CN104882297A - Process for preparing stretchable supercapacitor based on highly conductive graphene/nickel particle mixed structure - Google Patents
Process for preparing stretchable supercapacitor based on highly conductive graphene/nickel particle mixed structure Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 305
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 3
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
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- 238000001291 vacuum drying Methods 0.000 description 5
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- 239000002585 base Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
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- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
本发明涉及一种基于高导电石墨烯/镍颗粒混合结构的可拉伸超级电容器的制备方法，先用化学气相沉积方法在泡沫镍上制备海绵状石墨烯材料，将制备的石墨烯/泡沫镍浸泡在刻蚀溶液中，缓慢反应，使大部分镍金属被化学置换掉，使镍金属转变成一个个小的镍颗粒，然后将海绵状石墨烯/镍颗粒混合结构采用印章式捞法从刻蚀溶液中捞出、清洗、晾干，预拉伸弹性衬底慢慢恢复到原来的长度或面积，利用制备的可拉伸石墨烯/镍颗粒混合结构作为电极材料，按照弹性体/电极/固体电解质/电极/弹性体的结构制备全固态可拉伸超级电容器。本发明增加传统电容器电容量，减小接触电阻，拉伸稳定性好，次数多，性能优，且成本低，方法可控，适于大批量生产。
The invention relates to a preparation method of a stretchable supercapacitor based on a highly conductive graphene/nickel particle hybrid structure. First, a sponge-like graphene material is prepared on foamed nickel by chemical vapor deposition, and the prepared graphene/nickel foam is prepared Immersed in the etching solution, react slowly, so that most of the nickel metal is chemically replaced, so that the nickel metal is transformed into small nickel particles, and then the sponge-like graphene/nickel particle mixed structure is removed from the engraved The pre-stretched elastic substrate slowly returns to the original length or area, and the prepared stretchable graphene/nickel particle hybrid structure is used as the electrode material, according to the elastomer/electrode/ The structure of solid electrolyte/electrode/elastomer to prepare all-solid-state stretchable supercapacitors. The invention increases the capacitance of the traditional capacitor, reduces the contact resistance, has good tensile stability, many times, excellent performance, low cost, controllable method and is suitable for mass production.
Description
技术领域technical field
本发明涉及一种可拉伸电容器的制备方法，具体涉及一种高导电海绵状石墨烯/镍颗粒混合纳米结构的可拉伸超级电容器的制备方法，属于电容器技术领域。The invention relates to a preparation method of a stretchable capacitor, in particular to a preparation method of a stretchable supercapacitor with a highly conductive sponge-like graphene/nickel particle mixed nanostructure, belonging to the technical field of capacitors.
背景技术Background technique
作为当今新型的电子设备，可拉伸电子装置在承受较大机械应力的情况下仍能够展现良好的电学性能，在人体植入装置、柔性便携设备、可穿戴设备、无线感应装置等方面具有广泛的用途。为实现其独立驱动能力，发展可拉伸性的储能装置(如超级电容器)尤为重要。然而，相关的研究进展较为缓慢，主要原因是优异电学和电化学性能的可拉伸电极材料的制备比较困难。As a new type of electronic equipment today, stretchable electronic devices can still exhibit good electrical properties under the condition of large mechanical stress, and have a wide range of applications in human implants, flexible portable devices, wearable devices, wireless sensing devices, etc. the use of. To realize its independent driving ability, it is particularly important to develop stretchable energy storage devices such as supercapacitors. However, the progress of related research is relatively slow, mainly because it is difficult to prepare stretchable electrode materials with excellent electrical and electrochemical properties.
三维海绵状石墨烯具有二维石墨烯优异的电学性质，同时有更大的比表面积以及更加优良的柔韧性，一般程度的扭曲不会影响到材料的性质和特性，有利于制备储能大、稳定性好的柔性超级电容器。将柔性三维海绵状石墨烯转移到预拉伸的弹性衬底上，形成柔性的自组装结构，在拉伸-收缩过程中，其基本结构不会被破坏，使其具有超高拉伸性能，相较普通的石墨烯，其柔性更好，弹性更大，其电学及电化学性能在拉伸前后基本保持不变，这对制备可拉伸导电材料及其超级电容器具有十分重要的意义。Three-dimensional sponge-like graphene has the excellent electrical properties of two-dimensional graphene, and at the same time has a larger specific surface area and better flexibility. The general degree of distortion will not affect the properties and characteristics of the material, which is conducive to the preparation of large energy storage, Stable flexible supercapacitor. The flexible three-dimensional sponge-like graphene is transferred to the pre-stretched elastic substrate to form a flexible self-assembled structure. During the stretch-shrink process, its basic structure will not be destroyed, so that it has ultra-high stretchability, Compared with ordinary graphene, it has better flexibility and greater elasticity, and its electrical and electrochemical properties remain basically unchanged before and after stretching, which is of great significance for the preparation of stretchable conductive materials and supercapacitors.
另一方面，外接导体与活性电极材料之间的电阻严重影响超级电容器的性能和实际应用。由于活性石墨烯电极材料与外接导体的接触电阻较大，单独的三维海绵状石墨烯作为柔性导电电极具有缺陷。本项目研究新型的三维石墨烯/镍颗粒混合结构的柔性电极材料，其本身既起到活性电极材料作用，又起到柔性集流体的作用，与外接导体的接触电阻较小。更重要的是，由于三维石墨烯的柔性和可折叠性，柔性的石墨烯/镍颗粒混合结构可以被改造成周期性皱褶的可拉伸电极材料，从而具有超高拉伸性能。这为其在高性能可拉伸超级电容器的应用打开一条新的路径，对推动可拉伸超级电容器的进一步发展和广泛应用具有重要的作用。On the other hand, the resistance between the external conductor and the active electrode material seriously affects the performance and practical application of supercapacitors. Due to the large contact resistance between the active graphene electrode material and the external conductor, the three-dimensional sponge-like graphene alone has defects as a flexible conductive electrode. This project studies a new type of flexible electrode material with a three-dimensional graphene/nickel particle hybrid structure, which itself acts not only as an active electrode material, but also as a flexible current collector, and has a small contact resistance with an external conductor. More importantly, due to the flexibility and foldability of 3D graphene, the flexible graphene/nickel particle hybrid structure can be engineered into a periodically wrinkled stretchable electrode material with ultrahigh stretchability. This opens a new path for its application in high-performance stretchable supercapacitors, which plays an important role in promoting the further development and wide application of stretchable supercapacitors.
本课题着眼于柔性便携设备、可拉伸电子装置等方面的实际应用，通过制备新型的三维石墨烯/镍颗粒泡沫结构的柔性电极材料，来实现可拉伸超级电容器的制备和应用。本课题的研究不仅能够实现可拉伸超级电容器的制备，更能够为其他可拉伸器件的制备提供一种方法，为我国的新型可拉伸电子产品的研发做出贡献。This topic focuses on the practical application of flexible portable devices, stretchable electronic devices, etc., and realizes the preparation and application of stretchable supercapacitors by preparing a new type of flexible electrode material with a three-dimensional graphene/nickel particle foam structure. The research of this topic can not only realize the preparation of stretchable supercapacitors, but also provide a method for the preparation of other stretchable devices, and contribute to the research and development of new stretchable electronic products in my country.
