技术领域Technical Field
本发明属于碳纳米材料的分散领域，具体涉及一种可实现高分散稳定性的碳纳米材料(石墨烯/碳纳米管/导电炭黑)复合物及其制备方法。The invention belongs to the field of dispersion of carbon nanomaterials, and in particular relates to a carbon nanomaterial (graphene/carbon nanotube/conductive carbon black) composite capable of achieving high dispersion stability and a preparation method thereof.
背景技术Background Art
石墨烯等碳纳米材料具有良好的力学、电学及热学性能，是作为金属基复合材料增强体的良好选择。然而，碳纳米材料在使用过程中容易出现团聚，从而限制其应用。以石墨烯为例，石墨烯特有的薄层二维结构使其在自然状态下极易团聚，其独特的机械性能及优异的热、电传导性能会随着薄片的聚集而迅速下降。Carbon nanomaterials such as graphene have good mechanical, electrical and thermal properties and are a good choice as reinforcements for metal-based composites. However, carbon nanomaterials tend to aggregate during use, which limits their application. Take graphene as an example. Its unique thin-layer two-dimensional structure makes it very easy to aggregate in its natural state. Its unique mechanical properties and excellent thermal and electrical conductivity will rapidly decrease as the flakes aggregate.
近年来，解决石墨烯分散的方法主要有以下几种：In recent years, the main methods to solve graphene dispersion are as follows:
1)物理分散方法1) Physical dispersion method
通过外力作用打破片层与片层之间的范德华力，进而达到分散的效果，常见的方式有机械分散，超声以及微波辐射法。The van der Waals forces between the sheets are broken by external force to achieve the dispersion effect. Common methods include mechanical dispersion, ultrasound and microwave radiation.
2)化学分散法2) Chemical dispersion method
通常将石墨烯分散到含有改性剂的水溶液或有机溶液中，石墨烯的表面被改性分子包埋，通过静电力或分子间作用力克服片层间范德华力。化学分散法又分为下面两类：Graphene is usually dispersed in an aqueous solution or organic solution containing a modifier. The surface of graphene is embedded with modified molecules, and the inter-sheet van der Waals forces are overcome by electrostatic forces or intermolecular forces. Chemical dispersion methods are divided into the following two categories:
a)共价键法a) Covalent Bond Method
氧化石墨烯的边缘往往有缺陷，能与其它官能团发生化学反应结合，如异氰酸酯修饰氧化石墨烯，从而提高分散性。The edges of graphene oxide often have defects, which can react chemically with other functional groups, such as isocyanate-modified graphene oxide, thereby improving dispersibility.
b)非共价键法b) Non-covalent bond method
利用改性剂与石墨烯之间存在相互作用，在不破坏石墨烯的结构的情况下对其改性。常见的有通过Π-Π键、离子键、氢键或其他非共价键将石墨烯与功能分子结合。The interaction between the modifier and graphene is utilized to modify the graphene without destroying its structure. Common methods include combining graphene with functional molecules through π-π bonds, ionic bonds, hydrogen bonds or other non-covalent bonds.
中国发明专利(申请号CN113200538A)公布了加入分散剂，辅以搅拌，球磨等物理方法，从而制备石墨烯水相分散液，但仅仅利用离心的方法很难去除分散剂，且球磨的方式有可能破坏石墨烯的结构。中国发明专利(申请号CN113184841A)公布了在较为温和的条件下，通过加入少量有机溶剂，从而解决石墨烯的分散问题，但有机溶剂的存在可能会影响石墨烯分散液后续的应用。中国发明专利(申请号CN213913491U)公布了一种用于石墨烯浆料的双行星搅拌超声分散设备，能够有效的提升装置的搅拌速率，保证搅拌均匀性，但会产生较高的成本。目前市面上已有的一些碳纳米材料分散液，均以液体形式存在，其溶剂多为毒性液体，不利于输运和保存。在实际的实验和生产中，要求分散工艺更简洁，溶剂更常见且安全环保。因此，迫切需要开发一种具有良好分散性及稳定性的碳纳米材料分散方法。Chinese invention patent (application number CN113200538A) discloses adding dispersant, supplemented by stirring, ball milling and other physical methods, so as to prepare graphene aqueous phase dispersion, but it is difficult to remove dispersant by centrifugal method alone, and the ball milling method may destroy the structure of graphene. Chinese invention patent (application number CN113184841A) discloses solving the dispersion problem of graphene by adding a small amount of organic solvent under mild conditions, but the presence of organic solvent may affect the subsequent application of graphene dispersion. Chinese invention patent (application number CN213913491U) discloses a double planetary stirring ultrasonic dispersion device for graphene slurry, which can effectively improve the stirring rate of the device and ensure stirring uniformity, but it will produce higher cost. Some existing carbon nano material dispersions on the market are all in liquid form, and their solvents are mostly toxic liquids, which are not conducive to transportation and preservation. In actual experiments and production, it is required that the dispersion process is simpler, and the solvent is more common and safe and environmentally friendly. Therefore, it is urgent to develop a carbon nano material dispersion method with good dispersibility and stability.
