CN106044752B - A kind of preparation method of highly oriented graphene aerogel - Google Patents
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Abstract
本发明公开了一种高取向石墨烯气凝胶及其制备方法，首先制备石墨烯或氧化石墨烯的分散液，然后将石墨烯或氧化石墨烯分散液置于带电极的容器中，通过外加电场取向的方法，获得高取向的石墨烯或氧化石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，通过冷冻干燥或超临界干燥后获得高取向石墨烯气凝胶。所得高取向石墨烯气凝胶孔隙率高，孔隙沿着电场方向有很高的取向度，孔隙尺寸可控，可用于电池和超级电容器的电极材料、电子场发射源、隔热散热材料、吸附材料、高通量滤水材料和催化剂载体等。
The invention discloses a highly oriented graphene aerogel and a preparation method thereof. First, a dispersion of graphene or graphene oxide is prepared, and then the graphene or graphene oxide dispersion is placed in a container with electrodes, and the graphene or graphene oxide dispersion is placed in a container with electrodes. The method of electric field orientation obtains highly oriented graphene or graphene oxide dispersion, continues to maintain the electric field, freezes and solidifies in liquid nitrogen, and obtains highly oriented graphene aerogel after freeze drying or supercritical drying. The obtained highly oriented graphene aerogel has high porosity, the pores have a high degree of orientation along the direction of the electric field, and the pore size is controllable, and can be used as electrode materials for batteries and supercapacitors, electron field emission sources, thermal insulation materials, adsorption materials, high-throughput water filtration materials and catalyst supports, etc.
Description
技术领域technical field
本发明涉及石墨烯气凝胶的制备领域，尤其是涉及一种高取向石墨烯气凝胶的制备方法。The invention relates to the field of preparation of graphene aerogels, in particular to a preparation method of highly oriented graphene aerogels.
背景技术Background technique
石墨烯(Graphene)是一种单分子层二维晶体，具有已知材料最高的强度以及优异的导电性和导热性，是目前最理想的二维纳米材料，在材料、化学、生物、能源等领域具有广阔的应用前景。2010年，英国曼彻斯特大学的两位教授Andre Geim和KonstantinNovoselov因为首次成功分离出稳定的石墨烯获得诺贝尔物理学奖，掀起了全世界对石墨烯研究的热潮。宏观的石墨烯气凝胶是纳米级石墨烯的主要应用形式之一。因其充分发挥了石墨烯比表面积大，化学稳定性好，导电导热性好的优点，石墨烯气凝胶可以用作电池和超级电容器的电极材料、电子场发射源、隔热散热材料、吸附材料、高通量滤水材料和催化剂载体等。Graphene is a monolayer two-dimensional crystal with the highest strength of known materials and excellent electrical and thermal conductivity. It is currently the most ideal two-dimensional nanomaterial. The field has broad application prospects. In 2010, two professors from the University of Manchester, Andre Geim and Konstantin Novoselov, won the Nobel Prize in Physics for the first successful separation of stable graphene, setting off a worldwide upsurge in graphene research. Macroscopic graphene aerogel is one of the main application forms of nanoscale graphene. Because of its large specific surface area, good chemical stability, and good electrical and thermal conductivity of graphene, graphene aerogels can be used as electrode materials for batteries and supercapacitors, electron field emission sources, thermal insulation materials, adsorption materials, high-throughput water filtration materials and catalyst supports, etc.
通过化学气相沉淀法、冰模板法、自组装法和水热法等方法可以制备三维石墨烯气凝胶。化学气相沉淀法高度依赖于三维结构的金属模板，步骤繁琐，操作复杂，难以实现大规模的工业化制备；冰模板法是以石墨烯或氧化石墨烯水溶液冷冻过程中的冰晶为模板制备气凝胶的方法；自组装法和水热法利用石墨烯的液晶性和各向异性，在一定条件下获得具有一定取向度的气凝胶。Three-dimensional graphene aerogels can be prepared by chemical vapor deposition, ice template, self-assembly, and hydrothermal methods. The chemical vapor deposition method is highly dependent on the metal template of the three-dimensional structure, the steps are cumbersome, the operation is complicated, and it is difficult to achieve large-scale industrial preparation; the ice template method uses the ice crystal during the freezing process of graphene or graphene oxide aqueous solution as a template to prepare aerogels The self-assembly method and the hydrothermal method utilize the liquid crystallinity and anisotropy of graphene to obtain aerogels with a certain degree of orientation under certain conditions.
