技术领域technical field
本发明属于电容器技术领域，尤其涉及一种对称柔性超级电容器及其制备方法。The invention belongs to the technical field of capacitors, in particular to a symmetrical flexible supercapacitor and a preparation method thereof.
背景技术Background technique
物联网的发展促使纺织服装行业技术革新，智能可穿戴设备孕育而生，传统储能器件僵硬、不够柔软，难以满足可穿戴设备柔性化的发展需求。柔性超级电容器是一种介于传统电容器和电池之间的新型电化学储能器件，具有能量密度高、热稳定性好、充放电时间短、循环寿命长等优点，在可穿戴能源储存方面具有潜在的应用价值。纳米纤维膜因其具有理想的电容性能、比表面积大以及柔软性等特点，在柔性超级电容器显示出极大的优势。目前，纳米纤维膜的制备最常用的方法之一是静电纺丝，但存在高能耗和高危险系数等问题。The development of the Internet of Things has promoted technological innovation in the textile and garment industry, and smart wearable devices have been born. Traditional energy storage devices are stiff and not soft enough to meet the development needs of wearable devices for flexibility. Flexible supercapacitor is a new type of electrochemical energy storage device between traditional capacitors and batteries. It has the advantages of high energy density, good thermal stability, short charge and discharge time, and long cycle life. It has great potential in wearable energy storage. potential application value. Nanofibrous membranes show great advantages in flexible supercapacitors due to their ideal capacitive properties, large specific surface area, and softness. At present, one of the most commonly used methods for the preparation of nanofibrous membranes is electrospinning, but there are problems such as high energy consumption and high risk factor.
专利CN113808854A公开了一种柔性超级电容器，其是将带有铝膜表面的微晶纤维复合集流凝胶薄膜对正负极凝胶薄膜进行包边贴合，接着通过干膜压膜机将贴合好的凝胶薄膜压紧保护膜上所得。但其制备过程中正负极与封装膜需要粘合剂和压膜机进行组装，操作较复杂且粘合剂对环境有污染。Patent CN113808854A discloses a flexible supercapacitor, which is to wrap the positive and negative electrode gel films with the microcrystalline fiber composite current collector gel film on the surface of the aluminum film, and then use the dry film laminating machine to paste The combined gel film is pressed against the protective film. However, during the preparation process, the positive and negative electrodes and the packaging film need to be assembled with an adhesive and a film laminating machine, the operation is complicated and the adhesive pollutes the environment.
专利CN106229159A公开了一种柔性超级电容器及柔性超级电容器的制备方法，其介电材料采用隔膜浸泡于离子液体的凝胶电解质后吸附凝胶电解质制备而成。但其制备过程较复杂且隔膜循环稳定性差，不利于柔性超级电容器稳定持久地运行。Patent CN106229159A discloses a flexible supercapacitor and a method for preparing the flexible supercapacitor, the dielectric material of which is prepared by soaking the diaphragm in the gel electrolyte of the ionic liquid and then absorbing the gel electrolyte. However, its preparation process is complex and the cycle stability of the diaphragm is poor, which is not conducive to the stable and durable operation of flexible supercapacitors.
专利CN111180218A公开了一种柔性电极材料及其制备方法和柔性超级电容器，其通过静电纺丝得到共聚酰胺/尼龙6复合纳米纤维膜后，再热压处理得到增强复合纳米纤维膜，最后在增强复合纳米纤维上原位聚合生长聚吡咯，得到柔性电极材料。其以高比表面积的复合纳米纤维膜作为柔性基材，采用原位聚合法制到柔性电极材料，具有良好的力学强度及电导率，但制备过程较复杂，且静电纺丝所使用的高压电具有一定危险性。Patent CN111180218A discloses a flexible electrode material and its preparation method and a flexible supercapacitor, which obtains a copolyamide/nylon 6 composite nanofiber film by electrospinning, and then heats and presses to obtain a reinforced composite nanofiber film, and finally strengthens the composite Polypyrrole was in-situ polymerized and grown on nanofibers to obtain flexible electrode materials. It uses a composite nanofiber membrane with a high specific surface area as a flexible substrate, and uses an in-situ polymerization method to prepare a flexible electrode material. It has good mechanical strength and electrical conductivity, but the preparation process is complicated, and the high-voltage electricity used in electrospinning There is a certain risk.
专利CN107369561A公开了一种柔性电极、其制备方法及柔性超级电容器，CN112103090A公开了一种自支撑柔性超级电容器以及CN110211815A公开了一种柔性对称型超级电容器制备方法。但这些柔性超级电容器制备过程都需要组装，且繁琐复杂，制造效率低下，不利于大规模生产。Patent CN107369561A discloses a flexible electrode, its preparation method and flexible supercapacitor, CN112103090A discloses a self-supporting flexible supercapacitor and CN110211815A discloses a method for preparing a flexible symmetrical supercapacitor. However, the preparation process of these flexible supercapacitors requires assembly, which is cumbersome and complicated, and the manufacturing efficiency is low, which is not conducive to mass production.
另外，溶液吹喷纺丝相较于静电纺丝，使用高速气流取代高压电作为驱动力，降低了工艺的危险性，过程可控，且纳米纤维直径更小，由其制备的可穿戴设备更轻薄。因此，基于溶液吹喷纺丝技术发开一种新的柔性超级电容器将很有市场前景。In addition, compared with electrospinning, solution blowing spinning uses high-speed airflow instead of high-voltage electricity as the driving force, which reduces the risk of the process, the process is controllable, and the diameter of nanofibers is smaller. Wearable devices prepared by it Thinner. Therefore, the development of a new flexible supercapacitor based on solution blow-jet spinning technology will have great market prospects.
