CN111463027B - Method for improving performance of super capacitor - Google Patents

Method for improving performance of super capacitor Download PDF

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CN111463027B
CN111463027B CN202010275666.3A CN202010275666A CN111463027B CN 111463027 B CN111463027 B CN 111463027B CN 202010275666 A CN202010275666 A CN 202010275666A CN 111463027 B CN111463027 B CN 111463027B
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pvdf
slurry
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CN111463027A (en
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李祥元
白锋
李�浩
车景锋
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Xi'an Helong New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses a method for improving the performance of a Super capacitor, which comprises the following steps of firstly, taking N-methyl pyrrolidone as a solvent, sequentially adding PVDF, Super P and active carbon, mixing to prepare slurry, and coating the slurry on a carbon-coated aluminum foil; then, carrying out common drying on the coated carbon-coated aluminum foil, then carrying out vacuum drying, and finally rolling and compacting to prepare a pole piece; taking N, N-dimethylformamide as a solvent, taking a mixture of PVDF-HFP, PVP and a conductive nano carbon material as a solute, then preparing the solvent and the solute into slurry through ball milling and stirring, and then coating the slurry on the surface of the prepared pole piece; and finally, carrying out vacuum drying on the obtained pole piece, preparing a layer of polymer film on the surface of the pole piece, and then cutting and assembling the pole piece to prepare the surface modified activated carbon-based supercapacitor. The invention effectively improves the rate capability and the cycling stability of the material, and the prepared super capacitor has high energy density.

Description

Method for improving performance of super capacitor
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a method for improving the performance of a super capacitor.
Background
A supercapacitor, also called an electrochemical capacitor, is a device for storing electrical energy based on an interface formed between an electrode and an electrolyte, and is a new green energy storage device between a conventional capacitor and a secondary battery. The super capacitor has the characteristics of high specific capacitance, wide working voltage range, environmental friendliness, high energy density, high power density and the like, and has the capabilities of high power output of the traditional capacitor and charge storage of a secondary battery. Nowadays, super capacitors have been widely used in the fields of electronics, communications, medical treatment, national defense, aerospace and the like. The super capacitor forms a stable double electric layer on the surface of a charged electrode by means of electrolyte ions or stores energy by absorbing and desorbing in two-dimensional or three-dimensional space of the electrode, has the advantages of high power density, long cycle life, capability of realizing rapid charge and discharge and the like, and has great attention in the field of electrochemical energy storage.
In order to improve the performance of the electrode material of the activated carbon double-layer supercapacitor, researchers generally modify the surface of the electrode material, for example, plasma-treating or nitric-acid-treating the activated carbon material to make the surface of the activated carbon material carry oxygen-containing functional groups, or modify the material by immersing the activated carbon material in an organic solvent to deposit transition metal oxide particles on the surface of the material. The methods are all surface modification on active materials, and few articles report that the surface modification is carried out on the electrode plate of the super capacitor. The surface modification on the surface of the mature active carbon electrode material is an effective and simple method, the electrochemical performance of the material can be directly improved on the basis of an active carbon super capacitor, and meanwhile, the modified film does not influence the whole thickness and volume of the electrode, and has an instructive effect on realizing large-scale production of the modified super capacitor electrode.
Disclosure of Invention
The invention aims to provide a method for improving the performance of a super capacitor, which effectively improves the rate capability and the cycling stability of materials, and the prepared super capacitor has high energy density.
The technical scheme adopted by the invention is that the method for improving the performance of the super capacitor is implemented according to the following steps:
step 1, taking N-methyl pyrrolidone as a solvent, sequentially adding PVDF, Super P and active carbon, mixing to prepare slurry, and coating the slurry on a carbon-coated aluminum foil;
step 2, carrying out common drying on the coated carbon-coated aluminum foil, then carrying out vacuum drying, and finally rolling and compacting to prepare a pole piece;
step 3, taking N, N-dimethylformamide as a solvent and a mixture of PVDF-HFP, PVP and a conductive nano carbon material as a solute, then preparing the solvent and the solute into slurry through ball milling and stirring, and then coating the slurry on the surface of the pole piece prepared in the step 2;
and 4, putting the pole piece obtained in the step 3 into a blast oven for baking, performing vacuum drying, preparing a layer of polymer film on the surface of the pole piece, and finally cutting and assembling the pole piece to prepare the surface modified activated carbon-based supercapacitor.
