CN113363082A - Fluorine modified activated carbon electrode surface composite treatment method and application thereof - Google Patents

Fluorine modified activated carbon electrode surface composite treatment method and application thereof Download PDF

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CN113363082A
CN113363082A CN202110622106.5A CN202110622106A CN113363082A CN 113363082 A CN113363082 A CN 113363082A CN 202110622106 A CN202110622106 A CN 202110622106A CN 113363082 A CN113363082 A CN 113363082A
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electrode
activated carbon
binder
carbon
treatment
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CN113363082B (en
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吴晓东
韩晓刚
钱荣成
白宇鸽
李曼妮
陈韦蒙
李鸿杰
杨恒瑞
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Hangzhou Yangming New Energy Equipment 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
    • H01G11/22—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
    • H01G11/84—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

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Abstract

The invention discloses a fluorine modified activated carbon electrode surface composite treatment method and application thereof, wherein a binder, a conductive agent and activated carbon are added into a dispersing agent, and the mixture is magnetically stirred until the binder is dissolved to obtain mixed slurry; performing ball milling treatment on the mixed slurry to obtain electrode slurry; coating the electrode slurry on a carbon-coated aluminum foil, and sequentially carrying out blast drying and vacuum drying until a solvent is dried to obtain an electrode slice; treating the surface of the electrode slice by adopting a low-temperature plasma technology; and depositing metal oxide with the thickness of 1-10 nm on the electrode sheet after surface treatment by adopting an atomic layer deposition technology to obtain the fluorine modified activated carbon electrode subjected to composite treatment. The method is simple, efficient and rapid, can be used for preparing the high-energy-density activated carbon electrode super capacitor in batches, and has good market application prospect.

Description

Fluorine modified activated carbon electrode surface composite treatment method and application thereof
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a fluorine modified activated carbon electrode surface composite treatment method and application thereof.
Background
At present, carbon material activated carbon with high specific surface area is mainly used for a symmetrical electrode double-layer capacitor. However, the energy density of the electric double-layer supercapacitor is much lower than that of the secondary battery, and it is difficult to meet the energy demand of the load such as large-scale power equipment and electric vehicles, and the use scenario of the supercapacitor is greatly limited. Therefore, research for improving the energy density of the super capacitor is particularly important. According to this, increasing the specific capacitance of the electrode material and widening the voltage window of the supercapacitor can both increase its energy density.
The low-temperature plasma technology is a chemical treatment method for exciting low-temperature plasma by utilizing a radio frequency power supply. The low-temperature plasma has small destructive effect on the precursor in the reaction process, and is widely applied to the fields of catalysis, electronic devices and the like.
Atomic layer deposition is a method in which a precursor gas and a reaction gas are injected into a reaction chamber in a pulse manner, chemisorption is performed on the surface of a substrate, a reaction is performed, and a substance is plated on the surface of the substrate in the form of a monomolecular film. The surface reaction process of atomic layer deposition is self-limiting, the progress of the reaction is limited by the dose of the precursor or activator, and the reaction automatically stops when these two substances are depleted. The self-limiting atomic layer deposition of the reaction has the advantages of controllable reaction period number and film deposition thickness, capability of performing material treatment at a lower temperature and the like. The technology is mainly applied to the fields of transistor material preparation, energy storage devices, catalysis and the like at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a fluorine modified activated carbon electrode surface composite treatment method and application thereof aiming at the defects in the prior art, so that the specific capacitance of an electrode material is effectively improved; and the metal oxide layer can increase the wettability of the electrode to the electrolyte and improve the multiplying power performance of the super capacitor.