发明内容Summary of the invention
本发明的技术目的主要是针对当前碳纳米材料分散性差、分散稳定性难以保证、分散工艺复杂等问题，开发一种具有良好分散性及稳定性、无分散剂添加、且结构无损的碳纳米材料分散方法，在便于输运的情况下，按照说明书方法使用，可实现高分散稳定性的碳纳米材料复合物粉末，该粉末可在不同溶剂中再次实现高分散稳定性，适用于需要利用碳纳米材料优异力学、热学、电学性能的各种场合，实现与其他材料的高分散复合，从而最大化地发挥碳纳米材料的性能优势。The technical purpose of the present invention is mainly to address the current problems of poor dispersibility of carbon nanomaterials, difficulty in ensuring dispersion stability, and complex dispersion processes, and to develop a carbon nanomaterial dispersion method with good dispersibility and stability, no dispersant addition, and no structural damage. When used in accordance with the instructions while being easy to transport, a carbon nanomaterial composite powder with high dispersion stability can be achieved. The powder can achieve high dispersion stability again in different solvents and is suitable for various occasions that require the use of the excellent mechanical, thermal, and electrical properties of carbon nanomaterials, to achieve high dispersion composites with other materials, thereby maximizing the performance advantages of carbon nanomaterials.
一种可实现高分散稳定性的碳纳米材料复合物及其制备方法，是通过以下技术方案实现的。其步骤为：A carbon nanomaterial composite with high dispersion stability and a preparation method thereof are achieved by the following technical scheme. The steps are:
1)除杂；2)分散；3)烘干；4)使用。1) Remove impurities; 2) Disperse; 3) Dry; 4) Use.
具体如下：The details are as follows:
1)除杂：将碳纳米材料石墨烯、碳纳米管、导电炭黑，分别用去离子水离心清洗至中性，离心，并在真空烘箱中烘干，所得的碳纳米材料粉末分别置于惰性气氛中进行退火处理；1) impurity removal: the carbon nanomaterials graphene, carbon nanotubes, and conductive carbon black are centrifugally washed with deionized water until neutral, centrifuged, and dried in a vacuum oven. The obtained carbon nanomaterial powders are placed in an inert atmosphere for annealing treatment;
2)分散：将碳纳米材料石墨烯、碳纳米管、导电炭黑分别置于一定的溶剂中进行第一阶段超声分散，并间歇进行机械搅拌，得到石墨烯、碳纳米管、导电炭黑分散液；随后，按照石墨烯/碳纳米管/导电炭黑质量比为(1-15):1:(0-5)将石墨烯分散液、碳纳米管分散液、导电炭黑分散液进行混合后，进行第二阶段超声分散处理，并间歇进行机械搅拌；2) Dispersion: placing carbon nanomaterials graphene, carbon nanotubes, and conductive carbon black in a certain solvent for a first-stage ultrasonic dispersion, and intermittently performing mechanical stirring to obtain graphene, carbon nanotubes, and conductive carbon black dispersions; subsequently, mixing the graphene dispersion, carbon nanotube dispersion, and conductive carbon black dispersion according to a mass ratio of graphene/carbon nanotubes/conductive carbon black of (1-15):1:(0-5), and then performing a second-stage ultrasonic dispersion treatment, and intermittently performing mechanical stirring;
3)烘干：烘干：将所得分散液置于一定温度的水浴锅内加热，并伴随磁力搅拌至糊状，随后置于真空烘箱中烘干，将所得复合物研磨成粉状，并真空密封保存；3) Drying: Drying: The obtained dispersion is placed in a water bath at a certain temperature and heated, accompanied by magnetic stirring until it becomes a paste, and then placed in a vacuum oven for drying, the obtained composite is ground into powder, and vacuum-sealed for storage;
4)使用：将复合物在目标溶剂(去离子水，醇类、酮类、酯类、胺类等有机溶剂中的一种或几种，或含有溶质)中以一定浓度进行超声分散，获得具有高分散稳定性的碳纳米材料体系。4) Use: The complex is ultrasonically dispersed in a target solvent (deionized water, one or more organic solvents such as alcohols, ketones, esters, amines, etc., or containing solutes) at a certain concentration to obtain a carbon nanomaterial system with high dispersion stability.