The present invention is also characterized in that,
in the step 1, the ratio of solute formed by the activated carbon, the Super P and the PVDF to the N-methylpyrrolidone solvent is 1: 3-5, wherein the mass ratio of the activated carbon to the Super P to the PVDF is (8-7): (1-2): 1.
the coating thickness of the carbon-coated aluminum foil in the step 1 is 100-200 microns.
In the step 2, the common drying temperature of the coated carbon-coated aluminum foil is 80-100 ℃, the drying time is 2-4 hours, the vacuum degree of vacuum drying is lower than-1 MPa, the vacuum drying temperature is 70-100 ℃, and the vacuum drying time is 10-12 hours.
In the step 3, the mass ratio of solute formed by PVDF-HFP, PVP and the conductive nano carbon material to N, N-dimethylformamide solvent is 1: 3-5, wherein the mass percentage of PVDF-HFP, PVP and the conductive nano carbon material is 10% -25%: 5% -10%: 0.25 to 0.75 percent.
And 3, coating the surface of the prepared pole piece by using a scraper coating method or an electrostatic spinning method, wherein the conductive nano carbon material is formed by compounding conductive carbon black and graphene, or the conductive nano carbon material is formed by compounding conductive carbon black and a carbon nano tube, the conductive nano carbon material is in a powder structure, if the conductive nano carbon material is formed by compounding conductive carbon black and graphene, the graphene is in a single layer, an few layers or multiple layers, if the conductive nano carbon material is formed by compounding conductive carbon black and a carbon nano tube, the carbon nano tube is in a single-wall or multi-wall structure, when the scraper coating method is selected, PVP is used as a dispersing agent or a pore-forming agent, the molecular weight is less than 10000, when the electrostatic spinning method is selected for coating, PVP is used as a spinning auxiliary agent, and the molecular weight is more than 100000.
In the step 3, the stirring speed is 300-400 rpm.
And in the step 4, the thickness of the polymer film is less than or equal to 1/10 of the thickness of the pole piece.
And 4, in the step 4, the vacuum degree of vacuum drying is lower than-1 MPa, the temperature of vacuum drying is 70-100 ℃, and the time of vacuum drying is 10-12 hours.
The method for improving the performance of the supercapacitor has the beneficial effects that based on the PVDF-HFP film, the conductivity of the whole material can be improved by the conductive carbon nano material, and the electrochemical performance of the modified electrode is improved by the method for improving the specific capacitance of the electrode. When the proportion of PVDF-HFP and the conductive carbon nano material reaches a certain value, the modified electrode has the optimal electrochemical performance. The specific capacitance of the electrode is improved by 40% of high value, and the cycling stability and the multiplying power performance of the electrode are improved under the condition that the volume of a pole piece is not influenced, non-optimized tests show that the specific capacitance of the super capacitor can be improved by 35% -40%, and the multiplying power performance and the cycling performance are also obviously improved. The air blasting drying is used for quickly drying the wet pole piece which is just coated, and the solvent is quickly dried, so that air holes on the surface of the pole piece can not be generated due to vacuumizing. And the vacuumizing and drying is to exhaust the gas in the pole piece after the pole piece is dried, so that the pole piece is used for further preparing the battery in a glove box. The preparation method is flexible and controllable, and the polymer film can be covered on the electrode plate by a scraper coating method or an electrostatic spinning method. And can also be coated or spun on the separator. The thickness of the coating applied can be adjusted by means of the scale of the doctor blade. The thickness of the spun yarn can be regulated and controlled by the spinning time. The conductive carbon nanomaterial added to the polymer film may be a combination of one or more materials. The activated carbon in the electrode plate can be made of different sources of super-capacity carbon products according to factors such as specific cost budget, such as YP series of Cololi corporation, Korean PCT corporation, Shanxi coal chemical institute, Ningbo Zhongche, Shenzhen fibrate corporation and the like. The invention adopts thin-layer surface modification, and the mass and volume increased by the covered thin film can be ignored, thereby being beneficial to effectively and rapidly improving the performance of the super capacitor. The thickness of the polymer should not affect the overall volume of the overall material and therefore needs to be as small as possible. Furthermore, an increase in the thickness of the polymer causes an increase in the total mass of the material, which in turn reduces the mass ratio of the active, thereby affecting the specific capacitance magnitude. The coating film is coated on the surface of the pole piece, and the pole piece is dried again to keep the surface smooth. In conclusion, the method is simple, efficient and rapid, the preparation cost is low, and special treatment is not needed after the supercapacitor is scrapped.