The invention adopts the following technical scheme:
a fluorine modified activated carbon electrode surface composite treatment method comprises the following steps:
s1, adding a binder, a conductive agent and activated carbon into the dispersing agent, and magnetically stirring until the binder is dissolved to obtain mixed slurry;
s2, performing ball milling treatment on the mixed slurry obtained in the step S1 to obtain electrode slurry;
s3, coating the electrode slurry obtained in the step S2 on a carbon-coated aluminum foil, and sequentially carrying out blast drying and vacuum drying until a solvent is dried to obtain an electrode slice;
s4, processing the surface of the electrode slice obtained in the step S3 by adopting a low-temperature plasma technology;
and S5, depositing metal oxide with the thickness of 1-10 nm on the electrode sheet subjected to the surface treatment in the step S4 by adopting an atomic layer deposition technology to obtain the fluorine modified activated carbon electrode subjected to the composite treatment.
Specifically, in step S1, the mass ratio of the dispersing agent to the binder is (3-6): 1; the mass ratio of the activated carbon, the conductive agent and the binder is (6-9): (0.5-2).
Further, the dispersing agent is N-methyl pyrrolidone, and the binder comprises one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose and styrene butadiene rubber; the conductive agent is one of graphene, Super P, Ketjen black or carbon nano-tubes.
Specifically, in step S1, the binder is added into the dispersant, the stirring speed is controlled to be 300-500 r/min, and the stirring time is 1-3 h; and then adding a conductive agent and active carbon at room temperature, and controlling the stirring speed to be 300-500 r/min and the stirring time to be 12-15 h.
Specifically, in step S2, the ball milling time is 2-10 min, and the vibration frequency of the ball milling is 30-150 Hz.
Specifically, in step S3, the thickness of the electrode paste coated on the carbon-coated aluminum foil is 50 to 200 μm.
Specifically, in the step S3, the temperature of the forced air drying is 60-100 ℃, and the drying time is 2-4 hours; the temperature of vacuum drying is 60-120 ℃, and the drying time is 8-16 h.
Specifically, in step S4, carbon tetrafluoride gas or fluorine gas is used as a gas source of the low-temperature plasma, the gas pressure of the gas source is maintained at 20 to 80Pa, the power supply frequency is controlled at 13.56MHz, the power supply power in the treatment process is controlled at 60 to 150W, and the surface of the electrode sheet is treated for 30S to 10 min.
Specifically, in step S5, the metal oxide is TiO2Or Al2O3。
The invention also provides the application of the fluorine modified activated carbon electrode treated by the fluorine modified activated carbon electrode surface composite treatment method in the super capacitor.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention discloses a fluorine modified activated carbon electrode surface composite treatment method, and relates to an electrode for a super capacitor, wherein a metal oxide deposition layer and a fluorine modified layer are generated on the surface of an electrode material or an electrode pole piece to jointly improve the working voltage and specific capacitance of the super capacitor, so that the energy density of the super capacitor is improved, and the metal oxide deposition layer can provide dielectric capacitance for the super capacitor; the fluorine modified layer can increase the adsorption capacity of the electrode material to ions in the electrolyte, so that the specific capacitance of the supercapacitor is increased, and the metal oxide deposition layer and the fluorine modified layer can prevent side chain parasitic reaction between the active site of the electrode material and the electrolyte, so that the supercapacitor still has long service life under high voltage, and the voltage window of the supercapacitor is effectively widened; the method has the advantages that the atomic layer deposition and low-temperature plasma technology are adopted for surface treatment, the damage effect on electrode materials in the treatment process is small, the thickness of a deposited layer is thin, the quality change of the electrode can be ignored, the preparation method is time-saving, efficient and controllable, the voltage window of the super capacitor can be improved by about 1V, and the specific capacitance can be improved by about 25%.
Further, the mass ratio of the dispersing agent to the binder is (3-6): 1, the binder can be dissolved in the dispersing agent, the mass ratio of the activated carbon to the conductive agent to the binder is (6-9): (0.5-2), and the moderate concentration of the slurry after the activated carbon and the conductive agent are added and the proper quality of the active substances can be ensured.