以上方法缺乏对石墨烯分散体系的预处理和预取向，获得产品结构有序性差。制备具有高度取向结构的石墨烯气凝胶仍然是一个巨大的挑战。The above methods lack the pretreatment and pre-orientation of the graphene dispersion system, and the obtained products have poor structural order. The preparation of graphene aerogels with highly oriented structures remains a great challenge.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的上述问题，本申请人提供了一种高取向石墨烯气凝胶的制备方法。本发明所得高取向石墨烯气凝胶孔隙率高，孔隙沿着电场方向有很高的取向度，孔隙尺寸可控，可用于电池和超级电容器的电极材料、电子场发射源、隔热散热材料、吸附材料、高通量滤水材料和催化剂载体等。In view of the above problems existing in the prior art, the applicant provides a method for preparing a highly oriented graphene aerogel. The highly oriented graphene aerogel obtained by the invention has high porosity, the pores have a high degree of orientation along the direction of the electric field, and the pore size is controllable, and can be used as electrode materials, electron field emission sources, heat insulation and heat dissipation materials for batteries and supercapacitors , adsorption materials, high-flux water filtration materials and catalyst carriers, etc.
本发明的技术方案如下：The technical scheme of the present invention is as follows:
本申请人提供了一种高取向石墨烯气凝胶的制备方法，具体步骤如下：The applicant provides a kind of preparation method of highly oriented graphene aerogel, and the concrete steps are as follows:
(1)将1g的石墨烯与20～100g的水混合，超声分散后得到石墨烯分散液；(1) 1 g of graphene is mixed with 20 to 100 g of water, and a graphene dispersion is obtained after ultrasonic dispersion;
(2)将步骤(1)制备得到的石墨烯分散液置于带电极的容器中，通过外加电场对溶液取向1～100分钟，得到高取向的石墨烯分散液；所述外加交变电场的频率为10～1000Hz，强度为50～5000V/m；(2) placing the graphene dispersion prepared in step (1) in a container with electrodes, and orienting the solution by applying an electric field for 1 to 100 minutes to obtain a highly oriented graphene dispersion; The frequency is 10～1000Hz, and the intensity is 50～5000V/m;
(3)将步骤(2)得到的高取向的石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，再进一步冷冻干燥或者临界冷冻干燥，得到高取向石墨烯气凝胶。(3) the highly oriented graphene dispersion liquid obtained in step (2) continues to maintain the action of the electric field, freeze and solidify in liquid nitrogen, and further freeze-dry or critically freeze-dry to obtain a highly oriented graphene aerogel.
优选的，步骤(1)所述超声分散的时间为：10～100分钟。Preferably, the ultrasonic dispersion time in step (1) is 10-100 minutes.
优选的，步骤(2)通过外加电场对溶液取向1～100分钟，得到高取向的石墨烯分散液；所述外加交变电场的频率为10～500Hz，强度为10～2000V/m。Preferably, in step (2), the solution is oriented by an external electric field for 1-100 minutes to obtain a highly oriented graphene dispersion; the frequency of the applied alternating electric field is 10-500 Hz, and the intensity is 10-2000 V/m.
