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CN103545119A - Low-cost high-integrated flexible ultrathin ultralight supercapacitor - Google Patents

Low-cost high-integrated flexible ultrathin ultralight supercapacitor Download PDF

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CN103545119A
CN103545119A CN201310466541.9A CN201310466541A CN103545119A CN 103545119 A CN103545119 A CN 103545119A CN 201310466541 A CN201310466541 A CN 201310466541A CN 103545119 A CN103545119 A CN 103545119A
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electrode
polymer
ultra
polymer nanofiber
barrier film
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CN103545119B (en
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谢二庆
张鹏
何勇民
龚成师
陈万军
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Lanzhou University
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Abstract

本发明涉及一种低成本高集成化的柔性超薄超轻超级电容器，该电容器由厚度为40～150μm的聚合物纳米纤维隔膜及在所述聚合物纳米纤维隔膜正反面直接制备的正极和负极构成。同时，本发明还公开了该电容器的制备方法。本发明体积小，质量轻和储能高，制备方法简单，成本低廉，便于产业化，可广泛用于诸多领域，如轻质飞行器、便携式储能、可穿着式供能系统等。

Figure 201310466541

The invention relates to a low-cost and highly integrated flexible ultra-thin and ultra-light supercapacitor. The capacitor consists of a polymer nanofiber diaphragm with a thickness of 40-150 μm and positive and negative electrodes directly prepared on the front and back sides of the polymer nanofiber diaphragm. constitute. At the same time, the invention also discloses a preparation method of the capacitor. The invention has the advantages of small volume, light weight, high energy storage, simple preparation method, low cost, convenient industrialization, and can be widely used in many fields, such as lightweight aircraft, portable energy storage, wearable energy supply system and the like.

Figure 201310466541

Description

The low-cost highly integrated ultralight ultracapacitor of flexible ultra-thin
Technical field
The present invention relates to light flexible energy storage device technical field, relate in particular to the low-cost highly integrated ultralight ultracapacitor of flexible ultra-thin.
Background technology
Along with the development of electronic product, high-performance flexible energy storage device is brought into play the effect becoming more and more important in daily life because of advantages such as its portable and multifunctions.As a kind of novel energy storage device, electrochemical capacitor (claiming again ultracapacitor) causes numerous researchers' concern with advantages such as its high power, short charging interval, high reliability, long-lives, formed special technology and theoretical system, and fast-developing.
The ultracapacitor of application mostly adopts separated parts as work electrode at present, current collector and barrier film, and its preparation technology and flow process are complicated, and cost is higher, and weight and volume is larger, and flexible poor.Simultaneously, the ultracapacitor that this separating component forms is when the deformation such as bending or folding, relatively moving of each parts can greatly damage device architecture, cause its chemical property variation, energy storage and cyclical stability are belittled, and this is the key issue of the current flexible super capacitor based on separating component assembling.Therefore, the flexible super electric capacity of finding a kind of low cost and Highgrade integration is one of main task of industry, alleviates its range of application of attenuate device quality and thickness extension by the main trend that is flexible energy storage device development simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of simple and convenient, highly integrated ultralight ultracapacitor of flexible ultra-thin of low cost that can large-scale mass production.
Another technical problem to be solved by this invention is to provide the preparation method of the highly integrated ultralight ultracapacitor of flexible ultra-thin of this low cost.
For addressing the above problem, the ultralight ultracapacitor of flexible ultra-thin that low cost of the present invention is highly integrated, is characterized in that: this capacitor is the polymer nanofiber barrier film of 40 ~ 150 μ m and the positive pole of directly preparing at described polymer nanofiber barrier film positive and negative and negative pole formation by thickness.