Furthermore, N-methyl pyrrolidone is used as the dispersing agent, and is a conventional dispersing agent when the super capacitor electrolyte is an organic electrolyte. The binder PVDF can swell in N-methyl pyrrolidone, allowing better bonding of the electrode materials together. The conductive agent uses Super P, and is a conventional conductive agent for a Super capacitor with good conductivity.
Furthermore, a magnetic stirrer is used for stirring, the rotating speed is 300-500 r/min, and the binder and the conductive agent can be uniformly distributed in the dispersing agent.
Further, ball milling is carried out on the slurry, the processing time is 2-10 min, the vibration frequency of ball milling processing is 30-150 Hz, the particle size of particles in the slurry can be effectively reduced, and the prepared slurry is uniform and has no granular sensation.
Furthermore, the thickness of the electrode slurry coated on the carbon-coated aluminum foil is 50-200 microns, so that the quality of active materials on the electrode can be guaranteed, and the electrode plates can be prevented from cracking, falling powder and the like. Furthermore, the drying temperature of the blast air is 60-100 ℃, the drying time is 2-4 h, and most of the dispersing agent N-methyl pyrrolidone and water in the electrode can be effectively removed; the vacuum drying temperature is 60-120 ℃, the drying time is 8-16 h, the moisture contained in the electrode can be completely removed, and the influence on the performance of the super capacitor is avoided.
Further, carbon tetrafluoride gas or fluorine gas is used as a gas source of the low-temperature plasma, the gas pressure of the gas source is maintained at 20-80 Pa, the power frequency is controlled to be 13.56MHz, the power source power in the treatment process is 60-150W, the surface of the electrode plate is treated for 30 s-10 min, a fluorine-containing passivation layer is generated on the surface of the electrode, the electrode can be effectively protected in the charging and discharging process, and the working voltage of the super capacitor is increased.
Further, a metal oxide layer (TiO) is generated on the electrode by atomic layer deposition2Or Al2O3) Can suppress electricityParasitic side chain reaction between the active site of the electrode material and the electrolyte protects the electrode and improves the working voltage of the super capacitor.
In conclusion, the method is simple, efficient and rapid, can be used for preparing the high-energy-density activated carbon electrode super capacitor in batches, and has good market application prospect.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic diagram showing the change condition of a dynamic contact angle of 0-1 s after an electrolyte DLC306 is dripped into a pole piece;
FIG. 2 shows that 2nm TiO is respectively deposited on atomic layers after low-temperature plasma treatment for 9min2And 2nm Al2O3Typical CV curves for supercapacitors assembled with untreated electrodes;
FIG. 3 shows that 2nm TiO is deposited on atomic layers respectively after low-temperature plasma treatment for 9min2And 2nm Al2O3The change condition of the constant current charge-discharge capacity of the super capacitor assembled with the untreated electrode is shown at 8000 times under 3.5V and 1A/g;
FIG. 4 shows that 2nm TiO is deposited on atomic layers respectively after low-temperature plasma treatment for 9min2And 2nm Al2O3Specific capacitance plot of different current densities at 3.5V for the supercapacitor assembled with the untreated electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
Various structural schematics according to the disclosed embodiments of the invention are shown in the drawings. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of various regions, layers and their relative sizes and positional relationships shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, according to actual needs.
The invention provides a fluorine modified activated carbon electrode surface composite treatment method, which utilizes atomic layer deposition and low-temperature plasma technology to form a metal oxide deposition layer and a fluorine modified layer on the surface of an electrode active material or an electrode plate of a super capacitor, wherein the metal oxide deposition layer and the fluorine modified layer jointly have a protection effect on the electrode material, so that the activated carbon-based super capacitor still has long cycle life under high voltage, and the working voltage of the super capacitor is effectively improved; meanwhile, the metal oxide layer can also provide dielectric capacitance for the super capacitor, so that the specific capacitance of the electrode material is effectively improved; and the metal oxide layer can increase the wettability of the electrode to the electrolyte DLC306, and the multiplying power performance of the super capacitor is improved.