高性能的石墨烯基活性电极及其可拉伸超级电容器的制备研究还有两个亟需解决的问题：1.可拉伸石墨烯基活性材料的制备过程复杂，制备成本也较高。大部分制备方法都需要在较高温度、较高真空度等条件下多步处理，需要的制备时间较长，很多还需要利用复杂的湿法或干法转移过程；2.单独石墨烯和外接导线的接触电阻太大，影响超级电容器的性能。通常情况下，为了更好的将活性电极的电流导出，在制备超级电容器的过程中，还需要一层集流体(泡沫镍是一种常用的超级电容器的集流体)。然而，泡沫镍不能被拉伸，无法直接应用在可拉伸超级电容器中。若不使用集流体，由于石墨烯与导出电流的外接导体的接触电阻较大，影响可拉伸超级电容器的性能。There are still two problems that need to be solved urgently in the preparation of high-performance graphene-based active electrodes and their stretchable supercapacitors: 1. The preparation process of stretchable graphene-based active materials is complicated and the preparation cost is high. Most of the preparation methods require multi-step processing under conditions such as higher temperature and higher vacuum, which require a long preparation time, and many of them also need to use complicated wet or dry transfer processes; 2. Separate graphene and external The contact resistance of the wire is too large, which affects the performance of the supercapacitor. Usually, in order to better lead out the current of the active electrode, a layer of current collector (foamed nickel is a commonly used current collector for supercapacitors) is also required in the process of preparing the supercapacitor. However, nickel foam cannot be stretched and cannot be directly applied in stretchable supercapacitors. If no current collector is used, the performance of the stretchable supercapacitor will be affected due to the large contact resistance between graphene and the external conductor that leads the current.
发明内容Contents of the invention
本发明的目的是克服现有技术的不足，而提供一种基于高导电石墨烯/镍颗粒混合结构的可拉伸超级电容器的制备方法。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for preparing a stretchable supercapacitor based on a highly conductive graphene/nickel particle hybrid structure.
本发明采取的技术方案为：The technical scheme that the present invention takes is:
一种基于高导电石墨烯/镍颗粒混合结构的可拉伸超级电容器的制备方法，包括步骤如下：A method for preparing a stretchable supercapacitor based on a highly conductive graphene/nickel particle hybrid structure, comprising the following steps:
(一)化学气相沉积方法在泡沫镍上制备海绵状石墨烯材料(1) Preparation of sponge-like graphene material on nickel foam by chemical vapor deposition method
将泡沫镍放入真空反应炉加温区中，抽真空，同时加热，将氢气注入真空反应炉中，加热到预定温度100-500℃后恒温10-30分钟然后进行退火，再加热到预定温度900-1100℃后，将碳源通入真空反应炉，同时保持氢气流量不变，生长5-180分钟后关闭气体并降至室温即可得到直接沉积石墨烯的衬底，即石墨烯/镍；Put the nickel foam into the heating zone of the vacuum reaction furnace, vacuumize and heat at the same time, inject hydrogen into the vacuum reaction furnace, heat to the predetermined temperature of 100-500°C, keep the temperature for 10-30 minutes, then anneal, and then heat to the predetermined temperature After 900-1100°C, put the carbon source into the vacuum reaction furnace while keeping the hydrogen flow constant, turn off the gas after 5-180 minutes of growth and lower it to room temperature to obtain a substrate for direct deposition of graphene, that is, graphene/nickel ;
(二)可拉伸石墨烯/镍颗粒混合结构的制备及其转移(2) Preparation and transfer of stretchable graphene/nickel particle hybrid structure
将制备的石墨烯/泡沫镍浸泡在刻蚀溶液中，缓慢反应，使大部分泡沫镍被化学置换掉，使泡沫镍转变成一个个小的金属颗粒，然后将海绵状石墨烯/镍颗粒混合结构从刻蚀溶液中用印章式捞法捞出，分别在丙酮、酒精和去离子水中清洗，后将预拉伸弹性衬底黏在中空支架上，用同样的印章式捞法转移在预拉伸弹性衬底上，自然晾干，该衬底预拉伸为沿一个方向拉伸到原来长度的1.5到4倍，或者沿两个正交的方向拉伸到原来面积的2到10倍；然后让覆盖柔性石墨烯/镍颗粒混合结构的预拉伸弹性衬底慢慢恢复到原来的长度或面积，制备一种自组装皱褶的可拉伸石墨烯/镍颗粒混合结构；Soak the prepared graphene/nickel foam in the etching solution, react slowly, so that most of the foamed nickel is chemically replaced, and the foamed nickel is transformed into small metal particles, and then the spongy graphene/nickel particles are mixed The structure was fished out from the etching solution by stamp fishing method, cleaned in acetone, alcohol and deionized water respectively, and then the pre-stretched elastic substrate was glued to the hollow support, and transferred on the pre-stretched substrate by the same stamp fishing method. Stretch the elastic substrate and let it dry naturally. The substrate is pre-stretched to 1.5 to 4 times its original length in one direction, or 2 to 10 times its original area in two orthogonal directions; Then let the pre-stretched elastic substrate covering the flexible graphene/nickel particle hybrid structure slowly return to its original length or area, and prepare a self-assembled wrinkled stretchable graphene/nickel particle hybrid structure;
(三)全固态可拉伸超级电容器的制备(3) Preparation of all-solid-state stretchable supercapacitors
利用制备的可拉伸石墨烯/镍颗粒混合结构作为电极材料，按照弹性体/电极/固体电解质/电极/弹性体的结构制备全固态可拉伸超级电容器。Using the prepared stretchable graphene/nickel particle hybrid structure as the electrode material, an all-solid-state stretchable supercapacitor is prepared according to the structure of elastomer/electrode/solid electrolyte/electrode/elastomer.
上述制备方法中，In the above preparation method,
步骤(一)中所述泡沫镍的尺寸为1cm×1cm-30cm×30cm。所述碳源为甲烷、乙炔、乙烯中的一种或者几种。所述碳源的流量控制在1-300sccm，纯度高于99.99％；所述氢气的流量控制在1-100sccm，纯度高于99.99％。所述真空反应炉抽真空度为3×10-3-3×10-6Torr，以去除炉腔中的活性气体，保持清洁的生长环境。所述的退火指的是对衬底表面祛除氧化物等杂志的过程。得到直接沉积石墨烯的衬底后，关闭碳源气体阀门，保持氢气流量不变降温，之后取出沉积的石墨烯。The size of the nickel foam in step (1) is 1cm×1cm-30cm×30cm. The carbon source is one or more of methane, acetylene and ethylene. The flow rate of the carbon source is controlled at 1-300 sccm, and the purity is higher than 99.99%; the flow rate of the hydrogen gas is controlled at 1-100 sccm, and the purity is higher than 99.99%. The vacuum degree of the vacuum reaction furnace is 3×10 -3 -3×10 -6 Torr to remove active gas in the furnace chamber and maintain a clean growth environment. The annealing refers to the process of removing impurities such as oxides on the surface of the substrate. After obtaining the substrate on which graphene is directly deposited, close the carbon source gas valve, keep the flow of hydrogen gas constant to cool down, and then take out the deposited graphene.
取出衬底材料的方法在于等真空反应炉温度降到室温后，关闭氢气气体阀门、真空泵，用空气将反应炉腔体充满到一个大气压状态，然后将衬底材料取出。制备的石墨烯/泡沫金属中石墨烯的层数为1-10层。The method of taking out the substrate material is to wait for the temperature of the vacuum reactor to drop to room temperature, close the hydrogen gas valve and the vacuum pump, fill the chamber of the reactor with air to an atmospheric pressure state, and then take out the substrate material. The number of graphene layers in the prepared graphene/foam metal is 1-10 layers.
