CN104319117A - Preparation method of 3D bowl-shaped graphene super capacitor electrode material of mixed nanometer structure - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000002086 nanomaterial Substances 0.000 claims abstract description 43
- 229910052786 argon Inorganic materials 0.000 claims abstract description 41
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Abstract
一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，本发明涉及石墨烯超级电容器电极材料的制备方法。本发明要解决现有石墨烯制备方法中，温度过高可能会引起石墨烯结构性质的变化和石墨烯褶皱的形成，阻碍了电荷的传输，使电荷湮灭几率增大，也导致电荷传导和存储的有效面积大大降低，且二维平面基底的面积是一定的，限制了可沉积的石墨烯数量，使电极材料的有效比表面积无法继续提高的问题。方法：将基底材料置于等离子体增强化学气相沉积真空装置中，通入氩气，调节压强并升温，然后对基底材料进行退火处理，再通入碳源气体进行沉积，最后冷却至室温。本发明用于一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备。
A preparation method of a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material, the invention relates to a preparation method of a graphene supercapacitor electrode material. The present invention aims to solve the problem that in the existing graphene preparation method, too high temperature may cause changes in the structural properties of graphene and the formation of graphene wrinkles, which hinders the transmission of charges, increases the probability of charge annihilation, and also leads to charge conduction and storage. The effective area of the electrode material is greatly reduced, and the area of the two-dimensional planar substrate is certain, which limits the amount of graphene that can be deposited, making the effective specific surface area of the electrode material unable to continue to increase. Method: The base material is placed in a plasma-enhanced chemical vapor deposition vacuum device, argon gas is introduced, the pressure is adjusted and the temperature is raised, then the base material is annealed, and then carbon source gas is introduced for deposition, and finally cooled to room temperature. The invention is used for the preparation of a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
Description
技术领域technical field
本发明涉及石墨烯超级电容器电极材料的制备方法。The invention relates to a preparation method of a graphene supercapacitor electrode material.
背景技术Background technique
超级电容器是一种新型储能器件，具有高功率、高效率、寿命长、环境友好等特点，其发展和应用在国防、消费电子和汽车工业等多个领域具有良好前景。相比于传统的燃料电池和二次电池，超级电容器具有更高的功率密度，因此在汽车工业中，将其与燃料电池并联作为电动汽车的动力系统。同时，由于较低的成本和超长的循环使用寿命，超级电容器在消费电子产品中被广泛使用。虽然超级电容器的能量密度远高于传统的电解质电容器，但却低于燃料电池和二次电池，这一问题严重制约了超级电容器的应用。因此，开发高性能电极材料以提高其能量密度，是现在研究的重点之一。近年来，石墨烯成为制备超级电容器电极的热门材料，这主要由于二维共轭石墨结构使石墨烯及其复合材料具有很多独特的性能，包括优异的电学性能、力学性能和光学性能等，也赋予其巨大的比表面积，使其在提高超级电容器能量密度方面具有潜在价值。Supercapacitor is a new type of energy storage device, which has the characteristics of high power, high efficiency, long life, and environmental friendliness. Its development and application have good prospects in many fields such as national defense, consumer electronics, and automobile industry. Compared with traditional fuel cells and secondary batteries, supercapacitors have higher power density, so in the automotive industry, they are used in parallel with fuel cells as power systems for electric vehicles. Meanwhile, supercapacitors are widely used in consumer electronics due to their low cost and long cycle life. Although the energy density of supercapacitors is much higher than that of conventional electrolytic capacitors, it is lower than that of fuel cells and secondary batteries, which severely restricts the application of supercapacitors. Therefore, the development of high-performance electrode materials to increase their energy density is one of the focuses of current research. In recent years, graphene has become a popular material for the preparation of supercapacitor electrodes. This is mainly due to the two-dimensional conjugated graphite structure that makes graphene and its composites have many unique properties, including excellent electrical properties, mechanical properties, and optical properties. Endowed with a huge specific surface area, it has potential value in improving the energy density of supercapacitors.
然而，在传统石墨烯制备方法中，温度过高可能会引起石墨烯结构性质的变化和石墨烯褶皱的形成，最主要的是无法控制石墨烯的层数，易发生堆叠。大量堆叠的石墨烯不仅阻碍了电荷的传输，使电荷湮灭几率增大，也导致电荷传导和存储的有效面积大大降低。同时，二维平面基底的面积是一定的，限制了可沉积的石墨烯数量，使电极材料的有效比表面积无法继续提高。要提高沉积的石墨烯数量就必须增大其基底的面积，不利于在高集成度微纳米电子器件中的应用。However, in the traditional graphene preparation method, too high temperature may cause changes in the structural properties of graphene and the formation of graphene wrinkles. The most important thing is that the number of layers of graphene cannot be controlled, and stacking is prone to occur. A large amount of stacked graphene not only hinders the transport of charges and increases the probability of charge annihilation, but also greatly reduces the effective area for charge conduction and storage. At the same time, the area of the two-dimensional planar substrate is certain, which limits the amount of graphene that can be deposited, making it impossible to continue to increase the effective specific surface area of the electrode material. To increase the amount of deposited graphene, the area of its substrate must be increased, which is not conducive to the application in highly integrated micro-nano electronic devices.
