mol/L-0.05mol/L.

二、水热合成法2. Hydrothermal Synthesis

1) 将硝酸锌、六亚甲基四胺和聚乙烯亚胺溶于去离子水中,加入氨水后以300r/min~500r/min的转速磁力搅拌3min~5min,得到水热反应溶液:步骤二1)所述的水热反应溶液中硝酸锌的浓度为0.01mol/L~0.1mol/L;六亚甲基四胺的浓度为0.01mol/L~0.1mol/L;聚乙烯亚胺的浓度为0.001mol/L~0.005mol/L;氨水的浓度为0.1mol/L~1mol/L。1) Dissolve zinc nitrate, hexamethylenetetramine and polyethyleneimine in deionized water, add ammonia and stir magnetically at a speed of 300r/min~500r/min for 3min~5min to obtain a hydrothermal reaction solution: Step 2 1) The concentration of zinc nitrate in the hydrothermal reaction solution is 0.01mol/L~0.1mol/L; the concentration of hexamethylenetetramine is 0.01mol/L~0.1mol/L; the concentration of polyethyleneimine 0.001mol/L~0.005mol/L; the concentration of ammonia water is 0.1mol/L~1mol/L.

2) 将步骤二1)得到的水热反应溶液倒入反应釜中,然后将步骤一4)预制有氧化锌种子层的碳纳米纤维/玻璃倒立放置于反应釜中的混合溶液中,盖上反应釜盖子,在80℃~120℃的温度条件下反应8h~15h,然后取出在空气中自然冷却到室温,得到纳米复合材料,打开反应釜用蒸馏水将该复合材料清洗干净,并于400℃~450℃下保温1h~1.5h,随炉冷却至室温,即得到氧化锌纳米线阵列/碳纳米纤维复合材料。2) Pour the hydrothermal reaction solution obtained in Step 2 1) into the reactor, then place the carbon nanofiber/glass prefabricated with the zinc oxide seed layer in Step 1 4) upside down in the mixed solution in the reactor, and cover React the lid of the reaction kettle for 8h~15h at a temperature of 80°C~120°C, then take it out and cool it to room temperature naturally in the air to obtain a nanocomposite material, open the reactor and clean the composite material with distilled water, and put Keep it warm at ~450°C for 1h~1.5h, and cool down to room temperature with the furnace to obtain the zinc oxide nanowire array/carbon nanofiber composite material.

具体实施方式二:本实施方式与具体实施方式一不同的是:步骤1)中将1g聚丙烯腈粉末溶解于10mL二甲基甲酰胺溶液,并且在温度为110℃~130℃的条件下加热搅拌1h~2h,得到静电纺丝溶液。将该溶液转移到10mL的注射器中,再将注射器固定在注射泵上,控制静电纺丝电压为10KV~20KV,接收装置到纺丝针头的距离为8cm~12cm,溶液流速为1mL/h~2mL/h,于静电纺丝装置中进行静电纺丝得到聚丙烯腈纤维。其它与具体实施方式一相同。Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that in step 1), 1 g of polyacrylonitrile powder is dissolved in 10 mL of dimethylformamide solution, and heated at a temperature of 110 ° C to 130 ° C Stir for 1h~2h to obtain an electrospinning solution. Transfer the solution to a 10mL syringe, then fix the syringe on the syringe pump, control the electrospinning voltage to 10KV~20KV, the distance from the receiving device to the spinning needle is 8cm~12cm, and the solution flow rate is 1mL/h~2mL /h, electrospinning in an electrospinning device to obtain polyacrylonitrile fibers. Others are the same as in the first embodiment.

具体实施方式三:本实施方式与具体实施方式一或二之一不同的是:步骤一2)中将聚丙烯腈纤维置于箱式炉中,以1℃/min的速度升温到270℃~290℃,保温1h~1.5h进行稳定化处理。其它与具体实施方式一或二之一相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that in Step 1 2), the polyacrylonitrile fiber is placed in a box furnace, and the temperature is raised to 270°C at a rate of 1°C/min. 290°C, heat preservation for 1h~1.5h for stabilization treatment. Others are the same as those in the first or second embodiment.