The invention discloses a fluorine modified activated carbon electrode surface composite treatment method, which comprises the following steps:
s1, adding the binder, the conductive agent and the activated carbon into the dispersing agent, and stirring by using a magnetic stirrer until the binder is dissolved;
the dispersing agent is N-methyl pyrrolidone, and the binder comprises but is not limited to one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose and styrene butadiene rubber.
Firstly, adding a binder into a dispersing agent, and controlling the stirring speed to be 300-500 r/min and the stirring time to be 1-3 h; and then adding a conductive agent and active carbon at room temperature, and controlling the stirring speed to be 300-500 r/min and the stirring time to be 12-15 h.
The mass ratio of the dispersing agent to the binder is (3-6) to 1; the mass ratio of the dispersing agent to the binder is such that the binder can be dissolved in the dispersing agent and the slurry is moderately concentrated, viscous and non-caking after the addition of the activated carbon and the conductive agent.
The conductive agent is one of graphene, Super P, Ketjen black or carbon nano-tubes.
The mass ratio of the activated carbon, the conductive agent and the binder is (6-9): (0.5-2).
S2, performing ball milling treatment on the slurry obtained in the step S1 by using a micro ball mill;
during ball milling, the vibration frequency of the micro ball mill is 30-150 Hz, and the ball milling time is 2-10 min; the slurry after ball milling has no granular feeling and uniform concentration.
S3, coating the electrode slurry obtained in the step S2 on a carbon-coated aluminum foil, and sequentially putting the carbon-coated aluminum foil into a blast drying oven and a vacuum drying oven to dry the solvent;
the coating thickness is 50 to 200 μm. The coating thickness should be appropriate, neither too thick to cause cracking of the electrode slurry after drying, nor too thin to result in bare current collector and reduced energy density of the device.
When the electrode solvent is dried, the temperature of the blast drying oven is set to be 60-100 ℃, and the drying time is 2-4 h; the temperature of the vacuum drying oven is set to be 60-120 ℃, and the drying time is 8-16 h.
S4, processing the surface of the electrode slice obtained in the step S3 by using a low-temperature plasma technology;
the low-temperature plasma gas source uses carbon tetrafluoride gas or fluorine gas.
In the low-temperature plasma treatment process, the air pressure is maintained at 20-80 Pa.
The frequency of a power supply used in the low-temperature plasma treatment process is 13.56MHz, and the power supply power in the treatment process is 60-150W.
The low-temperature plasma treatment time is 30 s-10 min.
And S5, depositing metal oxide on the surface of the electrode slice or the electrode active material obtained in the step S4 by using an atomic layer deposition technology to obtain the fluorine modified activated carbon electrode.
Atomic layer deposition of metal oxides to TiO2Or Al2O3One kind of (1).
The thickness of the atomic layer deposition metal oxide is 1-10 nm.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 2600 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 2 hours at the speed of 400r/min by using a magnetic stirrer until polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of conductive agent Super P and 4000mg of active carbon, adding into the system, and stirring at the rotating speed of 400r/min for 12h at room temperature; and finally, ball milling for 6min by using a micro ball mill, wherein the vibration frequency is 50Hz, and obtaining uniform electrode slurry.
And (3) coating the electrode slurry on the carbon-coated aluminum foil by using a scraper with the diameter of 100 micrometers, drying the carbon-coated aluminum foil in an air-blast drying oven at the temperature of 80 ℃ for 2 hours, and drying the carbon-coated aluminum foil in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain the pole piece.
And (3) putting the pole piece into a low-temperature plasma processing device, setting the gas in a processing cabin to be carbon tetrafluoride, setting the power of a power supply to be 80W, setting the air pressure in the cabin to be 80Pa in the processing process, and processing the pole piece for 9 min.