发明内容Contents of the invention
本发明要解决现有石墨烯制备方法中，温度过高可能会引起石墨烯结构性质的变化和石墨烯褶皱的形成，阻碍了电荷的传输，使电荷湮灭几率增大，也导致电荷传导和存储的有效面积大大降低，且二维平面基底的面积是一定的，限制了可沉积的石墨烯数量，使电极材料的有效比表面积无法继续提高的问题，而提供一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法。The present invention aims to solve the problem that in the existing graphene preparation method, too high temperature may cause changes in the structural properties of graphene and the formation of graphene wrinkles, which hinders the transmission of charges, increases the probability of charge annihilation, and also leads to charge conduction and storage. The effective area of the electrode material is greatly reduced, and the area of the two-dimensional planar substrate is certain, which limits the amount of graphene that can be deposited, so that the effective specific surface area of the electrode material cannot be continuously improved, and a 3D bowl-shaped mixed nanostructured graphite is provided. Preparation method of ene supercapacitor electrode material.
一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：A preparation method of a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material is specifically carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为65sccm～95sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为100Pa～300Pa，并在压强为100Pa～300Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为700℃～900℃；1. Put the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 65sccm-95sccm, and adjust the vacuuming speed to put the plasma-enhanced chemical vapor deposition vacuum device The medium pressure is controlled at 100Pa～300Pa, and under the pressure of 100Pa～300Pa and argon atmosphere, the temperature is raised to 700℃～900℃ at a heating rate of 30℃/min;
二、在温度为700℃～900℃、压强为100Pa～300Pa和氩气气氛下对基底材料进行退火处理，退火时间为15min～60min；2. Anneal the base material at a temperature of 700°C to 900°C, a pressure of 100Pa to 300Pa and an argon atmosphere, and the annealing time is 15min to 60min;
三、通入碳源气体，调节碳源气体的气体流量为5sccm～35sccm、氩气的气体流量为65sccm～95sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa～1000Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为150W～250W、压强为200Pa～1000Pa和温度为700℃～900℃的条件下进行沉积，沉积时间为20min～60min；3. Introduce carbon source gas, adjust the gas flow rate of carbon source gas to 5sccm-35sccm, and the gas flow rate of argon gas to 65sccm-95sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa～ 1000Pa, and then deposit under the conditions that the RF power frequency of the deposition system is 13.56MHz, the RF power is 150W~250W, the pressure is 200Pa~1000Pa, and the temperature is 700℃~900℃, and the deposition time is 20min~60min;
所述的碳源气体与氩气的总气体流量为100sccm；The total gas flow of the carbon source gas and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为65sccm～95sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为100Pa～300Pa，在压强为100Pa～300Pa和氩气气氛下从温度为700℃～900℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed argon gas with a gas flow rate of 65 sccm to 95 sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 100Pa～300Pa, under the pressure of 100Pa～300Pa and argon atmosphere, the temperature is cooled from 700℃～900℃ to room temperature, and the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material is obtained.
本发明的有益效果是：1、本发明选用的基底材料为Pt/Ti/SiO2/Si多层混合衬底材料，通过在传统的Pt/Si基片间加入Ti，通过退火可实现平面基底转变为三维碗状结构。这主要是由于Pt的熔点相对较低，在700℃～900℃退火过程中会发生原子团聚现象。同时，Pt在Ti中的固溶度较低，且在Ti表面的润湿性较差，无法互溶或完全铺展。因此当Pt层很薄(150nm～200nm)时，通过优化退火温度及时间，在退火过程中Pt层会在Ti层表面发生原子团聚而形成碗状的三维多孔结构。这种碗状的三维多孔结构基底材料有利于提高垂直生长石墨烯的分布密度，可以进一步提高电极材料的比表面积。同时，Ti具有良好的导电性，有利于制备高性能的石墨烯基超级电容器。The beneficial effect of the present invention is: 1, the base material that the present invention selects is Pt/Ti/SiO 2 /Si multi-layer hybrid substrate material, by adding Ti between traditional Pt/Si substrates, can realize planar substrate by annealing into a three-dimensional bowl-like structure. This is mainly due to the relatively low melting point of Pt, and atomic agglomeration will occur during the annealing process at 700°C to 900°C. At the same time, the solid solubility of Pt in Ti is low, and the wettability on the Ti surface is poor, so it cannot be miscible or completely spread. Therefore, when the Pt layer is very thin (150nm-200nm), by optimizing the annealing temperature and time, the Pt layer will be atomically aggregated on the surface of the Ti layer during the annealing process to form a bowl-shaped three-dimensional porous structure. This bowl-shaped three-dimensional porous structure substrate material is conducive to improving the distribution density of vertically grown graphene, and can further increase the specific surface area of the electrode material. At the same time, Ti has good electrical conductivity, which is conducive to the preparation of high-performance graphene-based supercapacitors.