具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:步骤一3)中将步骤2)稳定化处理过后的聚丙烯腈纤维置于炉管中央,在氩气保护下从室温以3℃/min~8℃/min的速度升温到800℃~900℃,并在温度800℃~900℃的条件下保温80min~100min,然后随炉冷却到室温,得到碳纳米纤维。步骤一3)中所述的氩气的流速为400sccm。其它与具体实施方式一至三之一相同。Embodiment 4: The difference between this embodiment and one of Embodiments 1 to 3 is that in Step 1 3), the polyacrylonitrile fiber after the stabilization treatment in Step 2) is placed in the center of the furnace tube, and is removed from the furnace under the protection of argon. The room temperature is raised to 800-900°C at a rate of 3°C/min-8°C/min, and kept at a temperature of 800°C-900°C for 80min-100min, and then cooled to room temperature with the furnace to obtain carbon nanofibers. The flow rate of argon gas described in step 1 3) is 400 sccm. Others are the same as those in the first to third specific embodiments.

具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤一4)中将步骤3)得到的碳纳米纤维切割成面积为1cm2~1.5cm2的片,然后将切割好的碳纳米纤维固定到干净的玻璃上,再按每平方厘米有70μL~90μL的使用量,利用加样枪将氧化锌种子层溶液滴加到玻璃上的碳纳米纤维上,再置于温度为230℃~280℃的条件下保温60min~90min,得到预制有氧化锌种子层的碳纳米纤维/玻璃;步骤一4)中所述的干净的玻璃先后依次在丙酮中超声清洗15min~20min,乙醇中超声清洗15min~20min和去离子水中超声清洗15min~20min,在室温下自然干燥得到的;步骤一4)中所述的氧化锌种子层溶液是按以下步骤制备的:将醋酸锌溶于甲醇中,然后以300r/min~500r/min的转速磁力搅拌3min~5min,得到氧化锌种子层溶液,其中所述的氧化锌种子层溶液中醋酸锌的浓度为0.005mol/L~0.01mol/L。其它与具体实施方式一至四之一相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that the carbon nanofibers obtained in step 3) are cut into pieces with an area of 1 cm 2 ~1.5 cm 2 in step 1 4), and then the cut Fix the good carbon nanofibers on the clean glass, and then use the amount of 70μL~90μL per square centimeter, use the sample gun to drop the zinc oxide seed layer solution on the carbon nanofibers on the glass, and then place it at temperature Prefabricated carbon nanofiber/glass with zinc oxide seed layer is obtained under the condition of 230°C~280°C for 60min~90min; the clean glass described in step 14) is successively ultrasonically cleaned in acetone for 15min~20min, Ultrasonic cleaning in ethanol for 15min~20min and ultrasonic cleaning in deionized water for 15min~20min, and drying naturally at room temperature; the zinc oxide seed layer solution described in step 14) is prepared according to the following steps: dissolve zinc acetate in methanol, and then magnetically stirred at a speed of 300r/min~500r/min for 3min~5min to obtain a zinc oxide seed layer solution, wherein the concentration of zinc acetate in the zinc oxide seed layer solution is 0.005mol/L~0.01mol/ L. Others are the same as one of the specific embodiments 1 to 4.

具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:骤二1)中所述的水热反应溶液中硝酸锌的浓度为0.04mol/L~0.06mol/L;六亚甲基四胺的浓度为0.04mol/L~0.06mol/L;聚乙烯亚胺的浓度为0.001mol/L~0.003mol/L;氨水的浓度为0.3mol/L~0.6mol/L。其它与具体实施方式一至五之一相同。Specific embodiment 6: This embodiment differs from one of specific embodiments 1 to 5 in that: the concentration of zinc nitrate in the hydrothermal reaction solution described in Step 2 1) is 0.04mol/L~0.06mol/L; The concentration of methyltetramine is 0.04mol/L~0.06mol/L; the concentration of polyethyleneimine is 0.001mol/L~0.003mol/L; the concentration of ammonia water is 0.3mol/L~0.6mol/L. Others are the same as one of the specific embodiments 1 to 5.