本申请人还提供了一种高取向氧化石墨烯气凝胶的制备方法，具体步骤如下：The applicant also provides a method for preparing a highly oriented graphene oxide aerogel, the specific steps are as follows:
(1)将1g的氧化石墨烯与10～100g的水混合，超声分散后得到氧化石墨烯分散液；(1) 1 g of graphene oxide is mixed with 10 to 100 g of water, and a graphene oxide dispersion is obtained after ultrasonic dispersion;
(2)将步骤(1)制备得到的氧化石墨烯分散液置于带电极的容器中，通过外加电场对溶液取向1～100分钟，得到高取向的氧化石墨烯分散液；所述外加交变电场的频率为10～1000Hz，强度为50～5000V/m；(2) placing the graphene oxide dispersion liquid prepared in step (1) in a container with electrodes, and orienting the solution by applying an electric field for 1 to 100 minutes to obtain a highly oriented graphene oxide dispersion liquid; The frequency of the electric field is 10-1000Hz, and the intensity is 50-5000V/m;
(3)将步骤(2)得到的高取向的氧化石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，再进一步冷冻干燥或者临界冷冻干燥，得到高取向氧化石墨烯气凝胶。(3) the highly oriented graphene oxide dispersion liquid obtained in step (2) continues to maintain the action of the electric field, freeze and solidify in liquid nitrogen, and then further freeze-dry or critically freeze-dry to obtain a high-orientation graphene oxide aerogel.
将步骤(3)得到的高取向氧化石墨烯气凝胶通过热处理还原得到有序多孔的氧化石墨烯气凝胶；或者将步骤(3)得到的高取向氧化石墨烯气凝胶通过化学还原剂还原，经过洗涤干燥得到有序多孔的氧化石墨烯气凝胶。The highly oriented graphene oxide aerogel obtained in step (3) is reduced by heat treatment to obtain an ordered porous graphene oxide aerogel; or the highly oriented graphene oxide aerogel obtained in step (3) is passed through a chemical reducing agent reduction, washing and drying to obtain ordered and porous graphene oxide aerogels.
优选的，步骤(1)所述超声分散的时间为：5～50分钟。Preferably, the ultrasonic dispersion time in step (1) is 5-50 minutes.
优选的，步骤(2)通过外加电场对溶液取向1～100分钟，得到高取向的石墨烯分散液；所述外加交变电场的频率为10～500Hz，强度为10～2000V/m。Preferably, in step (2), the solution is oriented by an external electric field for 1-100 minutes to obtain a highly oriented graphene dispersion; the frequency of the applied alternating electric field is 10-500 Hz, and the intensity is 10-2000 V/m.
优选的，步骤(3)冷冻干燥或者临界冷冻干燥的时间为2-40h。Preferably, the freeze-drying or critical freeze-drying time of step (3) is 2-40h.
所述还原剂选自：The reducing agent is selected from:
质量分数为1％-40％的水合肼、质量分数为1％-40％的硼氢化钠水溶液、质量分数为5％-50％的维生素C水溶液、质量分数为1％-40％的葡萄糖水溶液、质量分数为1％-40％的氢碘酸水溶液、质量分数为1％-40％的醋酸水溶液、质量分数为1％-40％的苯肼水溶液、质量分数为1％-40％的氢溴酸水溶液、质量分数为1％-40％的茶多酚水溶液、质量分数为1％-40％的尿素水溶液、质量分数为1％-20％的硫代硫酸钠水溶液、质量分数为1％-5％的氢氧化钠水溶液、质量分数为1％-40％的氢氧化钾水溶液、或质量分数为1％-40％的苯酚水溶液。Hydrazine hydrate with mass fraction of 1%-40%, sodium borohydride aqueous solution with mass fraction of 1%-40%, vitamin C aqueous solution with mass fraction of 5%-50%, glucose aqueous solution with mass fraction of 1%-40% , 1%-40% hydroiodic acid aqueous solution, 1%-40% acetic acid aqueous solution, 1%-40% phenylhydrazine aqueous solution, 1%-40% hydrogen Bromic acid aqueous solution, tea polyphenol aqueous solution with mass fraction of 1%-40%, urea aqueous solution with mass fraction of 1%-40%, sodium thiosulfate aqueous solution with mass fraction of 1%-20%, mass fraction of 1% -5% sodium hydroxide aqueous solution, 1%-40% potassium hydroxide aqueous solution, or 1%-40% phenol aqueous solution.