2、本发明利用等离子体增强化学气相沉积方法，在衬底上原位生长出少层垂直生长的石墨烯，这种垂直生长的石墨烯具有其他多孔碳材料无法比拟的优势：竖直生长的石墨烯可以提供50μF/cm3～70μF/cm3的边缘平面(基面约为3μF/cm3)；参与电荷储存的边缘平面可以直接接触，减少电荷存储的再分配，从而增加储存能力和减小电荷湮灭几率；开放性的结构使材料的多孔效应大为降低，减小离子阻力；石墨烯不光本身导电性能好，而且可以在导电性能优异的材料表面生长，减小了电子阻力；垂直生长所形成的三维结构有效地增加了石墨烯材料的有效比表面积，克服了以往二维结构堆叠的石墨烯电极材料的缺点优化了电荷传输的途径，增加了电荷传导和储存的有效面积，进而提升超级电容器的电化学性能，且可直接利用3D碗状混合纳米结构石墨烯作为超级电容器的电极材料。2. The present invention utilizes the plasma-enhanced chemical vapor deposition method to in-situ grow a few layers of vertically grown graphene on the substrate. This vertically grown graphene has incomparable advantages over other porous carbon materials: vertically grown Graphene can provide an edge plane of 50μF/cm 3 ~70μF/cm 3 (basal plane is about 3μF/cm 3 ); the edge planes involved in charge storage can be in direct contact, reducing the redistribution of charge storage, thereby increasing storage capacity and reducing Small charge annihilation probability; the open structure greatly reduces the porous effect of the material and reduces ionic resistance; graphene not only has good electrical conductivity, but also can grow on the surface of materials with excellent electrical conductivity, reducing electronic resistance; vertical growth The formed three-dimensional structure effectively increases the effective specific surface area of graphene materials, overcomes the shortcomings of previous two-dimensional structure stacked graphene electrode materials, optimizes the way of charge transport, increases the effective area of charge conduction and storage, and then improves Electrochemical properties of supercapacitors, and 3D bowl-shaped mixed nanostructured graphene can be directly used as electrode materials for supercapacitors.
3、本发明一步完成对3D碗状混合纳米结构石墨烯电极材料的制备，方法简单，高效，低成本，便于工业化生产，制备得到的石墨烯质量高，在微纳米电子器件、太阳能电池电极、光电转换器、透明导电薄膜等领域具有良好的应用前景。3. The present invention completes the preparation of 3D bowl-shaped mixed nanostructure graphene electrode materials in one step. The method is simple, efficient, low-cost, convenient for industrial production, and the prepared graphene is of high quality. It can be used in micro-nano electronic devices, solar cell electrodes, Photoelectric converters, transparent conductive films and other fields have good application prospects.
本发明用于一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法。The invention is used for a preparation method of a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
附图说明Description of drawings
图1为实施例一制备的3D碗状混合纳米结构石墨烯超级电容器电极材料的扫描电镜图片；Fig. 1 is the scanning electron microscope picture of the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material that embodiment one prepares;
图2为实施例一制备的3D碗状混合纳米结构石墨烯超级电容器电极材料的拉曼光谱；1为D峰，2为G峰，3为2D峰；Fig. 2 is the Raman spectrum of the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material prepared by embodiment one; 1 is a D peak, 2 is a G peak, and 3 is a 2D peak;
图3为实施例一制备的3D碗状混合纳米结构石墨烯超级电容器电极材料的透射电镜图片；Fig. 3 is the transmission electron microscope picture of the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material that embodiment one prepares;
图4为实施例一制备的3D碗状混合纳米结构石墨烯直接作为电极材料的电化学测试结果，1为扫速50mV/s；2为扫速20mV/s；3为扫速10mV/s；4为扫速5mV/s；5为扫速2mV/s。Fig. 4 is the electrochemical test result of the 3D bowl-shaped mixed nanostructure graphene that embodiment one prepares directly as electrode material, and 1 is sweep speed 50mV/s; 2 is sweep speed 20mV/s; 3 is sweep speed 10mV/s; 4 means sweep speed 5mV/s; 5 means sweep speed 2mV/s.
具体实施方式Detailed ways
本发明技术方案不局限于以下所列举的具体实施方式，还包括各具体实施方式之间的任意组合。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
具体实施方式一：本实施方式所述的一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：Specific embodiment one: the preparation method of a kind of 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material described in this embodiment, specifically is carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为65sccm～95sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为100Pa～300Pa，并在压强为100Pa～300Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为700℃～900℃；1. Put the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 65sccm-95sccm, and adjust the vacuuming speed to put the plasma-enhanced chemical vapor deposition vacuum device The medium pressure is controlled at 100Pa～300Pa, and under the pressure of 100Pa～300Pa and argon atmosphere, the temperature is raised to 700℃～900℃ at a heating rate of 30℃/min;
二、在温度为700℃～900℃、压强为100Pa～300Pa和氩气气氛下对基底材料进行退火处理，退火时间为15min～60min；2. Anneal the base material at a temperature of 700°C to 900°C, a pressure of 100Pa to 300Pa and an argon atmosphere, and the annealing time is 15min to 60min;
三、通入碳源气体，调节碳源气体的气体流量为5sccm～35sccm、氩气的气体流量为65sccm～95sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa～1000Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为150W～250W、压强为200Pa～1000Pa和温度为700℃～900℃的条件下进行沉积，沉积时间为20min～60min；3. Introduce carbon source gas, adjust the gas flow rate of carbon source gas to 5sccm-35sccm, and the gas flow rate of argon gas to 65sccm-95sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa～ 1000Pa, and then deposit under the conditions that the RF power frequency of the deposition system is 13.56MHz, the RF power is 150W~250W, the pressure is 200Pa~1000Pa, and the temperature is 700℃~900℃, and the deposition time is 20min~60min;
所述的碳源气体与氩气的总气体流量为100sccm；The total gas flow of the carbon source gas and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为65sccm～95sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为100Pa～300Pa，在压强为100Pa～300Pa和氩气气氛下从温度为700℃～900℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed argon gas with a gas flow rate of 65 sccm to 95 sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 100Pa～300Pa, under the pressure of 100Pa～300Pa and argon atmosphere, the temperature is cooled from 700℃～900℃ to room temperature, and the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material is obtained.