步骤(二)中所述的刻蚀溶液为氯化铁或硝酸铁溶液，所述溶液浓度为0.5-5mol/L；所述弹性衬底为PMMA、PDFS等弹性衬底；所述化学置换反应时间为15-1000分钟，反应温度为10-50摄氏度；The etching solution described in the step (2) is ferric chloride or ferric nitrate solution, and the concentration of the solution is 0.5-5mol/L; the elastic substrate is elastic substrates such as PMMA and PDFS; the chemical replacement reaction The time is 15-1000 minutes, and the reaction temperature is 10-50 degrees Celsius;
所述印章式捞法具体为：用柔性的衬底覆盖在海绵状石墨烯/金属颗粒混合结构上，轻压10-30秒，然后慢慢从衬底的一个侧面轻轻抬起，利用石墨烯和衬底之间的小的接触力，将石墨烯衬底捞出。The stamp-type fishing method is as follows: cover the spongy graphene/metal particle hybrid structure with a flexible substrate, press lightly for 10-30 seconds, and then slowly lift it up from one side of the substrate, using graphite The small contact force between the graphene and the substrate pulls out the graphene substrate.
步骤(三)中所述弹性体为PMMA、PDFS等弹性体；所述固体电解质为PVA-酸、碱或中性电解质；所述镍颗粒大小为10-500nm；所述镍颗粒含量比例为0％-50％。The elastomer described in step (3) is the elastomer such as PMMA, PDFS; Described solid electrolyte is PVA-acid, alkali or neutral electrolyte; Described nickel particle size is 10-500nm; Described nickel particle content ratio is 0 %-50%.
可利用电化学工作站测试预拉伸的程度、拉伸-收缩的重复次数和速度对超级电容器相关性质(电容量，电容器循环寿命，电阻抗等)的影响；制备不同的石墨烯/镍颗粒含量比例的可拉伸导电薄膜，并组装成全固态可拉伸超级电容器。The electrochemical workstation can be used to test the influence of the degree of pre-stretching, the number of repetitions and speed of stretch-shrinkage on the relevant properties of supercapacitors (capacity, capacitor cycle life, electrical impedance, etc.); prepare different graphene/nickel particle contents proportional stretchable conductive film and assembled into an all-solid-state stretchable supercapacitor.
弹性体/电极/固体电解质/电极/弹性体的结构(即弹性体/石墨烯基活性材料/固体电解质/石墨烯基活性材料/弹性体的结构)制备方法包括步骤如下：The structure of elastomer/electrode/solid electrolyte/electrode/elastomer (i.e. the structure of elastomer/graphene-based active material/solid electrolyte/graphene-based active material/elastomer) preparation method comprises steps as follows:
1)分别在两个石墨烯/镍颗粒混合结构的一端制备电极，称为A端；1) Prepare electrodes at one end of the two graphene/nickel particle hybrid structures, called the A end;
2)在每个石墨烯/镍颗粒混合结构其未制备电极的一端涂上大面积PVA-酸、碱或中性电解质，称为B端；2) Coating a large area of PVA-acid, alkali or neutral electrolyte on one end of each graphene/nickel particle hybrid structure without preparing an electrode, called the B end;
3)将两个石墨烯/镍颗粒混合结构的B端重叠覆盖，使涂有电解质的部分大面积接触，使其黏贴在一起；3) Overlap and cover the B ends of the two graphene/nickel particle hybrid structures, so that the parts coated with the electrolyte are in contact with a large area to make them stick together;
4)使用PMMA或PDFS将其粘紧。4) Use PMMA or PDFS to glue it tight.
其中，步骤1)所述制备电极的方法有两种：其一，直接用胶带或胶水将可拉伸导电材料不连通的粘于石墨烯/镍颗粒混合结构的周边；Wherein, the method for preparing electrode described in step 1) has two kinds: one, directly use adhesive tape or glue to stick the stretchable conductive material disconnected to the periphery of the graphene/nickel particle mixed structure;
所述的可拉伸导电材料包括可拉伸导电碳纤维、导电碳纳米管纤维、导电石墨烯纤维等可拉伸纤维电极；注意电极材料与PVA-酸、碱或中性电解质不连通。The stretchable conductive material includes stretchable fiber electrodes such as stretchable conductive carbon fiber, conductive carbon nanotube fiber, and conductive graphene fiber; note that the electrode material is not connected with PVA-acid, alkali or neutral electrolyte.
其二是利用沉积设备直接在可拉伸石墨烯/镍颗粒混合结构的一端沉积上不连通的电极材料，具体包括以下制备步骤：The second is to use deposition equipment to directly deposit a disconnected electrode material on one end of the stretchable graphene/nickel particle hybrid structure, which specifically includes the following preparation steps:
(1)将石墨烯/镍颗粒混合结构放入低温沉积系统中；(1) Put the graphene/nickel particle hybrid structure into the low temperature deposition system;
(2)制备两端有长方形空条的遮挡板，置于石墨烯/镍颗粒混合结构的上方，注意不能接触混合结构，以免损坏制备的气敏材料；(2) Prepare a baffle plate with rectangular blank strips at both ends, place it above the graphene/nickel particle mixed structure, pay attention not to contact the mixed structure, so as not to damage the prepared gas-sensitive material;
(3)利用沉积设备在石墨烯/镍颗粒混合结构两端沉积不连通的金属电极；注意电极材料与PVA-酸、碱或中性电解质不连通。(3) Utilize deposition equipment to deposit non-connected metal electrodes at both ends of the graphene/nickel particle hybrid structure; note that the electrode material is not connected with PVA-acid, alkali or neutral electrolyte.
所述沉积设备包括磁控溅射沉积系统、蒸镀机、脉冲激光沉积系统等低温沉积系统；The deposition equipment includes low-temperature deposition systems such as magnetron sputtering deposition systems, vapor deposition machines, and pulsed laser deposition systems;
所述电极材料包括铜、铁、银、铂金等金属材料。The electrode material includes metal materials such as copper, iron, silver, and platinum.
本发明利用超级电容器的集流体-泡沫镍，提出了一种新型柔性三维海绵状石墨烯/镍颗粒混合结构的电极材料的制备方法；利用一种超高拉伸性能(拉伸长度大于300％)的电极制备方法，制备可拉伸的兼具活性电极和集流体作用的混合结构；利用电极/电解质/电极的三明治结构，制备性能优异的全固态可拉伸超级电容器。The present invention utilizes the current collector of the supercapacitor-nickel foam, proposes a preparation method of an electrode material with a novel flexible three-dimensional sponge-like graphene/nickel particle hybrid structure; utilizes a kind of ultra-high tensile performance (stretch length greater than 300%) ) electrode preparation method, to prepare a stretchable hybrid structure with both active electrodes and current collectors; to use the electrode/electrolyte/electrode sandwich structure to prepare an all-solid-state stretchable supercapacitor with excellent performance.
本发明的有益效果是：The beneficial effects of the present invention are:
1)海绵状石墨烯生长温度精确控制；1) Precise control of the growth temperature of sponge-like graphene;
2)生长的石墨烯缺陷峰低，具有极高的晶体质量；2) The grown graphene has a low defect peak and has extremely high crystal quality;
3)生长的石墨烯/镍颗粒具有极好的电导率；3) The grown graphene/nickel particles have excellent electrical conductivity;
4)生长的石墨烯尺寸只受CVD腔体的限制，可实现石墨烯的大面积生长；4) The size of the grown graphene is only limited by the CVD chamber, which can realize the large-area growth of graphene;
5)湿法转移过程中不需要使用PMMA胶，省时省力；5) No need to use PMMA glue during the wet transfer process, saving time and effort;
6)转移过程采用印章式转移，石墨烯不会在溶液中任意飘移，避免转移过程中石墨烯的6) The transfer process adopts stamp transfer, and the graphene will not drift arbitrarily in the solution, avoiding the loss of graphene during the transfer process.
损伤，过程简单易行。Damage, the process is simple and easy.
