CN110718402A - Flexible and foldable super capacitor and preparation method thereof - Google Patents
Flexible and foldable super capacitor and preparation method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
Abstract
The invention belongs to the technical field of novel advanced energy storage devices, and discloses a flexible foldable super capacitor and a preparation method thereof, wherein a carbon nano tube macroscopic film is selected as a current collector, and a near-integrated composite electrode is constructed by loading active substances on the surface; and then preparing the flexible foldable super capacitor through the processes of drying, cutting, welding, laminating, assembling, injecting liquid and packaging. The carbon nano tube macroscopic film current collector and the active substance layer form a nearly integrated composite electrode through mutual embedding and anchoring, the composite electrode has stable interface structure and high efficiency of electron/ion conduction/diffusion, and meanwhile, the porous carbon nano tube macroscopic film current collector can store electrolyte to ensure the stability of electrochemical performance. The assembled super capacitor has high volume energy density, can be bent and folded at will, is suitable for wide working temperature, can be applied to various portable electronic devices, has a simple preparation method, and is convenient for large-scale development and application.
Description
Technical Field
The invention belongs to the technical field of novel advanced energy storage devices, and particularly relates to a flexible foldable super capacitor and a preparation method thereof.
Background
Currently, the closest prior art:
with the rapid development of modern science and technology, various portable wearable intelligent electronic devices come out in succession, and these electronic devices gradually develop towards miniaturization, planarization, flexibility and the like, and can even continuously and stably work under various special environments such as pressing, pulling, folding and the like. However, the existing energy storage and supply devices are often too thick, too heavy and poor in flexibility, and cannot well meet the requirements of the emerging industry, so that the key for developing the multifunctional wearable electronic equipment is to develop an energy storage device matched with the multifunctional wearable electronic equipment, and the energy storage device is required to have long endurance capacity, and more importantly, to be capable of maintaining a stable working state under the special environmental conditions. Therefore, the research on the novel high-performance flexible foldable energy storage device has very important significance.
Super capacitors have received much attention as an efficient, clean, sustainable energy source. The super capacitor has the advantages of high power density, good low-temperature performance, long service life (up to tens of thousands of times), high safety and the like, and meanwhile, the super capacitor serving as an energy storage element also develops towards the directions of small size, light weight, flexibility and the like. The energy density of the conventional super capacitor is low, and meanwhile, because metals such as nickel, copper and aluminum are selected as a current collector, the super capacitor is easy to crack under the deformation condition including bending, winding, folding and the like, the metal current collector is broken even and then transmission of electrons is blocked, in addition, electrolyte on the surface of the current collector is extruded under the deformation action, diffusion of ions is inhibited, and meanwhile, active substances loaded on the surface are easy to fall off and separate, so that the performance of the super capacitor is attenuated and even loses efficacy, and therefore, the flexible current collector is developed and applied to the super capacitor, and the super capacitor has important value.
The flexible electrode is expected to realize the flexibility of the supercapacitor by further constructing the flexible electrode by preparing the flexible carbon-based current collector, for example, active substances are loaded on current collectors such as carbon cloth and carbon nano tubes by hydrothermal method, electrochemical deposition and other technologies. Then, there is also an interface problem between the active material and the current collector: in order to solve the interface problem, the Zheng Bo introduces graphene as a bridging point between a current collector (foam carbon, foam carbon cloth) and an active material, enriches the transmission path of electrons, and improves the structural stability and electrochemical characteristics of the device (adv. mater.2013,25, 5799-doped 5806). It is noted that after the graphene is introduced, the graphene and the current collector generate an interface again. Recently, Yongmin Ko et al adopt a chemical self-assembly method to improve the contact problem between a flexible substrate (non-conductive substrate) and an active material, and improve the flexibility of a super capacitor device (nat. Comm.,2017,8(1): 536).
However, the current collectors have no flexibility or conductivity, and cannot achieve both excellent flexibility and high conductivity, thereby limiting the development of flexible supercapacitors. Therefore, the interface structure needs to be further optimized, so that the interface problems of electron transmission, structural stability and the like are essentially solved, and the flexible and foldable super capacitor with high energy density and power density is realized.
In summary, the problems of the prior art are as follows:
(1) in the prior art, the flexible characteristic and the conductive characteristic of a supercapacitor device cannot be optimized at the same time, so that the development of a flexible supercapacitor is limited. And the preparation method of the super capacitor in the prior art is complex, and is not convenient for large-scale development and application.