本实施方式步骤二使其形成三维多孔结构。In the second step of this embodiment, a three-dimensional porous structure is formed.
本实施方式步骤三在基底上沉积石墨烯，使碳源气体、氩气在射频电源的作用下离化，分解成为等离子体，通过化学反应，最终在基底上沉积石墨烯。Step 3 of this embodiment is to deposit graphene on the substrate, ionize the carbon source gas and argon gas under the action of radio frequency power, decompose into plasma, and finally deposit graphene on the substrate through chemical reaction.
本实施方式的有益效果是：1、本实施方式选用的基底材料为Pt/Ti/SiO2/Si多层混合衬底材料，通过在传统的Pt/Si基片间加入Ti，通过退火可实现平面基底转变为三维碗状结构。这主要是由于Pt的熔点相对较低，在700℃～900℃退火过程中会发生原子团聚现象。同时，Pt在Ti中的固溶度较低，且在Ti表面的润湿性较差，无法互溶或完全铺展。因此当Pt层很薄(150nm～200nm)时，通过优化退火温度及时间，在退火过程中Pt层会在Ti层表面发生原子团聚而形成碗状的三维多孔结构。这种碗状的三维多孔结构基底材料有利于提高垂直生长石墨烯的分布密度，可以进一步提高电极材料的比表面积。同时，Ti具有良好的导电性，有利于制备高性能的石墨烯基超级电容器。The beneficial effects of this embodiment are: 1. The base material selected in this embodiment is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material. By adding Ti between traditional Pt/Si substrates, annealing can achieve The planar base transforms into a three-dimensional bowl-like structure. This is mainly due to the relatively low melting point of Pt, and atomic agglomeration will occur during the annealing process at 700°C to 900°C. At the same time, the solid solubility of Pt in Ti is low, and the wettability on the Ti surface is poor, so it cannot be miscible or completely spread. Therefore, when the Pt layer is very thin (150nm-200nm), by optimizing the annealing temperature and time, the Pt layer will be atomically aggregated on the surface of the Ti layer during the annealing process to form a bowl-shaped three-dimensional porous structure. This bowl-shaped three-dimensional porous structure substrate material is conducive to improving the distribution density of vertically grown graphene, and can further increase the specific surface area of the electrode material. At the same time, Ti has good electrical conductivity, which is conducive to the preparation of high-performance graphene-based supercapacitors.
2、本实施方式利用等离子体增强化学气相沉积方法，在衬底上原位生长出少层垂直生长的石墨烯，这种垂直生长的石墨烯具有其他多孔碳材料无法比拟的优势：竖直生长的石墨烯可以提供50μF/cm3～70μF/cm3的边缘平面(基面约为3μF/cm3)；参与电荷储存的边缘平面可以直接接触，减少电荷存储的再分配，从而增加储存能力和减小电荷湮灭几率；开放性的结构使材料的多孔效应大为降低，减小离子阻力；石墨烯不光本身导电性能好，而且可以在导电性能优异的材料表面生长，减小了电子阻力；垂直生长所形成的三维结构有效地增加了石墨烯材料的有效比表面积，克服了以往二维结构堆叠的石墨烯电极材料的缺点优化了电荷传输的途径，增加了电荷传导和储存的有效面积，进而提升超级电容器的电化学性能，且可直接利用3D碗状混合纳米结构石墨烯作为超级电容器的电极材料。2. In this embodiment, the plasma-enhanced chemical vapor deposition method is used to in-situ grow a few layers of vertically grown graphene on the substrate. This vertically grown graphene has an incomparable advantage over other porous carbon materials: vertical growth Graphene can provide an edge plane of 50μF/cm 3 ~70μF/cm 3 (basal plane is about 3μF/cm 3 ); the edge planes involved in charge storage can be in direct contact, reducing the redistribution of charge storage, thereby increasing storage capacity and Reduce the probability of charge annihilation; the open structure greatly reduces the porous effect of the material and reduces ionic resistance; graphene not only has good electrical conductivity itself, but also can grow on the surface of materials with excellent electrical conductivity, reducing electronic resistance; vertical The three-dimensional structure formed by the growth effectively increases the effective specific surface area of graphene materials, overcomes the shortcomings of previous two-dimensional structure stacked graphene electrode materials, optimizes the way of charge transport, increases the effective area of charge conduction and storage, and then Improve the electrochemical performance of supercapacitors, and directly use 3D bowl-shaped mixed nanostructured graphene as electrode materials for supercapacitors.
3、本实施方式一步完成对3D碗状混合纳米结构石墨烯电极材料的制备，方法简单，高效，低成本，便于工业化生产，制备得到的石墨烯质量高，在微纳米电子器件、太阳能电池电极、光电转换器、透明导电薄膜等领域具有良好的应用前景。3. This embodiment completes the preparation of 3D bowl-shaped mixed nanostructure graphene electrode materials in one step. The method is simple, efficient, low-cost, convenient for industrial production, and the prepared graphene is of high quality. It can be used in micro-nano electronic devices and solar cell electrodes. , photoelectric converters, transparent conductive films and other fields have good application prospects.
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤一中所述基底材料为Pt/Ti/SiO2/Si多层混合衬底材料。其它与具体实施方式一相同。Embodiment 2: This embodiment differs from Embodiment 1 in that the base material in step 1 is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material. Others are the same as in the first embodiment.