本发明有益的技术效果在于：The beneficial technical effects of the present invention are:
(1)使用石墨烯或氧化石墨烯为原料，适合大规模工业化制备；(1) Use graphene or graphene oxide as raw material, suitable for large-scale industrial production;
(2)制备方法充分利用石墨烯液晶属性，操作简便、绿色环保，不需要添加其他辅助性材料；(2) The preparation method makes full use of the properties of graphene liquid crystal, is easy to operate, green and environmentally friendly, and does not need to add other auxiliary materials;
(3)外加电场频率和强度可控，制备的石墨烯气凝胶取向度可以自由控制；(3) The frequency and intensity of the applied electric field are controllable, and the orientation degree of the prepared graphene aerogel can be freely controlled;
(4)制得的高取向石墨烯气凝胶密度可以调节，垂直于取向电场的方向有良好的弹性，同时有着优异的热导性和导电性。(4) The obtained highly oriented graphene aerogel can be adjusted in density, has good elasticity in the direction perpendicular to the oriented electric field, and has excellent thermal conductivity and electrical conductivity at the same time.
附图说明Description of drawings
图1为电场诱导取向石墨烯或者氧化石墨烯分散液的原理示意图；Fig. 1 is the principle schematic diagram of electric field induced oriented graphene or graphene oxide dispersion;
图2为石墨烯气凝胶断面的电子扫描显微镜照片。Figure 2 is a scanning electron microscope photograph of a graphene aerogel section.
具体实施方式Detailed ways
下面结合附图，对本发明进行具体描述。The present invention will be described in detail below with reference to the accompanying drawings.
如图1所示，利用石墨烯液晶对外加电场的响应性制备三维的石墨烯气凝胶。As shown in Figure 1, three-dimensional graphene aerogels were prepared by utilizing the responsiveness of graphene liquid crystals to an applied electric field.
本方法得到的高取向石墨烯气凝胶，石墨烯取向排列形成沿电场方向通孔，密度为0.02-0.5g/cm3，垂直于取向电场方向的压缩强度为1-15MPa，导电率大于1000S/m，孔隙率为80％-99.5％。这种具有大孔隙通孔结构的石墨烯气凝胶可以用作大表面积的结构材料，作为电极材料有利于离子的扩散，作为水处理材料可以迅速吸附滤除污染物并保持大通量，通过负载不同客体材料可以实现多种功能。In the highly oriented graphene aerogel obtained by the method, the graphene is oriented and arranged to form through holes along the electric field direction, the density is 0.02-0.5 g/cm 3 , the compressive strength perpendicular to the orientation electric field direction is 1-15 MPa, and the electrical conductivity is greater than 1000S /m, the porosity is 80%-99.5%. This graphene aerogel with large pores and through-hole structure can be used as a structural material with a large surface area, as an electrode material, which is conducive to the diffusion of ions, and as a water treatment material, it can quickly absorb and filter out pollutants and maintain a large flux. Loading different guest materials can achieve a variety of functions.
下面结合实施例对本发明作具体描述，本实施例只用于对本发明做进一步的说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整，均属于本发明的保护范围。The present invention will be specifically described below in conjunction with the embodiments. The present embodiment is only used to further illustrate the present invention, and should not be construed as a limitation on the protection scope of the present invention. Those skilled in the art make some non-essential changes according to the content of the above-mentioned invention. and adjustment, all belong to the protection scope of the present invention.