(2) In the prior art, active substances are grown in situ, and the loading capacity of the active substances is low, so that the overall energy density of the device is low, and the long-time energy requirement of intelligent electronic equipment cannot be met.
(3) In the prior art, the prepared super capacitor is in a flexible folding process, electrolyte is subjected to external force, and secondary distribution of the electrolyte is uneven on the surface of an electrode, so that energy supply of the super capacitor is influenced, and stable work in a flexible and foldable environment cannot be truly realized.
The difficulty of solving the technical problems is as follows:
the preparation of the flexible current collector, the stable loading of the active material and the uniform distribution of the electrolyte in the electrode.
The significance of solving the technical problems is as follows: the flexible foldable super capacitor is prepared on a large scale, the electronic transmission, the charge diffusion and the stability of the device are improved, and the stable and normal operation of the device in a flexible foldable environment is met.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a flexible foldable super capacitor and a preparation method thereof.
The invention is realized in such a way, the method for preparing the flexible foldable super capacitor based on the carbon nano tube macroscopic film near-integration electrode selects the carbon nano tube macroscopic film as a current collector, active substances are loaded on the surface of the current collector to construct the near-integration composite electrode, and then the flexible foldable super capacitor is prepared by the processes of drying, cutting, welding, laminating, assembling, injecting liquid, packaging and the like.
The method comprises the following specific steps:
step one, preparing a pole piece: firstly, weighing an active substance, a conductive agent and a binder according to a ratio of 8:1:1, then adding the binder into an N, N-dimethylformamide solvent, placing the solvent at a high temperature of 100 ℃ and 120 ℃ for accelerated dissolution, after the binder is fully dissolved, continuously adding the active substance and the conductive agent for stirring, placing the mixed raw materials into an agate tank, placing the tank into a planetary ball mill, preparing slurry with proper viscosity after ball milling for 12h, then uniformly coating the slurry on the surface of a flattened carbon nanotube macroscopic film current collector, and finally placing a pole piece into a drying box for drying.
Secondly, assembling the super capacitor: and cutting the dried pole piece according to a fixed size, welding a pole lug, stacking the pole piece, the diaphragm and the pole piece in sequence, and finally assembling the pole piece and the diaphragm by using an outer packaging film to obtain the supercapacitor.
Thirdly, liquid injection and packaging of the super capacitor: and injecting an electrolyte into the prepared super capacitor, standing for 24 hours, and then performing air exhaust and packaging to obtain the final super capacitor.
Furthermore, the carbon nanotube macroscopic film has excellent conductivity and physical and mechanical properties, and more importantly, the porous structure formed by ordered or disordered arrangement of the carbon nanotube macroscopic film can adsorb and store electrolyte.
Furthermore, the electrode is formed by embedding and anchoring a carbon nano tube macroscopic film current collector and an active substance into each other to form a nearly integrated structure.
Further, as the active material, mainly used are activated carbon, graphene, a conductive polymer (polyaniline, polypyrrole, polythiophene, and the like), a metal compound (manganese dioxide, ruthenium oxide, titanium carbide, and the like), and the like.
Further, the composite electrode is prepared by a coating method, electrostatic spinning, a liquid phase method, an electrochemical deposition method and other processes.
Furthermore, the thickness of the carbon nano tube macroscopic film is 1-50 μm. The surface density is 0.1-1mg/cm2。
Further, the coating thickness of the active substance is 10-200 μm, and the loading is 1-20mg/cm2。
Furthermore, the size of the electrode cutting piece can reach 20cm multiplied by 20 cm.
Further, the energy density may be higher than 50 Wh/kg.
Furthermore, the flexible foldable super capacitor can be bent and folded at any angle, and the flexible foldable super capacitor can still normally work after the bending and folding cycle times are more than 1000.
Further, the flexible foldable super capacitor can work normally under severe environments such as low temperature (< 40 ℃), low voltage (< 0.1Kpa) and the like.
The invention also aims to provide a flexible foldable super capacitor based on the carbon nano tube macroscopic film near-integrated electrode, which is prepared by the preparation method of the flexible foldable super capacitor based on the carbon nano tube macroscopic film near-integrated electrode.