本具体实施方式所述的基底材料可作为超级电容器的集电体使用。The base material described in this specific embodiment can be used as a current collector of a supercapacitor.
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：所述的Pt层厚度为150nm～200nm；所述的Ti层厚度为20nm；所述的SiO2层厚度为300nm。其它与具体实施方式一或二相同。Specific embodiment three: the difference between this embodiment and specific embodiment one or two is: the thickness of the Pt layer is 150nm～200nm; the thickness of the Ti layer is 20nm; the thickness of the SiO2 layer is 300nm . Others are the same as 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：步骤三中所述的碳源气体为甲烷。其它与具体实施方式一至三相同。Embodiment 4: The difference between this embodiment and one of Embodiments 1 to 3 is that the carbon source gas described in step 3 is methane. Others are the same as the specific embodiments 1 to 3.
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：步骤一中在压强为100Pa～300Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为800℃。其它与具体实施方式一至四相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that in Step 1, the temperature is raised to 800° C. at a heating rate of 30° C./min under a pressure of 100 Pa to 300 Pa and an argon atmosphere. . Others are the same as 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：步骤二中在温度为700℃～900℃、压强为100Pa～300Pa和氩气气氛下对基底材料进行退火处理，退火时间为60min。其它与具体实施方式一至五相同。Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is that in step 2, the base material is annealed at a temperature of 700°C to 900°C, a pressure of 100Pa to 300Pa, and an argon atmosphere. The time is 60 minutes. Others are the same as those in 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：步骤三中调节碳源气体的气体流量为10sccm、氩气的气体流量为90sccm。其它与具体实施方式一至六相同。Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that: in step 3, the gas flow rate of the carbon source gas is adjusted to 10 sccm, and the gas flow rate of the argon gas is adjusted to 90 sccm. Others are the same as those in Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：步骤三中调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为600Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为200W、压强为600Pa和温度为800℃条件下进行沉积，沉积时间为60min。其它与具体实施方式一至七相同。Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that in step 3, the vacuuming speed is adjusted to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 600 Pa, and then the radio frequency power supply frequency of the deposition system is Deposition was carried out under the conditions of 13.56MHz, radio frequency power of 200W, pressure of 600Pa and temperature of 800°C, and the deposition time was 60min. Others are the same as those in Embodiments 1 to 7.
采用以下实施例验证本发明的有益效果：Adopt the following examples to verify the beneficial effects of the present invention:
实施例一：Embodiment one:
本实施例所述的一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：The preparation method of a kind of 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material described in the present embodiment is specifically carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为90sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，并在压强为200Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为800℃；1. Place the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 90 sccm, and adjust the vacuum speed to reduce the pressure in the plasma-enhanced chemical vapor deposition vacuum device The temperature is controlled at 200Pa, and under the pressure of 200Pa and argon atmosphere, the temperature is raised to 800°C at a heating rate of 30°C/min;
二、在温度为800℃、压强为200Pa和氩气气氛下对基底材料进行退火处理，退火时间为60min；2. Anneal the substrate material at a temperature of 800°C, a pressure of 200Pa, and an argon atmosphere, and the annealing time is 60 minutes;
三、通入碳源气体，调节碳源气体的气体流量为10sccm、氩气的气体流量为90sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为600Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为200W、压强为600Pa和温度为800℃的条件下进行沉积，沉积时间为60min；3. Introduce the carbon source gas, adjust the gas flow rate of the carbon source gas to 10sccm, and the gas flow rate of the argon gas to 90sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 600Pa, and then in the deposition system The RF power frequency is 13.56MHz, the RF power is 200W, the pressure is 600Pa and the temperature is 800°C, and the deposition time is 60min;
所述的碳源气体与氩气的总气体流量为100sccm；The total gas flow of the carbon source gas and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为90sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，在压强为200Pa和氩气气氛下从温度为800℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed the argon gas with a gas flow rate of 90 sccm, and adjust the vacuuming speed to control the pressure in the plasma enhanced chemical vapor deposition vacuum device to 200Pa , and cooled from a temperature of 800 ° C to room temperature under a pressure of 200 Pa and an argon atmosphere to obtain a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
步骤一中所述基底材料为Pt/Ti/SiO2/Si多层混合衬底材料；The base material described in step 1 is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material;
所述的Pt层厚度为150nm；所述的Ti层厚度为20nm；所述的SiO2层厚度为300nm；The thickness of the Pt layer is 150nm; the thickness of the Ti layer is 20nm; the thickness of the SiO2 layer is 300nm;
步骤三中所述的碳源气体为甲烷。The carbon source gas described in step three is methane.
图1为实施例一制备的3D碗状混合纳米结构石墨烯超级电容器电极材料的扫描电镜图片；从扫描电镜图片可看出，基底表面具有大量均匀密集分布的碗状孔洞，直径约为800nm，形成蜂窝状疏松多孔结构。片层状的石墨烯均匀垂直生长在碗状孔洞表面，共同构成三维结构。Fig. 1 is the scanning electron microscope picture of the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material that embodiment one prepares; As can be seen from the scanning electron microscope picture, the substrate surface has a large number of evenly densely distributed bowl-shaped holes with a diameter of about 800nm. A honeycomb porous structure is formed. Sheet-like graphene grows evenly and vertically on the surface of the bowl-shaped hole, forming a three-dimensional structure together.