其中步骤(1)中石墨烯尺寸6-100μm，层数<10层，厚度1-3nm，纯度>95％；碳纳米管为无官能团的单壁，双壁或多壁碳纳米管，长度0.5-10μm，直径4-100nm，纯度>95％；导电炭黑粒径30-40nm；The graphene in step (1) has a size of 6-100 μm, a number of layers <10, a thickness of 1-3 nm, and a purity >95%; the carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes without functional groups, with a length of 0.5-10 μm, a diameter of 4-100 nm, and a purity >95%; and the conductive carbon black particle size is 30-40 nm;
进一步步骤1)中除杂过程，离心速率为4000-8000r min-1；烘箱烘干温度为60-100℃；除杂过程中，退火处理的气氛为N2或Ar，退火温度为300-600℃，退火处理时间为2-4h。In the impurity removal process in step 1), the centrifugal speed is 4000-8000 r min-1 ; the oven drying temperature is 60-100° C.; during the impurity removal process, the annealing atmosphere is N2 or Ar, the annealing temperature is 300-600° C., and the annealing time is 2-4 h.
进一步，步骤(2)超声分散过程中，所使用的溶剂为去离子水或乙醇，碳纳米材料在溶剂中的浓度为1g/(2000-10000)ml，超声分散处理的超声功率为200-600W，溶液温度控制在20-30℃；第一阶段超声时间为5-15min，间歇机械搅拌的时间间隔为2-5min；第二阶段的超声时间为35-100min，间歇机械搅拌的时间间隔为5-10min。Furthermore, in the ultrasonic dispersion process of step (2), the solvent used is deionized water or ethanol, the concentration of the carbon nanomaterial in the solvent is 1g/(2000-10000)ml, the ultrasonic power of the ultrasonic dispersion treatment is 200-600W, and the solution temperature is controlled at 20-30°C; the ultrasonic time of the first stage is 5-15min, and the time interval of intermittent mechanical stirring is 2-5min; the ultrasonic time of the second stage is 35-100min, and the time interval of intermittent mechanical stirring is 5-10min.
步骤2)石墨烯尺寸S与碳纳米管直径OD应保持在S/OD＝1±0.6，且当S≤50μm时，石墨烯/碳纳米管/导电炭黑质量比为(9-15):1:(0-3)；当S>50μm时，石墨烯/碳纳米管/导电炭黑质量比为(1-9):1:(3-5)。Step 2) The graphene size S and the carbon nanotube diameter OD should be maintained at S/OD=1±0.6, and when S≤50μm, the mass ratio of graphene/carbon nanotube/conductive carbon black is (9-15):1:(0-3); when S>50μm, the mass ratio of graphene/carbon nanotube/conductive carbon black is (1-9):1:(3-5).
进一步步骤3)，烘干过程中，水浴锅的温度t为60-100℃，磁力搅拌速度v范围为500-2500r/min，期间根据溶液蒸发程度设定水浴锅温度，与磁力搅拌速度满足如下关系v＝-50t+5000；In a further step 3), during the drying process, the temperature t of the water bath is 60-100°C, and the magnetic stirring speed v ranges from 500-2500 r/min. During this period, the water bath temperature is set according to the degree of evaporation of the solution, and the magnetic stirring speed satisfies the following relationship v=-50t+5000;
步骤3)烘干过程中，真空烘箱初始温度与水浴锅最终温度一致，直至溶液烘干，烘干过程每延长1h，烘箱温度降低5-10℃；Step 3) During the drying process, the initial temperature of the vacuum oven is consistent with the final temperature of the water bath until the solution is dried. For every hour of the drying process, the oven temperature is reduced by 5-10°C;
步骤4)使用过程中，目标溶剂可按照实际应用情况选择，碳纳米材料复合物在目标溶剂中的浓度为1g/(1000-5000)ml，对碳纳米材料复合物的超声功率为200-600W，超声时间为10-30min，所得分散液静置30天后，其紫外吸光度较静置前分散液的紫外吸光度降低不超过20％；Step 4) During use, the target solvent can be selected according to the actual application situation. The concentration of the carbon nanomaterial composite in the target solvent is 1g/(1000-5000)ml, the ultrasonic power of the carbon nanomaterial composite is 200-600W, the ultrasonic time is 10-30min, and the ultraviolet absorbance of the obtained dispersion liquid after standing for 30 days is reduced by no more than 20% compared with the ultraviolet absorbance of the dispersion liquid before standing;
本发明提供的可实现高分散稳定性的碳纳米材料复合物具有显著的优点：The carbon nanomaterial composite with high dispersion stability provided by the present invention has significant advantages:
本发明利用石墨烯/碳纳米管/导电炭黑三种碳纳米材料在不同尺寸维度的优势特征，搭建稳固的低维多尺度三维结构，碳纳米材料彼此互相分散，不添加任何分散剂，且操作条件温和，保证了碳纳米材料的结构完整性，所获得的碳纳米材料复合物为粉末材料，便于输运，可用于各种需要利用碳纳米材料优异性能的场合，在保障其分散稳定性的前提下，充分利用碳纳米材料的优势性能，从而进一步拓展碳纳米材料的应用领域。The present invention utilizes the advantageous characteristics of three carbon nanomaterials, graphene/carbon nanotubes/conductive carbon black, in different size dimensions to build a stable low-dimensional multi-scale three-dimensional structure. The carbon nanomaterials are dispersed with each other without adding any dispersant, and the operating conditions are mild, thereby ensuring the structural integrity of the carbon nanomaterials. The obtained carbon nanomaterial composite is a powder material, which is easy to transport and can be used in various occasions that require the excellent performance of carbon nanomaterials. Under the premise of ensuring its dispersion stability, the advantageous performance of carbon nanomaterials is fully utilized, thereby further expanding the application field of carbon nanomaterials.