7)成本低廉，方法简单可控，适于大批量生产，应用价值高。7) The cost is low, the method is simple and controllable, suitable for mass production, and has high application value.
附图说明Description of drawings
图1为可拉伸石墨烯/镍颗粒混合电极的制备路线图；Figure 1 is a roadmap for the preparation of stretchable graphene/nickel particle hybrid electrodes;
图2为可拉伸电极的SEM形貌；(对应实施例1)Fig. 2 is the SEM appearance of stretchable electrode; (corresponding to embodiment 1)
图3为制备可拉伸超级电容器的C-V循环曲线。(对应实施例1)Figure 3 is the C-V cycle curve of the prepared stretchable supercapacitor. (corresponding to embodiment 1)
具体实施方式Detailed ways
以下结合附图对本发明的优选实施例进行说明。Preferred embodiments of the present invention will be described below in conjunction with the accompanying drawings.
实施例1Example 1
1.取尺寸为8cm×8cm泡沫镍置于管式炉中；1. Take nickel foam with a size of 8cm×8cm and place it in a tube furnace;
2.打开真空泵将管式炉的气压抽至极限真空状态3×10-6托(Torr)；2. Turn on the vacuum pump to pump the air pressure of the tube furnace to the ultimate vacuum state of 3×10 -6 Torr (Torr);
3.保持真空状态3×10-6Torr 15分钟后(真空15分钟的作用是祛除石英管内部的杂质、空气等，确保反应腔洁净)，将石英管3的气压升到3×10-3Torr；3. After maintaining a vacuum state of 3×10 -6 Torr for 15 minutes (the function of vacuum for 15 minutes is to remove impurities, air, etc. inside the quartz tube to ensure that the reaction chamber is clean), raise the air pressure of the quartz tube 3 to 3×10 -3 Torr;
4.氢气流量计设定为100sccm，将氢气注入真空腔中；4. Set the hydrogen flow meter to 100sccm, and inject hydrogen into the vacuum chamber;
5.管式炉温度升温到300℃后，恒温20分钟进行退火；5. After the tube furnace temperature rises to 300°C, anneal at a constant temperature for 20 minutes;
6.管式炉温度升温到1000℃后，将甲烷注入真空腔中，气体流量计设定为200sccm，停留30分钟进行生长；6. After the tube furnace temperature rises to 1000°C, inject methane into the vacuum chamber, set the gas flow meter to 200 sccm, and stay for 30 minutes for growth;
7.关闭甲烷气体流量计并将管式炉温度以50℃/min的速度快速降至室温；7. Turn off the methane gas flow meter and quickly lower the temperature of the tube furnace to room temperature at a rate of 50°C/min;
8.关闭氢气流量计以及真空泵；8. Turn off the hydrogen flow meter and vacuum pump;
9.打开阀门，用空气将石英管气压充满到一个大气压状态；9. Open the valve and fill the quartz tube with air to an atmospheric pressure state;
10.打开石英管真空接口，取出已沉积石墨烯的泡沫镍；10. Open the vacuum port of the quartz tube and take out the nickel foam that has deposited graphene;
11.将FeCl3按照一定质量加入去离子水中溶解，制备一定浓度的刻蚀溶液FeCl3(4.5mol/L)；11. Dissolve FeCl 3 in deionized water according to a certain mass to prepare a certain concentration of etching solution FeCl 3 (4.5mol/L);
12.制备的石墨烯/泡沫镍浸泡在20℃的FeCl3(4.5mol/L)溶液中140分钟；12. Soak the prepared graphene/nickel foam in FeCl 3 (4.5mol/L) solution at 20°C for 140 minutes;
13.观察石墨烯/泡沫镍的形貌，直到其结构变成柔性石墨烯/镍颗粒混合结构；13. Observe the morphology of graphene/nickel foam until its structure becomes a mixed structure of flexible graphene/nickel particles;
14.将柔性衬底紧压在柔性石墨烯/镍颗粒混合结构表面，轻压25秒；14. Press the flexible substrate tightly on the surface of the flexible graphene/nickel particle hybrid structure for 25 seconds;
15.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯和衬底之间的小的接触力，将石墨烯镍颗粒混合结构捞出；15. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene and the substrate to fish out the graphene-nickel particle mixed structure;
16.将海绵状石墨烯用丙酮、乙醇和去离子水分别清洗3分钟；16. The spongy graphene was cleaned with acetone, ethanol and deionized water for 3 minutes respectively;
17.将PDFS弹性衬底沿一个方向拉伸到原来长度的1.5到4倍，或者沿两个正交的方向拉伸到原来面积的2到10倍；17. Stretch the PDFS elastic substrate to 1.5 to 4 times its original length in one direction, or stretch it to 2 to 10 times its original area in two orthogonal directions;
18.将拉伸后的弹性衬底上黏贴在圆形中空支架上；18. Paste the stretched elastic substrate on the circular hollow support;
19.将支架上的弹性衬底一面紧压在柔性石墨烯/镍颗粒混合结构表面，轻压20秒；19. Press the elastic substrate side on the bracket tightly on the surface of the flexible graphene/nickel particle hybrid structure, and press lightly for 20 seconds;
20.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯镍颗粒混合结构和衬底之间的小的接触力，将石墨烯/镍颗粒混合结构捞出；20. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene-nickel particle mixed structure and the substrate to fish out the graphene/nickel particle mixed structure;
21.在真空干燥箱中晾3小时；21. Dry in a vacuum oven for 3 hours;
22.从中空的圆形或方形支架上将覆盖有石墨烯/镍颗粒混合结构的弹性衬底取下，一侧粘于支架上；22. Remove the elastic substrate covered with the graphene/nickel particle hybrid structure from the hollow circular or square support, and stick one side to the support;
23.在真空干燥箱中自然恢复5小时，使其恢复到原来尺寸，依此来制备一种自组装皱褶的可拉伸石墨烯/镍颗粒混合结构。23. Naturally recover for 5 hours in a vacuum drying oven to make it return to its original size, so as to prepare a self-assembled wrinkled stretchable graphene/nickel particle hybrid structure.
24.用胶带或胶水将可拉伸导电碳纤维不连通的分别粘于两个石墨烯/镍颗粒混合结构的一端；24. Use adhesive tape or glue to stick the stretchable conductive carbon fiber disconnected to one end of the two graphene/nickel particle hybrid structures;
25.在其未粘贴可拉伸导电碳纤维的一端涂上大面积的PVA-酸，注意PVA-酸与导电纤维不连通；25. Apply a large area of PVA-acid on one end of the stretchable conductive carbon fiber that is not pasted, and pay attention that the PVA-acid is not connected to the conductive fiber;
26.将两个石墨烯/镍颗粒混合结构涂有PVA-酸的一端重叠覆盖，使其相接触从而黏贴在一起；26. Overlap and cover the ends of the two graphene/nickel particle hybrid structures coated with PVA-acid to make them contact and stick together;
27.使用PMMA或PDFS将接触端粘紧。27. Use PMMA or PDFS to glue the contact end tightly.