Followed by depositing TiO 2nm thick on the low temperature plasma treated electrode plate using atomic layer deposition2。
Example 2
Weighing 2200 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 3h at the speed of 300r/min by using a magnetic stirrer until polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of conductive agent Super P and 4000mg of active carbon, adding into the system, and stirring at the rotating speed of 300r/min for 12h at room temperature; and finally, ball milling for 3min by using a micro ball mill, wherein the vibration frequency is 30Hz, and obtaining uniform electrode slurry.
And (3) coating the electrode slurry on the carbon-coated aluminum foil by using a 150-micron scraper, drying for 4 hours in an air-blast drying oven at 60 ℃, and drying for 16 hours in a vacuum drying oven at 60 ℃ to obtain the pole piece.
And (3) putting the pole piece into a low-temperature plasma processing device, setting the power of a power supply to be 100W, setting the air pressure in the chamber to be 60Pa in the processing process, and processing the pole piece for 3 min.
Then, Al with the thickness of 1nm is deposited on the electrode plate after the low-temperature plasma treatment by using the atomic layer deposition2O3。
Example 3
Weighing 2400 mu L of N-methyl pyrrolidone, weighing 400mg of polyvinylidene fluoride, adding polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 2 hours at the speed of 400r/min by using a magnetic stirrer until polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 400mg of conductive agent Super P and 4000mg of active carbon, adding into the system, and stirring at the rotating speed of 400r/min for 13h at room temperature; and finally, ball milling for 2min by using a micro ball mill, wherein the vibration frequency is 150Hz, and obtaining uniform electrode slurry.
And (3) coating the electrode slurry on the carbon-coated aluminum foil by using a scraper with the diameter of 200 mu m, drying the carbon-coated aluminum foil in an air-blast drying oven at the temperature of 90 ℃ for 2h, and drying the carbon-coated aluminum foil in a vacuum drying oven at the temperature of 120 ℃ for 16h to obtain the pole piece.
And (3) putting the pole piece into a low-temperature plasma processing device, setting the power of a power supply to be 150W, setting the air pressure in the chamber to be 80Pa in the processing process, and processing the pole piece for 1 min.
Followed by depositing TiO 10nm thick on the low temperature plasma treated electrode plate using atomic layer deposition2。
Example 4
Weighing 2800 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 1h at the speed of 500r/min by using a magnetic stirrer until polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of conductive agent Super P and 4000mg of active carbon, adding into the system, and stirring at the rotating speed of 500r/min for 14h at room temperature; and finally, ball milling for 8min by using a micro ball mill, wherein the vibration frequency is 120Hz, and obtaining uniform electrode slurry.
And (3) coating the electrode slurry on the carbon-coated aluminum foil by using a scraper with the thickness of 50 micrometers, drying the carbon-coated aluminum foil in an air-blast drying oven at the temperature of 100 ℃ for 2 hours, and drying the carbon-coated aluminum foil in a vacuum drying oven at the temperature of 100 ℃ for 8 hours to obtain the pole piece.
And (3) putting the pole piece into a low-temperature plasma processing device, setting the gas in a processing cabin to be carbon tetrafluoride, setting the power supply to be 60W, setting the air pressure in the cabin to be 80Pa in the processing process, and processing the pole piece for 30 s.
Followed by depositing TiO 3nm thick on the low temperature plasma treated electrode plate using atomic layer deposition2。
Example 5
Weighing 3000 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 3h at the speed of 450r/min by using a magnetic stirrer until polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of conductive agent Super P and 3800mg of active carbon, adding into the system, and stirring at the rotation speed of 400r/min for 15h at room temperature; and finally, ball milling for 10min by using a micro ball mill, wherein the vibration frequency is 50Hz, and obtaining uniform electrode slurry.
And (3) coating the electrode slurry on the carbon-coated aluminum foil by using a scraper with the diameter of 100 micrometers, drying the carbon-coated aluminum foil in an air-blast drying oven at the temperature of 80 ℃ for 3 hours, and drying the carbon-coated aluminum foil in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain the pole piece.