实施例1：Example 1:
(1)加入1g的石墨烯，6g的水，于24℃以12KHz的超声处理1小时，得到石墨烯分散液；(1) add 1g of graphene, 6g of water, and at 24 ° C with 12KHz ultrasonic treatment for 1 hour to obtain a graphene dispersion;
(2)将步骤(1)得到的石墨烯分散液置于带电极的容器中，通过频率为1000Hz，强度为2000V/m的外加电场对溶液取向100分钟，获得高取向的石墨烯分散液；(2) the graphene dispersion liquid obtained in step (1) is placed in a container with electrodes, and the solution is oriented for 100 minutes by an applied electric field with a frequency of 1000 Hz and an intensity of 2000 V/m to obtain a highly oriented graphene dispersion;
(3)将步骤(2)得到的高取向的石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，再进一步冷冻干燥或者临界冷冻干燥40h，得到高取向石墨烯气凝胶；(3) the highly oriented graphene dispersion liquid obtained in step (2) continues to maintain the action of the electric field, freeze and solidify in liquid nitrogen, and further freeze-dry or critically freeze-dry for 40h to obtain a highly oriented graphene aerogel;
如图2所示，所得的高取向石墨烯气凝胶，石墨烯取向排列形成沿电场方向通孔，密度为0.2g/cm3，垂直于取向电场方向的压缩强度为15MPa，取向度大于80％，导电率大于1000S/m，孔隙率为90％，可以作为高效水处理材料，污染物浓度低于20mg/mL时，吸附率可以达到95％。As shown in Figure 2, in the obtained highly oriented graphene aerogel, the graphene is oriented and arranged to form through holes along the electric field direction, the density is 0.2 g/cm 3 , the compressive strength perpendicular to the orientation electric field direction is 15 MPa, and the orientation degree is greater than 80 %, the conductivity is greater than 1000S/m, and the porosity is 90%. It can be used as a high-efficiency water treatment material. When the pollutant concentration is lower than 20mg/mL, the adsorption rate can reach 95%.
实施例2：Example 2:
(1)加入1g的石墨烯，100g的水，于60℃以5KHz的超声处理10小时，得到石墨烯分散液；(1) adding 1 g of graphene, 100 g of water, and ultrasonically treating at 60° C. with 5 KHz for 10 hours to obtain a graphene dispersion;
(2)将步骤(1)制备的石墨烯分散液置于带电极的容器中，通过频率为50Hz，强度为1000V/m的外加电场对溶液取向80分钟，获得高取向的石墨烯分散液；(2) placing the graphene dispersion prepared in step (1) in a container with electrodes, and orienting the solution for 80 minutes by an applied electric field with a frequency of 50 Hz and an intensity of 1000 V/m to obtain a highly oriented graphene dispersion;
(3)将步骤(2)得到的高取向的石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，再进一步冷冻干燥或者临界冷冻干燥3h，得到高取向石墨烯气凝胶；(3) the highly oriented graphene dispersion liquid obtained in step (2) continues to maintain the action of the electric field, freeze and solidify in liquid nitrogen, and then further freeze-dry or critically freeze-dry for 3h to obtain a highly oriented graphene aerogel;
所得的高取向石墨烯气凝胶，石墨烯取向排列形成沿电场方向通孔，密度为0.01g/cm3，垂直于取向电场方向的压缩强度为1MPa，取向度大于90％，导电率大于1000S/m，孔隙率为99％。In the obtained highly oriented graphene aerogel, the graphene is oriented and arranged to form through holes along the electric field direction, the density is 0.01 g/cm 3 , the compressive strength perpendicular to the orientation electric field direction is 1 MPa, the orientation degree is greater than 90%, and the electrical conductivity is greater than 1000S /m, the porosity is 99%.