Drawings
FIG. 1 is an SEM image of the electrode surface of a supercapacitor after being treated by a typical electrospinning method according to example 3, wherein FIG. 1(a) is after treatment and FIG. 1(b) is untreated;
fig. 2 is a schematic view of charging and discharging of a typical supercapacitor after pole pieces are processed by electrostatic spinning in example 3, wherein fig. 2(a) is a charging and discharging magnification diagram; FIG. 2(b) is a charge/discharge cycle chart at a current density of 1A/g.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, taking N-methyl pyrrolidone as a solvent, sequentially adding PVDF, Super P and active carbon, mixing to prepare slurry, and coating the slurry on a carbon-coated aluminum foil;
in the step 1, the ratio of solute formed by the activated carbon, the Super P and the PVDF to the N-methylpyrrolidone solvent is 1: 3-5, wherein the mass ratio of the activated carbon to the Super P to the PVDF is (8-7): (1-2): 1.
the coating thickness of the carbon-coated aluminum foil in the step 1 is 100-200 microns.
Step 2, carrying out common drying on the coated carbon-coated aluminum foil, then carrying out vacuum drying, and finally rolling and compacting to prepare a pole piece;
in the step 2, the common drying temperature of the coated carbon-coated aluminum foil is 80-100 ℃, the drying time is 2-4 hours, the vacuum degree of vacuum drying is lower than-1 MPa, the vacuum drying temperature is 70-100 ℃, and the vacuum drying time is 10-12 hours.
Step 3, taking N, N-dimethylformamide as a solvent and a mixture of PVDF-HFP, PVP and a conductive nano carbon material as a solute, then preparing the solvent and the solute into slurry through ball milling and stirring, and then coating the slurry on the surface of the pole piece prepared in the step 2;
in the step 3, the mass ratio of solute formed by PVDF-HFP, PVP and the conductive nano carbon material to N, N-dimethylformamide solvent is 1: 3-5, wherein the mass percentage of PVDF-HFP, PVP and the conductive nano carbon material is 10% -25%: 5% -10%: 0.25 to 0.75 percent.
And 3, coating the surface of the prepared pole piece by using a scraper coating method or an electrostatic spinning method, wherein the conductive nano carbon material is formed by compounding conductive carbon black and graphene, or the conductive nano carbon material is formed by compounding conductive carbon black and a carbon nano tube, the conductive nano carbon material is in a powder structure, if the conductive nano carbon material is formed by compounding conductive carbon black and graphene, the graphene is in a single layer, an few layers or multiple layers, if the conductive nano carbon material is formed by compounding conductive carbon black and a carbon nano tube, the carbon nano tube is in a single-wall or multi-wall structure, when the scraper coating method is selected, PVP is used as a dispersing agent or a pore-forming agent, the molecular weight is less than 10000, when the electrostatic spinning method is selected for coating, PVP is used as a spinning auxiliary agent, and the molecular weight is more than 100000.
In the step 3, the stirring speed is 300-400 rpm.
And 4, putting the pole piece obtained in the step 3 into a blast oven for baking, performing vacuum drying, preparing a layer of polymer film on the surface of the pole piece, and finally cutting and assembling the pole piece to prepare the surface modified activated carbon-based supercapacitor.
And in the step 4, the thickness of the polymer film is less than or equal to 1/10 of the thickness of the pole piece.
And 4, in the step 4, the vacuum degree of vacuum drying is lower than-1 MPa, the temperature of vacuum drying is 70-100 ℃, and the time of vacuum drying is 10-12 hours.
Example 1
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, 0.8 g of activated carbon, 0.1 g of Super P and 0.1 g of PVDF are weighed and mixed into 3 ml of N-methylpyrrolidone (NMP) solvent, and stirred at the rotating speed of 300rpm by ball milling to form uniform electrode slurry, and the uniform electrode slurry is coated on a carbon-coated aluminum foil with the thickness of 18 microns by a 200-micron scraper.