In summary, the advantages and positive effects of the invention are: the electrode has the advantages that the flexibility is excellent, the conductivity is high, the carbon nano tube macroscopic film is used as a current collector, active substances are loaded on the surface of the current collector to prepare a nearly integrated electrode, the porous carbon nano tube macroscopic film can anchor the active substances, the structural stability of the electrode in the folding process is guaranteed, meanwhile, the uniform distribution of electrolyte can be realized, and the stable and excellent electrochemical energy storage characteristic is displayed.
In order to enable the energy storage device to be more flexible so as to meet the requirements of portable electronic equipment, the invention selects the carbon nano tube macroscopic film as a current collector surface loaded with active substances to prepare an electrode, and the preparation of the flexible foldable super capacitor is realized through processes of cutting, welding, laminating, assembling, injecting liquid, packaging and the like. The carbon nano tube macroscopic film current collector and the active substance layer form a nearly integrated composite electrode through mutual embedding and anchoring, the composite electrode has stable interface structure and high efficiency of electron/ion conduction/diffusion, and meanwhile, the porous carbon nano tube macroscopic film current collector can store electrolyte to ensure the stability of electrochemical performance. The assembled super capacitor has high volume energy density, can be bent and folded randomly (the radius is less than 1mm), is suitable for wide working temperature, can be applied to various portable electronic devices, has a simple preparation method, and is convenient for large-scale development and application.
Drawings
Fig. 1 is a flow chart of a method for preparing a flexible foldable supercapacitor based on a carbon nanotube macroscopic film near-integration electrode according to an embodiment of the invention.
Fig. 2 is a schematic diagram of a supercapacitor and an electrode structure thereof according to an embodiment of the present invention.
Fig. 3 is a scanning electron micrograph of carbon nanotube fibers according to an embodiment of the present invention.
Fig. 4 is a schematic diagram of a composite electrode based on a carbon nanotube macroscopic film current collector according to an embodiment of the present invention.
Fig. 5 is a display diagram showing the operation of the flexible and foldable super capacitor provided by the embodiment of the invention in different bending states.
Fig. 6 is a specific capacity variation curve diagram of the flexible and foldable supercapacitor provided by the embodiment of the invention under different deformation states.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the prior art, the flexible characteristic and the conductive characteristic of a supercapacitor device cannot be optimized at the same time, so that the development of a flexible supercapacitor is limited. And the preparation method of the super capacitor in the prior art is complex, and is not convenient for large-scale development and application.
Aiming at the problems in the prior art, the invention provides a flexible foldable super capacitor and a preparation method thereof, and the invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, a method for preparing a flexible foldable supercapacitor based on a carbon nanotube macroscopic film near-integrated electrode provided by the embodiment of the present invention includes the following specific steps:
s101, preparing slurry: weighing a certain amount of active substances, a graphite conductive agent and polyvinylidene fluoride (PVDF), and placing the active substances, the graphite conductive agent and the PVDF in a drying oven at 120 ℃ for drying for more than 24 hours. Firstly, weighing a certain amount of polyvinylidene fluoride as a binder, adding the polyvinylidene fluoride into an N, N-dimethylformamide solution, stirring, and then placing the mixture at a high temperature of 100 ℃ and 120 ℃ for accelerated dissolution, wherein the whole process approximately needs 2 hours. Drying the raw materials according to the following active substances: SP: and weighing PVDF in a mass ratio of 8:1:1, and after the PVDF is dissolved, continuously adding the active substance and the conductive agent and stirring. And putting the mixed raw materials into an agate tank, adding a plurality of ball mills, putting the mixture into a planetary ball mill, and preparing the mixture into slurry with proper viscosity after ball milling for 12 hours.
S102, preparing an active substance/carbon nano tube composite film electrode: and a thickness scraper for uniformly scraping the slurry obtained in the step S101 on the surface of the carbon nanotube film. And reserving a carbon nanotube film with the length of 30-50mm as a tab part during coating, and after the coating is finished, putting the whole pole piece together in an oven at the temperature of 60-100 ℃ for drying to obtain the activated carbon/carbon nanotube composite film. And finally, rolling the active substance/carbon nanotube composite film by using a rolling machine because the carbon nanotube film pole piece has excellent flexibility. The prepared pole piece is placed and flattened by using a flat die and is placed in a drying oven at 60 ℃ for later use.