具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:步骤二2)中将步骤二1)得到的水热反应溶液倒入反应釜中,然后将步骤一4)预制有氧化锌种子层的碳纳米纤维倒立放置于反应釜中的混合溶液中,盖上反应釜盖子,在90℃~110℃的温度条件下反应8h~12h,然后取出在空气中自然冷却到室温,得到纳米复合材料,打开反应釜用蒸馏水将该复合材料清洗干净,并于430℃~450℃下保温1h~1.5h,随炉冷却至室温,即得到氧化锌纳米线阵列/碳纳米纤维复合材料。其它与具体实施方式一至六之一相同。Embodiment 7: The difference between this embodiment and one of Embodiments 1 to 6 is that in Step 2 2), the hydrothermal reaction solution obtained in Step 2 1) is poured into the reactor, and then Step 1 4) is prefabricated The carbon nanofibers of the zinc oxide seed layer are placed upside down in the mixed solution in the reactor, the lid of the reactor is covered, and the reaction is carried out at a temperature of 90°C~110°C for 8h~12h, and then taken out and naturally cooled to room temperature in the air. To obtain the nanocomposite material, open the reaction kettle and clean the composite material with distilled water, keep it warm at 430°C~450°C for 1h~1.5h, and cool down to room temperature with the furnace to obtain the zinc oxide nanowire array/carbon nanofiber composite material . Others are the same as one of the specific embodiments 1 to 6.

采用下述试验验证本发明效果:Adopt following test to verify effect of the present invention:

本试验的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法是按以下方法实现的:The preparation method of a kind of zinc oxide nanowire array/carbon nanofiber composite material of this test is realized as follows:

一、静电纺丝法1. Electrospinning method

1) 将1g聚丙烯腈粉末溶解于10mL二甲基甲酰胺溶液,并且在温度为120℃的条件下加热搅拌2h,得到静电纺丝溶液。将该溶液转移到10mL的注射器中,再将注射器固定在注射泵上,控制静电纺丝电压为20KV,接收装置到纺丝针头的距离为10cm,溶液流速为1mL/h,于静电纺丝装置中进行静电纺丝得到聚丙烯腈纤维。1) Dissolve 1g of polyacrylonitrile powder in 10mL of dimethylformamide solution, and heat and stir at 120°C for 2h to obtain an electrospinning solution. Transfer the solution to a 10mL syringe, then fix the syringe on the syringe pump, control the electrospinning voltage to 20KV, the distance from the receiving device to the spinning needle to 10cm, and the solution flow rate to 1mL/h. Electrospinning was carried out to obtain polyacrylonitrile fibers.

2) 将聚丙烯腈纤维置于箱式炉中,以1℃/min的速度升温到280℃,保温1h进行稳定化处理。2) Place the polyacrylonitrile fiber in a box furnace, raise the temperature to 280°C at a rate of 1°C/min, and keep it warm for 1 hour for stabilization.

3) 碳化过程在石英管式炉中进行。将步骤2)稳定化处理过后的聚丙烯腈纤维置于炉管中央,在氩气保护下从室温以5℃/min的速度升温到900℃,并在温度900℃的条件下保温60min,然后随炉冷却到室温,得到碳纳米纤维。步骤一3)中所述的氩气的流速为400sccm。3) The carbonization process is carried out in a quartz tube furnace. Place the stabilized polyacrylonitrile fiber in step 2) in the center of the furnace tube, raise the temperature from room temperature to 900°C at a rate of 5°C/min under the protection of argon, and keep it at 900°C for 60 minutes, then Cool down to room temperature with the furnace to obtain carbon nanofibers. The flow rate of argon gas described in step 1 3) is 400 sccm.