图2为实施例一制备的3D碗状混合纳米结构石墨烯超级电容器电极材料的拉曼光谱，激光波长为532nm；通过拉曼光谱中D，G，2D峰的位置以及相对的峰强比值，可以说明获得的碳纳米材料质量好，缺陷较少，且为少层石墨烯。Fig. 2 is the Raman spectrum of the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material prepared by embodiment one, and the laser wavelength is 532nm; by D in the Raman spectrum, G, the position of the 2D peak and the relative peak intensity ratio, It can be shown that the obtained carbon nanomaterials are of good quality, have fewer defects, and are few-layer graphene.
图3为实施例一制备的3D碗状混合纳米结构石墨烯超级电容器电极材料的透射电镜图片；由图可知，石墨烯片尺寸在100nm左右，石墨烯呈变透明状，层数在3～5层之间，属于少层石墨烯，说明PECVD制备得到的石墨烯质量较高，比表面积大，适用于超级电容器的电极材料。Fig. 3 is the transmission electron microscope picture of the 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material prepared in Example 1; As can be seen from the figure, the size of the graphene sheet is about 100nm, and the graphene becomes transparent, and the number of layers is between 3 and 5 Between the layers, it belongs to few-layer graphene, indicating that the graphene prepared by PECVD has high quality and large specific surface area, which is suitable for electrode materials of supercapacitors.
图4为实施例一制备的3D碗状混合纳米结构石墨烯直接作为电极材料的电化学测试结果，1为扫速50mV/s；2为扫速20mV/s；3为扫速10mV/s；4为扫速5mV/s；5为扫速2mV/s；利用电化学工作站测试在扫描速率为50mV/s、20mV/s、10mV/s、5mV/s和2mV/s时比电容分别为703μF/cm2、755μF/cm2、810μF/cm2、882μF/cm2和1052μF/cm2。相比于传统使用二维平面材料基底制备的石墨烯超级电容器电极，其比电容提高了约70％(使用二维平面材料基底制备的石墨烯电极材料的比电容最高约600μF/cm2)。Fig. 4 is the electrochemical test result of the 3D bowl-shaped mixed nanostructure graphene that embodiment one prepares directly as electrode material, and 1 is sweep speed 50mV/s; 2 is sweep speed 20mV/s; 3 is sweep speed 10mV/s; 4 is the scan rate of 5mV/s; 5 is the scan rate of 2mV/s; when the scan rate is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s, the specific capacitance is 703μF respectively. /cm 2 , 755 μF/cm 2 , 810 μF/cm 2 , 882 μF/cm 2 and 1052 μF/cm 2 . Compared with traditional graphene supercapacitor electrodes prepared using two-dimensional planar material substrates, the specific capacitance is increased by about 70% (the specific capacitance of graphene electrode materials prepared using two-dimensional planar material substrates is up to about 600 μF/cm2).
由以上可知，实施例通过选用多层混合基底并对其进行热处理，使平面基底形成三维多孔结构，提高了石墨烯的分布密度，进而增大了材料的比表面积。同时，利用等离子体化学气相沉积的技术，在三维多孔结构的基底上原位垂直生长少层石墨烯，由于等离子体的引入，不仅使反应所需温度有所降低，同时也有利于石墨烯在基底上原位垂直生长，不易发生堆叠现象。利用此方法制得的3D碗状混合纳米结构石墨烯电极材料，与电解液的有效接触面积大，离子阻力小，有利于电荷的传输及存储，电荷湮灭几率减小，使材料的储能能力提高。It can be seen from the above that, in the embodiment, by selecting a multi-layer mixed substrate and heat-treating it, the planar substrate forms a three-dimensional porous structure, which improves the distribution density of graphene, thereby increasing the specific surface area of the material. At the same time, using plasma chemical vapor deposition technology, in-situ vertical growth of few-layer graphene on a three-dimensional porous structure substrate, due to the introduction of plasma, not only reduces the temperature required for the reaction, but also facilitates the development of graphene in the In situ vertical growth on the substrate, and stacking phenomenon is not easy to occur. The 3D bowl-shaped mixed nanostructure graphene electrode material prepared by this method has a large effective contact area with the electrolyte and low ionic resistance, which is conducive to the transmission and storage of charges, and the probability of charge annihilation is reduced, which improves the energy storage capacity of the material. improve.