实施例2Example 2
在泡沫镍衬底上生长石墨烯并最终生长石墨烯/镍颗粒混合结构，从而制备可拉伸电容器，包括以下制备步骤Graphene is grown on a nickel foam substrate and finally a graphene/nickel particle hybrid structure is grown to prepare a stretchable capacitor, including the following preparation steps
1.取尺寸为8cm×9cm泡沫镍置于管式炉中；1. Take nickel foam with a size of 8cm×9cm and place it in a tube furnace;
2.打开真空泵将管式炉的气压抽至极限真空状态3×10-6托(Torr)；2. Turn on the vacuum pump to pump the air pressure of the tube furnace to the ultimate vacuum state of 3×10 -6 Torr (Torr);
3.保持真空状态3×10-6Torr 15分钟后(真空15分钟的作用是祛除石英管内部的杂质、空气等，确保反应腔洁净)，将石英管3的气压升到3×10-3Torr；3. After maintaining a vacuum state of 3×10 -6 Torr for 15 minutes (the function of vacuum for 15 minutes is to remove impurities, air, etc. inside the quartz tube to ensure that the reaction chamber is clean), raise the air pressure of the quartz tube 3 to 3×10 -3 Torr;
4.氢气流量计设定为100sccm，将氢气注入真空腔中；4. Set the hydrogen flow meter to 100sccm, and inject hydrogen into the vacuum chamber;
5.管式炉温度升温到300℃后，恒温20分钟进行退火；5. After the tube furnace temperature rises to 300°C, anneal at a constant temperature for 20 minutes;
6.管式炉温度升温到1000℃后，将甲烷注入真空腔中，,气体流量计设定为200sccm，停留40分钟进行生长；6. After the tube furnace temperature rises to 1000°C, inject methane into the vacuum chamber, set the gas flow meter to 200 sccm, and stay for 40 minutes for growth;
7.关闭甲烷气体流量计并将管式炉温度以60℃/min的速度快速降至室温；7. Turn off the methane gas flow meter and quickly lower the temperature of the tube furnace to room temperature at a rate of 60°C/min;
8.关闭氢气流量计以及真空泵；8. Turn off the hydrogen flow meter and vacuum pump;
9.打开阀门，用空气将石英管气压充满到一个大气压状态；9. Open the valve and fill the quartz tube with air to an atmospheric pressure state;
10.打开石英管真空接口，取出已沉积石墨烯的泡沫镍；10. Open the vacuum port of the quartz tube and take out the nickel foam that has deposited graphene;
11.将FeCl3按照一定质量加入去离子水中溶解，制备一定浓度的刻蚀溶液FeCl3(0.5mol/L)；11. Dissolve FeCl 3 in deionized water according to a certain mass to prepare a certain concentration of etching solution FeCl 3 (0.5mol/L);
12.制备的石墨烯/泡沫镍浸泡在40℃的FeCl3(0.5mol/L)溶液中150分钟；12. Soak the prepared graphene/nickel foam in FeCl 3 (0.5mol/L) solution at 40°C for 150 minutes;
13.观察石墨烯/泡沫镍的形貌，直到其结构变成柔性石墨烯/镍颗粒混合结构；13. Observe the morphology of graphene/nickel foam until its structure becomes a mixed structure of flexible graphene/nickel particles;
14.将柔性衬底紧压在柔性石墨烯/镍颗粒混合结构表面，轻压15秒；14. Press the flexible substrate tightly on the surface of the flexible graphene/nickel particle hybrid structure for 15 seconds;
15.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯和衬底之间的小的接触力，将石墨烯镍颗粒混合结构捞出；15. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene and the substrate to fish out the graphene-nickel particle mixed structure;
16.将海绵状石墨烯用丙酮、乙醇和去离子水分别清洗3分钟；16. The spongy graphene was cleaned with acetone, ethanol and deionized water for 3 minutes respectively;
17.将PDFS弹性衬底沿两个正交的方向拉伸到原来面积的5倍；17. Stretch the PDFS elastic substrate to 5 times the original area along two orthogonal directions;
18.将拉伸后的弹性衬底上黏贴在中空方形支架上；18. Paste the stretched elastic substrate on the hollow square support;
19.将支架上的弹性衬底一面紧压在柔性石墨烯/镍颗粒混合结构表面，轻压30秒；19. Press the elastic substrate side on the bracket tightly on the surface of the flexible graphene/nickel particle hybrid structure, and press lightly for 30 seconds;
20.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯镍颗粒混合结构和衬底之间的小的接触力，将石墨烯/镍颗粒混合结构捞出；20. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene-nickel particle mixed structure and the substrate to fish out the graphene/nickel particle mixed structure;
21.在真空干燥箱中晾3小时；21. Dry in a vacuum oven for 3 hours;
22.从方形支架上将覆盖有石墨烯/镍颗粒混合结构的弹性衬底取下，一侧粘于支架上；22. Remove the elastic substrate covered with the graphene/nickel particle hybrid structure from the square support, and stick one side to the support;
23.在真空干燥箱中自然恢复3-5小时，使其恢复到原来尺寸，依此来制备一种自组装皱褶的可拉伸石墨烯/镍颗粒混合结构。23. Naturally recover in a vacuum drying oven for 3-5 hours to make it return to its original size, so as to prepare a self-assembled wrinkled stretchable graphene/nickel particle hybrid structure.
24.将石墨烯/镍颗粒混合结构放入低温沉积系统中；24. Put the graphene/nickel particle hybrid structure into the low temperature deposition system;
25.制备两端有长方形空条的遮挡板，置于石墨烯/镍颗粒混合结构的上方，皱褶的可拉伸石墨烯/镍颗粒混合结构。25. Prepare a baffle plate with rectangular empty strips at both ends, place it above the graphene/nickel particle hybrid structure, and wrinkle stretchable graphene/nickel particle hybrid structure.
26.利用蒸镀机分别在两个石墨烯/镍颗粒混合结构的一端沉积不联通的铜电极。26. Deposit unconnected copper electrodes at one end of the two graphene/nickel particle hybrid structures using an evaporation machine.
27.在其未沉积电极的一端涂上大面积的PVA-酸，注意PVA-酸与铜电极不连通；27. Apply a large area of PVA-acid on one end of the undeposited electrode, and pay attention that the PVA-acid is not connected to the copper electrode;
28.将两个石墨烯/镍颗粒混合结构涂有PVA-酸的一端重叠覆盖，使其相接触从而黏贴在一起；28. Overlap and cover the ends of the two graphene/nickel particle hybrid structures coated with PVA-acid so that they are in contact and stick together;
29.使用PMMA将重叠部位粘紧。29. Use PMMA to glue the overlapping parts tightly.