And (3) putting the pole piece into a low-temperature plasma processing device, setting the power of a power supply to be 60W, setting the air pressure in the chamber to be 20Pa in the processing process, and processing the pole piece for 10 min.
Followed by depositing TiO 5nm thick on the low temperature plasma treated electrode plate using atomic layer deposition2。
And testing and analyzing the processed pole piece and the super capacitor.
FIG. 1 shows the change of the dynamic contact angle of 0-1 s after the pole piece is dripped with the electrolyte DLC 306. The contact angle of the untreated AC electrode decreased from 26.3 ° at 0s to 5.4 ° at 1 s. Respectively depositing 2nm Al on atomic layers after low-temperature plasma treatment for 9min2O3Electrode Al of2O3the/F @ AC contact angle was reduced from 28.1 to 26.5. The electrode 9MF contact angle for only low temperature plasma treatment 9min was reduced to 146.5 ° to 117.6 °. The surface wettability of the electrode modified only by fluorine is poor due to the influence of the F element, and the surface wettability of the fluorine modified electrode deposited by the atomic layer is obviously improved, so that the super capacitor is favorable for charging and discharging under high current, and has better rate performance.
FIG. 2 shows that 2nm TiO is respectively deposited on atomic layers after low-temperature plasma treatment for 9min2And 2nm Al2O3A typical CV curve for a supercapacitor assembled with untreated electrodes at a sweep rate of 20 mV/s. The CV curves of the three groups of supercapacitors have no oxidation reduction peak, fluctuation, wrinkle and the like, and the result shows that the supercapacitor energy storage mode assembled by the electrodes subjected to atomic layer deposition and low-temperature plasma treatment mainly depends on an electric double layer.
FIG. 3 shows atomic layer deposition after low temperature plasma treatment for 9minTiO 2nm in volume2And 2nm of Al2O3And 8000 constant current charge and discharge capacity changes of the super capacitor assembled with the untreated electrode under the conditions of 3.5V and 1A/g. AC. TiO 22/F @ AC and Al2O3The specific capacitance of the/F @ AC three-group super capacitor is 97.23%, 100.00% and 99.34% of 1A/g at the current density of 10A/g respectively. Due to the improvement of the wettability of the electrode surface, the multiplying power performance of the two groups of capacitors with the electrode surfaces subjected to double-layer treatment is close to 100.00 percent and is superior to that of the AC capacitor without surface treatment.
FIG. 4 shows that TiO 2nm is deposited on atomic layers respectively after low-temperature plasma treatment for 9min2And 2nm of Al2O3Specific capacitance at 3.5V for different current densities for supercapacitors assembled with untreated electrodes. The initial specific capacitance of the AC super capacitor is 80.64F/g, the specific capacitance after 8000 times of charging and discharging is 56.02F/g, and the capacity retention rate is 69.46%. TiO 22The initial specific capacitance of the/F @ AC super capacitor is 104.06F/g, which is 29.04% higher than that of the AC super capacitor; after 8000 times of charging and discharging, the specific capacitance value is reduced to 93.53F/g, and the capacity retention rate is 89.88%. Al (Al)2O3The specific capacitance of the/F @ AC supercapacitor is reduced from 102.31F/g to 92.18F/g, the initial capacity is improved by 26.87% compared with that of the AC supercapacitor, and the capacity retention rate is 90.10%. TiO 22/F @ AC and Al2O3The capacity of the/F @ AC super capacitor is kept stable in 8000 cycles, and the service life of the capacitor is obviously longer than that of a control group.