实施例二：Embodiment two:
本实施例所述的一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：The preparation method of a kind of 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material described in the present embodiment is specifically carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为90sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，并在压强为200Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为800℃；1. Place the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 90 sccm, and adjust the vacuum speed to reduce the pressure in the plasma-enhanced chemical vapor deposition vacuum device Controlled to 200Pa, and under the pressure of 200Pa and argon atmosphere, the temperature was raised to 800°C at a heating rate of 30°C/min;
所述基底材料为Pt/Ti/SiO2/Si多层混合衬底材料；The base material is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material;
所述的Pt层厚度为150nm；所述的Ti层厚度为20nm；所述的SiO2层厚度为300nm；The thickness of the Pt layer is 150nm; the thickness of the Ti layer is 20nm; the thickness of the SiO2 layer is 300nm;
二、在温度为800℃、压强为200Pa和氩气气氛下对基底材料进行退火处理，退火时间为15min；2. Anneal the substrate material at a temperature of 800°C, a pressure of 200Pa and an argon atmosphere, and the annealing time is 15 minutes;
三、通入碳源气体，调节碳源气体的气体流量为10sccm、氩气的气体流量为90sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为600Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为200W、压强为600Pa和温度为800℃的条件下进行沉积，沉积时间为60min；3. Introduce the carbon source gas, adjust the gas flow rate of the carbon source gas to 10sccm, and the gas flow rate of the argon gas to 90sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 600Pa, and then in the deposition system The RF power frequency is 13.56MHz, the RF power is 200W, the pressure is 600Pa and the temperature is 800°C, and the deposition time is 60min;
所述的碳源气体为甲烷与氩气的总气体流量为100sccm；Described carbon source gas is that the total gas flow rate of methane and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为90sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，在压强为200Pa和氩气气氛下从温度为800℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed the argon gas with a gas flow rate of 90 sccm, and adjust the vacuuming speed to control the pressure in the plasma enhanced chemical vapor deposition vacuum device to 200Pa , and cooled from a temperature of 800 ° C to room temperature under a pressure of 200 Pa and an argon atmosphere to obtain a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
实施例二制备的3D碗状混合纳米结构石墨烯直接作为电极材料的电化学测试结果，利用电化学工作站测试在扫描速率为50mV/s、20mV/s、10mV/s、5mV/s和2mV/s时比电容分别为337μF/cm2、425μF/cm2、561μF/cm2、642μF/cm2和779μF/cm2。The 3D bowl-shaped mixed nanostructure graphene prepared in embodiment two is directly used as the electrochemical test result of the electrode material, and the electrochemical workstation is used to test that the scanning rate is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s The specific capacitance at s time is 337μF/cm 2 , 425μF/cm 2 , 561μF/cm 2 , 642μF/cm 2 and 779μF/cm 2 .
实施例三：Embodiment three:
本实施例所述的一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：The preparation method of a kind of 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material described in the present embodiment is specifically carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为90sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，并在压强为200Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为800℃；1. Place the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 90 sccm, and adjust the vacuum speed to reduce the pressure in the plasma-enhanced chemical vapor deposition vacuum device Controlled to 200Pa, and under the pressure of 200Pa and argon atmosphere, the temperature was raised to 800°C at a heating rate of 30°C/min;
所述基底材料为Pt/Ti/SiO2/Si多层混合衬底材料；The base material is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material;
所述的Pt层厚度为150nm；所述的Ti层厚度为20nm；所述的SiO2层厚度为300nm；The thickness of the Pt layer is 150nm; the thickness of the Ti layer is 20nm; the thickness of the SiO2 layer is 300nm;
二、在温度为800℃、压强为200Pa和氩气气氛下对基底材料进行退火处理，退火时间为30min；2. Anneal the substrate material at a temperature of 800°C, a pressure of 200Pa, and an argon atmosphere, and the annealing time is 30 minutes;
三、通入碳源气体，调节碳源气体的气体流量为10sccm、氩气的气体流量为90sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为600Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为200W、压强为600Pa和温度为800℃的条件下进行沉积，沉积时间为60min；3. Introduce the carbon source gas, adjust the gas flow rate of the carbon source gas to 10sccm, and the gas flow rate of the argon gas to 90sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 600Pa, and then in the deposition system The RF power frequency is 13.56MHz, the RF power is 200W, the pressure is 600Pa and the temperature is 800°C, and the deposition time is 60min;
所述的碳源气体为甲烷与氩气的总气体流量为100sccm；Described carbon source gas is that the total gas flow rate of methane and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为90sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，在压强为200Pa和氩气气氛下从温度为800℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed the argon gas with a gas flow rate of 90 sccm, and adjust the vacuuming speed to control the pressure in the plasma enhanced chemical vapor deposition vacuum device to 200Pa , and cooled from a temperature of 800 ° C to room temperature under a pressure of 200 Pa and an argon atmosphere to obtain a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
实施例三制备的3D碗状混合纳米结构石墨烯直接作为电极材料的电化学测试结果，利用电化学工作站测试在扫描速率为50mV/s、20mV/s、10mV/s、5mV/s和2mV/s时比电容分别为358μF/cm2、502μF/cm2、671μF/cm2、792μF/cm2和913μF/cm2。The 3D bowl-shaped mixed nanostructure graphene prepared by embodiment three is directly used as the electrochemical test result of the electrode material, and the electrochemical workstation is used to test that the scanning rate is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s The specific capacitance at s time is 358μF/cm 2 , 502μF/cm 2 , 671μF/cm 2 , 792μF/cm 2 and 913μF/cm 2 .