实施例3Example 3
在泡沫镍衬底上生长石墨烯并最终生长石墨烯/镍颗粒混合结构，制备高导电可拉伸电容器，包括以下制备步骤：Graphene is grown on a nickel foam substrate and finally a graphene/nickel particle hybrid structure is grown to prepare a highly conductive stretchable capacitor, including the following preparation steps:
1.取尺寸为5cm×9cm泡沫镍置于管式炉中；1. Take nickel foam with a size of 5cm×9cm and place it in a tube furnace;
2.打开真空泵将管式炉的气压抽至极限真空状态3×10-6托(Torr)；2. Turn on the vacuum pump to pump the air pressure of the tube furnace to the ultimate vacuum state of 3×10 -6 Torr (Torr);
3.保持真空状态3×10-6Torr 15分钟后(真空15分钟的作用是祛除石英管内部的杂质、空气等，确保反应腔洁净)，将石英管3的气压升到3×10-3Torr；3. After maintaining a vacuum state of 3×10 -6 Torr for 15 minutes (the function of vacuum for 15 minutes is to remove impurities, air, etc. inside the quartz tube to ensure that the reaction chamber is clean), raise the air pressure of the quartz tube 3 to 3×10 -3 Torr;
4.氢气流量计设定为100sccm，将氢气注入真空腔中；4. Set the hydrogen flow meter to 100sccm, and inject hydrogen into the vacuum chamber;
5.管式炉温度升温到300℃后，恒温20分钟进行退火；5. After the tube furnace temperature rises to 300°C, anneal at a constant temperature for 20 minutes;
6.管式炉温度升温到1000℃后，将甲烷注入真空腔中，,气体流量计设定为200sccm，停留40分钟进行生长；6. After the tube furnace temperature rises to 1000°C, inject methane into the vacuum chamber, set the gas flow meter to 200 sccm, and stay for 40 minutes for growth;
7.关闭甲烷气体流量计并将管式炉温度以30-60℃/min的速度快速降至室温；7. Turn off the methane gas flow meter and quickly lower the temperature of the tube furnace to room temperature at a rate of 30-60°C/min;
8.关闭氢气流量计以及真空泵；8. Turn off the hydrogen flow meter and vacuum pump;
9.打开阀门，用空气将石英管气压充满到一个大气压状态；9. Open the valve and fill the quartz tube with air to an atmospheric pressure state;
10.打开石英管真空接口，取出已沉积石墨烯的泡沫镍；10. Open the vacuum port of the quartz tube and take out the nickel foam that has deposited graphene;
11.将FeCl3按照一定质量加入去离子水中溶解，制备一定浓度的刻蚀溶液FeCl3(4mol/L)；11. Dissolve FeCl 3 in deionized water according to a certain mass to prepare a certain concentration of etching solution FeCl 3 (4mol/L);
12.制备的石墨烯/泡沫镍浸泡在27℃的FeCl3(4mol/L)溶液中150分钟；12. Soak the prepared graphene/nickel foam in FeCl 3 (4mol/L) solution at 27°C for 150 minutes;
13.观察石墨烯/泡沫镍的形貌，直到其结构变成柔性石墨烯/镍颗粒混合结构；13. Observe the morphology of graphene/nickel foam until its structure becomes a mixed structure of flexible graphene/nickel particles;
14.将柔性衬底紧压在柔性石墨烯/镍颗粒混合结构表面，轻压15秒；14. Press the flexible substrate tightly on the surface of the flexible graphene/nickel particle hybrid structure for 15 seconds;
15.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯和衬底之间的小的接触力，将石墨烯镍颗粒混合结构捞出；15. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene and the substrate to fish out the graphene-nickel particle mixed structure;
16.将海绵状石墨烯用丙酮、乙醇和去离子水分别清洗3分钟；16. The spongy graphene was cleaned with acetone, ethanol and deionized water for 3 minutes respectively;
17.将PMMA弹性衬底沿两个正交的方向拉伸到原来面积的8倍；17. Stretch the PMMA elastic substrate to 8 times the original area along two orthogonal directions;
18.将拉伸后的弹性衬底上黏贴在中空方形支架上；18. Paste the stretched elastic substrate on the hollow square support;
19.将支架上的弹性衬底一面紧压在柔性石墨烯/镍颗粒混合结构表面，轻压30秒；19. Press the elastic substrate side on the bracket tightly on the surface of the flexible graphene/nickel particle hybrid structure, and press lightly for 30 seconds;
20.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯镍颗粒混合结构和衬底之间的小的接触力，将石墨烯/镍颗粒混合结构捞出；20. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene-nickel particle mixed structure and the substrate to fish out the graphene/nickel particle mixed structure;
21.在真空干燥箱中晾3小时；21. Dry in a vacuum oven for 3 hours;
22.从方形支架上将覆盖有石墨烯/镍颗粒混合结构的弹性衬底取下，一侧粘于支架上；22. Remove the elastic substrate covered with the graphene/nickel particle hybrid structure from the square support, and stick one side to the support;
23.在真空干燥箱中自然恢复3-5小时，使其恢复到原来尺寸，依此来制备一种自组装皱褶的可拉伸石墨烯/镍颗粒混合结构。23. Naturally recover in a vacuum drying oven for 3-5 hours to make it return to its original size, so as to prepare a self-assembled wrinkled stretchable graphene/nickel particle hybrid structure.
24.将石墨烯/镍颗粒混合结构放入低温沉积系统中；24. Put the graphene/nickel particle hybrid structure into the low temperature deposition system;
25.制备两端有长方形空条的遮挡板，置于石墨烯/镍颗粒混合结构的上方，但不能接触混合结构，以免损坏制备的气敏材料；25. Prepare a baffle plate with rectangular empty strips at both ends, and place it above the graphene/nickel particle mixed structure, but cannot touch the mixed structure, so as not to damage the prepared gas-sensitive material;
26.最后利用脉冲激光沉积系统分别在两个石墨烯/镍颗粒混合结构的一端沉积不联通的银电极。26. Finally, a pulsed laser deposition system is used to deposit disconnected silver electrodes on one end of the two graphene/nickel particle hybrid structures.
27.在未沉积银电极的一端涂上大面积的PVA-碱，注意PVA-碱与银电极不连通；27. Apply a large area of PVA-alkali to one end of the non-deposited silver electrode, and pay attention that the PVA-alkali is not connected to the silver electrode;
28.将两个石墨烯/镍颗粒混合结构涂有PVA-碱的一端重叠覆盖，使其相接触从而黏贴在一起；28. Overlap and cover the ends of the two graphene/nickel particle hybrid structures coated with PVA-alkali, so that they are in contact and pasted together;
29.使用胶水将重叠部分粘紧。29. Use glue to secure the overlaps.
实施例4Example 4
在泡沫镍衬底上生长石墨烯并最终生长石墨烯/镍颗粒混合结构，从而制备可拉伸超级电容器包括以下制备步骤：The growth of graphene on the nickel foam substrate and finally the growth of graphene/nickel particle hybrid structure to prepare a stretchable supercapacitor includes the following preparation steps:
1.取尺寸为7cm×7cm泡沫镍置于管式炉中；1. Take nickel foam with a size of 7cm×7cm and place it in a tube furnace;
2.打开真空泵将管式炉的气压抽至极限真空状态3×10-6托(Torr)；2. Turn on the vacuum pump to pump the air pressure of the tube furnace to the ultimate vacuum state of 3×10 -6 Torr (Torr);
3.保持真空状态3×10-6Torr 15分钟后(真空15分钟的作用是祛除石英管内部的杂质、空气等，确保反应腔洁净)，将石英管3的气压升到3×10-3Torr；3. After maintaining a vacuum state of 3×10 -6 Torr for 15 minutes (the function of vacuum for 15 minutes is to remove impurities, air, etc. inside the quartz tube to ensure that the reaction chamber is clean), raise the air pressure of the quartz tube 3 to 3×10 -3 Torr;
4.氢气流量计设定为100sccm，将氢气注入真空腔中；4. Set the hydrogen flow meter to 100sccm, and inject hydrogen into the vacuum chamber;
5.管式炉温度升温到300℃后，恒温20分钟进行退火；5. After the tube furnace temperature rises to 300°C, anneal at a constant temperature for 20 minutes;
6.管式炉温度升温到1000℃后，将甲烷注入真空腔中，,气体流量计设定为200sccm，停留35分钟进行生长；6. After the tube furnace temperature rises to 1000°C, inject methane into the vacuum chamber, set the gas flow meter to 200 sccm, and stay for 35 minutes for growth;
7.关闭甲烷气体流量计并将管式炉温度以30-60℃/min的速度快速降至室温；7. Turn off the methane gas flow meter and quickly lower the temperature of the tube furnace to room temperature at a rate of 30-60°C/min;
8.关闭氢气流量计以及真空泵；8. Turn off the hydrogen flow meter and vacuum pump;
9.打开阀门，用空气将石英管气压充满到一个大气压状态；9. Open the valve and fill the quartz tube with air to an atmospheric pressure state;
10.打开石英管真空接口，取出已沉积石墨烯的泡沫镍；10. Open the vacuum port of the quartz tube and take out the nickel foam that has deposited graphene;
11.将FeCl3按照一定质量加入去离子水中溶解，制备一定浓度的刻蚀溶液FeCl3(1mol/L)；11. Dissolve FeCl 3 in deionized water according to a certain mass to prepare a certain concentration of etching solution FeCl 3 (1mol/L);