发明内容Contents of the invention
为此，本发明所要解决的技术问题在于克服现有技术中柔性超级电容器制备过程复杂，且需粘合剂、需要组装等问题。Therefore, the technical problem to be solved by the present invention is to overcome the problems in the prior art that the preparation process of the flexible supercapacitor is complex, and requires adhesives and assembly.
为解决上述技术问题，本发明提供了一种对称柔性超级电容器及其制备方法。该对称柔性超级电容器制备过程简单可控，无需粘合剂进行自组装，且轻薄柔软，具有高能量密度、良好的循环稳定性和机械性，适合作为储能器结合在可穿戴设备上。In order to solve the above technical problems, the present invention provides a symmetrical flexible supercapacitor and a preparation method thereof. The preparation process of the symmetric flexible supercapacitor is simple and controllable, no adhesive is required for self-assembly, and it is light, thin and soft, with high energy density, good cycle stability and mechanical properties, and is suitable for being combined as an energy storage device on wearable devices.
本发明的第一个目的是提供一种对称柔性超级电容器的制备方法，以溶液吹喷纺丝装置为发生装置，包括溶液吹喷纺丝机和接收装置，所述的制备方法包括以下步骤，The first object of the present invention is to provide a method for preparing a symmetrical flexible supercapacitor, using a solution blowing spinning device as a generating device, including a solution blowing spinning machine and a receiving device, the preparation method comprising the following steps,
S1、依次将二氧化硅纳米颗粒、聚醚酰亚胺-聚氨酯复合物溶于二甲基甲酰胺，混匀得到隔膜层纺丝液；所述聚醚酰亚胺-聚氨酯复合物是由聚醚酰亚胺和聚氨酯按照质量比1-3：1混合得到；S1, dissolving silica nanoparticles and polyetherimide-polyurethane compound in dimethylformamide in turn, and mixing to obtain a diaphragm layer spinning solution; the polyetherimide-polyurethane compound is composed of polyetherimide-polyurethane compound It is obtained by mixing etherimide and polyurethane according to the mass ratio of 1-3:1;
依次将吲哚单体、对甲苯磺酸、聚环氧乙烷和碳纳米管溶于氯仿，混匀得到电极层纺丝液；sequentially dissolving indole monomer, p-toluenesulfonic acid, polyethylene oxide and carbon nanotubes in chloroform, and mixing to obtain an electrode layer spinning solution;
将醋酸纤维素溶于混合溶剂，混匀得到封装层纺丝液；Dissolving cellulose acetate in a mixed solvent and mixing to obtain a spinning solution for the packaging layer;
S2、通过溶液吹喷纺丝技术分别喷射S1所述的隔膜层纺丝液、电极层纺丝液和封装层纺丝液，在接收装置上依次形成第一封装层、第一电极层、隔膜层、第二电极层和第二封装层，得到所述的对称柔性超级电容器。S2. Spray the membrane layer spinning solution, the electrode layer spinning solution and the packaging layer spinning solution described in S1 respectively by the solution blow-jet spinning technology, and form the first packaging layer, the first electrode layer and the separator in sequence on the receiving device layer, a second electrode layer and a second encapsulation layer to obtain the symmetric flexible supercapacitor.
在本发明的一个实施例中，在S1中，所述隔膜层纺丝液中二氧化硅纳米颗粒和聚醚酰亚胺-聚氨酯复合物的质量比为5-11:100。In one embodiment of the present invention, in S1, the mass ratio of silica nanoparticles to polyetherimide-polyurethane composite in the spinning solution for the separator layer is 5-11:100.
在本发明的一个实施例中，在S1中，所述隔膜层纺丝液中二氧化硅纳米颗粒和聚醚酰亚胺-聚氨酯复合物的总质量分数为5％-10％。In one embodiment of the present invention, in S1, the total mass fraction of silica nanoparticles and polyetherimide-polyurethane composite in the spinning solution for the separator layer is 5%-10%.
在本发明的一个实施例中，在S1中，所述电极层纺丝液中吲哚单体、对甲苯磺酸、聚环氧乙烷和碳纳米管的质量比为4:4:1:1。In one embodiment of the present invention, in S1, the mass ratio of indole monomer, p-toluenesulfonic acid, polyethylene oxide and carbon nanotubes in the electrode layer spinning solution is 4:4:1: 1.
在本发明的一个实施例中，在S1中，所述电极层纺丝液中吲哚单体的质量分数为1.8％-2.05％。In one embodiment of the present invention, in S1, the mass fraction of indole monomer in the electrode layer spinning solution is 1.8%-2.05%.
在本发明的一个实施例中，在S1中，所述封装层纺丝液的浓度为0.1g/mL-0.3g/mL。In one embodiment of the present invention, in S1, the concentration of the encapsulating layer spinning solution is 0.1 g/mL-0.3 g/mL.
在本发明的一个实施例中，在S1中，所述混合溶剂是由丙酮和N,N-二甲基乙酰胺按照体积比3:2混合得到。In one embodiment of the present invention, in S1, the mixed solvent is obtained by mixing acetone and N,N-dimethylacetamide at a volume ratio of 3:2.