4) 将步骤3)得到的碳纳米纤维切割成面积为1cm2的片,然后将切割好的碳纳米纤维固定到干净的玻璃上,再按每平方厘米有90μL的使用量,利用加样枪将氧化锌种子层溶液滴加到玻璃上的碳纳米纤维上,再置于温度为250℃的条件下保温60min,得到预制有氧化锌种子层的碳纳米纤维/玻璃;步骤一4)中所述的氧化锌种子层溶液是按以下步骤制备的:将醋酸锌溶于甲醇中,然后以400r/min的转速磁力搅拌5min,得到氧化锌种子层溶液,其中所述的氧化锌种子层溶液中醋酸锌的浓度为0.01mol/L。4) Cut the carbon nanofibers obtained in step 3) into pieces with an area of 1cm 2 , then fix the cut carbon nanofibers on clean glass, and then use a sample injection gun with an amount of 90 μL per square centimeter Add the zinc oxide seed layer solution dropwise to the carbon nanofibers on the glass, and then place it at a temperature of 250°C for 60 minutes to obtain the carbon nanofiber/glass prefabricated with the zinc oxide seed layer; step 1 4) The zinc oxide seed layer solution is prepared according to the following steps: dissolve zinc acetate in methanol, then magnetically stir at a speed of 400r/min for 5min to obtain the zinc oxide seed layer solution, wherein the zinc oxide seed layer solution is The concentration of zinc acetate is 0.01mol/L.

二、水热合成法2. Hydrothermal Synthesis

1) 将硝酸锌、六亚甲基四胺和聚乙烯亚胺溶于去离子水中,加入氨水后以400r/min的转速磁力搅拌5min,得到水热反应溶液:步骤二1)所述的水热反应溶液中硝酸锌和六亚甲基四胺的浓度均为0.05mol/L;聚乙烯亚胺的浓度为0.002mol/L;氨水的浓度为0.5mol/L。1) Dissolve zinc nitrate, hexamethylenetetramine and polyethyleneimine in deionized water, add ammonia and stir magnetically at a speed of 400r/min for 5 minutes to obtain a hydrothermal reaction solution: the water described in Step 2 1) The concentrations of zinc nitrate and hexamethylenetetramine in the thermal reaction solution are both 0.05mol/L; the concentration of polyethyleneimine is 0.002mol/L; and the concentration of ammonia water is 0.5mol/L.

2) 将步骤二1)得到的水热反应溶液倒入反应釜中,然后将步骤一4)预制有氧化锌种子层的碳纳米纤维倒立放置于反应釜中的混合溶液中,盖上反应釜盖子,在80℃~120℃的温度条件下反应8h~15h,然后取出在空气中自然冷却到室温,得到纳米复合材料,打开反应釜用蒸馏水将该复合材料清洗干净,并于450℃下保温1h,随炉冷却至室温,即得到氧化锌纳米线阵列/碳纳米纤维复合材料。2) Pour the hydrothermal reaction solution obtained in Step 2 1) into the reaction kettle, then place the carbon nanofibers prefabricated with the zinc oxide seed layer in Step 1 4) upside down in the mixed solution in the reaction kettle, and cover the reaction kettle Cover the lid, react at a temperature of 80°C~120°C for 8h~15h, then take it out and cool it down to room temperature naturally in the air to obtain a nanocomposite material, open the reactor and clean the composite material with distilled water, and keep it warm at 450°C After 1 hour, it was cooled down to room temperature with the furnace, and the zinc oxide nanowire array/carbon nanofiber composite material was obtained.

图1是静电纺丝制备的碳纳米纤维(CNF)的扫描电镜照片,从图中可以看出,碳纳米纤维表面滑光直径分布均匀,碳纳米纤维的直径为200~300nm。Figure 1 is a scanning electron micrograph of carbon nanofibers (CNF) prepared by electrospinning. It can be seen from the figure that the surface of carbon nanofibers is smooth and smooth, and the diameter distribution is uniform, and the diameter of carbon nanofibers is 200-300nm.

图2是在氩气气氛下不同温度碳化得到的碳纳米纤维的直径。从图中可以看出,随着碳化时间的延长和碳化温度的提高,碳纳米纤维的直径逐渐下降。Fig. 2 is the diameter of carbon nanofibers obtained by carbonization at different temperatures under an argon atmosphere. It can be seen from the figure that with the prolongation of carbonization time and the increase of carbonization temperature, the diameter of carbon nanofibers gradually decreases.