S103, cutting the pole piece, and cutting the rolled electrode strip into the length and the width required by capacitor assembly according to different capacitor models for subsequent assembly.
And S104, assembling the flexible foldable super capacitor, and welding the carbon nanotube film cut in the step S103 with a lug. The positive plate, the diaphragm and the negative plate are aligned and placed in the order from top to bottom, and the diaphragm is adhered to the periphery of the activated carbon/carbon nanotube composite film by high-temperature glue. Secondly put into the plastic-aluminum membrane again and pack the electric core, sealed wherein three side, follow this and annotate the one side of leaving in the liquid room through dehumidifying, pour into electrolyte into, at last hot pressing is sealed.
And S105, transferring the flexible foldable super capacitor obtained in the step S104 to a glove box filled with inert gas, injecting a proper amount of electrolyte, then placing the capacitor injected with the electrolyte into a vacuum box (the vacuum degree is lower than minus 80Kpa), standing for 20min, accelerating the wetting of an electrode material by the electrolyte, and finally utilizing a packaging machine to carry out hot-pressing sealing on an injection end, thus completing the manufacturing of the capacitor.
In the embodiment of the invention, the selected current collector carbon nanotube film is prepared by a floating catalytic Chemical Vapor Deposition (CVD) method through constraint design, so that the flexible foldable supercapacitor based on the carbon nanotube macroscopic film near-integrated electrode has the multifunctional functions of serving as a material support substrate, conducting, radiating and the like, and the carbon nanotube film is prepared in a continuous batch mode.
The macroscopic film thickness of the carbon nano tube of the current collector material is 1 to 50 mu m, and the mass surface density is 0.1 to 1.0mg/cm2And the area size can be cut and controlled according to different size requirements.
The surface of the carbon nanotube film of the current collector material is rough and has a bundle-shaped porous structure, which is beneficial to the combination of the electrode material and the carbon nanotube film and can greatly improve the loading capacity of active substances in unit area.
In the above slurry, the active material: binder PVDF: the mass ratio of the conductive agent SP is 8:1:1, and the solid-liquid ratio is 10-20%.
The carbon nano tube on the surface of the current collector can be embedded into the active substance, so that the active substance is anchored on the surface of the carbon nano tube membrane, the interface strength between the active substance and the current collector is improved, and meanwhile, the transmission path of electrons between interfaces is enriched.
The active substance/carbon nano tube composite film is coated by adopting a scraper blade coating method, the thickness is 10-200 mu m, and the thickness of the composite film is controlled by adjusting process parameters.
The mass and surface density of the active material is controlled to be 2-20mg/cm2。
In a preferred embodiment of the present invention, a polyolefin porous film formed into a thin film with commercial high strength is used as the separator.
After the pole piece is dried, the back cut piece is rolled under the pressure of 3.5T. The carbon nanotube film is cut into a predetermined shape and then weighed.
The capacitance of the prepared flexible foldable super capacitor is 40-48F/cm3The current density is 0.1-5A/g.
As a preferred embodiment of the invention, the prepared flexible foldable super capacitor has enough flexibility, basically has no influence on the electrochemical behavior in different bending states, can be used in series and in parallel and can be used as a power supply for driving small electronic equipment to work.
The flexible foldable super capacitor disclosed by the invention has the advantages of higher volume energy density, good device stability and simple preparation process, and provides an excellent device foundation for the research and development of flexible electronic equipment.
The working cut-off voltage of the prepared flexible foldable super capacitor is 2.7V.
The invention is further described with reference to specific examples.
Example 1
The embodiment of the invention provides a preparation method of a flexible foldable super capacitor based on a carbon nanotube macroscopic film near-integration electrode, which comprises the following steps:
the preparation of the active carbon slurry comprises the steps of weighing 1.0g of PVDF (polyvinylidene fluoride) as a binder, adding 50g N N-dimethylformamide solution into the PVDF solution, uniformly stirring the mixture, then placing the mixture at a high temperature of 100 ℃ to accelerate dissolution for 2 hours, weighing 8.0g of active carbon and 1.0g of SP (conductive agent) into the PVDF which is completely dissolved, transferring the mixed raw materials into an agate tank, adding ball mill, placing the mixture into a planetary ball mill, and preparing the slurry with proper viscosity after ball milling for 12 hours.