实施例四：Embodiment four:
本实施例所述的一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：The preparation method of a kind of 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material described in the present embodiment is specifically carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为90sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，并在压强为200Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为800℃；1. Place the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 90 sccm, and adjust the vacuum speed to reduce the pressure in the plasma-enhanced chemical vapor deposition vacuum device Controlled to 200Pa, and under the pressure of 200Pa and argon atmosphere, the temperature was raised to 800°C at a heating rate of 30°C/min;
所述基底材料为Pt/Ti/SiO2/Si多层混合衬底材料；The base material is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material;
所述的Pt层厚度为150nm；所述的Ti层厚度为20nm；所述的SiO2层厚度为300nm；The thickness of the Pt layer is 150nm; the thickness of the Ti layer is 20nm; the thickness of the SiO2 layer is 300nm;
二、在温度为800℃、压强为200Pa和氩气气氛下对基底材料进行退火处理，退火时间为60min；2. Anneal the substrate material at a temperature of 800°C, a pressure of 200Pa, and an argon atmosphere, and the annealing time is 60 minutes;
三、通入碳源气体，调节碳源气体的气体流量为20sccm、氩气的气体流量为80sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为600Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为200W、压强为600Pa和温度为800℃的条件下进行沉积，沉积时间为60min；3. Introduce the carbon source gas, adjust the gas flow rate of the carbon source gas to 20 sccm, and the gas flow rate of the argon gas to 80 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 600 Pa, and then in the deposition system The RF power frequency is 13.56MHz, the RF power is 200W, the pressure is 600Pa and the temperature is 800°C, and the deposition time is 60min;
所述的碳源气体为甲烷与氩气的总气体流量为100sccm；Described carbon source gas is that the total gas flow rate of methane and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为90sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，在压强为200Pa和氩气气氛下从温度为800℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed the argon gas with a gas flow rate of 90 sccm, and adjust the vacuuming speed to control the pressure in the plasma enhanced chemical vapor deposition vacuum device to 200Pa , and cooled from a temperature of 800 ° C to room temperature under a pressure of 200 Pa and an argon atmosphere to obtain a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
实施例四制备的3D碗状混合纳米结构石墨烯直接作为电极材料的电化学测试结果，利用电化学工作站测试在扫描速率为50mV/s、20mV/s、10mV/s、5mV/s和2mV/s时比电容分别为377μF/cm2、512μF/cm2、642μF/cm2、709μF/cm2和788μF/cm2。The 3D bowl-shaped mixed nanostructure graphene prepared in Example 4 is directly used as the electrochemical test result of the electrode material, and the electrochemical workstation is used to test at a scan rate of 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s The specific capacitance at s time is 377μF/cm 2 , 512μF/cm 2 , 642μF/cm 2 , 709μF/cm 2 and 788μF/cm 2 .
实施例五：Embodiment five:
本实施例所述的一种3D碗状混合纳米结构石墨烯超级电容器电极材料的制备方法，具体是按照以下步骤进行的：The preparation method of a kind of 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material described in the present embodiment is specifically carried out according to the following steps:
一、将基底材料置于等离子体增强化学气相沉积真空装置中，抽真空至压强为5Pa以下，以气体流量为90sccm通入氩气，调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，并在压强为200Pa和氩气气氛下，以升温速率为30℃/min将温度升温至为800℃；1. Place the substrate material in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to a pressure below 5Pa, feed argon gas with a gas flow rate of 90 sccm, and adjust the vacuum speed to reduce the pressure in the plasma-enhanced chemical vapor deposition vacuum device Controlled to 200Pa, and under the pressure of 200Pa and argon atmosphere, the temperature was raised to 800°C at a heating rate of 30°C/min;
所述基底材料为Pt/Ti/SiO2/Si多层混合衬底材料；The base material is a Pt/Ti/SiO 2 /Si multilayer mixed substrate material;
所述的Pt层厚度为150nm；所述的Ti层厚度为20nm；所述的SiO2层厚度为300nm；The thickness of the Pt layer is 150nm; the thickness of the Ti layer is 20nm; the thickness of the SiO2 layer is 300nm;
二、在温度为800℃、压强为200Pa和氩气气氛下对基底材料进行退火处理，退火时间为60min；2. Anneal the substrate material at a temperature of 800°C, a pressure of 200Pa, and an argon atmosphere, and the annealing time is 60 minutes;
三、通入碳源气体，调节碳源气体的气体流量为30sccm、氩气的气体流量为70sccm，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为600Pa，然后在沉积系统射频电源频率为13.56MHz、射频功率为200W、压强为600Pa和温度为800℃的条件下进行沉积，沉积时间为60min；3. Introduce the carbon source gas, adjust the gas flow rate of the carbon source gas to 30 sccm, and the gas flow rate of the argon gas to 70 sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 600 Pa, and then in the deposition system The RF power frequency is 13.56MHz, the RF power is 200W, the pressure is 600Pa and the temperature is 800°C, and the deposition time is 60min;
所述的碳源气体为甲烷与氩气的总气体流量为100sccm；Described carbon source gas is that the total gas flow rate of methane and argon is 100 sccm;
四、沉积结束后，关闭射频电源和加热电源，停止通入碳源气体，继续以气体流量为90sccm通入氩气，并调节抽真空速度将等离子体增强化学气相沉积真空装置中压强控制为200Pa，在压强为200Pa和氩气气氛下从温度为800℃冷却至室温，即得到3D碗状混合纳米结构石墨烯超级电容器电极材料。4. After the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed the argon gas with a gas flow rate of 90 sccm, and adjust the vacuuming speed to control the pressure in the plasma enhanced chemical vapor deposition vacuum device to 200Pa , and cooled from a temperature of 800 ° C to room temperature under a pressure of 200 Pa and an argon atmosphere to obtain a 3D bowl-shaped mixed nanostructure graphene supercapacitor electrode material.
实施例五制备的3D碗状混合纳米结构石墨烯直接作为电极材料的电化学测试结果，利用电化学工作站测试在扫描速率为50mV/s、20mV/s、10mV/s、5mV/s和2mV/s时比电容分别为321μF/cm2、489μF/cm2、576μF/cm2、654μF/cm2和703μF/cm2。The 3D bowl-shaped mixed nanostructure graphene prepared in embodiment five is directly used as the electrochemical test result of the electrode material, and the electrochemical workstation is used to test that the scanning rate is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s The specific capacitances at s time are 321μF/cm 2 , 489μF/cm 2 , 576μF/cm 2 , 654μF/cm 2 and 703μF/cm 2 .
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