图3是氩气气氛下不同温度碳化得到的碳纳米纤维的电导性。低温时,碳纳米纤维的电导性很低,温度升高电导性增加,900℃热处理时,碳纳米纤维的电导性达到~3S/cm。Fig. 3 is the electrical conductivity of carbon nanofibers obtained by carbonization at different temperatures in an argon atmosphere. At low temperature, the electrical conductivity of carbon nanofibers is very low, and the electrical conductivity increases as the temperature rises. When heat-treated at 900°C, the electrical conductivity of carbon nanofibers reaches ~3S/cm.

图4是合成的氧化锌纳米线阵列/碳纳米纤维复合材料的扫描电镜照片,从图中可以看出,在每一根碳纳米纤维的表面有无数的垂直于碳纳米纤维的氧化锌纳米线阵列。Figure 4 is a scanning electron microscope photo of the synthesized zinc oxide nanowire array/carbon nanofiber composite material. It can be seen from the figure that there are countless zinc oxide nanowires perpendicular to the carbon nanofiber on the surface of each carbon nanofiber array.

图5是合成的氧化锌纳米线阵列/碳纳米纤维复合材料截面的扫描电镜照片,由图可以看出氧化锌纳米线阵列围绕每一根碳纳米纤维上垂直生长且分布均匀。氧化锌纳米线的直径为~40nm,长度为2μm。Fig. 5 is a scanning electron microscope photo of the cross-section of the synthesized zinc oxide nanowire array/carbon nanofiber composite material. It can be seen from the figure that the zinc oxide nanowire array grows vertically around each carbon nanofiber and distributes evenly. The ZnO nanowires are ~40 nm in diameter and 2 μm in length.

图6是静电纺丝得到的碳纳米纤维的拉曼图谱,其中在~1380cm-1和~1618cm-1处的两个特征峰分别对应sp 2石墨结构碳和sp 3无序结构碳,分别是D带(1360cm-1)和G(1590cm-1)带。Figure 6 is the Raman spectrum of carbon nanofibers obtained by electrospinning, in which the two characteristic peaks at ~1380cm -1 and ~1618cm -1 correspond to sp 2 graphitic carbon and sp 3 disordered carbon, respectively. D band (1360cm -1 ) and G (1590cm -1 ) band.

图7是制备的氧化锌纳米线阵列/碳纳米纤维复合材料的X射线衍射图谱,●碳纳米纤维的衍射峰,22.6°处的衍射峰对应于石墨结构的(002)晶面。◆氧化锌的衍射峰,所有衍射峰很好与ZnO的特征峰对应。表明得到了氧化锌纳米线阵列/碳纳米纤维复合材料。Fig. 7 is the X-ray diffraction pattern of the prepared zinc oxide nanowire array/carbon nanofiber composite material, the diffraction peak of the carbon nanofiber, and the diffraction peak at 22.6° corresponds to the (002) crystal plane of the graphite structure. ◆The diffraction peaks of zinc oxide, all the diffraction peaks correspond to the characteristic peaks of ZnO very well. It shows that the zinc oxide nanowire array/carbon nanofiber composite material has been obtained.

Claims (7)