Preparing an active carbon/carbon nanotube composite film, uniformly coating the slurry on the surface of the carbon nanotube film, reserving the carbon nanotube film with the length of 30mm as a tab part during coating, and after coating is finished, putting the whole pole piece together into a 100 ℃ oven for drying to obtain the active carbon/carbon nanotube composite film pole piece. And finally, rolling the active carbon/carbon nanotube composite film by using a rolling machine, wherein the active carbon/carbon nanotube composite film pole piece has bending property. The prepared pole piece is flattened by using a flat die and is placed in a vacuum drying oven for later use.
Cutting the diaphragm and the pole piece, wherein the size length of the positive pole piece is 50mm, and the width of the positive pole piece is 50 mm; the length of the size of the negative pole piece is 55mm, and the width of the negative pole piece is 55 mm; the diaphragm dimensions were 60mm in length and 60mm in width.
And welding a tab on the cut active carbon/carbon nanotube composite film. The positive plate, the diaphragm and the negative plate are aligned and placed in the order from top to bottom, and the diaphragm is adhered to the periphery of the activated carbon/carbon nanotube composite film by high-temperature glue. Secondly put into the plastic-aluminum membrane again and pack the electric core, sealed wherein three side, follow this and annotate the one side of leaving in the liquid room through dehumidifying, pour into electrolyte into, at last hot pressing is sealed. And (6) finishing the assembly.
And (3) testing electrical properties: standing the obtained flexible foldable super capacitor for 24h at constant temperature, testing the specific capacity of the flexible super capacitor, and flatly laying the obtained super capacitor at 0 DEG, wherein the tested specific capacity is 45.8F/cm3。
Example 2
The embodiment of the invention provides a preparation method of a flexible foldable super capacitor based on a carbon nanotube macroscopic film near-integration electrode, which comprises the following steps:
preparing activated carbon slurry, namely weighing 1.0g of PVDF (polyvinylidene fluoride) binder by using an electronic balance, adding 50g N N-dimethylformamide solution into the PVDF, uniformly stirring, then placing the PVDF in a high temperature environment of 100 ℃ to accelerate dissolution for 2 hours, weighing 8.0g of activated carbon and 1.0g of SP (conductive agent), adding the activated carbon and the SP into the PVDF which is completely dissolved, transferring the mixed raw materials into an agate tank, adding ball mill, placing the mixture in a planetary ball mill, and preparing the slurry with proper viscosity after ball milling for 12 hours.
Preparing an active carbon/carbon nanotube composite film, uniformly coating the slurry on the surface of the carbon nanotube film, reserving the carbon nanotube film with the length of 30mm as a tab part during coating, and after coating is finished, putting the whole pole piece together into a 100 ℃ oven for drying to obtain the active carbon/carbon nanotube composite film pole piece. And finally, rolling the active carbon/carbon nanotube composite film by using a rolling machine, wherein the active carbon/carbon nanotube composite film pole piece has bending property. The prepared pole piece is flattened by using a flat die and is placed in a vacuum drying oven for later use.
Cutting the diaphragm and the pole piece, wherein the size length of the positive pole piece is 50mm, and the width of the positive pole piece is 50 mm; the length of the size of the negative pole piece is 55mm, and the width of the negative pole piece is 55 mm; the diaphragm dimensions were 60mm in length and 60mm in width.
And welding the cut carbon nanotube film with a tab. The positive plate, the diaphragm and the negative plate are aligned and placed in the order from top to bottom, and the diaphragm is adhered to the periphery of the activated carbon/carbon nanotube composite film by high-temperature glue. Secondly put into the plastic-aluminum membrane again and pack the electric core, sealed wherein three side, follow this and annotate the one side of leaving in the liquid room through dehumidifying, pour into electrolyte into, at last hot pressing is sealed. And (6) finishing the assembly.
And (3) testing electrical properties: standing the obtained flexible foldable super capacitor for 24h at constant temperature, testing the specific capacity of the flexible super capacitor, and folding the obtained super capacitor to be in a 90-degree state, wherein the tested specific capacity is 45.5F/cm3。
Example 3
The embodiment of the invention provides a preparation method of a flexible foldable super capacitor based on a carbon nanotube macroscopic film near-integration electrode, which comprises the following steps:
preparing activated carbon slurry, namely weighing 1.0g of PVDF (polyvinylidene fluoride) binder by using an electronic balance, adding 50g N N-dimethylformamide solution into the PVDF, uniformly stirring, then placing the PVDF in a high temperature environment of 100 ℃ to accelerate dissolution for 2 hours, weighing 8.0g of activated carbon and 1.0g of SP (conductive agent), adding the activated carbon and the SP into the PVDF which is completely dissolved, transferring the mixed raw materials into an agate tank, adding ball mill, placing the mixture in a planetary ball mill, and preparing the slurry with proper viscosity after ball milling for 12 hours.