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1(a)是实施例4中制备的石墨烯/碳纳米管/导电炭黑分散液室温静置30天的宏观照片。图1(b)是实施例4中制备的石墨烯/碳纳米管/导电炭黑分散液室温静置30天后离心30min的宏观照片。Figure 1(a) is a macroscopic photograph of the graphene/carbon nanotube/conductive carbon black dispersion prepared in Example 4 after standing at room temperature for 30 days. Figure 1(b) is a macroscopic photograph of the graphene/carbon nanotube/conductive carbon black dispersion prepared in Example 4 after standing at room temperature for 30 days and centrifuging for 30 minutes.
图2(a)是实施例4中石墨烯分散液静置30天透射电镜图及分散液宏观照片。图2(b)是实施例4中碳纳米管分散液静置30天透射电镜图及分散液宏观照片。图2(c)是实施例4中炭黑分散液静置30天透射电镜图及分散液宏观照片。图2(d)是实施例4中石墨烯/碳纳米管/导电炭黑分散液静置30天透射电镜图及分散液宏观照片。Figure 2(a) is a transmission electron microscope image of the graphene dispersion in Example 4 after standing for 30 days and a macroscopic photograph of the dispersion. Figure 2(b) is a transmission electron microscope image of the carbon nanotube dispersion in Example 4 after standing for 30 days and a macroscopic photograph of the dispersion. Figure 2(c) is a transmission electron microscope image of the carbon black dispersion in Example 4 after standing for 30 days and a macroscopic photograph of the dispersion. Figure 2(d) is a transmission electron microscope image of the graphene/carbon nanotube/conductive carbon black dispersion in Example 4 after standing for 30 days and a macroscopic photograph of the dispersion.
图3是实施例4中石墨烯/碳纳米管/导电炭黑分散液静置0天和30天的紫外光谱图。FIG3 is a UV spectrum of the graphene/carbon nanotube/conductive carbon black dispersion in Example 4 after standing for 0 days and 30 days.
具体实施方式DETAILED DESCRIPTION
下面结合实施例对本发明做进一步说明，但本发明冰冰限于以下实施例。The present invention will be further described below in conjunction with embodiments, but the present invention is not limited to the following embodiments.
实施例1：Embodiment 1:
1)除杂：将碳纳米材料(石墨烯、碳纳米管、导电炭黑，其中，石墨烯尺寸6μm，层数<10层，厚度1-3nm，纯度>95％；碳纳米管为无官能团的单壁，双壁或多壁碳纳米管，长度0.5μm，直径4nm，纯度>95％；导电炭黑粒径30-40nm)分别用去离子水离心清洗至中性，离心速率为4000r min-1，并在真空烘箱中烘干(温度为60℃)，所得的碳纳米材料粉末分别置于N2惰性气氛中在300℃温度下进行4h的退火处理；1) Impurity removal: carbon nanomaterials (graphene, carbon nanotubes, conductive carbon black, wherein graphene has a size of 6 μm, a number of layers <10, a thickness of 1-3 nm, and a purity of >95%; carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes without functional groups, with a length of 0.5 μm, a diameter of 4 nm, and a purity of >95%; conductive carbon black has a particle size of 30-40 nm) are respectively washed by centrifugation with deionized water until neutral, at a centrifugal speed of 4000 r min-1 , and dried in a vacuum oven (at a temperature of 60° C.), and the obtained carbon nanomaterial powders are respectively placed in a N2 inert atmosphere at a temperature of 300° C. for annealing for 4 h;
2)分散：将碳纳米材料分别以浓度为1g/2000ml置于去离子水中，在600W功率、溶液温度20℃下，进行第一阶段超声分散处理，并间歇进行机械搅拌，超声时间为5min，间歇机械搅拌的时间间隔为2min，随后，将碳纳米材料按照石墨烯/碳纳米管/导电炭黑为15：1：1质量比进行分散液混合后，进行第二阶段超声分散处理，并间歇进行机械搅拌，超声时间为100min，间歇机械搅拌的时间间隔为5min；2) Dispersion: The carbon nanomaterials were placed in deionized water at a concentration of 1 g/2000 ml, and the first stage of ultrasonic dispersion treatment was carried out at a power of 600 W and a solution temperature of 20° C., and mechanical stirring was performed intermittently. The ultrasonic time was 5 min, and the time interval of the intermittent mechanical stirring was 2 min. Subsequently, the carbon nanomaterials were mixed with a dispersion liquid according to a mass ratio of graphene/carbon nanotubes/conductive carbon black of 15:1:1, and then the second stage of ultrasonic dispersion treatment was carried out, and mechanical stirring was performed intermittently. The ultrasonic time was 100 min, and the time interval of the intermittent mechanical stirring was 5 min.