在本发明的一个实施例中，所述隔膜层纺丝液中采用的聚醚酰亚胺-聚氨酯复合物(PEI-PU)本身具有良好的阻燃性、热稳定性和耐磨性，使隔膜具有良好的热稳定性和高化学稳定性以及良好的尺寸稳定性；而二氧化硅纳米颗粒(SiO2 NPs)的加入，在一定程度上增大了隔膜层的孔隙率、均匀性和循环性。得益于二氧化硅纳米颗粒、PEI-PU的高孔隙率、互穿网络结构和协同作用，隔膜层表现出均匀的孔径分布、高离子电导率和良好的电化学稳定性。In one embodiment of the present invention, the polyetherimide-polyurethane compound (PEI-PU) used in the spinning solution of the diaphragm layer itself has good flame retardancy, thermal stability and wear resistance, so that The separator has good thermal stability, high chemical stability and good dimensional stability; while the addition of silica nanoparticles (SiO2 NPs) increases the porosity, uniformity and circulation of the separator layer to a certain extent. sex. Thanks to the high porosity, interpenetrating network structure, and synergistic effect of silica nanoparticles, PEI-PU, the separator layer exhibits uniform pore size distribution, high ionic conductivity, and good electrochemical stability.
在本发明的一个实施例中，所述电极层纺丝液中采用的纯聚吲哚Pind是导电聚合物之一，具有良好的热稳定性，高氧化还原活性以及缓慢的降解速率等特性，但用作超级电容器中的电极活性材料时，电容较低，而CNTs的加入能一定程度上提高Pind的比表面积和导电性，从而赋予柔性超级电容器优异的导电性、机械性和电化学稳定性。In one embodiment of the present invention, the pure polybenzazole Pind used in the electrode layer spinning solution is one of the conductive polymers, which has good thermal stability, high redox activity, and slow degradation rate. However, when used as an electrode active material in a supercapacitor, the capacitance is low, and the addition of CNTs can increase the specific surface area and conductivity of Pind to a certain extent, thereby endowing the flexible supercapacitor with excellent conductivity, mechanical and electrochemical stability. .
在本发明的一个实施例中，所述封装层纺丝液中采用的醋酸纤维素(CA)具有较好的亲肤性、机械性和透气性好。In one embodiment of the present invention, the cellulose acetate (CA) used in the spinning solution of the encapsulation layer has good skin-friendly properties, good mechanical properties and good air permeability.
在本发明的一个实施例中，在S2中，所述溶液吹喷纺丝技术的工艺参数为：喷嘴内径为2mm，牵伸风压为0.08MPa-0.4MPa，挤出速度为1.2mL/h-30mL/h，接收距离为20cm-60cm，接收装置的转速为1000rpm-2000rpm。In one embodiment of the present invention, in S2, the process parameters of the solution blowing spinning technology are: the inner diameter of the nozzle is 2mm, the drafting wind pressure is 0.08MPa-0.4MPa, and the extrusion speed is 1.2mL/h -30mL/h, the receiving distance is 20cm-60cm, the speed of the receiving device is 1000rpm-2000rpm.
在本发明的一个实施例中，在S2中，所述溶液吹喷纺丝技术的环境参数为：温度为23±2℃，相对湿度为45±3℃。In one embodiment of the present invention, in S2, the environmental parameters of the solution blowing spinning technology are: temperature is 23±2°C, and relative humidity is 45±3°C.
本发明的第二个目的是提供一种所述的方法制备的对称柔性超级电容器，所述隔膜层的厚度为50μm-60μm，平均纤维直径为400nm-500nm；The second object of the present invention is to provide a symmetrical flexible supercapacitor prepared by the method, the thickness of the diaphragm layer is 50 μm-60 μm, and the average fiber diameter is 400nm-500nm;
所述第一电极层和所述第二电极层的厚度独立地为45μm-51μm，平均纤维直径为320nm-400nm；The thickness of the first electrode layer and the second electrode layer are independently 45 μm-51 μm, and the average fiber diameter is 320nm-400nm;
所述第一封装层和所述第二封装层的厚度独立地为20μm-25μm，平均纤维直径为120nm-165nm。The thicknesses of the first encapsulation layer and the second encapsulation layer are independently 20 μm-25 μm, and the average fiber diameter is 120 nm-165 nm.
本发明的技术方案相比现有技术具有以下优点：Compared with the prior art, the technical solution of the present invention has the following advantages:
(1)本发明所述的制备方法在制备完前一层纳米纤维膜会有少量纺丝液残留，这样在制备后一层纳米纤维膜时可直接粘附，无需干膜压膜机压紧或者使用任何粘合剂，操作简便且绿色环保。(1) In the preparation method of the present invention, there will be a small amount of spinning solution remaining after the preparation of the previous layer of nanofiber membrane, so that it can be directly adhered when the latter layer of nanofiber membrane is prepared, without the need for a dry film pressing machine to compress Or use any adhesive, easy and green to operate.
(2)本发明所述的制备方法采用溶液吹喷纺丝工艺，制备过程简单可控，且得益于二氧化硅纳米颗粒、PEI-PU的高孔隙率、互穿网络结构和协同作用，增大了隔膜层的孔隙率、均匀性和循环性，有利于离子的快速传输，使柔性超级电容器具有优异的循环稳定性、热稳定性、高能量密度。(2) The preparation method of the present invention adopts the solution blowing spinning process, the preparation process is simple and controllable, and benefits from the high porosity, interpenetrating network structure and synergistic effect of silica nanoparticles and PEI-PU, The increased porosity, uniformity, and circulation of the separator layer are conducive to the rapid transport of ions, making the flexible supercapacitor have excellent cycle stability, thermal stability, and high energy density.