The preparation method of the ultralight ultracapacitor of flexible ultra-thin that low cost as above is highly integrated, comprises the following steps:
(1) prepared polymer solution: 1g polymer dissolution, at 9gN, in N solvent dimethylformamide, is at room temperature stirred 2 hours, obtain the polymer solution of transparent clarification;
(2) prepare polymer nanofiber barrier film:
Described polymer solution is packed in the syringe with spinning head, by add 10 ~ 30kV high voltage between spinning head and collecting board, form highfield, now injection stream is accelerated, is pullled under the effect of highfield, volatilization and fiber that diameter constantly reduces simultaneous solvent solidify, and finally on described collecting board, obtain the polymer nanofiber barrier film that thickness is 40 ~ 150 μ m;
With the method for magnetron sputtering or electron beam evaporation described polymer nanofiber barrier film mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 100 ~ 1000nm, then in the aqueous solution that contains electroactive material that is 0.01 ~ 0.05M using described polymer nanofiber barrier film immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on described metal conducting layer, deposit the positive pole that electroactive material forms capacitance electrode) and negative pole after, obtain ultracapacitor.
The polymer of described step in (1) refers to a kind of in polyacrylonitrile, polyacrylic acid, polyethylene glycol, polyoxyethylene, polymethyl methacrylate, polyvinyl alcohol, polysiloxanes, Kynoar, Kynoar-hexafluoropropylene copolymer, Polyetherimide.
Described step (2) in distance between spinning head and collecting board be 10 ~ 25cm.
Described step (3) middle magnetically controlled sputter method refers at stainless-steel vacuum indoor, gas pressure intensity is under the condition of 0.2 ~ 2Pa, electronics bumps with Ar atom under the effect of electric field, produce Ar plasma, under electric field action, Ar plasma flies to cathode target, and with the high-energy bombardment target surface of 10 ~ 30eV, make metal targets generation sputter, thereby make metal material be deposited on described polymer nanofiber barrier film mutually over against the surface of positive and negative form metal conducting layer.
Described step (3) in the method for electron beam evaporation refer at stainless-steel vacuum indoorly, gas pressure intensity is 10 -4~ 10 -2under the condition of Pa, the metal material of wanted evaporation is utilized electron beam to be heated to fusion temperature and makes its evaporation, and be attached to described polymer nanofiber barrier film mutually over against the surface of positive and negative form metal conducting layer.
Described step (3) in electroactive material refer to oxide or hydroxide and the conducting polymer of transition metal; The oxide of described transition metal or hydroxide are RuO 2, Fe 3o 4, NiO, MnO 2, Co 3o 4, Ni (OH) 2in a kind of; Described conducting polymer is polyaniline, polyurethane, polypyrrole, a kind of in polythiophene.
The present invention compared with prior art has the following advantages:
1, traditional flexible super electric capacity of preparing is all that its separated parts of assembling are as work electrode, current collector and barrier film, the present invention is directly integrated in electrode on barrier film, can greatly reduce device quality like this and improve its mechanical strength, making device there is longer life-span and the stability of work simultaneously.
2, method is simple, with low cost, is convenient to industrialization.
The barrier film the present invention relates to, metal electrode and active material, its corresponding preparation method (electrostatic spinning, magnetron sputtering or electron beam evaporation, electrochemical deposition) is simple, and cost compare is cheap, can large-scale production, be convenient to the industrialization of this device.
3, polymer nanofiber barrier film of the present invention is to prepare by electrospinning process, and its productive rate is high, and porosity is large, and mechanical strength is good, and thickness is controlled.Meanwhile, the metal conducting layer resistance that the present invention is prepared by magnetron sputtering or electron beam evaporation is little, is conducive to the transmission of electronics in energy storage course of reaction, and therefore, the present invention is all excellent in traditional capacitance at chemical property and energy-storage property.
4, the present invention carries out electron-microscope scanning and can find out that polymer nanofiber barrier film and metal conducting layer all have higher porosity, and metal conducting layer is attached directly to polymer nanofiber surface, does not change the structure of polymer nanofiber; And as can be seen from the figure the pattern of polymer nanofiber is fuzzyyer, the pattern of metal conducting layer is very clear, and the conductivity fine (referring to Fig. 2, Fig. 3) of the metal conducting layer of preparation is described.