And 2, putting the coated pole piece into a blast oven for drying for 3 hours at the temperature of 80 ℃, putting the pole piece into a vacuumizing oven for drying for 12 hours at the temperature of 80 ℃, taking the pole piece out, and putting the pole piece on an electric double-roll machine for rolling and compacting, wherein the rolling thickness is set to be 80% of that before rolling.
And step 3, sequentially adding 1 g of PVDF-HFP,0.025 g of carbon nano tube, 0.025 g of PVP and 3.95 g of N, N-Dimethylformamide (DMF) into a ball milling tank for ball milling and stirring at the rotating speed of 350 rpm.
And 4, scraping the stirred slurry on the surface of the prepared electrode plate by a scraper with the thickness of 25 micrometers, baking the electrode plate in a blast oven at the temperature of 80 ℃ for 2 hours, and then baking the electrode plate in a vacuum oven at the temperature of 80 ℃ for 12 hours.
And 5, cutting the processed pole piece, assembling the pole piece into a battery and performing electrochemical test.
Example 2
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, respectively weighing 0.7 g of activated carbon, 0.2 g of Super P and 0.1 g of PVDF, mixing the materials into 3.5 ml of N-methylpyrrolidone (NMP) solvent, forming uniform electrode slurry by ball milling and stirring, and coating the uniform electrode slurry on a carbon-coated aluminum foil with the thickness of 15 microns by using a 150-micron scraper.
And 2, putting the coated pole piece into a blast oven for drying for 2 hours at 100 ℃, then putting the pole piece into a vacuumizing oven for drying for 12 hours at 80 ℃, taking out the pole piece, and putting the pole piece on an electric double-roll machine for rolling and compacting, wherein the rolling thickness is set to be 90% of that before rolling.
And 3, sequentially adding 1 g of PVDF-HFP,0.02 g of carbon nano tube, 0.005 g of graphene, 0.025 g of PVP and 3.95 g of N, N-Dimethylformamide (DMF) into a ball milling tank for ball milling and stirring at the rotating speed of 350 rpm.
And 4, scraping the stirred slurry on the surface of the prepared electrode plate by using a scraper with the thickness of 30 microns, baking the electrode plate in a blast oven at the temperature of 80 ℃ for 4 hours, and then baking the electrode plate in a vacuum oven at the temperature of 60 ℃ for 12 hours.
And 5, cutting the processed pole piece, assembling the pole piece into a battery and performing electrochemical test.
Example 3
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, respectively weighing 0.8 g of activated carbon, 0.1 g of Super P and 0.1 g of PVDF, mixing the materials into 4 ml of N-methylpyrrolidone (NMP) solvent, stirring the mixture at a rotating speed of 400rpm by ball milling to form uniform electrode slurry, and coating the uniform electrode slurry on a carbon-coated aluminum foil with the thickness of 20 microns by using a scraper with the thickness of 100 microns.
And 2, putting the coated pole piece into a blast oven for drying for 2 hours at 90 ℃, then putting the pole piece into a vacuumizing oven for drying for 12 hours at 70 ℃, taking out the pole piece, and putting the pole piece on an electric double-roll machine for rolling and compacting, wherein the rolling thickness is set to 80% of that before rolling.
And step 3, sequentially adding 1 g of PVDF-HFP,0.025 g of carbon nano tube, 0.025 g of PVP and 3.95 g of N, N-Dimethylformamide (DMF) into a ball milling tank for ball milling and stirring at the rotating speed of 350 rpm.
And 4, scraping the stirred slurry on the surface of the prepared electrode plate by a scraper with the thickness of 50 microns, baking the electrode plate in a blast oven at the temperature of 80 ℃ for 3 hours, and then baking the electrode plate in a vacuum oven at the temperature of 60 ℃ for 12 hours.
And 5, cutting the processed pole piece, assembling the pole piece into a battery and performing electrochemical test.
Fig. 1 is an SEM image of the electrode surface of the supercapacitor after being treated by the typical electrospinning method in example 3, wherein fig. 1(a) is after treatment, fig. 1(b) is not after treatment, fig. 2 is a schematic view of charging and discharging of the supercapacitor after being treated by the typical electrospinning pole piece in example 3, and fig. 2(a) is a charging and discharging magnification diagram; FIG. 2(b) is a charge-discharge cycle diagram under a current density of 1A/g, and it can be seen from the diagram that the benefit of the present invention is that the surface of the original pole piece is spun, the thickness is only 1/10 or less of the thickness of the original pole piece, and the volume change of the pole piece is not affected, and meanwhile, the surface of the pole piece is a porous structure built by spinning, and the wettability of the electrolyte on the pole piece is not affected. The surface modification method not only improves the specific capacitance of the pole piece, but also improves the cycle performance and the multiplying power performance of the material.