3)烘干：将所得分散液置于60℃温度的水浴锅内加热，并伴随2000r/min磁力搅拌至糊状，随后置于真空烘箱中烘干，其初始温度与水浴锅最终温度一致，直至溶液烘干，且烘干过程每延长1h，烘箱温度降低5℃，再将所得复合物研磨成粉状，并真空密封保存；3) Drying: The obtained dispersion is heated in a water bath at 60°C and stirred with a magnetic force at 2000 r/min until it becomes a paste, and then dried in a vacuum oven, the initial temperature of which is consistent with the final temperature of the water bath, until the solution is dried, and the oven temperature is reduced by 5°C for every 1 hour of the drying process, and then the obtained composite is ground into powder and stored in a vacuum seal;
4)使用：将复合物在去离子水中以1g/1000ml浓度混合并进行超声分散(超声功率为600W，超声时间为30min)得到分散液，其0天的紫外吸光度为2.598。所得分散液静置30天后，其紫外吸光度为2.133，较静置前分散液的紫外吸光度降低17.9％。4) Use: The complex was mixed in deionized water at a concentration of 1 g/1000 ml and ultrasonically dispersed (ultrasonic power of 600 W, ultrasonic time of 30 min) to obtain a dispersion, the ultraviolet absorbance of which was 2.598 on day 0. After the dispersion was allowed to stand for 30 days, the ultraviolet absorbance was 2.133, which was 17.9% lower than that of the dispersion before standing.
实施例2：Embodiment 2:
1)除杂：将碳纳米材料(石墨烯、碳纳米管、导电炭黑，其中，石墨烯尺寸30μm，层数<10层，厚度1-3nm，纯度>95％；碳纳米管为无官能团的单壁，双壁或多壁碳纳米管，长度0.5μm，直径40nm，纯度>95％；导电炭黑粒径30-40nm)分别用去离子水离心清洗至中性，离心速率为5000r min-1，并在真空烘箱中烘干(温度为70℃)，所得的碳纳米材料粉末分别置于N2惰性气氛中在400℃温度下进行4h的退火处理；1) Impurity removal: carbon nanomaterials (graphene, carbon nanotubes, conductive carbon black, wherein graphene has a size of 30 μm, a number of layers <10, a thickness of 1-3 nm, and a purity of >95%; carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes without functional groups, with a length of 0.5 μm, a diameter of 40 nm, and a purity of >95%; conductive carbon black has a particle size of 30-40 nm) are respectively washed by centrifugation with deionized water until neutral, at a centrifugal speed of 5000 r min-1 , and dried in a vacuum oven (at a temperature of 70° C.), and the obtained carbon nanomaterial powders are respectively placed in a N2 inert atmosphere at a temperature of 400° C. for annealing for 4 h;
2)分散：将碳纳米材料分别以浓度为1g/4000ml置于去离子水中，在500W功率、溶液温度25℃下，进行第一阶段超声分散处理，并间歇进行机械搅拌，超声时间为8min，间歇机械搅拌的时间间隔为2min，随后，将碳纳米材料按照石墨烯/碳纳米管/导电炭黑为11：1：2质量比进行分散液混合后，进行第二阶段超声分散处理，并间歇进行机械搅拌，超声时间为80min，间歇机械搅拌的时间间隔为6min；2) Dispersion: The carbon nanomaterials were placed in deionized water at a concentration of 1 g/4000 ml, and the first stage of ultrasonic dispersion treatment was carried out at a power of 500 W and a solution temperature of 25°C, and mechanical stirring was performed intermittently. The ultrasonic time was 8 minutes, and the time interval of the intermittent mechanical stirring was 2 minutes. Subsequently, the carbon nanomaterials were mixed with a dispersion liquid according to a mass ratio of graphene/carbon nanotubes/conductive carbon black of 11:1:2, and then the second stage of ultrasonic dispersion treatment was carried out, and mechanical stirring was performed intermittently. The ultrasonic time was 80 minutes, and the time interval of the intermittent mechanical stirring was 6 minutes;