(3)本发明所述的制备方法采用溶液吹喷纺丝工艺制备了具有高比表面积和电活性、无粘结剂的纳米纤维电极层，相较于静电纺丝，使用高速气流取代高压电作为驱动力，降低了工艺的危险性，过程简单可控，纳米纤维直径更小，可直接用作电极，无需进行热压处理或使用任何粘合剂，且碳纳米管的引入进一步增加了吲哚单体的比表面积和导电性，使基于纳米纤维电极层的柔性超级电容器具有出色的电气性能、快速充放电和循环稳定性。(3) The preparation method of the present invention adopts the solution blowing spinning process to prepare a nanofiber electrode layer with high specific surface area and electroactivity and no binder. Compared with electrospinning, high-speed airflow is used to replace high-pressure Electricity as the driving force reduces the risk of the process, the process is simple and controllable, the diameter of the nanofiber is smaller, and it can be directly used as an electrode without hot pressing or using any adhesive, and the introduction of carbon nanotubes further increases The specific surface area and electrical conductivity of indole monomers enable flexible supercapacitors based on nanofibrous electrode layers to exhibit excellent electrical performance, fast charge-discharge, and cycle stability.
(4)本发明所述的制备方法采用三个喷嘴间隔喷丝，在接收装置上一次性制备出高能量密度、良好的机械性能和循环稳定性的对称柔性超级电容器，无需组装，极大简化了制作过程。(4) The preparation method of the present invention uses three nozzles to spin at intervals, and a symmetrical flexible supercapacitor with high energy density, good mechanical properties and cycle stability is prepared on the receiving device at one time, without assembly, which greatly simplifies the production process.
附图说明Description of drawings
为了使本发明的内容更容易被清楚地理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中：In order to make the content of the present invention more easily understood, the present invention will be described in further detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:
图1为本发明实施例1的对称柔性超级电容器的制备示意图；1 is a schematic diagram of the preparation of a symmetrical flexible supercapacitor according to Example 1 of the present invention;
图2为本发明实施例1的对称柔性超级电容器的结构示意图；2 is a schematic structural view of a symmetrical flexible supercapacitor according to Embodiment 1 of the present invention;
附图标记说明：1-高压气源、2-蠕动泵、3-接收装置、4-密封烧杯、51-上侧注射器、52-左侧注射器、53-右侧注射器、6-不锈钢喷嘴、7-对称柔性超级电容器、8-封装层、9-电极层、10-隔膜层。Explanation of reference numerals: 1-high pressure gas source, 2-peristaltic pump, 3-receiving device, 4-sealed beaker, 51-upper side syringe, 52-left side syringe, 53-right side syringe, 6-stainless steel nozzle, 7 -Symmetric flexible supercapacitor, 8-encapsulation layer, 9-electrode layer, 10-diaphragm layer.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and implement it, but the examples given are not intended to limit the present invention.
在本发明中，除非另有说明，对称柔性超级电容器的制备以溶液吹喷纺丝装置为发生装置如图1所示，包括溶液吹喷纺丝机和接收装置。溶液吹喷纺丝机是将纺丝液分别装入密封烧杯4中，蠕动泵2通过对软管进行挤压来泵送纺丝液至注射器(隔膜层纺丝液至上侧注射器51，电极层纺丝液至左侧注射器52，封装层纺丝液至右侧注射器53)中，注射器上分别设有不锈钢喷嘴6，不锈钢喷嘴6在喷丝的同时受到高压气源1提供的高速热气流的喷吹，向接收装置3上喷射纺丝液，三个不锈钢喷嘴6受蠕动泵2控制轮流喷射纺丝，逐层叠加，沉积形成对称柔性超级电容器7。In the present invention, unless otherwise specified, the preparation of the symmetric flexible supercapacitor takes the solution blow spinning device as the generating device, as shown in Figure 1, including the solution blow spinning machine and the receiving device. The solution blowing spinning machine is to put the spinning solution into the sealed beaker 4 respectively, and the peristaltic pump 2 pumps the spinning solution to the syringe by squeezing the hose (the diaphragm layer spinning solution to the upper side injector 51, the electrode layer The spinning solution is sent to the left side syringe 52, and the packaging layer spinning solution is sent to the right side syringe 53). The syringes are respectively provided with stainless steel nozzles 6, and the stainless steel nozzles 6 are subjected to the high-speed hot air flow provided by the high-pressure air source 1 while spinning. Spraying, spraying the spinning liquid onto the receiving device 3, three stainless steel nozzles 6 are controlled by the peristaltic pump 2 to spray spinning in turn, superimposed layer by layer, deposited to form a symmetrical flexible supercapacitor 7.
在本发明中，除非另有说明，在整个工艺过程中还包括纺丝液的制备等用于形成对称柔性超级电容器的制备和后处理。In the present invention, unless otherwise specified, the whole process also includes the preparation of spinning solution and post-treatment for forming a symmetrical flexible supercapacitor.
下述实施例和对比例中，所使用的实验方法无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。In the following examples and comparative examples, the experimental methods used are conventional methods unless otherwise specified, and the materials and reagents used can be obtained from commercial sources unless otherwise specified.