Example 4
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, 0.8 g of activated carbon, 0.1 g of Super P and 0.1 g of PVDF are respectively weighed and mixed into 3.5 ml of N-methylpyrrolidone (NMP) solvent, and are stirred by ball milling at the rotating speed of 400rpm to form uniform electrode slurry, and the uniform electrode slurry is coated on a carbon-coated aluminum foil with the thickness of 20 microns by a scraper with the thickness of 200 microns.
And 2, putting the coated pole piece into a blast oven for baking for 2 hours at 100 ℃, then putting into a vacuumizing oven for baking for 10 hours at 80 ℃, taking out, and putting on an electric double-roll machine for rolling and compacting.
And step 3, sequentially adding 1 g of PVDF-HFP,0.025 g of carbon nano tubes, 0.25 g of PVP and 3.725 g of N, N-Dimethylformamide (DMF) into a ball milling tank for ball milling and stirring at the rotating speed of 300 rpm.
And 4, spinning the stirred slurry on the surface of the pole piece for 15 minutes by an electrostatic spinning method, putting the spun pole piece into a blast oven, baking for 3 hours at the temperature of 80 ℃, and then putting the pole piece into a vacuumizing oven, and baking for 12 hours at the temperature of 60 ℃.
And 5, cutting the processed pole piece, assembling the pole piece into a battery and performing electrochemical test.
Example 5
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, 0.8 g of activated carbon, 0.1 g of Super P and 0.1 g of PVDF are respectively weighed and mixed into 3 ml of N-methylpyrrolidone (NMP) solvent, and are stirred at the rotating speed of 400rpm by ball milling to form uniform electrode slurry, and the uniform electrode slurry is coated on a carbon-coated aluminum foil with the thickness of 18 microns by a scraper with the thickness of 200 microns.
And 2, putting the coated pole piece into a blast oven to be baked for 2 hours at 100 ℃, putting the pole piece into a vacuumizing oven to be baked for 12 hours at 80 ℃, taking out the pole piece, and putting the pole piece on an electric double-roll machine to be rolled and compacted, wherein the rolling thickness is set to 85% of that of the pole piece which is not rolled.
And step 3, sequentially adding 1 g of PVDF-HFP,0.01 g of graphene, 0.25 g of PVP and 3.74 g of N, N-Dimethylformamide (DMF) into a ball milling tank, and carrying out ball milling and stirring at the rotating speed of 300 rpm.
And 4, spinning the stirred slurry on the surface of the pole piece for 20 minutes by an electrostatic spinning method, putting the spun pole piece into a blast oven, baking for 2 hours at the temperature of 80 ℃, and putting the pole piece into a vacuumizing oven, and baking for 12 hours at the temperature of 60 ℃.
And 5, cutting the processed pole piece, assembling the pole piece into a battery and performing electrochemical test.
Example 6
The invention relates to a method for improving the performance of a super capacitor, which is implemented according to the following steps:
step 1, 0.8 g of activated carbon, 0.1 g of Super P and 0.1 g of PVDF are respectively weighed and mixed into 3.5 ml of N-methylpyrrolidone (NMP) solvent, and are stirred by ball milling at the rotating speed of 350rpm to form uniform electrode slurry, and the uniform electrode slurry is coated on a carbon-coated aluminum foil with the thickness of 18 microns by a 150-micron scraper.
And 2, putting the coated pole piece into a blast oven for baking for 2 hours at 90 ℃, then putting into a vacuumizing oven for baking for 10 hours at 80 ℃, taking out, and putting on an electric double-roll machine for rolling and compacting.
And step 3, sequentially adding 1 g of PVDF-HFP,0.025 g of carbon nano tubes, 0.25 g of PVP and 3.725 g of N, N-Dimethylformamide (DMF) into a ball milling tank for ball milling and stirring at the rotating speed of 350 rpm.