3)烘干：将所得分散液置于60℃温度的水浴锅内加热，并伴随2000r/min磁力搅拌至糊状，随后置于真空烘箱中烘干，其初始温度与水浴锅最终温度一致，直至溶液烘干，且烘干过程每延长1h，烘箱温度降低6℃，再将所得复合物研磨成粉状，并真空密封保存；3) Drying: The obtained dispersion is heated in a water bath at 60°C and stirred with a magnetic force at 2000 r/min until it becomes a paste, and then dried in a vacuum oven, the initial temperature of which is consistent with the final temperature of the water bath, until the solution is dried, and the oven temperature is reduced by 6°C for every 1 h of the drying process, and then the obtained composite is ground into powder and stored in a vacuum seal;
4)使用：将复合物在异丙醇中以1g/2000ml浓度混合并进行超声分散(超声功率为500W，超声时间为25min)得到分散液，其0天的紫外吸光度为2.673。所得分散液静置30天后，其紫外吸光度为2.213，较静置前分散液的紫外吸光度降低17.2％。4) Use: The complex was mixed in isopropanol at a concentration of 1 g/2000 ml and ultrasonically dispersed (ultrasonic power of 500 W, ultrasonic time of 25 min) to obtain a dispersion, whose ultraviolet absorbance on day 0 was 2.673. After the obtained dispersion was allowed to stand for 30 days, its ultraviolet absorbance was 2.213, which was 17.2% lower than the ultraviolet absorbance of the dispersion before standing.
实施例3：Embodiment 3:
1)除杂：将碳纳米材料(石墨烯、碳纳米管、导电炭黑，其中，石墨烯尺寸50μm，层数<10层，厚度1-3nm，纯度>95％；碳纳米管为无官能团的单壁，双壁或多壁碳纳米管，长度0.5μm，直径50nm，纯度>95％；导电炭黑粒径30-40nm)分别用无水乙醇离心清洗至中性，离心速率为6000r min-1，并在真空烘箱中烘干(温度为80℃)，所得的碳纳米材料粉末分别置于Ar惰性气氛中在450℃温度下进行3h的退火处理；1) Impurity removal: carbon nanomaterials (graphene, carbon nanotubes, conductive carbon black, wherein graphene has a size of 50 μm, a number of layers <10, a thickness of 1-3 nm, and a purity of >95%; carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes without functional groups, with a length of 0.5 μm, a diameter of 50 nm, and a purity of >95%; conductive carbon black has a particle size of 30-40 nm) are respectively washed by centrifugation with anhydrous ethanol until neutrality is obtained at a centrifugal speed of 6000 r min-1 , and dried in a vacuum oven (temperature of 80° C.), and the obtained carbon nanomaterial powders are respectively placed in an Ar inert atmosphere at a temperature of 450° C. for annealing for 3 h;
2)分散：将碳纳米材料分别以浓度为1g/6000ml置于去离子水中，在400W功率、溶液温度25℃下，进行第一阶段超声分散处理，并间歇进行机械搅拌，超声时间为10min，间歇机械搅拌的时间间隔为2min，随后，将碳纳米材料按照石墨烯/碳纳米管/导电炭黑为9：1：3质量比进行分散液混合后，进行第二阶段超声分散处理，并间歇进行机械搅拌，超声时间为60min，间歇机械搅拌的时间间隔为7min；2) Dispersion: The carbon nanomaterials were placed in deionized water at a concentration of 1 g/6000 ml, and the first stage of ultrasonic dispersion treatment was carried out at a power of 400 W and a solution temperature of 25° C., and mechanical stirring was performed intermittently. The ultrasonic time was 10 min, and the time interval of the intermittent mechanical stirring was 2 min. Subsequently, the carbon nanomaterials were mixed with a dispersion liquid according to a mass ratio of graphene/carbon nanotubes/conductive carbon black of 9:1:3, and then the second stage of ultrasonic dispersion treatment was carried out, and mechanical stirring was performed intermittently. The ultrasonic time was 60 min, and the time interval of the intermittent mechanical stirring was 7 min.