SiO2 NPs购于阿拉丁化学有限公司，规格(颗粒直径：7nm-40nm，比表面积：120m2/g)；PEI购于常州德毅新材料科技有限公司；PU购于巴斯夫有限公司；DMF、DMAC购于广州德井化工有限公司；吲哚单体(纯度99％)、过硫酸铵、p-TSA均购于上海国药控股化学试剂有限公司；PEO购于广州市利厚贸易有限公司，规格：分子量50万；CNT购于上海凯射丰实业有限公司；氯仿购于上海凌峰化学试剂有限公司，规格：含量>99.5％；CA、丙酮购于南京化学试剂有限公司。SiO2 NPs were purchased from Aladdin Chemical Co., Ltd., specifications (particle diameter: 7nm-40nm, specific surface area: 120m2 /g); PEI was purchased from Changzhou Deyi New Material Technology Co., Ltd.; PU was purchased from BASF Co., Ltd.; DMF, DMAC was purchased from Guangzhou Dejing Chemical Co., Ltd.; indole monomer (purity 99%), ammonium persulfate, and p-TSA were purchased from Shanghai Sinopharm Chemical Reagent Co., Ltd.; PEO was purchased from Guangzhou Lihou Trading Co., Ltd., specifications : molecular weight 500,000; CNT was purchased from Shanghai Kaishefeng Industrial Co., Ltd.; chloroform was purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd., specification: content >99.5%; CA and acetone were purchased from Nanjing Chemical Reagent Co., Ltd.
实施例1Example 1
参照图1所示，本发明的对称柔性超级电容器及其制备方法，具体包括以下步骤：Referring to Fig. 1, the symmetrical flexible supercapacitor of the present invention and its preparation method specifically comprise the following steps:
S1、纺丝液的制备S1, preparation of spinning solution
S11、隔膜层纺丝液：将SiO2 NPs(二氧化硅纳米颗粒)溶解在有机溶剂DMF(二甲基甲酰胺)中，超声分散均匀，然后将一定量的PEI-PU(聚醚酰亚胺-聚氨酯)复合溶液(SiO2NPs和PEI-PU复合物的质量比为8:100)加入到SiO2的DMF分散液中，机械搅拌12h，得到隔膜层纺丝液；其中，PEI-PU复合物中PEI和PU的质量比为1:1，隔膜层纺丝液中SiO2 NPs和PEI-PU的总的质量分数7％。S11. Spinning solution for diaphragm layer: Dissolve SiO2 NPs (silicon dioxide nanoparticles) in DMF (dimethylformamide), an organic solvent, and disperse evenly by ultrasonic, and then add a certain amount of PEI-PU (polyetherimide Amine-polyurethane) composite solution (the mass ratio of SiO2 NPs and PEI-PU composite is 8:100) was added to the DMF dispersion of SiO2 , and mechanically stirred for 12h to obtain the diaphragm layer spinning solution; among them, PEI-PU The mass ratio of PEI and PU in the composite is 1:1, and the total mass fraction of SiO2 NPs and PEI-PU in the spinning solution of the diaphragm layer is 7%.
S12、电极层纺丝液：将Pund(吲哚单体)与p-TSA(对甲苯磺酸)按1：1混合制成Pind(聚吲哚混合溶液)，然后立即加入PEO(聚环氧乙烷)，磁力搅拌12h，超声处理分散均匀，最后加入CNTs(碳纳米管)，在氯仿中磁力搅拌12h，超声分散均匀，得到电极层纺丝液；其中，电极层纺丝液中Pund的质量分数为1.95％，Pund、p-TSA、PEO和CNTs质量比为4:4:1:1。S12. Electrode layer spinning solution: mix Pund (indole monomer) and p-TSA (p-toluenesulfonic acid) at 1:1 to make Pind (polybenzazole mixed solution), and then immediately add PEO (polyepoxy Ethane), magnetically stirred for 12h, ultrasonically dispersed evenly, finally added CNTs (carbon nanotubes), magnetically stirred in chloroform for 12h, ultrasonically dispersed uniformly, and obtained the electrode layer spinning solution; wherein, the Pund in the electrode layer spinning solution The mass fraction is 1.95%, and the mass ratio of Pund, p-TSA, PEO and CNTs is 4:4:1:1.
S13、封装层纺丝液：将2.5g CA(醋酸纤维素)溶解在丙酮和DMAC(N,N-二甲基乙酰胺)(丙酮和DMAC的体积比为3:2)的混合物中，然后将混合物在室温下搅拌24h，直至完全溶解，得到浓度为0.2g/mL的封装层纺丝液。S13, packaging layer spinning solution: 2.5g CA (cellulose acetate) is dissolved in the mixture of acetone and DMAC (N,N-dimethylacetamide) (the volume ratio of acetone and DMAC is 3:2), and then The mixture was stirred at room temperature for 24 h until it was completely dissolved to obtain an encapsulation layer spinning solution with a concentration of 0.2 g/mL.
S2、对称柔性超级电容器的制备S2. Preparation of symmetrical flexible supercapacitors
S21、将10mL隔膜层纺丝液注入上侧密封烧杯、10mL电极层纺丝液注入左侧密封烧杯以及10mL封装层纺丝液注入右侧密封烧杯，蠕动泵通过对软管进行挤压来泵送纺丝液至注射器中，注射器分别位于接收装置的上侧、左侧和右侧，内径2mm的不锈钢喷嘴安装在注射器上。S21. Inject 10mL of the membrane layer spinning solution into the upper sealed beaker, 10mL of the electrode layer spinning solution into the left sealed beaker, and 10mL of the packaging layer spinning solution into the right sealed beaker. The peristaltic pump pumps by squeezing the hose. Send the spinning solution into the syringes, which are respectively located on the upper side, the left side and the right side of the receiving device, and the stainless steel nozzles with an inner diameter of 2mm are installed on the syringes.