And 4, spinning the stirred slurry on the surface of the pole piece for 10 minutes by an electrostatic spinning method, putting the spun pole piece into a blast oven, baking for 2 hours at the temperature of 80 ℃, and putting the pole piece into a vacuumizing oven, and baking for 12 hours at the temperature of 60 ℃.
And 5, cutting the processed pole piece, assembling the pole piece into a battery and performing electrochemical test.
The above embodiments are all experiments implemented based on surface modification of the pole piece, and a layer of conductive polymer film is added on the surface of the pole piece under the condition that the volume of the pole piece is not affected, so that the specific capacitance of the pole piece is improved, the cycle performance and the rate performance of the pole piece are enhanced, and the possibility is provided for realizing a high-power long-cycle supercapacitor.

Claims (8)

1. A method for improving the performance of a super capacitor is characterized by comprising the following steps:
step 1, taking N-methyl pyrrolidone as a solvent, sequentially adding PVDF, Super P and active carbon, mixing to prepare slurry, and coating the slurry on a carbon-coated aluminum foil;
step 2, carrying out common drying on the coated carbon-coated aluminum foil, then carrying out vacuum drying, and finally rolling and compacting to prepare a pole piece;
step 3, taking N, N-dimethylformamide as a solvent and a mixture of PVDF-HFP, PVP and a conductive nano carbon material as a solute, then preparing the solvent and the solute into slurry through ball milling and stirring, and then coating the slurry on the surface of the pole piece prepared in the step 2;
coating the surface of the prepared pole piece by using a scraper coating method or an electrostatic spinning method in the step 3, wherein the conductive nano carbon material is formed by compounding conductive carbon black and graphene, or the conductive nano carbon material is formed by compounding conductive carbon black and a carbon nano tube, the conductive nano carbon material is in a powder structure, if the conductive nano carbon material is formed by compounding conductive carbon black and graphene, the graphene is in a single layer, an few layers or multiple layers, if the conductive nano carbon material is formed by compounding conductive carbon black and a carbon nano tube, the carbon nano tube is in a single-wall or multi-wall structure, when the scraper coating method is selected, PVP is used as a dispersing agent or a pore-forming agent, the molecular weight is less than 10000, when the electrostatic spinning method is selected, PVP is used as a spinning auxiliary agent, and the molecular weight is more than 100000;
and 4, putting the pole piece obtained in the step 3 into a blast oven for baking, performing vacuum drying, preparing a layer of polymer film on the surface of the pole piece, and finally cutting and assembling the pole piece to prepare the surface modified activated carbon-based supercapacitor.
2. The method for improving the performance of the supercapacitor according to claim 1, wherein the ratio of the solute composed of the activated carbon, the Super P and the PVDF and the N-methylpyrrolidone solvent in the step 1 is 1: 3-5, wherein the mass ratio of the activated carbon to the Super P to the PVDF is (8-7): (1-2): 1.
3. the method for improving the performance of the supercapacitor according to claim 1, wherein the coating thickness on the carbon-coated aluminum foil in the step 1 is 100-200 microns.
4. The method for improving the performance of the supercapacitor according to claim 1, wherein in the step 2, the carbon-coated aluminum foil after being coated is subjected to common drying at a temperature of 80-100 ℃ for 2-4 hours, the vacuum degree of vacuum drying is lower than-1 MPa, the temperature of vacuum drying is 70-100 ℃, and the time of vacuum drying is 10-12 hours.
5. The method for improving the performance of the supercapacitor according to claim 1, wherein the mass ratio of the solute formed by PVDF-HFP, PVP and the conductive nano carbon material to the N, N-dimethylformamide solvent in the step 3 is 1: 3-5, wherein the mass percentage of PVDF-HFP, PVP and the conductive nano carbon material is 10% -25%: 5% -10%: 0.25 to 0.75 percent.
6. The method for improving the performance of the supercapacitor according to claim 1, wherein the stirring speed in the step 3 is 300-400 rpm.
7. The method for improving the performance of the supercapacitor according to claim 1, wherein the thickness of the polymer film in the step 4 is less than or equal to 1/10 of the thickness of the pole piece.
8. The method for improving the performance of the supercapacitor according to claim 1, wherein the vacuum degree of vacuum drying in the step 4 is lower than-1 MPa, the temperature of vacuum drying is 70-100 ℃, and the time of vacuum drying is 10-12 hours.
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