5, take electroactive material as MnO 2for example, as can be seen from Figure 4 cyclic voltammetry curve of the present invention has the profile of similar rectangle, illustrates that its invertibity is better; As can be seen from Figure 5 charge-discharge characteristic curve of the present invention is in the shape that presents symmetrical triangle in interval that discharges and recharges of 0 ~ 1.0V, and voltage and the time linear, therefore, the present invention has good super capacitor character.
6, volume of the present invention is little, and quality is light and energy storage is high, can be widely used in numerous areas, as lightweight aircraft, portable energy-storing, can Wearable energy supplying system etc.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is structural representation of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph (ESEM model is Hitachi S-4800 field emission scanning electron microscope) of polymer nanofiber barrier film in the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of metal conducting layer in the present invention.
Fig. 4 is that (electroactive material is MnO for the cyclic voltammetry curve figure of ultracapacitor of the present invention 2).
Fig. 5 is that (electroactive material is MnO for the charge-discharge characteristic curve of ultracapacitor of the present invention 2).
In figure: 1-polymer nanofiber barrier film 2-positive pole, 3-negative pole.
Embodiment
As shown in Figure 1, the low-cost highly integrated ultralight ultracapacitor of flexible ultra-thin, this capacitor is the polymer nanofiber barrier film 1 of 40 ~ 150 μ m and the positive pole 2 of directly preparing at polymer nanofiber barrier film 1 positive and negative and negative pole 3 formations by thickness.
embodiment 1the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution: 1g polymer dissolution, at 9gN, in N solvent dimethylformamide, is at room temperature stirred 2 hours, obtain the polymer solution of transparent clarification.
Wherein: polymer refers to polyacrylonitrile.
(2) prepare polymer nanofiber barrier film 1:
Polymer solution is packed in the syringe with spinning head, by add 10 ~ 30kV high voltage between spinning head and collecting board, form highfield, now injection stream is accelerated, is pullled under the effect of highfield, volatilization and fiber that diameter constantly reduces simultaneous solvent solidify, and finally on collecting board, obtaining thickness is the polymer nanofiber barrier film 1 of 40 ~ 150 μ m.
Wherein: the distance between spinning head and collecting board is 10 ~ 25cm.
With the method for magnetron sputtering polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 100 ~ 200nm, then in the aqueous solution that contains electroactive material that is 0.01M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
Magnetically controlled sputter method refers at stainless-steel vacuum indoor, gas pressure intensity is under the condition of 0.2Pa, electronics bumps with Ar atom under the effect of electric field, produce Ar plasma, under electric field action, Ar plasma flies to cathode target, and with the high-energy bombardment target surface of 10eV, make metal targets generation sputter, thereby make metal material be deposited on polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to RuO 2.
embodiment 2the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to polyacrylic acid.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
With the method for magnetron sputtering polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 200 ~ 400nm, then in the aqueous solution that contains electroactive material that is 0.02M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
Magnetically controlled sputter method refers at stainless-steel vacuum indoor, gas pressure intensity is under the condition of 0.5Pa, electronics bumps with Ar atom under the effect of electric field, produce Ar plasma, under electric field action, Ar plasma flies to cathode target, and with the high-energy bombardment target surface of 15eV, make metal targets generation sputter, thereby make metal material be deposited on polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to Fe 3o 4.
embodiment 3the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to polyethylene glycol.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
With the method for magnetron sputtering polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 400 ~ 600nm, then in the aqueous solution that contains electroactive material that is 0.03M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
Magnetically controlled sputter method refers at stainless-steel vacuum indoor, gas pressure intensity is under the condition of 1.0Pa, electronics bumps with Ar atom under the effect of electric field, produce Ar plasma, under electric field action, Ar plasma flies to cathode target, and with the high-energy bombardment target surface of 20eV, make metal targets generation sputter, thereby make metal material be deposited on polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to NiO.