S22、开始溶液吹喷纺丝，在牵伸风压为0.1MPa，挤出速度为20mL/h，接收距离为40cm，在环境温度为23℃和环境相对湿度为45℃的条件下，不锈钢喷嘴在喷丝的同时受到高压气源提供的高速热气流的喷吹，向转速为1500rpm的接收装置喷射纳米纤维，沉积形成纳米纤维膜层。S22. Start solution blowing and spinning. When the drafting wind pressure is 0.1MPa, the extrusion speed is 20mL/h, the receiving distance is 40cm, and the ambient temperature is 23°C and the ambient relative humidity is 45°C, the stainless steel nozzle While spinning, it is blown by the high-speed hot air flow provided by the high-pressure air source, and the nanofiber is sprayed to the receiving device with a rotation speed of 1500rpm, and the nanofiber film layer is deposited and formed.
S23、将连接封装层纺丝液的蠕动泵运行，喷嘴喷丝，2h后在接收装置上形成一层封装层(第一封装层)，蠕动泵停止输送，喷丝暂停；再将连接电极层纺丝液的蠕动泵运行，喷嘴喷丝，其中部分纺丝液会残留在封装层上，使其具有一定粘性，电极层可直接叠加在封装层上(第一电极层)，3h后停止喷丝；再将连接隔膜层纺丝液的蠕动泵运行，喷嘴喷丝，2.5h后在接收装置上形成一层隔膜层，蠕动泵停止输送，喷丝暂停；依次按照第一封装层、第一电极层、隔膜层、第二电极层、第二封装层的顺序进行喷丝叠加，一次性制作5层纳米纤维膜层，放入烘干机烘干，得到如图2所示的对称柔性超级电容器，包括隔膜层10、设置于隔膜层10两侧的电极层9、设置于电极层9外侧上的封装层8；其中，封装层厚度均约为20μm，平均纤维直径约为145nm；电极层厚度均约为45μm，平均纤维直径约为360nm；隔膜层厚度约为50μm，平均纤维直径约为450nm。S23, run the peristaltic pump connecting the spinning solution of the encapsulation layer, spray the nozzle, form a layer of encapsulation layer (first encapsulation layer) on the receiving device after 2 hours, stop the peristaltic pump, and suspend the spinning; then connect the electrode layer The peristaltic pump of the spinning liquid is running, and the nozzle is spinning, and part of the spinning liquid will remain on the packaging layer to make it have a certain viscosity. The electrode layer can be directly superimposed on the packaging layer (the first electrode layer), and stop spraying after 3 hours. Then run the peristaltic pump connected to the spinning solution of the diaphragm layer, and the nozzle will spin. After 2.5 hours, a diaphragm layer will be formed on the receiving device, the peristaltic pump will stop conveying, and the spinning will be suspended. The electrode layer, diaphragm layer, second electrode layer, and second encapsulation layer were sprayed and superimposed in sequence, and five nanofiber membrane layers were produced at one time, and dried in a dryer to obtain a symmetrical flexible superstructure as shown in Figure 2. The capacitor includes a diaphragm layer 10, an electrode layer 9 arranged on both sides of the diaphragm layer 10, and an encapsulation layer 8 arranged on the outer side of the electrode layer 9; wherein, the thickness of the encapsulation layer is about 20 μm, and the average fiber diameter is about 145 nm; the electrode layer The thickness is about 45 μm, and the average fiber diameter is about 360 nm; the thickness of the diaphragm layer is about 50 μm, and the average fiber diameter is about 450 nm.
实施例2Example 2
本发明的对称柔性超级电容器及其制备方法，具体包括以下步骤：The symmetrical flexible supercapacitor of the present invention and its preparation method specifically comprise the following steps:
基本同实施例1，不同之处在于：Basically the same as embodiment 1, the difference is:
在S1中，隔膜层纺丝液中SiO2 NPs和PEI-PU的总的质量分数为5％。In S1, the total mass fraction of SiO2 NPs and PEI-PU in the separator layer spinning solution was 5%.
在S1中，PEI-PU复合物中PEI和PU的质量比为1.5:1。In S1, the mass ratio of PEI and PU in the PEI-PU composite was 1.5:1.
在S1中，隔膜层纺丝液中SiO2 NPs和PEI-PU复合物的质量比为5:100。In S1, the mass ratio of SiO2 NPs and PEI-PU composites in the spinning solution of the separator layer was 5:100.
在S1中，电极层纺丝液中Pund的质量分数为1.8％。In S1, the mass fraction of Pund in the electrode layer spinning solution was 1.8%.
在S1中，封装层纺丝液浓度为0.15g/mL。In S1, the concentration of the spinning solution for the encapsulation layer was 0.15 g/mL.
在S2中，溶液吹喷纺丝的工艺参数为：在牵伸风压为0.4MPa，挤出速度为30mL/h，接收距离为35cm，环境温度为25℃和环境相对湿度为47℃，接收装置的转速为1000rpm。In S2, the process parameters of solution blow-jet spinning are as follows: when the drafting wind pressure is 0.4MPa, the extrusion speed is 30mL/h, the receiving distance is 35cm, the ambient temperature is 25°C and the ambient relative humidity is 47°C, the receiving The rotational speed of the apparatus was 1000 rpm.
得到的对称柔性超级电容器的封装层厚度均约为23μm，平均纤维直径约为154nm；电极层厚度均约为51μm，平均纤维直径约为400nm；隔膜层厚度约为56μm，平均纤维直径约为410nm。The thickness of the encapsulation layer of the obtained symmetrical flexible supercapacitor is about 23 μm, and the average fiber diameter is about 154 nm; the thickness of the electrode layer is about 51 μm, and the average fiber diameter is about 400 nm; the thickness of the diaphragm layer is about 56 μm, and the average fiber diameter is about 410 nm. .