1.一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法是按以下步骤进行的:1. a preparation method of zinc oxide nanowire array/carbon nanofiber composite material is characterized in that the preparation method of zinc oxide nanowire array/carbon nanofiber composite material is carried out according to the following steps: 一、静电纺丝法1. Electrospinning method 1) 将1g聚丙烯腈粉末溶解于10mL二甲基甲酰胺溶液,并且在温度为100℃~150℃的条件下加热搅拌1h~2h,得到静电纺丝的溶液;将该溶液转移到10mL的注射器中,再将注射器固定在注射泵上,控制静电纺丝电压为10kV~20kV,接收装置到纺丝针头的距离为5cm~15cm,溶液流速为1mL/h~2mL/h,于静电纺丝装置中进行静电纺丝得到聚丙烯腈纤维;1) Dissolve 1g of polyacrylonitrile powder in 10mL of dimethylformamide solution, and heat and stir at 100°C~150°C for 1h~2h to obtain an electrospinning solution; transfer the solution to a 10mL In the syringe, fix the syringe on the syringe pump, control the electrospinning voltage to 10kV~20kV, the distance from the receiving device to the spinning needle is 5cm~15cm, and the solution flow rate is 1mL/h~2mL/h. Electrospinning is carried out in the device to obtain polyacrylonitrile fibers; 2) 将聚丙烯腈纤维置于鼓风干燥箱中,以1℃/min的速度升温到250℃~300℃,保温1h~1.5h进行稳定化处理;2) Put the polyacrylonitrile fiber in a blast drying oven, raise the temperature to 250°C~300°C at a rate of 1°C/min, and keep it warm for 1h~1.5h for stabilization treatment; 3) 碳化过程在石英管式炉中进行;将步骤2)稳定化处理过后的聚丙烯腈纤维置于炉管中央,在氩气保护下从室温以3℃/min~8℃/min的速度升温到700℃~1000℃,并在温度700℃~1000℃的条件下保温60min~120min,然后随炉冷却到室温,得到碳纳米纤维;步骤一3)中所述的氩气的流速为380sccm~400sccm;3) The carbonization process is carried out in a quartz tube furnace; the polyacrylonitrile fiber after the stabilization treatment in step 2) is placed in the center of the furnace tube, and it is heated from room temperature at a speed of 3°C/min to 8°C/min under the protection of argon. Raise the temperature to 700°C~1000°C, keep it warm for 60min~120min at a temperature of 700°C~1000°C, and then cool down to room temperature with the furnace to obtain carbon nanofibers; the flow rate of argon gas described in step 13) is 380sccm ~400sccm; 4) 将步骤3)得到的碳纳米纤维切割成面积为1cm2~2cm2的片,然后将切割好的碳纳米纤维固定到干净的玻璃上,再按每平方厘米有50μL~100μL的使用量,利用加样枪将氧化锌种子层溶液滴加到玻璃上的碳纳米纤维上,再置于温度为200℃~300℃的条件下保温60min~90min,得到预制有氧化锌种子层的碳纳米纤维;步骤一4)中所述的氧化锌种子层溶液是按以下步骤制备的:将醋酸锌溶于甲醇中,然后以300r/min~500r/min的转速磁力搅拌3min~5min,得到氧化锌种子层溶液,其中所述的氧化锌种子层溶液中醋酸锌的浓度为0.005mol/L~0.05mol/L;4) Cut the carbon nanofibers obtained in step 3) into pieces with an area of 1cm 2 ~2cm 2 , then fix the cut carbon nanofibers on clean glass, and use 50μL~100μL per square centimeter , use a sample gun to drop the zinc oxide seed layer solution onto the carbon nanofibers on the glass, and then place it at a temperature of 200 ° C ~ 300 ° C for 60 min ~ 90 min to obtain prefabricated carbon nanofibers with a zinc oxide seed layer. Fiber; the zinc oxide seed layer solution described in step 14) is prepared according to the following steps: dissolve zinc acetate in methanol, and then magnetically stir at a speed of 300r/min~500r/min for 3min~5min to obtain zinc oxide Seed layer solution, wherein the concentration of zinc acetate in the zinc oxide seed layer solution is 0.005mol/L~0.05mol/L; 二、水热合成法2. Hydrothermal Synthesis 1) 将硝酸锌、六亚甲基四胺和聚乙烯亚胺溶于去离子水中,加入氨水后以300r/min~500 r/min的转速磁力搅拌3min~5 min,得到水热反应溶液:步骤二1)所述的水热反应溶液中硝酸锌的浓度为0.01mol/L~0.1 mol/L;六亚甲基四胺的浓度为0.01mol/L~0.1 mol/L;聚乙烯亚胺的浓度为0.001mol/L~0.005 mol/L;氨水的浓度为0.1mol/L~1 mol/L;1) Dissolve zinc