embodiment 4the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to polyoxyethylene.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
With the method for magnetron sputtering polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 600 ~ 800nm, then in the aqueous solution that contains electroactive material that is 0.04M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
Magnetically controlled sputter method refers at stainless-steel vacuum indoor, gas pressure intensity is under the condition of 1.5Pa, electronics bumps with Ar atom under the effect of electric field, produce Ar plasma, under electric field action, Ar plasma flies to cathode target, and with the high-energy bombardment target surface of 25eV, make metal targets generation sputter, thereby make metal material be deposited on polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to MnO 2.
embodiment 5the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to polymethyl methacrylate.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
With the method for magnetron sputtering polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 800 ~ 1000nm, then in the aqueous solution that contains electroactive material that is 0.05M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
Magnetically controlled sputter method refers at stainless-steel vacuum indoor, gas pressure intensity is under the condition of 2Pa, electronics bumps with Ar atom under the effect of electric field, produce Ar plasma, under electric field action, Ar plasma flies to cathode target, and with the high-energy bombardment target surface of 30eV, make metal targets generation sputter, thereby make metal material be deposited on polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material is Co 3o 4.
embodiment 6the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to polyvinyl alcohol.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
The method of deposited by electron beam evaporation polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 100 ~ 300nm, then in the aqueous solution that contains electroactive material that is 0.01M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
The method of electron beam evaporation refers at stainless-steel vacuum indoor, and gas pressure intensity is 10 -4under the condition of Pa, the metal material of wanted evaporation is utilized electron beam to be heated to fusion temperature and makes its evaporation, and be attached to polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to Ni (OH) 2.
embodiment 7the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to polysiloxanes.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
The method of deposited by electron beam evaporation polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 300 ~ 500nm, then in the aqueous solution that contains electroactive material that is 0.02M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
The method of electron beam evaporation refers at stainless-steel vacuum indoor, and gas pressure intensity is 10 -3under the condition of Pa, the metal material of wanted evaporation is utilized electron beam to be heated to fusion temperature and makes its evaporation, and be attached to polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to polyaniline.
embodiment 8the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to Kynoar.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
The method of deposited by electron beam evaporation polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 500 ~ 700nm, then in the aqueous solution that contains electroactive material that is 0.03M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
The method of electron beam evaporation refers at stainless-steel vacuum indoor, and gas pressure intensity is 10 -2under the condition of Pa, the metal material of wanted evaporation is utilized electron beam to be heated to fusion temperature and makes its evaporation, and be attached to polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to polyurethane.
embodiment 9the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to Kynoar-hexafluoropropylene copolymer.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
The method of deposited by electron beam evaporation polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 700 ~ 900nm, then in the aqueous solution that contains electroactive material that is 0.04M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
The method of electron beam evaporation refers at stainless-steel vacuum indoor, and gas pressure intensity is 10 -4under the condition of Pa, the metal material of wanted evaporation is utilized electron beam to be heated to fusion temperature and makes its evaporation, and be attached to polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to polypyrrole.
embodiment 10the preparation method of this ultracapacitor, comprises the following steps:
(1) prepared polymer solution is same embodiment 1.Wherein: polymer refers to Polyetherimide.
(2) prepare polymer nanofiber barrier film 1 same embodiment 1.
The method of deposited by electron beam evaporation polymer nanofiber barrier film 1 mutually over against positive and negative make positive electrode and negative material form the metal conducting layer that thickness is 900 ~ 1000nm, then in the aqueous solution that contains electroactive material that is 0.05M using polymer nanofiber barrier film 1 immersion concentration or metal salt solution and as work electrode, platinum electrode is as to electrode, saturated calomel is as reference electrode, with electrochemical workstation to work electrode with to the voltage of 0 ~ 1.0V is provided between electrode, on metal conducting layer, deposit after the positive pole 2 and negative pole 3 of electroactive material formation capacitance electrode, obtain ultracapacitor.