实施例3Example 3
本发明的对称柔性超级电容器及其制备方法，具体包括以下步骤：The symmetrical flexible supercapacitor of the present invention and its preparation method specifically comprise the following steps:
基本同实施例1，不同之处在于：Basically the same as embodiment 1, the difference is:
在S1中，隔膜层纺丝液中SiO2 NPs和PEI-PU的总的质量分数为10％。In S1, the total mass fraction of SiO2 NPs and PEI-PU in the spinning solution of the separator layer was 10%.
在S1中，PEI-PU复合物中PEI和PU的质量比为2:1。In S1, the mass ratio of PEI and PU in the PEI-PU composite was 2:1.
在S1中，隔膜层纺丝液中SiO2 NPs和PEI-PU复合物的质量比为11:100。In S1, the mass ratio of SiO2 NPs and PEI-PU composite in the spinning solution of the separator layer was 11:100.
在S1中，电极层纺丝液中Pund的质量分数为2.0％。In S1, the mass fraction of Pund in the electrode layer spinning solution was 2.0%.
在S1中，封装层纺丝液浓度为0.26g/mL。In S1, the concentration of the spinning solution for the encapsulation layer was 0.26 g/mL.
在S2中，溶液吹喷纺丝的工艺参数为：在牵伸风压为0.08MPa，挤出速度为24mL/h，接收距离为50cm，环境温度为24℃和环境相对湿度为46℃，接收装置的转速为1200rpm。In S2, the process parameters of solution blow-jet spinning are as follows: when the drafting wind pressure is 0.08MPa, the extrusion speed is 24mL/h, the receiving distance is 50cm, the ambient temperature is 24°C and the ambient relative humidity is 46°C, the receiving The rotational speed of the apparatus was 1200 rpm.
得到的对称柔性超级电容器的封装层厚度均约为25μm，平均纤维直径约为162nm；电极层厚度均约为49μm，平均纤维直径约为385nm；隔膜层厚度约为60μm，平均纤维直径约为500nm。The thickness of the encapsulation layer of the obtained symmetrical flexible supercapacitor is about 25 μm, and the average fiber diameter is about 162 nm; the thickness of the electrode layer is about 49 μm, and the average fiber diameter is about 385 nm; the thickness of the diaphragm layer is about 60 μm, and the average fiber diameter is about 500 nm. .
对比例1Comparative example 1
基本同实施例1，不同之处在于：Basically the same as embodiment 1, the difference is:
在S2中，将溶液吹喷纺丝换成静电纺丝，静电纺丝的工艺参数为：挤出速度为0.48mL/h，接收距离为20cm，静电电压为18KV，环境温度为25℃，环境相对湿度为43℃的条件下，纺丝液在强电场中进行喷射纺丝，受电场力作用被牵引到接收装置上，接收装置的转速为50rpm。In S2, solution blow-jet spinning was replaced by electrospinning. The process parameters of electrospinning were: extrusion speed 0.48mL/h, receiving distance 20cm, electrostatic voltage 18KV, ambient temperature 25°C, ambient Under the condition of relative humidity of 43°C, the spinning solution is jet-spun in a strong electric field, and is drawn to the receiving device by the force of the electric field, and the rotating speed of the receiving device is 50 rpm.
对比例2Comparative example 2
基本同实施例1，不同之处在于：电极层纺丝液中不加入CNTs。It is basically the same as in Example 1, except that no CNTs are added to the electrode layer spinning solution.
对比例3Comparative example 3
基本同实施例1，不同之处在于：隔膜层纺丝液中不加入二氧化硅纳米颗粒。It is basically the same as in Example 1, except that no silica nanoparticles are added to the spinning solution for the membrane layer.
测试例1test case 1
对上述实施例1-3和对比例1-3所制备的电容器进行平均厚度测量，能量密度、功率密度、机械性测试和循环性能测试，测试依据的标准如下：Average thickness measurement, energy density, power density, mechanical test and cycle performance test are carried out to the capacitor prepared by above-mentioned embodiment 1-3 and comparative example 1-3, the standard of test basis is as follows:
能量密度、功率密度测试指标：DL/T 2081-2020《电力储能用超级电容器试验规程》Energy density and power density test indicators: DL/T 2081-2020 "Test Regulations for Supercapacitors for Electric Energy Storage"
机械性能测试指标：DL/T 2080-2020《电力储能用超级电容器》；Mechanical performance test indicators: DL/T 2080-2020 "Supercapacitors for Electric Energy Storage";
循环性能测试指标：DL/T 2081-2020《电力储能用超级电容器试验规程》；表1所示为最终测得的电容器的相关参数：Cyclic performance test index: DL/T 2081-2020 "Test Regulations for Supercapacitors for Power Energy Storage"; Table 1 shows the relevant parameters of the final measured capacitors:
表1Table 1
从表1可以看出，实施例1-3制备的对称柔性超级电容器的平均厚度、能量密度、功率密度、机械性和循环性五个指标均优于对比例1-3的对称柔性超级电容器，具有更佳的性能。It can be seen from Table 1 that the average thickness, energy density, power density, mechanical properties and cycle performance of the symmetrical flexible supercapacitor prepared in Examples 1-3 are better than those of the symmetrical flexible supercapacitor in Comparative Examples 1-3. with better performance.