3)烘干：将所得分散液置于70℃温度的水浴锅内加热，并伴随1500r/min磁力搅拌至糊状，随后置于真空烘箱中烘干，其初始温度与水浴锅最终温度一致，直至溶液烘干，且烘干过程每延长1h，烘箱温度降低7℃，再将所得复合物研磨成粉状，并真空密封保存；3) Drying: The obtained dispersion is heated in a water bath at 70°C and stirred with a magnetic force at 1500 r/min until it becomes a paste, and then dried in a vacuum oven, the initial temperature of which is consistent with the final temperature of the water bath, until the solution is dried, and the oven temperature is reduced by 7°C for every 1 h of the drying process, and then the obtained composite is ground into powder and stored in a vacuum seal;
4)使用：将复合物在十二烷基苯硫酸钠水溶液(浓度为4×10-3mol/L)中以1g/3000ml浓度混合并进行超声分散(超声功率为400W，超声时间为20min)得到分散液，其0天的紫外吸光度为2.696。所得分散液静置30天后，其紫外吸光度为2.270，较静置前分散液的紫外吸光度降低15.8％。4) Use: The complex was mixed in a sodium dodecylbenzene sulfate aqueous solution (concentration of 4×10-3 mol/L) at a concentration of 1 g/3000 ml and subjected to ultrasonic dispersion (ultrasonic power of 400 W, ultrasonic time of 20 min) to obtain a dispersion whose ultraviolet absorbance on day 0 was 2.696. After the dispersion was allowed to stand for 30 days, its ultraviolet absorbance was 2.270, which was 15.8% lower than the ultraviolet absorbance of the dispersion before standing.
实施例4：Embodiment 4:
1)除杂：将碳纳米材料(石墨烯、碳纳米管、导电炭黑，其中，石墨烯尺寸80μm，层数<10层，厚度1-3nm，纯度>95％；碳纳米管为无官能团的单壁，双壁或多壁碳纳米管，长度0.5μm，直径60nm，纯度>95％；导电炭黑粒径30-40nm)分别用无水乙醇离心清洗至中性，离心速率为7000r min-1，并在真空烘箱中烘干(温度为90℃)，所得的碳纳米材料粉末分别置于Ar惰性气氛中在500℃温度下进行2h的退火处理；1) Impurity removal: carbon nanomaterials (graphene, carbon nanotubes, conductive carbon black, wherein graphene has a size of 80 μm, a number of layers <10, a thickness of 1-3 nm, and a purity of >95%; carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes without functional groups, with a length of 0.5 μm, a diameter of 60 nm, and a purity of >95%; conductive carbon black has a particle size of 30-40 nm) are respectively washed by centrifugation with anhydrous ethanol until neutrality is obtained at a centrifugal speed of 7000 r min-1 , and dried in a vacuum oven (temperature of 90° C.), and the obtained carbon nanomaterial powders are respectively placed in an Ar inert atmosphere at a temperature of 500° C. for annealing for 2 h;
2)分散：将碳纳米材料分别以浓度为1g/8000ml置于去离子水中，在300W功率、溶液温度25℃下，进行第一阶段超声分散处理，并间歇进行机械搅拌，超声时间为12min，间歇机械搅拌的时间间隔为2min，随后，将碳纳米材料按照石墨烯/碳纳米管/导电炭黑为3：1：4质量比进行分散液混合后，进行第二阶段超声分散处理，并间歇进行机械搅拌，超声时间为50min，间歇机械搅拌的时间间隔为8min；2) Dispersion: The carbon nanomaterials were placed in deionized water at a concentration of 1 g/8000 ml, and the first stage of ultrasonic dispersion treatment was carried out at a power of 300 W and a solution temperature of 25°C, and mechanical stirring was performed intermittently. The ultrasonic time was 12 min, and the time interval of the intermittent mechanical stirring was 2 min. Subsequently, the carbon nanomaterials were mixed with a dispersion liquid according to a mass ratio of graphene/carbon nanotubes/conductive carbon black of 3:1:4, and then the second stage of ultrasonic dispersion treatment was carried out, and mechanical stirring was performed intermittently. The ultrasonic time was 50 min, and the time interval of the intermittent mechanical stirring was 8 min.
3)烘干：将所得分散液置于80℃温度的水浴锅内加热，并伴随1000r/min磁力搅拌至糊状，随后置于真空烘箱中烘干，其初始温度与水浴锅最终温度一致，直至溶液烘干，且烘干过程每延长1h，烘箱温度降低8℃，再将所得复合物研磨成粉状，并真空密封保存；3) Drying: The obtained dispersion is heated in a water bath at 80°C and stirred with a magnetic force at 1000 r/min until it becomes a paste, and then dried in a vacuum oven, the initial temperature of which is consistent with the final temperature of the water bath, until the solution is dried, and the oven temperature is reduced by 8°C for every 1 h of the drying process, and then the obtained composite is ground into powder and stored in a vacuum seal;
4)使用：将复合物在无水乙醇溶剂中以1g/4000ml浓度混合并进行超声分散(超声功率为300W，超声时间为15min)得到分散液，其0天的紫外吸光度为2.967。所得分散液静置30天后，其紫外吸光度为2.564，较静置前分散液的紫外吸光度降低13.6％。4) Use: The complex was mixed in anhydrous ethanol solvent at a concentration of 1 g/4000 ml and ultrasonically dispersed (ultrasonic power of 300 W, ultrasonic time of 15 min) to obtain a dispersion, whose ultraviolet absorbance on day 0 was 2.967. After the obtained dispersion was allowed to stand for 30 days, its ultraviolet absorbance was 2.564, which was 13.6% lower than the ultraviolet absorbance of the dispersion before standing.