12.制备的石墨烯/泡沫镍浸泡在35℃的FeCl3(1mol/L)溶液中190分钟；12. Soak the prepared graphene/nickel foam in FeCl 3 (1mol/L) solution at 35°C for 190 minutes;
13.观察石墨烯/泡沫镍的形貌，直到其结构变成柔性石墨烯/镍颗粒混合结构；13. Observe the morphology of graphene/nickel foam until its structure becomes a mixed structure of flexible graphene/nickel particles;
14.将柔性衬底紧压在柔性石墨烯/镍颗粒混合结构表面，轻压15秒；14. Press the flexible substrate tightly on the surface of the flexible graphene/nickel particle hybrid structure for 15 seconds;
15.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯和衬底之间的小的接触力，将石墨烯镍颗粒混合结构捞出；15. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene and the substrate to fish out the graphene-nickel particle mixed structure;
16.将海绵状石墨烯用丙酮、乙醇和去离子水分别清洗3分钟；16. The spongy graphene was cleaned with acetone, ethanol and deionized water for 3 minutes respectively;
17.将PMMA弹性衬底沿一个方向拉伸到原来长度的2.5倍；17. Stretch the PMMA elastic substrate to 2.5 times its original length in one direction;
18.将拉伸后的弹性衬底上黏贴在中空圆形支架上；18. Paste the stretched elastic substrate on the hollow circular support;
19.将支架上的弹性衬底一面紧压在柔性石墨烯/镍颗粒混合结构表面，轻压30秒；19. Press the elastic substrate side on the bracket tightly on the surface of the flexible graphene/nickel particle hybrid structure, and press lightly for 30 seconds;
20.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯镍颗粒混合结构和衬底之间的小的接触力，将石墨烯/镍颗粒混合结构捞出；20. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene-nickel particle mixed structure and the substrate to fish out the graphene/nickel particle mixed structure;
21.在真空干燥箱中晾3小时；21. Dry in a vacuum oven for 3 hours;
22.从中空的圆形上将覆盖有石墨烯/镍颗粒混合结构的弹性衬底取下，一侧粘于支架上；22. Remove the elastic substrate covered with the graphene/nickel particle hybrid structure from the hollow circle, and stick one side to the bracket;
23.在真空干燥箱中自然恢复3-5小时，使其恢复到原来尺寸，依此来制备一种自组装皱褶的可拉伸石墨烯/镍颗粒混合结构。23. Naturally recover in a vacuum drying oven for 3-5 hours to make it return to its original size, so as to prepare a self-assembled wrinkled stretchable graphene/nickel particle hybrid structure.
24.将石墨烯/镍颗粒混合结构放入低温沉积系统中；24. Put the graphene/nickel particle hybrid structure into the low temperature deposition system;
25.制备两端有长方形空条的遮挡板，置于石墨烯/镍颗粒混合结构的上方，但不能接触混合结构，以免损坏皱褶的可拉伸石墨烯/镍颗粒混合结构。25. Prepare a baffle plate with rectangular empty strips at both ends, and place it above the graphene/nickel particle hybrid structure, but cannot touch the hybrid structure, so as not to damage the wrinkled stretchable graphene/nickel particle hybrid structure.
26.利用磁控溅射沉积系统分别在两个石墨烯/镍颗粒混合结构的一端沉积不联通的铂金电极；26. Using a magnetron sputtering deposition system to deposit disconnected platinum electrodes on one end of the two graphene/nickel particle hybrid structures;
27.在未沉积电极的一端涂上大面积的PVA-碱，注意PVA-碱与铂金电极不连通；27. Apply a large area of PVA-base on one end of the undeposited electrode, and pay attention that the PVA-base is not connected to the platinum electrode;
28.将两个石墨烯/镍颗粒混合结构涂有PVA-碱的一端重叠覆盖，使其相接触从而黏贴在一起；28. Overlap and cover the ends of the two graphene/nickel particle hybrid structures coated with PVA-alkali, so that they are in contact and pasted together;
29.使用PMMA将其粘紧。29. Use PMMA to glue it tight.
实施例5Example 5
在泡沫镍衬底上生长石墨烯并生长石墨烯/镍颗粒混合结构，从而制备高导电可拉伸超级电容器，包括以下制备步骤Graphene is grown on a nickel foam substrate and a graphene/nickel particle hybrid structure is grown to prepare a highly conductive stretchable supercapacitor, including the following preparation steps
1.取尺寸为6cm×8cm泡沫镍置于管式炉中；1. Take nickel foam with a size of 6cm×8cm and place it in a tube furnace;
2.打开真空泵将管式炉的气压抽至极限真空状态3×10-6托(Torr)；2. Turn on the vacuum pump to pump the air pressure of the tube furnace to the ultimate vacuum state of 3×10 -6 Torr (Torr);
3.保持真空状态3×10-6Torr 15分钟后(真空15分钟的作用是祛除石英管内部的杂质、空气等，确保反应腔洁净)，将石英管3的气压升到3×10-3Torr；3. After maintaining a vacuum state of 3×10 -6 Torr for 15 minutes (the function of vacuum for 15 minutes is to remove impurities, air, etc. inside the quartz tube to ensure that the reaction chamber is clean), raise the air pressure of the quartz tube 3 to 3×10 -3 Torr;
4.氢气流量计设定为100sccm，将氢气注入真空腔中；4. Set the hydrogen flow meter to 100sccm, and inject hydrogen into the vacuum chamber;
5.管式炉温度升温到300℃后，恒温20分钟进行退火；5. After the tube furnace temperature rises to 300°C, anneal at a constant temperature for 20 minutes;
6.管式炉温度升温到1000℃后，将甲烷注入真空腔中，气体流量计设定为200sccm，停留30分钟进行生长；6. After the tube furnace temperature rises to 1000°C, inject methane into the vacuum chamber, set the gas flow meter to 200 sccm, and stay for 30 minutes for growth;
7.关闭甲烷气体流量计并将管式炉温度以30-60℃/min的速度快速降至室温；7. Turn off the methane gas flow meter and quickly lower the temperature of the tube furnace to room temperature at a rate of 30-60°C/min;
8.关闭氢气流量计以及真空泵；8. Turn off the hydrogen flow meter and vacuum pump;
9.打开阀门，用空气将石英管气压充满到一个大气压状态；9. Open the valve and fill the quartz tube with air to an atmospheric pressure state;
10.打开石英管真空接口，取出已沉积石墨烯的泡沫镍；10. Open the vacuum port of the quartz tube and take out the nickel foam that has deposited graphene;
11.将FeCl3按照一定质量加入去离子水中溶解，制备一定浓度的刻蚀溶液FeCl3(3mol/L)；11. Dissolve FeCl 3 in deionized water according to a certain mass to prepare a certain concentration of etching solution FeCl 3 (3mol/L);
12.制备的石墨烯/泡沫镍浸泡在30℃的FeCl3(3mol/L)溶液中150分钟；12. Soak the prepared graphene/nickel foam in FeCl 3 (3mol/L) solution at 30°C for 150 minutes;
13.观察石墨烯/泡沫镍的形貌，直到其结构变成柔性石墨烯/镍颗粒混合结构；13. Observe the morphology of graphene/nickel foam until its structure becomes a mixed structure of flexible graphene/nickel particles;
14.将柔性衬底紧压在柔性石墨烯/镍颗粒混合结构表面，轻压20秒；14. Press the flexible substrate tightly on the surface of the flexible graphene/nickel particle hybrid structure for 20 seconds;
15.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯和衬底之间的小的接触力，将石墨烯镍颗粒混合结构捞出；15. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene and the substrate to fish out the graphene-nickel particle mixed structure;
16.将海绵状石墨烯用丙酮、乙醇和去离子水分别清洗4分钟；16. The spongy graphene was cleaned with acetone, ethanol and deionized water for 4 minutes respectively;
17.将PDFS弹性衬底沿一个方向拉伸到原来长度的1.5到4倍，或者沿两个正交的方向拉伸到原来面积的2到10倍；17. Stretch the PDFS elastic substrate to 1.5 to 4 times its original length in one direction, or stretch it to 2 to 10 times its original area in two orthogonal directions;
18.将拉伸后的弹性衬底上黏贴在中空支架上；18. Paste the stretched elastic substrate on the hollow support;
19.将支架上的弹性衬底一面紧压在柔性石墨烯/镍颗粒混合结构表面，轻压20秒；19. Press the elastic substrate side on the bracket tightly on the surface of the flexible graphene/nickel particle hybrid structure, and press lightly for 20 seconds;
20.慢慢从衬底的一个侧面轻轻抬起，利用石墨烯镍颗粒混合结构和衬底之间的小的接触力，将石墨烯/镍颗粒混合结构捞出；20. Slowly lift gently from one side of the substrate, and use the small contact force between the graphene-nickel particle mixed structure and the substrate to fish out the graphene/nickel particle mixed structure;
21.在真空干燥箱中晾3小时；21. Dry in a vacuum oven for 3 hours;
22.从中空的圆形或方形支架上将覆盖有石墨烯/镍颗粒混合结构的弹性衬底取下，一侧粘于支架上；22. Remove the elastic substrate covered with the graphene/nickel particle hybrid structure from the hollow circular or square support, and stick one side to the support;
23.在真空干燥箱中自然恢复4小时，使其恢复到原来尺寸，依此来制备一种自组装皱褶的可拉伸石墨烯/镍颗粒混合结构。23. Naturally recover for 4 hours in a vacuum drying oven to make it return to its original size, so as to prepare a self-assembled wrinkled stretchable graphene/nickel particle hybrid structure.