Preparing an active carbon/carbon nanotube composite film, uniformly coating the slurry on the surface of the carbon nanotube film, reserving the carbon nanotube film with the length of 30mm as a tab part during coating, and after coating is finished, putting the whole pole piece together into a 100 ℃ oven for drying to obtain the active carbon/carbon nanotube composite film pole piece. And finally, rolling the active carbon/carbon nanotube composite film by using a rolling machine, wherein the active carbon/carbon nanotube composite film pole piece has bending property. The prepared pole piece is flattened by using a flat die and is placed in a vacuum drying oven for later use.
Cutting the diaphragm and the pole piece, wherein the size length of the positive pole piece is 50mm, and the width of the positive pole piece is 50 mm; the length of the size of the negative pole piece is 55mm, and the width of the negative pole piece is 55 mm; the diaphragm dimensions were 60mm in length and 60mm in width.
And welding the cut carbon nanotube film with a tab. The positive plate, the diaphragm and the negative plate are aligned and placed in the order from top to bottom, and the diaphragm is adhered to the periphery of the activated carbon/carbon nanotube composite film by high-temperature glue. Secondly put into the plastic-aluminum membrane again and pack the electric core, sealed wherein three side, follow this and annotate the one side of leaving in the liquid room through dehumidifying, pour into electrolyte into, at last hot pressing is sealed. And (6) finishing the assembly.
And (3) testing electrical properties: standing the obtained flexible foldable super capacitor for 24h at constant temperature, testing the specific capacity of the flexible super capacitor, and flatly laying the obtained super capacitor at 180 degrees, wherein the tested specific capacity is 45.6F/cm3。
Example 4
The embodiment of the invention provides a preparation method of a flexible foldable super capacitor based on a carbon nanotube macroscopic film near-integration electrode, which comprises the following steps:
the preparation of the active carbon slurry comprises the steps of weighing 1.0g of PVDF as a binder by an electronic balance, adding 50g N N-dimethylformamide solution into the PVDF, uniformly stirring the mixture, then placing the mixture at a high temperature of 100 ℃ to accelerate dissolution for 2 hours, weighing 8.0g of active carbon and 1.0g of SP as a conductive agent, adding the active carbon and the conductive agent into the PVDF which is completely dissolved, transferring the mixed raw materials into an agate tank, adding ball mill, placing the mixture into a planetary ball mill, and preparing the slurry with proper viscosity after ball milling for 12 hours.
Preparing an active carbon/carbon nanotube composite film, uniformly coating the slurry on the surface of the carbon nanotube film, reserving the carbon nanotube film with the length of 30mm as a tab part during coating, and after coating is finished, putting the whole pole piece together into a 100 ℃ oven for drying to obtain the active carbon/carbon nanotube composite film pole piece. And finally, rolling the active carbon/carbon nanotube composite film by using a rolling machine, wherein the active carbon/carbon nanotube composite film pole piece has bending property. The prepared pole piece is flattened by using a flat die and is placed in a vacuum drying oven for later use.
Cutting the diaphragm and the pole piece, wherein the size length of the positive pole piece is 50mm, and the width of the positive pole piece is 50 mm; the length of the size of the negative pole piece is 55mm, and the width of the negative pole piece is 55 mm; the diaphragm dimensions were 60mm in length and 60mm in width.
And welding the cut carbon nanotube film with a tab. The positive plate, the diaphragm and the negative plate are aligned and placed in the order from top to bottom, and the diaphragm is adhered to the periphery of the activated carbon/carbon nanotube composite film by high-temperature glue. Secondly put into the plastic-aluminum membrane again and pack the electric core, sealed wherein three side, follow this and annotate the one side of leaving in the liquid room through dehumidifying, pour into electrolyte into, at last hot pressing is sealed. And (6) finishing the assembly.