实施例3：Example 3:
(1)加入1g的氧化石墨烯，30g的水，于40℃以10KHz的超声处理5小时，得到氧化石墨烯分散液；(1) add the graphene oxide of 1g, the water of 30g, at 40 ℃ with the ultrasonic treatment of 10KHz for 5 hours, obtain the graphene oxide dispersion liquid;
(2)将步骤(1)制备的氧化石墨烯分散液置于带电极的容器中，通过频率为500Hz，强度为2000V/m的外加电场对溶液取向50分钟，获得高取向的氧化石墨烯分散液；(2) placing the graphene oxide dispersion liquid prepared in step (1) in a container with electrodes, and orienting the solution for 50 minutes by an applied electric field with a frequency of 500 Hz and an intensity of 2000 V/m to obtain highly oriented graphene oxide dispersion liquid;
(3)将步骤(2)得到的高取向的氧化石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，再进一步冷冻干燥25h，得到高取向氧化石墨烯气凝胶；(3) the highly oriented graphene oxide dispersion liquid obtained in step (2) continues to maintain the action of the electric field, freeze and solidify in liquid nitrogen, and further freeze-dry for 25h to obtain a highly oriented graphene oxide aerogel;
(4)将步骤(3)获得的有序多孔氧化氧化石墨烯气凝胶通过热处理还原得到有序多孔的氧化石墨烯气凝胶；(4) reducing the ordered porous graphene oxide aerogel obtained in step (3) by heat treatment to obtain an ordered porous graphene oxide aerogel;
所得的高取向石墨烯气凝胶，石墨烯取向排列形成沿电场方向通孔，密度为0.5g/cm3，垂直于取向电场方向的压缩强度为6MPa，取向度大于85％，导电率大于1000S/m，孔隙率为95.8％。In the obtained highly oriented graphene aerogel, the graphene is oriented and arranged to form through holes along the electric field direction, the density is 0.5 g/cm 3 , the compressive strength perpendicular to the orientation electric field direction is 6 MPa, the degree of orientation is greater than 85%, and the electrical conductivity is greater than 1000S /m, the porosity is 95.8%.
实施例4：Example 4:
(1)加入1g的氧化石墨烯，5g的水，于35℃以15KHz的超声处理1小时，得到氧化石墨烯分散液；(1) add the graphene oxide of 1g, the water of 5g, at 35 ℃ with the ultrasonic treatment of 15KHz for 1 hour, obtain the graphene oxide dispersion liquid;
(2)将步骤1制备的氧化石墨烯分散液置于带电极的容器中，通过频率为50Hz，强度为2000V/m的外加电场对溶液取向75分钟，获得高取向的氧化石墨烯分散液；(2) the graphene oxide dispersion liquid prepared in step 1 is placed in a container with electrodes, and the solution is oriented for 75 minutes by an applied electric field with a frequency of 50 Hz and an intensity of 2000 V/m to obtain a highly oriented graphene oxide dispersion liquid;
(3)将步骤(2)得到的高取向的氧化石墨烯分散液，继续保持电场作用，在液氮中冷冻凝固，再进一步临界冷冻干燥25h，得到高取向氧化石墨烯气凝胶；(3) the highly oriented graphene oxide dispersion liquid obtained in step (2) continues to maintain the action of the electric field, freezes and solidifies in liquid nitrogen, and is further critically freeze-dried for 25h to obtain a highly oriented graphene oxide aerogel;
(4)将步骤(3)获得的有序多孔氧化石墨烯膜置于质量分数为10％水合肼中还原8小时，洗涤干燥得到石墨烯多孔有序膜。(4) placing the ordered porous graphene oxide film obtained in step (3) in 10% hydrazine hydrate for reduction for 8 hours, washing and drying to obtain the graphene porous ordered film.
所得的高取向石墨烯气凝胶，石墨烯取向排列形成沿电场方向通孔，密度为0.03-0.07g/cm3，垂直于取向电场方向的压缩强度为2-4MPa，取向度大于85％，导电率大于1000S/m，孔隙率为94％，可以作为高效水处理材料，污染物浓度低于20mg/mL时，吸附率可以达到98％。In the obtained highly oriented graphene aerogel, the graphene is oriented and arranged to form through holes along the electric field direction, the density is 0.03-0.07 g/cm 3 , the compressive strength perpendicular to the orientation electric field direction is 2-4 MPa, and the orientation degree is greater than 85%, The conductivity is greater than 1000S/m and the porosity is 94%, which can be used as a high-efficiency water treatment material. When the pollutant concentration is lower than 20mg/mL, the adsorption rate can reach 98%.
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