In summary, according to the fluorine modified activated carbon electrode surface composite treatment method and the application thereof, the atomic layer deposition technology and the low-temperature plasma technology are applied to the preparation of the supercapacitor electrode, the metal oxide deposition layer and the fluorine modified layer on the electrode surface together slow down the deterioration of the active material, and improve the specific capacitance of the electrode material, so that the supercapacitor can have long cycle life and high rate performance under a high voltage of 3.5V, and the energy density of the activated carbon-based supercapacitor is effectively improved while the power density of the activated carbon-based supercapacitor is maintained.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. A fluorine modified activated carbon electrode surface composite treatment method is characterized by comprising the following steps:
s1, adding a binder, a conductive agent and activated carbon into the dispersing agent, and magnetically stirring until the binder is dissolved to obtain mixed slurry;
s2, performing ball milling treatment on the mixed slurry obtained in the step S1 to obtain electrode slurry;
s3, coating the electrode slurry obtained in the step S2 on a carbon-coated aluminum foil, and sequentially carrying out blast drying and vacuum drying until a solvent is dried to obtain an electrode slice;
s4, processing the surface of the electrode slice obtained in the step S3 by adopting a low-temperature plasma technology;
and S5, depositing metal oxide with the thickness of 1-10 nm on the electrode sheet subjected to the surface treatment in the step S4 by adopting an atomic layer deposition technology to obtain the fluorine modified activated carbon electrode subjected to the composite treatment.
2. The method according to claim 1, wherein in step S1, the mass ratio of the dispersing agent to the binder is (3-6): 1; the mass ratio of the activated carbon, the conductive agent and the binder is (6-9): (0.5-2).
3. The method of claim 2, wherein the dispersant is N-methyl pyrrolidone, and the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and styrene butadiene rubber; the conductive agent is one of graphene, Super P, Ketjen black or carbon nano-tubes.
4. The method according to claim 1, wherein in step S1, the binder is added into the dispersant, the stirring speed is controlled to be 300-500 r/min, and the stirring time is controlled to be 1-3 h; and then adding a conductive agent and active carbon at room temperature, and controlling the stirring speed to be 300-500 r/min and the stirring time to be 12-15 h.
5. The method according to claim 1, wherein in step S2, the ball milling time is 2-10 min, and the vibration frequency of the ball milling is 30-150 Hz.
6. The method according to claim 1, wherein the thickness of the electrode paste applied to the carbon-coated aluminum foil in step S3 is 50 to 200 μm.
7. The method according to claim 1, wherein in step S3, the temperature of forced air drying is 60-100 ℃, and the drying time is 2-4 h; the temperature of vacuum drying is 60-120 ℃, and the drying time is 8-16 h.
8. The method according to claim 1, wherein in step S4, the carbon tetrafluoride gas or fluorine gas is used as a gas source of the low-temperature plasma, the gas pressure of the gas source is maintained at 20 to 80Pa, the power supply frequency is controlled at 13.56MHz, the power supply power during the treatment process is controlled at 60 to 150W, and the surface of the electrode sheet is treated for 30S to 10 min.
9. The method of claim 1, wherein in step S5, the metal oxide is TiO2Or Al2O3。
10. Use of a fluorine modified activated carbon electrode treated according to the method of claim 1 in a supercapacitor.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2006068291A1 (en) * 2004-12-21 2006-06-29 Teijin Limited Electric double layer capacitor
US20110292571A1 (en) * 2010-05-27 2011-12-01 Kishor Purushottam Gadkaree Halogenated activated carbon materials for high energy density ultracapacitors
DE202015104572U1 (en) * 2014-12-29 2015-09-17 Ningbo Csr New Energy Technology Co., Ltd. A hybrid supercapacitor
CN110957143A (en) * 2019-12-03 2020-04-03 西安交通大学 Electrode for supercapacitor and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006068291A1 (en) * 2004-12-21 2006-06-29 Teijin Limited Electric double layer capacitor
US20110292571A1 (en) * 2010-05-27 2011-12-01 Kishor Purushottam Gadkaree Halogenated activated carbon materials for high energy density ultracapacitors
DE202015104572U1 (en) * 2014-12-29 2015-09-17 Ningbo Csr New Energy Technology Co., Ltd. A hybrid supercapacitor
CN110957143A (en) * 2019-12-03 2020-04-03 西安交通大学 Electrode for supercapacitor and preparation method and application thereof

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