Wherein:
The method of electron beam evaporation refers at stainless-steel vacuum indoor, and gas pressure intensity is 10 -2under the condition of Pa, the metal material of wanted evaporation is utilized electron beam to be heated to fusion temperature and makes its evaporation, and be attached to polymer nanofiber barrier film 1 mutually over against the surface of positive and negative form metal conducting layer.
Electroactive material refers to polythiophene.

Claims (7)

1.低成本高集成化的柔性超薄超轻超级电容器，其特征在于：该电容器由厚度为40~150μm的聚合物纳米纤维隔膜（1）及在所述聚合物纳米纤维隔膜（1）正反面直接制备的正极（2）和负极（3）构成。 1. A low-cost and highly integrated flexible ultra-thin and ultra-light supercapacitor, characterized in that: the capacitor is composed of a polymer nanofiber diaphragm (1) with a thickness of 40-150 μm and the polymer nanofiber diaphragm (1) positive The positive electrode (2) and the negative electrode (3) prepared directly on the opposite side constitute. 2.如权利要求1所述的低成本高集成化的柔性超薄超轻超级电容器的制备方法，包括以下步骤： 2. the preparation method of the flexible ultra-thin ultra-light ultracapacitor of low cost high integration as claimed in claim 1, comprises the following steps: ⑴配制聚合物溶液：将1g聚合物溶解在9gN，N二甲基甲酰胺溶剂中，在室温下搅拌2小时，即得透明澄清的聚合物溶液； (1) Preparation of polymer solution: Dissolve 1 g of polymer in 9 g of N, N dimethylformamide solvent and stir at room temperature for 2 hours to obtain a transparent and clear polymer solution; ⑵制备聚合物纳米纤维隔膜（1）： ⑵Preparation of polymer nanofiber separator (1): 将所述聚合物溶液装入带有喷丝头的注射器内，通过在喷丝头和收集板之间加10~30kV高电压形成强电场，此时喷射流在强电场的作用下加速、拉扯，直径不断减小同时伴随着溶剂的挥发和纤维固化，最终在所述收集板上获得厚度为40~150μm的聚合物纳米纤维隔膜（1）； Put the polymer solution into a syringe with a spinneret, and form a strong electric field by applying a high voltage of 10~30kV between the spinneret and the collecting plate, and at this time, the jet stream is accelerated and pulled under the action of the strong electric field , the diameter decreases continuously accompanied by solvent volatilization and fiber solidification, and finally a polymer nanofiber membrane (1) with a thickness of 40-150 μm is obtained on the collecting plate; ⑶用磁控溅射或电子束蒸发的方法在所述聚合物纳米纤维隔膜（1）相互正对的正反面使正极材料和负极材料形成厚度均为100~1000nm的金属导电层，然后将所述聚合物纳米纤维隔膜（1）浸入浓度为0.01~0.05M的含有电活性物质的水溶液或金属盐溶液中并作为工作电极，铂电极作为对电极，饱和甘汞作为参比电极，用电化学工作站给工作电极和对电极之间提供0~1.0V的电压，在所述金属导电层上沉积电活性物质形成电容电极的正极（2）和负极（3）后，即得超级电容器。 (3) Use magnetron sputtering or electron beam evaporation to form a metal conductive layer with a thickness of 100-1000 nm on the front and back sides of the polymer nanofiber separator (1) facing each other, and then place the The polymer nanofiber separator (1) is immersed in an aqueous solution or metal salt solution containing electroactive substances at a concentration of 0.01-0.05M and used as a working electrode, a platinum electrode as a counter electrode, and saturated calomel as a reference electrode. The workstation provides a voltage of 0-1.0V between the working electrode and the counter electrode, and after depositing an electroactive material on the metal conductive layer to form the positive electrode (2) and negative electrode (3) of the capacitor electrode, a supercapacitor is obtained. 