实施例5：Embodiment 5:
1)除杂：将碳纳米材料(石墨烯、碳纳米管、导电炭黑，其中，石墨烯尺寸100μm，层数<10层，厚度1-3nm，纯度>95％；碳纳米管为无官能团的单壁，双壁或多壁碳纳米管，长度0.5μm，直径100nm，纯度>95％；导电炭黑粒径30-40nm)分别用无水乙醇离心清洗至中性，离心速率为8000r min-1，并在真空烘箱中烘干(温度为100℃)，所得的碳纳米材料粉末分别置于Ar惰性气氛中在600℃温度下进行2h的退火处理；1) Impurity removal: carbon nanomaterials (graphene, carbon nanotubes, conductive carbon black, wherein graphene has a size of 100 μm, a number of layers <10, a thickness of 1-3 nm, and a purity of >95%; carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes without functional groups, with a length of 0.5 μm, a diameter of 100 nm, and a purity of >95%; conductive carbon black has a particle size of 30-40 nm) are respectively centrifuged and washed with anhydrous ethanol until neutral, at a centrifugal speed of 8000 r min-1 , and dried in a vacuum oven (at a temperature of 100° C.), and the obtained carbon nanomaterial powders are respectively placed in an Ar inert atmosphere and annealed at a temperature of 600° C. for 2 h;
2)分散：将碳纳米材料分别以浓度为1g/10000ml置于去离子水中，在200W功率、溶液温度20℃下，进行第一阶段超声分散处理，并间歇进行机械搅拌，超声时间为15min，间歇机械搅拌的时间间隔为2min，随后，将碳纳米材料按照石墨烯/碳纳米管/导电炭黑为2：1：3质量比进行分散液混合后，进行第二阶段超声分散处理，并间歇进行机械搅拌，超声时间为35min，间歇机械搅拌的时间间隔为10min；2) Dispersion: The carbon nanomaterials were placed in deionized water at a concentration of 1 g/10000 ml, and the first stage of ultrasonic dispersion treatment was carried out at a power of 200 W and a solution temperature of 20° C., and mechanical stirring was performed intermittently. The ultrasonic time was 15 min, and the time interval of the intermittent mechanical stirring was 2 min. Subsequently, the carbon nanomaterials were mixed with a dispersion liquid according to a mass ratio of graphene/carbon nanotubes/conductive carbon black of 2:1:3, and then the second stage of ultrasonic dispersion treatment was carried out, and mechanical stirring was performed intermittently. The ultrasonic time was 35 min, and the time interval of the intermittent mechanical stirring was 10 min.
3)烘干：将所得分散液置于90℃温度的水浴锅内加热，并伴随500r/min磁力搅拌至糊状，随后置于真空烘箱中烘干，其初始温度与水浴锅最终温度一致，直至溶液烘干，且烘干过程每延长1h，烘箱温度降低10℃，再将所得复合物研磨成粉状，并真空密封保存；3) Drying: The obtained dispersion is heated in a water bath at 90°C and stirred with a magnetic force at 500 r/min until it becomes a paste, and then dried in a vacuum oven, the initial temperature of which is consistent with the final temperature of the water bath, until the solution is dried, and the oven temperature is reduced by 10°C for every 1 hour of the drying process, and then the obtained composite is ground into powder and stored in a vacuum seal;
4)使用：将复合物在三聚氰胺水溶液(浓度为0.2g/5000ml)中以1g/5000ml浓度混合并进行超声分散(超声功率为200W，超声时间为10min)得到分散液，其0天的紫外吸光度为3.136。所得分散液静置30天后，其紫外吸光度为2.521，较静置前分散液的紫外吸光度降低19.6％。4) Use: The complex was mixed with a melamine aqueous solution (concentration of 0.2 g/5000 ml) at a concentration of 1 g/5000 ml and subjected to ultrasonic dispersion (ultrasonic power of 200 W, ultrasonic time of 10 min) to obtain a dispersion, the ultraviolet absorbance of which was 3.136 on day 0. After the obtained dispersion was allowed to stand for 30 days, the ultraviolet absorbance was 2.521, which was 19.6% lower than the ultraviolet absorbance of the dispersion before standing.
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