And (3) testing electrical properties: standing the obtained flexible foldable super capacitor for 24h at constant temperature, testing the specific capacity of the flexible super capacitor, and flatly laying the obtained super capacitor at 360 degrees, wherein the tested specific capacity is 45.2F/cm3。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a flexible foldable super capacitor based on a carbon nano tube macroscopic film near-integration electrode is characterized in that the preparation method of the flexible foldable super capacitor based on the carbon nano tube macroscopic film near-integration electrode selects a carbon nano tube macroscopic film as a current collector, and active substances are loaded on the surface of the current collector to construct a near-integration composite electrode;
and then preparing the flexible foldable super capacitor through the processes of drying, cutting, welding, laminating, assembling, injecting liquid and packaging.
2. The method for preparing the flexible and foldable supercapacitor based on the carbon nanotube macroscopic film near-integrated electrode according to claim 1, wherein the composite electrode is prepared by a coating method, electrostatic spinning, a liquid phase method and an electrochemical deposition method.
3. The method for preparing the flexible and foldable supercapacitor based on the carbon nanotube macroscopic film near-integrated electrode as claimed in claim 1, wherein the method for preparing the flexible and foldable supercapacitor based on the carbon nanotube macroscopic film near-integrated electrode specifically comprises:
step one, preparing a pole piece: firstly, weighing an active substance, a conductive agent and a binder according to a ratio of 8:1:1, then adding the binder into an N, N-dimethylformamide solvent, placing the N, N-dimethylformamide solvent at a high temperature of 100 ℃ for accelerated dissolution at 120 ℃, continuously adding the active substance and the conductive agent for stirring after the binder is fully dissolved, placing the mixed raw materials into an agate tank, placing the raw materials into a planetary ball mill, preparing slurry with proper viscosity after ball milling for 12 hours, then uniformly coating the slurry on the surface of a flattened carbon nanotube macroscopic film current collector, and finally placing a pole piece into a drying box for drying;
secondly, assembling the super capacitor: cutting the dried pole piece according to a fixed size, welding a pole lug, stacking the pole piece, a diaphragm and the pole piece in sequence, and finally assembling by using an outer packaging film to obtain the super capacitor;
thirdly, liquid injection and packaging of the super capacitor: and injecting an electrolyte into the prepared super capacitor, standing for 24 hours, and then performing air exhaust and packaging to obtain the final super capacitor.
4. The method for preparing the flexible and foldable super capacitor based on the carbon nanotube macroscopic film near-integrated electrode as claimed in claim 3, wherein in the first step, the carbon nanotube macroscopic film is orderly or disorderly arranged to form a porous structure for adsorbing and storing the electrolyte.
5. The method for preparing the flexible foldable super capacitor based on the carbon nanotube macroscopic film near-integration electrode as claimed in claim 3, wherein in the first step, the electrode is formed by embedding and anchoring the carbon nanotube macroscopic film current collector and the active material into each other to form a near-integration composite electrode structure.
6. The method for preparing the flexible foldable super capacitor based on the carbon nano tube macroscopic film near-integration electrode as claimed in claim 3, wherein in the first step, the active material adopts activated carbon, graphene, conductive polymer and metal compound; the conductive polymer comprises polyaniline, polypyrrole and polythiophene; the metal compounds include manganese dioxide, ruthenium oxide and titanium carbide.
7. The method for preparing a flexible and foldable supercapacitor based on carbon nanotube macroscopic film near-integrated electrodes according to claim 3, wherein in the first step, the thickness of the carbon nanotube macroscopic film is 1-50 μm; the surface density is 0.1-1mg/cm2。
8. The method for preparing the flexible and foldable super capacitor based on the carbon nano tube macroscopic film near-integrated electrode as claimed in claim 3, wherein in the first step, the coating thickness of the active material is 10-200 μm, and the loading capacity is 1-20mg/cm2。
9. The method for preparing the flexible foldable super capacitor based on the carbon nano tube macroscopic film near-integrated electrode as claimed in claim 3, wherein in the second step, the size of the electrode cut piece is 20cm x 20 cm;
in the third step, the energy density of the super capacitor is higher than 50 Wh/kg; the operating cut-off voltage was 2.7V.
10. A flexible foldable super capacitor based on a carbon nanotube macroscopic film near-integrated electrode, prepared by the method for preparing the flexible foldable super capacitor based on the carbon nanotube macroscopic film near-integrated electrode as claimed in any one of claims 1 to 9.
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