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Apparently, the above-mentioned embodiments are only examples for clear description, and are not intended to limit the implementation. For those of ordinary skill in the art, on the basis of the above description, other changes or changes in various forms can also be made. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310522058.1ACN116504543B (en) | 2023-05-10 | 2023-05-10 | A symmetrical flexible supercapacitor and a method for preparing the same |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310522058.1ACN116504543B (en) | 2023-05-10 | 2023-05-10 | A symmetrical flexible supercapacitor and a method for preparing the same |
| Publication Number | Publication Date |
|---|---|
| CN116504543Atrue CN116504543A (en) | 2023-07-28 |
| CN116504543B CN116504543B (en) | 2024-07-23 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310522058.1AActiveCN116504543B (en) | 2023-05-10 | 2023-05-10 | A symmetrical flexible supercapacitor and a method for preparing the same |
| Country | Link |
|---|---|
| CN (1) | CN116504543B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1071148A2 (en)* | 1999-07-22 | 2001-01-24 | Nec Corporation | Secondary battery and capacitor using indole polymeric compound |
| WO2010101338A1 (en)* | 2009-03-04 | 2010-09-10 | Gwangju Institute Of Science And Technology | Fabrication method for capacitor electrode |
| WO2017011822A1 (en)* | 2015-07-16 | 2017-01-19 | Georgia Tech Research Corporation | Processable polymers and methods of making and using thereof |
| CN109216035A (en)* | 2017-12-12 | 2019-01-15 | 中国科学院大连化学物理研究所 | A kind of all solid state plane asymmetric miniature ultracapacitor device and preparation method thereof |
| CN109979763A (en)* | 2019-04-30 | 2019-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Folding stack-type one dimension fibre shape flexibility energy storage device and preparation method thereof |
| CN112599925A (en)* | 2020-12-16 | 2021-04-02 | 宁波日新恒力科技有限公司 | Composite diaphragm for battery capacitor and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1071148A2 (en)* | 1999-07-22 | 2001-01-24 | Nec Corporation | Secondary battery and capacitor using indole polymeric compound |
| WO2010101338A1 (en)* | 2009-03-04 | 2010-09-10 | Gwangju Institute Of Science And Technology | Fabrication method for capacitor electrode |
| WO2017011822A1 (en)* | 2015-07-16 | 2017-01-19 | Georgia Tech Research Corporation | Processable polymers and methods of making and using thereof |
| CN109216035A (en)* | 2017-12-12 | 2019-01-15 | 中国科学院大连化学物理研究所 | A kind of all solid state plane asymmetric miniature ultracapacitor device and preparation method thereof |
| CN109979763A (en)* | 2019-04-30 | 2019-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Folding stack-type one dimension fibre shape flexibility energy storage device and preparation method thereof |
| CN112599925A (en)* | 2020-12-16 | 2021-04-02 | 宁波日新恒力科技有限公司 | Composite diaphragm for battery capacitor and preparation method thereof |
| Title |
|---|
| MEHMET GIRAYHAN SAY: "Spray-coated paper supercapacitors", FLEXIBLE ELECTRONICS, vol. 4, no. 14, 31 December 2020 (2020-12-31)* |
| 潘殿坤: "基于聚苯硫醚纤维材料柔性电极的制 备及其电化学性能研究", 中国优秀硕士学位论文全文库, 31 December 2022 (2022-12-31)* |
| Publication number | Publication date |
|---|---|
| CN116504543B (en) | 2024-07-23 |
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Progress in cellulose/carbon nanotube composite flexible electrodes for supercapacitors | |
| CN102242464B (en) | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof | |
| CN106450101B (en) | A method of preparing lithium battery diaphragm with coaxial electrostatic spinning | |
| CN103741230B (en) | A kind of cross-linked rubber nano-fiber material and method for making thereof and purposes | |
| CN103194858B (en) | Elastic composite of a kind of high dielectric constant and low dielectric loss and preparation method thereof | |
| CN103469488A (en) | Preparation method of reinforced electrostatic spinning nano-fiber lithium-ion battery separator | |
| WO2021114321A1 (en) | Flexible conductive fiber membrane material and preparation method therefor | |
| CN105970485B (en) | A kind of polyimides/zirconium dioxide composite nano-fiber membrane and preparation method thereof | |
| CN104674383A (en) | Carbon nano fiber aerogel electrostatic spinning construction method | |
| CN104036971B (en) | Preparation method for graphene/carbon nano-tube composite fibre-based super capacitor | |
| CN110379642B (en) | A stretchable nanofiber, its application, a stretchable capacitor electrode comprising the same, and a preparation method | |
| CN101748560B (en) | Spinning method of electrostatically spun composite material of multiple nano level holes | |
| CN103972452B (en) | A kind of preparation method of unidirectional enhancement mode Static Spinning lithium ion battery separator | |
| CN110323074A (en) | All solid state fibrous flexible super capacitor of a kind of asymmetrical type and preparation method thereof | |
| CN103247446A (en) | Fibrous super capacitor with coaxial structure and preparation method and application thereof | |
| CN105820372A (en) | Conductive aerogel and preparation method thereof | |
| CN112397849B (en) | High-temperature-resistant flame-retardant battery diaphragm and preparation method and application thereof | |
| CN104746236B (en) | A kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof | |
| CN114086320B (en) | Method for enhancing mechanical properties of electrospun fiber membrane | |
| CN106925033A (en) | A kind of composite nano fiber PM2.5 filtering materials and preparation method thereof | |
| CN111020745A (en) | Preparation method of sodium alginate and chitosan composite nanofiber | |
| CN115110189A (en) | Preparation method and application of elastic fiber | |
| CN104746239B (en) | A kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane and preparation method thereof | |
| CN115522320A (en) | Preparation method of high-modulus polytetrafluoroethylene nanofiber membrane | |
| CN104733190B (en) | Composite diaphragm and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |