CN113363082B - Fluorine modified active carbon electrode surface composite treatment method and application thereof - Google Patents

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

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CN113363082B
CN113363082B CN202110622106.5A CN202110622106A CN113363082B CN 113363082 B CN113363082 B CN 113363082B CN 202110622106 A CN202110622106 A CN 202110622106A CN 113363082 B CN113363082 B CN 113363082B
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electrode
carbon
activated carbon
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fluorine modified
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CN113363082A (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 magnetic stirring is carried out until the binder is dissolved to obtain mixed slurry; ball milling the mixed slurry to obtain electrode slurry; coating electrode slurry on a carbon-coated aluminum foil, and sequentially carrying out forced air drying and vacuum drying until a solvent is dried to obtain an electrode slice; the surface of the electrode plate is treated by adopting a low-temperature plasma technology; and depositing metal oxide with the thickness of 1-10 nm on the electrode slice after the surface treatment by adopting an atomic layer deposition technology to obtain the fluorine modified activated carbon electrode subjected to the composite treatment. The method is simple, efficient and quick, can prepare the active carbon electrode super capacitor with high energy density in batches, and has good market application prospect.

Description

Fluorine modified active 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
Currently, symmetrical electrode double layer capacitors mainly use activated carbon, which is a carbon material with a high specific surface area. However, the energy density of the double-layer super capacitor is far lower than that of the secondary battery, so that the energy demand of loads such as large power equipment and electric automobiles is difficult to meet, and the use of the super capacitor is greatly limited. Therefore, research to increase the energy density of supercapacitors is particularly important. According to the method, the specific capacitance of the electrode material is increased, and the voltage window of the supercapacitor is widened, so that the energy density of the supercapacitor can be improved.
The low-temperature plasma technology is a chemical treatment method for exciting low-temperature plasma by using a radio frequency power supply. The low-temperature plasma has small damage to 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 precursor gas and reaction gas are injected into a reaction chamber in a pulsed manner, chemisorption occurs on the surface of a substrate, and a reaction is performed to plate a substance on the surface of the substrate in the form of a monolayer. The surface reaction process of atomic layer deposition is self-limiting, and the progress of the reaction is limited by the dosage of precursor or activator, and the reaction automatically stops when the two substances are consumed. The self-limiting atomic layer deposition has the advantages of controllable reaction cycle number and film deposition thickness, capability of carrying out 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
Aiming at the defects in the prior art, the invention provides a fluorine modified activated carbon electrode surface composite treatment method and application thereof, which effectively improves the specific capacitance of electrode materials; and the metal oxide layer can increase the wettability of the electrode to the electrolyte, so that the rate capability of the supercapacitor is improved.
The invention adopts the following technical scheme:
a fluorine modified active carbon electrode surface composite treatment method comprises the following steps:
s1, adding a binder, a conductive agent and active carbon into a 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 forced air drying and vacuum drying until the solvent is dried to obtain an electrode slice;
s4, treating the surface of the electrode plate 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 slice 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 the step S1, the mass ratio of the dispersing agent to the binder is (3-6): 1; the mass ratio of the active 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 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 tube.
Specifically, in the step S1, firstly, a binder is added into a dispersing agent, the stirring speed is controlled to be 300-500 r/min, and the stirring time is controlled to be 1-3 h; then adding conductive agent and active carbon under the condition of room temperature, controlling the stirring speed to be 300-500 r/min, and stirring for 12-15 h.
Specifically, in the step S2, the time of the ball milling treatment is 2-10 min, and the vibration frequency of the ball milling treatment is 30-150 Hz.
Specifically, in step S3, the thickness of the electrode slurry coated on the carbon-coated aluminum foil is 50-200 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 low-temperature plasma, the gas pressure of the gas source is maintained at 20-80 Pa, the power frequency is controlled at 13.56MHz, the power in the treatment process is 60-150W, and the surface of the electrode plate is treated for 30S-10 min.
Specifically, in step S5, the metal oxide is TiO 2 Or Al 2 O 3 。
The invention also discloses an application of the fluorine modified activated carbon electrode treated according to the surface composite treatment method of the fluorine modified activated carbon electrode in a super capacitor.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a fluorine modified active carbon electrode surface composite treatment method, which 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, so that the working voltage and specific capacitance of the super capacitor are improved together, the energy density of the super capacitor is improved, and the metal oxide deposition layer can provide a dielectric capacitor 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 can still have long service life under high voltage, and the voltage window of the supercapacitor is effectively widened; the electrode prepared by adopting the scheme can improve the voltage window of the super capacitor by about 1V and the specific capacitance by about 25%.
Further, the mass ratio of the dispersant to the binder is (3-6): 1, the binder can be dissolved in the dispersing agent, the mass ratio of the active carbon to the conductive agent to the binder is (6-9) (0.5-2), the moderate concentration of the slurry after the active carbon and the conductive agent are added can be ensured, and the quality of the active substance is proper.
Further, N-methyl pyrrolidone is used as the dispersing agent, and when the supercapacitor electrolyte is an organic electrolyte, the dispersing agent is a conventional dispersing agent. The binder PVDF can swell in N-methylpyrrolidone, so that the electrode materials are better bonded together. Super P is used as the conductive agent, and is a conventional conductive agent for Super capacitor with good conductivity.
Further, the adhesive and the conductive agent can be uniformly distributed in the dispersing agent by stirring with a magnetic stirrer at a rotating speed of 300-500 r/min.
Furthermore, ball milling is used for the slurry, the treatment time is 2-10 min, the vibration frequency of ball milling treatment 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 particle feel.
Furthermore, the thickness of the electrode slurry coated on the carbon-coated aluminum foil is 50-200 mu m, so that the conditions of cracking, powder falling and the like of the electrode plate can be prevented while the quality of the active material on the electrode is ensured. Further, the blast drying temperature is 60-100 ℃ and the drying time is 2-4 hours, so that most of dispersing agent N-methyl pyrrolidone and water in the electrode can be effectively removed; the vacuum drying temperature is 60-120 ℃ and the drying time is 8-16 h, so that the moisture contained in the electrode can be completely removed, and the influence on the performance of the supercapacitor is avoided.
Furthermore, carbon tetrafluoride gas or fluorine gas is used as a gas source of low-temperature plasma, the gas pressure of the gas source is maintained at 20-80 Pa, the power frequency is controlled at 13.56MHz, the power in the treatment process is 60-150W, and the surface of the electrode plate is treated for 30 s-10 min, so that a fluorine-containing passivation layer is generated on the surface of the electrode, the electrode can be effectively protected in the charging and discharging processes, and the working voltage of the supercapacitor is improved.
Further, a metal oxide layer (TiO 2 Or Al 2 O 3 ) The parasitic side chain reaction between the active site of the electrode material and the electrolyte can be inhibited, the electrode is protected, and the working voltage of the supercapacitor is improved.
In conclusion, the method is simple, efficient and quick, can be used for preparing the active carbon electrode super capacitor with high energy density in batches, and has good market application prospect.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic diagram of the change of the dynamic contact angle of 0-1 s after the electrolyte DLC306 is added to the pole piece in a dropwise manner;
FIG. 2 shows atomic layer deposition of 2nm TiO after low temperature plasma treatment for 9min 2 And 2nm Al 2 O 3 Typical CV plots for supercapacitors assembled with untreated electrodes;
FIG. 3 is a graph showing atomic layer deposition of 2nm TiO after 9min of low temperature plasma treatment 2 And 2nm Al 2 O 3 The super capacitor assembled with the untreated electrode is subjected to 8000 times of constant current charge-discharge capacity change condition diagrams under the conditions of 3.5V and 1A/g;
FIG. 4 is a graph showing atomic layer deposition of 2nm TiO after 9min of low temperature plasma treatment 2 And 2nm Al 2 O 3 Specific capacitance plots for different current densities at 3.5V for supercapacitors assembled with untreated electrodes.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "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 is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification 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 the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
Various structural schematic diagrams according to the disclosed embodiments of the present invention are shown in the accompanying drawings. The figures are not drawn to scale, wherein certain details are exaggerated for clarity of presentation and may have been omitted. The shapes of the various regions, layers and their relative sizes, positional relationships shown in the drawings are merely exemplary, may in practice deviate due to manufacturing tolerances or technical limitations, and one skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions as actually required.
The invention provides a fluorine modified active carbon electrode surface composite treatment method, which utilizes atomic layer deposition and low-temperature plasma technology to enable the surface of an electrode active material or an electrode plate of a super capacitor to form a metal oxide deposition layer and a fluorine modified layer, and the metal oxide deposition layer and the fluorine modified layer jointly generate a protection effect on the electrode material, so that the active 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, so that the rate capability of the supercapacitor is improved.
The invention discloses a fluorine modified activated carbon electrode surface composite treatment method, which comprises the following steps:
s1, adding a binder, a conductive agent and active carbon into a 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 one or a mixture of more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose and styrene butadiene rubber.
Firstly, adding a binder into a dispersing agent, controlling the stirring speed to be 300-500 r/min, and stirring for 1-3 h; then adding conductive agent and active carbon under the condition of room temperature, controlling the stirring speed to be 300-500 r/min, and stirring for 12-15 h.
The mass ratio of the dispersant to the binder is (3-6) 1; the mass ratio of dispersant to binder should be such that the binder can be dissolved in the dispersant and the slurry concentration is moderate after the addition of activated carbon and conductive agent, viscous but not caking.
The conductive agent is one of graphene, super P, ketjen black or carbon nano tube.
The mass ratio of the active carbon, the conductive agent and the binder is (6-9) (0.5-2).
S2, ball milling is carried out on the slurry obtained in the step S1 by using a miniature ball mill;
the vibration frequency of the miniature ball mill is 30-150 Hz during ball milling, and the ball milling time is 2-10 min; the slurry after ball milling has no granular feel 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 box and a vacuum drying box to dry the solvent;
the coating thickness is 50-200 mu m. The coating thickness should be suitable to not be too thick to cause cracking of the electrode paste after drying nor too thin, resulting in bare current collector and reduced device energy density.
When the electrode solvent is dried, the temperature of the blast drying box 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, treating the surface of the electrode plate 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 low temperature plasma treatment process uses a power supply frequency of 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 plate or the electrode active material obtained in the step S4 by using an atomic layer deposition technology to obtain the fluorine modified active carbon electrode.
The atomic layer deposited metal oxide is TiO 2 Or Al 2 O 3 One of them.
The thickness of the atomic layer deposition metal oxide is 1-10 nm.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, 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 invention, as 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 made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Measuring 2600 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding the polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 2 hours at a speed of 400r/min by using a magnetic stirrer until the polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of Super P as a conductive agent and 4000mg of active carbon, adding the conductive agent into a system, and stirring the mixture for 12 hours at the room temperature and the rotating speed of 400 r/min; finally ball milling is carried out for 6min by using a miniature ball mill, and the vibration frequency is 50Hz, thus obtaining uniform electrode slurry.
And coating the electrode slurry on a carbon-coated aluminum foil by using a 100 mu m scraper, putting the carbon-coated aluminum foil into a blast drying oven for drying for 2 hours at 80 ℃, and then putting the carbon-coated aluminum foil into a vacuum drying oven for drying for 12 hours at 80 ℃ to obtain the pole piece.
The pole piece is placed in a low-temperature plasma treatment device, the gas in the treatment cabin is carbon tetrafluoride, the power of a power supply is set to be 80W, the air pressure in the cabin in the treatment process is set to be 80Pa, and the pole piece is treated for 9min.
Next, atomic layer deposition was used to deposit 2nm thick TiO on the low temperature plasma treated electrode sheet 2 。
Example 2
Weighing 2200 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding the polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 3 hours at a speed of 300r/min by using a magnetic stirrer until the polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of Super P as a conductive agent and 4000mg of active carbon, adding the conductive agent into a system, and stirring the mixture for 12 hours at the room temperature and the rotating speed of 300 r/min; finally ball milling is carried out for 3min by using a miniature ball mill, and the vibration frequency is 30Hz, thus obtaining uniform electrode slurry.
And coating the electrode slurry on a carbon-coated aluminum foil by using a scraper with the thickness of 150 mu m, putting the carbon-coated aluminum foil into a blast drying oven for drying at 60 ℃ for 4 hours, and putting the carbon-coated aluminum foil into a vacuum drying oven for drying at 60 ℃ for 16 hours to obtain the pole piece.
The pole piece is placed in a low-temperature plasma treatment device, the gas in the treatment cabin is carbon tetrafluoride, the power of the power supply is set to be 100W, the air pressure in the cabin in the treatment process is set to be 60Pa, and the pole piece is treated for 3min.
Next, 1nm thick Al is deposited on the electrode sheet after low temperature plasma treatment by atomic layer deposition 2 O 3 。
Example 3
2400 mu L of N-methyl pyrrolidone is measured, 400mg of polyvinylidene fluoride is weighed, polyvinylidene fluoride is added into the N-methyl pyrrolidone, and the mixture is stirred 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 Super P as a conductive agent and 4000mg of active carbon, adding the conductive agent into a system, and stirring the mixture at the room temperature at the rotation speed of 400r/min for 13 hours; finally ball milling is carried out for 2min by using a miniature ball mill, and the vibration frequency is 150Hz, thus obtaining uniform electrode slurry.
Coating the electrode slurry on a carbon-coated aluminum foil by using a 200 mu m scraper, putting the carbon-coated aluminum foil into a blast drying oven for drying at 90 ℃ for 2 hours, and then putting the carbon-coated aluminum foil into a vacuum drying oven for drying at 120 ℃ for 16 hours to obtain the pole piece.
The pole piece is placed in a low-temperature plasma treatment device, the gas in the treatment cabin is carbon tetrafluoride, the power of a power supply is set to be 150W, the air pressure in the cabin in the treatment process is 80Pa, and the pole piece is treated for 1min.
Next, atomic layer deposition was used to deposit 10nm thick TiO on the low temperature plasma treated electrode sheet 2 。
Example 4
Measuring 2800 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding the polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 1h at a speed of 500r/min by using a magnetic stirrer until the polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of Super P as a conductive agent and 4000mg of active carbon, adding the conductive agent into a system, and stirring the mixture for 14 hours at the room temperature and the rotating speed of 500 r/min; finally ball milling is carried out for 8min by using a miniature ball mill, and the vibration frequency is 120Hz, thus obtaining uniform electrode slurry.
And coating the electrode slurry on a carbon-coated aluminum foil by using a 50 mu m scraper, putting the carbon-coated aluminum foil into a blast drying oven for drying at 100 ℃ for 2 hours, and then putting the carbon-coated aluminum foil into a vacuum drying oven for drying at 100 ℃ for 8 hours to obtain the pole piece.
The pole piece is placed in a low-temperature plasma treatment device, the gas in the treatment cabin is carbon tetrafluoride, the power of a power supply is set to be 60W, the air pressure in the cabin in the treatment process is 80Pa, and the pole piece is treated for 30s.
Next, atomic layer deposition was used to deposit TiO 3nm thick on the low temperature plasma treated electrode sheet 2 。
Example 5
Measuring 3000 mu L of N-methyl pyrrolidone, weighing 500mg of polyvinylidene fluoride, adding the polyvinylidene fluoride into the N-methyl pyrrolidone, and stirring for 3 hours at the speed of 450r/min by using a magnetic stirrer until the polyvinylidene fluoride powder is completely dissolved in the N-methyl pyrrolidone; weighing 500mg of Super P as a conductive agent, 3800mg of activated carbon, adding the conductive agent into the system, and stirring at a rotation speed of 400r/min for 15h at room temperature; finally ball milling is carried out for 10min by using a miniature ball mill, and the vibration frequency is 50Hz, thus obtaining uniform electrode slurry.
And coating the electrode slurry on a carbon-coated aluminum foil by using a 100 mu m scraper, putting the carbon-coated aluminum foil into a blast drying oven for drying for 3 hours at 80 ℃, and then putting the carbon-coated aluminum foil into a vacuum drying oven for drying for 12 hours at 80 ℃ to obtain the pole piece.
The pole piece is placed in a low-temperature plasma treatment device, the gas in the treatment cabin is carbon tetrafluoride, the power of a power supply is set to be 60W, the air pressure in the cabin in the treatment process is set to be 20Pa, and the pole piece is treated for 10min.
Next, atomic layer deposition was used to deposit TiO 5nm thick on the low temperature plasma treated electrode sheet 2 。
And testing and analyzing the processed pole piece and the supercapacitor.
FIG. 1 shows the change of the dynamic contact angle of the pole piece after the electrolyte DLC306 is added dropwise. The contact angle of the untreated AC electrode was reduced from 26.3 ° at 0s to 5.4 ° at 1 s. Atomic layers are respectively deposited with 2nm Al after the low-temperature plasma treatment for 9min 2 O 3 Electrode Al of (2) 2 O 3 The contact angle of the/F@AC was reduced from 28.1 deg. to 26.5 deg.. The electrode 9MF contact angle 146.5 ° for the low temperature plasma treatment for 9min only was reduced to 117.6 °. The electrode modified by fluorine only has poor surface wettability due to the influence of F element, and the surface wettability of the fluorine modified electrode deposited by atomic layer is obviously improved, which is beneficial to the charge and discharge of the super capacitor under high current, so that the super capacitor has better rate capability.
FIG. 2 shows atomic layer deposition of 2nm TiO after low temperature plasma treatment for 9min 2 And 2nm Al 2 O 3 Typical CV curves for supercapacitors assembled with untreated electrodes are 20mV/s at scan rate. The CV curves of the three groups of super capacitors do not have oxidation-reduction peaks, fluctuation, wrinkles and the like, which indicates that the energy storage mode of the super capacitors assembled by the electrodes after atomic layer deposition and low-temperature plasma treatment mainly depends on an electric double layer.
FIG. 3 shows atomic layer deposition of 2nm TiO after low temperature plasma treatment for 9min 2 And 2nm of Al 2 O 3 And 8000 times of constant-current charge-discharge capacity change of the super capacitor assembled with the untreated electrode under the conditions of 3.5V and 1A/g. AC. TiO (titanium dioxide) 2 F@AC and Al 2 O 3 The specific capacitances of the three groups of supercapacitors per F@AC were 97.23%, 100.00% and 99.34% of 1A/g, respectively, at a current density of 10A/g. The electrode surface has the advantage that the wettability of the electrode surface is improved, and the multiplying power performance of the two groups of capacitors with double layers is close to 100.00 percent, which is superior to that of the AC capacitors without surface treatment.
FIG. 4 shows the atomic layer deposition of 2nm TiO after 9min of low temperature plasma treatment 2 And 2nm of Al 2 O 3 And the specific capacitance of the untreated electrode assembled supercapacitor at 3.5V at different current densities. The initial specific capacitance of the AC supercapacitor is 80.64F/g, and the specific capacitance after 8000 times of charge and discharge is 56.02F/g, the capacity retention was 69.46%. TiO (titanium dioxide) 2 The initial specific capacitance of the/F@AC supercapacitor is 104.06F/g, and is improved by 29.04% compared with the AC supercapacitor; after 8000 times of charge and discharge, the specific capacitance value is reduced to 93.53F/g, and the capacity retention rate is 89.88%. Al (Al) 2 O 3 The specific capacitance of the/F@AC supercapacitor is reduced from 102.31F/g to 92.18F/g, the initial capacity is increased by 26.87% compared with that of the AC supercapacitor, and the capacity retention rate is 90.10%. TiO (titanium dioxide) 2 F@AC and Al 2 O 3 The capacity of the/F@AC supercapacitor is kept stable in 8000 cycles, and the service life of the super capacitor is obviously longer than that of a control group.
In summary, the fluorine modified activated carbon electrode surface composite treatment method and the application thereof, disclosed by the invention, are applied to the preparation of the supercapacitor electrode by adopting an atomic layer deposition technology and a low-temperature plasma technology, the metal oxide deposition layer and the fluorine modified layer on the electrode surface jointly slow down the degradation of an 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 high voltage of 3.5V, and the energy density of the supercapacitor can be effectively improved while the power density of the activated carbon-based supercapacitor is maintained.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (2)

1. The surface composite treatment method of the fluorine modified activated carbon electrode is characterized by comprising the following steps of:
s1, adding carboxymethyl cellulose, carbon nano tubes and activated carbon into N-methyl pyrrolidone, and magnetically stirring until a binder is dissolved to obtain mixed slurry, wherein the mass ratio of the N-methyl pyrrolidone to the carboxymethyl cellulose is 3:1; the mass ratio of the activated carbon, the carbon nano tube and the carboxymethyl cellulose is 6:0.5:0.5, specifically: firstly, adding carboxymethyl cellulose into N-methyl pyrrolidone, controlling the stirring speed to be 300r/min, and stirring for 1-3 h; then adding the carbon nano tube and the activated carbon under the condition of room temperature, controlling the stirring speed to be 300r/min, and stirring for 12 hours;
s2, performing ball milling treatment on the mixed slurry obtained in the step S1 for 2min to obtain electrode slurry, wherein the vibration frequency of the ball milling treatment is 30Hz;
s3, coating the electrode slurry obtained in the step S2 on a carbon-coated aluminum foil, wherein the coating thickness is 50 mu m, and sequentially carrying out forced air drying and vacuum drying until the solvent is dried to obtain an electrode slice, wherein the forced air drying temperature is 60 ℃, and the drying time is 2 hours; the temperature of vacuum drying is 60 ℃ and the drying time is 8 hours;
s4, treating the surface of the electrode plate obtained in the step S3 by adopting a low-temperature plasma technology, adopting carbon tetrafluoride gas or fluorine gas as a gas source of low-temperature plasma, maintaining the gas pressure of the gas source at 20Pa, controlling the power frequency to be 13.56MHz, controlling the power of the power supply to be 60W in the treatment process, and treating the surface of the electrode plate for 30S;
s5, depositing TiO with thickness of 1nm on the electrode sheet subjected to the surface treatment in the step S4 by adopting an atomic layer deposition technology 2 Or Al 2 O 3 Obtaining the fluorine modified activated carbon electrode subjected to composite treatment.
2. Use of a fluorine modified activated carbon electrode treated according to the method of claim 1 in a supercapacitor.
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