3.如权利要求2所述的低成本高集成化的柔性超薄超轻超级电容器的制备方法，其特征在于：所述步骤⑴中的聚合物是指聚丙烯腈、聚丙烯酸、聚乙二醇、聚氧乙烯、聚甲基丙烯酸甲酯、聚乙烯醇、聚硅氧烷、聚偏氟乙烯、聚偏氟乙烯-六氟丙烯共聚物、聚醚酰亚胺中的一种。 3. the preparation method of the flexible ultra-thin ultra-light ultracapacitor of low cost high integration as claimed in claim 2, it is characterized in that: the polymer in the described step (1) refers to polyacrylonitrile, polyacrylic acid, polyethylene glycol Alcohol, polyoxyethylene, polymethyl methacrylate, polyvinyl alcohol, polysiloxane, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyetherimide. 4.如权利要求2所述的低成本高集成化的柔性超薄超轻超级电容器的制备方法，其特征在于：所述步骤⑵中喷丝头与收集板之间的距离为10~25cm。 4. The method for preparing a low-cost and highly integrated flexible ultra-thin and ultra-light supercapacitor according to claim 2, wherein the distance between the spinneret and the collecting plate in the step (2) is 10-25 cm. 5.如权利要求2所述的低成本高集成化的柔性超薄超轻超级电容器的制备方法，其特征在于：所述步骤⑶中磁控溅射方法是指在不锈钢真空室内，气体压强在0.2~2Pa的条件下，电子在电场的作用下与Ar原子发生碰撞，产生Ar等离子体，在电场作用下Ar等离子体飞向阴极靶，并以10~30eV的高能量轰击靶表面，使金属靶材发生溅射，从而使金属材料沉积在所述聚合物纳米纤维隔膜（1）相互正对的正反面的表面形成金属导电层。 5. the preparation method of the flexible ultra-thin ultra-light ultracapacitor of low cost high integration as claimed in claim 2, it is characterized in that: in described step (3) magnetron sputtering method refers to in stainless steel vacuum chamber, gas pressure is at Under the condition of 0.2~2Pa, electrons collide with Ar atoms under the action of electric field to generate Ar plasma. The target material is sputtered, so that the metal material is deposited on the opposite surfaces of the polymer nanofiber membrane (1) to form a metal conductive layer. 6.如权利要求2所述的低成本高集成化的柔性超薄超轻超级电容器的制备方法，其特征在于：所述步骤⑶中电子束蒸发的方法是指在不锈钢真空室内，气体压强在10-4~10-2Pa的条件下将所要蒸镀的金属材料利用电子束加热到熔化温度使其蒸发，并附着在所述聚合物纳米纤维隔膜（1）相互正对的正反面的表面形成金属导电层。 6. the preparation method of the flexible ultra-thin ultra-light supercapacitor of low cost high integration as claimed in claim 2, it is characterized in that: the method for electron beam evaporation in the described step (3) refers to that in a stainless steel vacuum chamber, the gas pressure is between Under the condition of 10 -4 ~10 -2 Pa, the metal material to be evaporated is heated to the melting temperature by an electron beam to be evaporated, and attached to the surfaces of the opposite sides of the polymer nanofiber membrane (1) facing each other Form the metal conductive layer. 7.如权利要求2所述的低成本高集成化的柔性超薄超轻超级电容器的制备方法，其特征在于：所述步骤⑶中电活性物质是指过渡金属的氧化物或氢氧化物及导电聚合物；所述过渡金属的氧化物或氢氧化物为RuO2, Fe3O4, NiO, MnO2, Co3O4, Ni(OH) 2中的一种；所述导电聚合物为聚苯胺，聚氨酯，聚吡咯，聚噻吩中的一种。 7. The method for preparing a flexible ultra-thin ultra-light supercapacitor with low cost and high integration as claimed in claim 2, characterized in that: in the step (3), the electroactive substance refers to oxides or hydroxides of transition metals and Conductive polymer; the oxide or hydroxide of the transition metal is one of RuO 2 , Fe 3 O 4 , NiO, MnO 2 , Co 3 O 4 , Ni(OH) 2 ; the conductive polymer is One of polyaniline, polyurethane, polypyrrole, and polythiophene.
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