24.用胶带或胶水将可拉伸导电石墨烯纤维分别不连通的粘于两个石墨烯/镍颗粒混合结构的一端。24. Use adhesive tape or glue to glue the stretchable conductive graphene fibers to one end of the two graphene/nickel particle hybrid structures separately.
25.在未粘贴石墨烯纤维的一端涂上大面积的PVA-碱，注意PVA-碱与电石墨烯纤维不连通；25. Apply a large area of PVA-base on the end of the unpasted graphene fiber, pay attention that the PVA-base is not connected to the graphene fiber;
26.将两个石墨烯/镍颗粒混合结构涂有PVA-碱的一端重叠覆盖，使其相接触从而黏贴在一起；26. Overlap and cover the ends of the two graphene/nickel particle hybrid structures coated with PVA-alkali so that they touch each other and stick them together;
27.使用胶水将重叠端粘紧。27. Use glue to secure the overlapping ends.
最后应该说明的是，以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, it should be noted that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still The technical solutions described in the foregoing embodiments may be modified, or part of them may be equivalently replaced. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105783695A (en) * | 2016-04-22 | 2016-07-20 | 武汉大学深圳研究院 | Graphene composite nano gold thin film flexible strain sensor manufacturing method and strain sensor thereof |
| CN106129536A (en) * | 2016-08-12 | 2016-11-16 | 复旦大学 | A kind of stretchable lithium-air battery and preparation method thereof |
| CN106546720A (en) * | 2016-10-31 | 2017-03-29 | 山东师范大学 | A kind of preparation method of the stretchable biosensor material of three-dimensional grapheme/silver nano flower-like |
| CN106653158A (en) * | 2016-12-26 | 2017-05-10 | 哈尔滨工业大学 | High-elasticity conductive film material and preparation method thereof |
| CN108155387A (en) * | 2016-12-06 | 2018-06-12 | 华为技术有限公司 | A kind of elastic collector and preparation method thereof, cell electrode piece and flexible lithium ion battery |
| CN111807416A (en) * | 2020-07-22 | 2020-10-23 | 哈尔滨工业大学 | A kind of preparation method of hollow tubular structure FeOOH@rGO lithium ion battery anode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545121A (en) * | 2013-10-23 | 2014-01-29 | 南京大学 | Supercapacitor electrode material preparation method based on three-dimensional graphene |
| CN103680974A (en) * | 2012-09-14 | 2014-03-26 | 海洋王照明科技股份有限公司 | Graphene/nickel composite material, preparation method thereof, electrode plate and capacitor |
| CN103903880A (en) * | 2014-03-03 | 2014-07-02 | 广东工业大学 | Method for in-situ preparation of graphene supercapacitor electrode based on nickel foam |
| US20140255500A1 (en) * | 2013-03-11 | 2014-09-11 | Samsung Electronics Co., Ltd. | Method for preparing graphene |
-
2015
- 2015-04-09 CN CN201510165881.7A patent/CN104882297B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680974A (en) * | 2012-09-14 | 2014-03-26 | 海洋王照明科技股份有限公司 | Graphene/nickel composite material, preparation method thereof, electrode plate and capacitor |
| US20140255500A1 (en) * | 2013-03-11 | 2014-09-11 | Samsung Electronics Co., Ltd. | Method for preparing graphene |
| CN103545121A (en) * | 2013-10-23 | 2014-01-29 | 南京大学 | Supercapacitor electrode material preparation method based on three-dimensional graphene |
| CN103903880A (en) * | 2014-03-03 | 2014-07-02 | 广东工业大学 | Method for in-situ preparation of graphene supercapacitor electrode based on nickel foam |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105783695A (en) * | 2016-04-22 | 2016-07-20 | 武汉大学深圳研究院 | Graphene composite nano gold thin film flexible strain sensor manufacturing method and strain sensor thereof |
| CN106129536A (en) * | 2016-08-12 | 2016-11-16 | 复旦大学 | A kind of stretchable lithium-air battery and preparation method thereof |
| CN106129536B (en) * | 2016-08-12 | 2019-07-05 | 复旦大学 | A kind of stretchable lithium-air battery and preparation method thereof |
| CN106546720A (en) * | 2016-10-31 | 2017-03-29 | 山东师范大学 | A kind of preparation method of the stretchable biosensor material of three-dimensional grapheme/silver nano flower-like |
| CN108155387A (en) * | 2016-12-06 | 2018-06-12 | 华为技术有限公司 | A kind of elastic collector and preparation method thereof, cell electrode piece and flexible lithium ion battery |
| CN108155387B (en) * | 2016-12-06 | 2020-08-25 | 华为技术有限公司 | An elastic current collector and preparation method thereof, battery electrode sheet and flexible lithium ion battery |
| CN106653158A (en) * | 2016-12-26 | 2017-05-10 | 哈尔滨工业大学 | High-elasticity conductive film material and preparation method thereof |
| CN106653158B (en) * | 2016-12-26 | 2018-07-17 | 哈尔滨工业大学 | A kind of high resiliency conducting membrane material and preparation method thereof |
| CN111807416A (en) * | 2020-07-22 | 2020-10-23 | 哈尔滨工业大学 | A kind of preparation method of hollow tubular structure FeOOH@rGO lithium ion battery anode material |
| CN111807416B (en) * | 2020-07-22 | 2022-10-04 | 哈尔滨工业大学 | Preparation method of hollow tubular structure FeOOH @ rGO lithium ion battery anode material |
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