nitrate, hexamethylenetetramine and polyethyleneimine in deionized water, add ammonia water, and stir magnetically at a speed of 300r/min~500r/min for 3min~5min to obtain a hydrothermal reaction solution: Step 2 1) The concentration of zinc nitrate in the hydrothermal reaction solution is 0.01mol/L~0.1mol/L; the concentration of hexamethylenetetramine is 0.01mol/L~0.1mol/L; polyethyleneimine The concentration of ammonia water is 0.001mol/L~0.005 mol/L; the concentration of ammonia water is 0.1mol/L~1 mol/L; 2) 将步骤二1)得到的水热反应溶液倒入反应釜中,然后将步骤一4)预制有氧化锌种子层的碳纳米纤维/玻璃倒立放置于反应釜中的混合溶液中,盖上反应釜盖子,在80℃~120℃的温度条件下保温8h~15h,然后取出在空气中自然冷却到室温,得到纳米复合材料,打开反应釜用蒸馏水将该复合材料清洗干净,并于400℃~450℃下保温1h~1.5h,随炉冷却至室温,即得到氧化锌纳米线阵列/碳纳米纤维复合材料。2) Pour the hydrothermal reaction solution obtained in Step 2 1) into the reactor, then place the carbon nanofiber/glass prefabricated with the zinc oxide seed layer in Step 1 4) upside down in the mixed solution in the reactor, and cover The lid of the reaction kettle was kept at 80°C~120°C for 8h~15h, then it was taken out and cooled to room temperature naturally in the air to obtain a nanocomposite material. Open the reaction kettle and clean the composite material with distilled water. Keep it warm at ~450°C for 1h~1.5h, and cool down to room temperature with the furnace to obtain the zinc oxide nanowire array/carbon nanofiber composite material. 2.根据权利要求1所述的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于步骤一1)中将1g聚丙烯腈粉末溶解于10mL二甲基甲酰胺溶液,并且在温度为110℃~130℃的条件下加热搅拌1h~2h,得到静电纺丝溶液;将该溶液转移到10mL的注射器中,再将注射器固定在注射泵上,控制静电纺丝电压为10kV~20kV,接收装置到纺丝针头的距离为8cm~12cm,溶液流速为1mL/h~2mL/h,于静电纺丝装置中进行静电纺丝得到聚丙烯腈纤维。2. The preparation method of a zinc oxide nanowire array/carbon nanofiber composite material according to claim 1, characterized in that in step 1) 1g of polyacrylonitrile powder is dissolved in 10mL of dimethylformamide solution, And heated and stirred at a temperature of 110°C~130°C for 1h~2h to obtain an electrospinning solution; transfer the solution into a 10mL syringe, then fix the syringe on the syringe pump, and control the electrospinning voltage to 10kV ~20kV, the distance from the receiving device to the spinning needle is 8cm~12cm, the flow rate of the solution is 1mL/h~2mL/h, and the polyacrylonitrile fiber is obtained by electrospinning in the electrospinning device. 3.根据权利要求1所述的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于步骤一2)中将聚丙烯腈纤维置于鼓风干燥箱中,以1℃/min的速度升温到270℃~290℃,保温1h~1.5h进行稳定化处理。3. The preparation method of a zinc oxide nanowire array/carbon nanofiber composite material according to claim 1, characterized in that in step 1 and 2), the polyacrylonitrile fiber is placed in a blast drying oven and heated at 1°C The temperature is raised to 270°C~290°C at a speed of 1/min, and the temperature is kept for 1h~1.5h for stabilization. 4.根据权利要求1所述的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于步骤一3)中将步骤2)稳定化处理过后的聚丙烯腈纤维置于管式炉管中央,在氩气保护下从室温以3℃/min~8℃/min的速度升温到800℃~900℃,并在温度800℃~900℃的条件下保温80min~100min,然后随炉冷却到室温,得到碳纳米纤维;步骤一3)中所述的氩气的流速为400sccm。4. The preparation method of a zinc oxide nanowire array/carbon nanofiber composite material according to claim 1, characterized in that in step 13), the polyacrylonitrile fiber after the stabilization treatment in step 2) is placed in the tube In the center of the type furnace tube, under the protection of argon, the temperature is raised from room temperature at a rate of 3°C/min to 8°C/min to 800°C~900°C, and kept at 800°C~900°C for 80min~100min, and then The furnace was cooled to room temperature to obtain carbon nanofibers; the flow rate of argon gas in Step 1 3) was 400 sccm. 5.根据权利要求1所述的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于步骤一4)中将步骤3)得到的碳纳米纤维切割成面积为1cm2~1.5cm2的片,然后将切割好的碳纳米纤维固定到干净的玻璃上,再按每平方厘米有70μL~90μL的使用量,利用加样枪将氧化锌种子层溶液滴加到玻璃上的碳纳米纤维上,再置于温度为230℃~280℃的条件下保温60min~90min,得到预制有氧化锌种子层的碳纳米纤维/玻璃;步骤一4)中所述的氧化锌种子层溶液是按以下步骤制备的:将醋酸锌溶于甲醇中,然后以300r/min~500r/min的转速磁力搅拌3min~5min,得到氧化锌种子层溶液,其中所述的氧化锌种子层溶液中醋酸锌的浓度为0.005mol/L~0.01mol/L。5. The preparation method of a zinc oxide nanowire array/carbon nanofiber composite material according to claim 1, characterized in that the carbon nanofibers obtained in step 3) are cut into an area of 1 cm 2 ~ 1.5cm2 piece, and then fix the cut carbon nanofibers on the clean glass, and then use the amount of 70μL~90μL per square centimeter, use the sample gun to drop the zinc oxide seed layer solution on the glass. on the carbon nanofibers, and then placed at a temperature of 230°C to 280°C for 60min to 90min to obtain carbon nanofibers/glass with prefabricated zinc oxide seed layers; the zinc oxide seed layer solution described in step 14) It is prepared according to the following steps: dissolve zinc acetate in methanol, then magnetically stir at a speed of 300r/min~500r/min for 3min~5min to obtain a zinc oxide seed layer solution, wherein the acetic acid in the zinc oxide seed layer solution The concentration of zinc is 0.005mol/L~0.01mol/L. 6.根据权利要求1所述的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于步骤二1)中所述的水热反应溶液中硝酸锌的浓度为0.04mol/L~0.06mol/L;六亚甲基四胺的浓度为0.04mol/L~0.06mol/L;聚乙烯亚胺的浓度为0.001mol/L~0.003mol/L;氨水的浓度为0.3mol/L~0.6mol/L。6. The preparation method of a zinc oxide nanowire array/carbon nanofiber composite material according to claim 1, characterized in that the concentration of zinc nitrate in the hydrothermal reaction solution described in step 2 1) is 0.04mol/ L~0.06mol/L; the concentration of hexamethylenetetramine is 0.04mol/L~0.06mol/L; the concentration of polyethyleneimine is 0.001mol/L~0.003mol/L; the concentration of ammonia water is 0.3mol/L L~0.6mol/L. 7.根据权利要求1所述的一种氧化锌纳米线阵列/碳纳米纤维复合材料的制备方法,其特征在于步骤二2)中将步骤二1)得到的水热反应溶液倒入反应釜中,然后将步骤一4)预制有氧化锌种子层的碳纳米纤维/玻璃倒立放置于反应釜中的混合溶液中,盖上反应釜盖子,在90℃~110℃的温度条件下反应8h~12h,然后取出在空气中自然冷却到室温,得到复合材料,打开反应釜用蒸馏水将复合材料清洗干净,并于430℃~450℃下保温1h~1.5h,随炉冷却至室温,即得到氧化锌纳米线阵列/碳纳米纤维复合材料。7. The preparation method of a zinc oxide nanowire array/carbon nanofiber composite material according to claim 1, characterized in that in step 2 2), the hydrothermal reaction solution obtained in step 2 1) is poured into the reactor , then place the carbon nanofiber/glass prefabricated with the zinc oxide seed layer in step 14) upside down in the mixed solution in the reactor, cover the lid of the reactor, and react at a temperature of 90°C~110°C for 8h~12h , then take it out and cool it down to room temperature naturally in the air to get the composite material, open the reactor to clean the composite material with distilled water, keep it warm at 430°C~450°C for 1h~1.5h, and cool down to room temperature with the furnace to get zinc oxide Nanowire Array/Carbon Nanofiber Composites.
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