CN111883365B - Multi-dimensional assembled composite film electrode and preparation method and application thereof - Google Patents

Multi-dimensional assembled composite film electrode and preparation method and application thereof Download PDF

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CN111883365B
CN111883365B CN202010654353.9A CN202010654353A CN111883365B CN 111883365 B CN111883365 B CN 111883365B CN 202010654353 A CN202010654353 A CN 202010654353A CN 111883365 B CN111883365 B CN 111883365B
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张旋
钟艳莉
张文乔
陈远东
郝常山
颜悦
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AECC Beijing Institute of Aeronautical Materials
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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
    • H01G11/24—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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • 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
    • H01G11/46—Metal oxides
    • 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
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention relates to a multi-dimensional assembled composite film electrode, which is a flexible self-supporting film formed by microscopically interweaving and assembling three materials, namely 0-dimensional conductive polymer nano-particles, 1-dimensional vanadium pentoxide nanowires and 2-dimensional carbon nano-sheets. The prepared self-supporting flexible composite film is used as an electrode for preparing a solid flexible super capacitor, has a simple preparation process, and has excellent electrochemical properties such as capacity and multiplying power and excellent bending-resistant flexible property.

Description

Multi-dimensional assembled composite film electrode and preparation method and application thereof
Technical Field
The invention relates to a multi-dimensional assembled composite film electrode and a preparation method and application thereof, belonging to the technical field of electrochemical capacitors.
Background
As wearable smart devices gradually enter people's lives, it is an urgent technical need to develop portable energy storage devices (batteries or capacitors) that are small in size, thin in thickness, light in weight, and mechanically flexible. The super capacitor, also called as an electrochemical capacitor, is a novel energy storage device with the advantages of high power density (rapid charge and discharge), wide temperature use range (-40-70 ℃), long cycle life (100 ten thousand times), and the like. The flexible super capacitor can still keep working under repeated bending and twisting, and is particularly suitable to be used as an energy supply element of wearable equipment.
The performance of supercapacitors is largely determined by the electrode material. According to different energy storage mechanisms, electrode materials of the super capacitor are divided into an electric double layer electrode material and a pseudocapacitance electrode material. The former carbon material having a high specific surface areaPrimarily, it relies on charge separation at the electrode and electrolyte interfaces to form an electric double layer to store charge. The latter includes metal oxides and conductive polymers, and relies on the electrode active material to undergo a fast reversible redox reaction to store charge. Generally speaking, pseudocapacitors have higher specific capacitance values than electric double layer capacitors, such as ruthenium oxide free hydrate (RuO)2·nH2O) reaches 920Fg-1However, the high cost of precious metals has limited their widespread commercial use. Many transition metal oxides, e.g. MnO2,V2O5,Co3O4,NiO,Fe2O3Has been widely studied to replace ruthenium oxide as a pseudocapacitive electrode material. However, most of these metal oxides have low conductivity, thus limiting their charge transfer kinetics.
In addition, obtaining high performance flexible electrodes is the most important factor that restricts flexible supercapacitors. Generally speaking, a self-made carbon nanotube or graphene film, carbon cloth and a composite material of the carbon nanotube or graphene film and a pseudocapacitance material are used as a flexible electrode to prepare a flexible supercapacitor.
Disclosure of Invention
The invention provides a multi-dimensional assembled composite film electrode, a preparation method and application thereof aiming at solving the current situation and the existing defects of the prior art, and aims to obtain a high-performance flexible electrode.
The purpose of the invention is realized by the following technical scheme:
the multidimensional assembled composite film electrode is formed by microscopically interweaving and assembling three materials, namely 0-dimensional conductive polymer nano particles, 1-dimensional vanadium pentoxide nanowires and 2-dimensional carbon nano sheets to form an interpenetrating network, so that the flexible self-supporting film is formed, and the electrochemical performance cannot be degraded even if the flexible self-supporting film is bent for many times.
The key point for obtaining the high-performance flexible super capacitor is to prepare the high-performance flexible electrode. Experiments show that the self-supporting flexible electrode with good mechanical property is difficult to obtain by singly adopting the vanadium pentoxide nanowire; and the conductive polymer or the carbon nano sheet is adopted alone, so that the self-supporting flexible electrode is easy to prepare, but is limited to an energy storage mechanism, and the storage capacity is unsatisfactory. The nano material is nano-sized in at least one dimension on the microscopic morphology of the material, and comprises 0-dimensional, 1-dimensional, 2-dimensional nano materials and the like. In order to obtain a high-performance flexible electrode and fully play the high conductivity of a conductive polymer, the high capacity of vanadium pentoxide, the high stability of a carbon material and the synergistic effect of nano materials with different dimensions, the invention combines 0-dimensional conductive polymer nano particles, 1-dimensional vanadium pentoxide nano wires and 2-dimensional carbon nano sheets, and forms the flexible film electrode in a vacuum filtration assembly mode. In addition to the properties of the material itself, such as high conductivity, flexibility, good film forming properties of the conductive polymer, and high stability of the carbon nanomaterial, with high theoretical capacity of the metal oxide. And the excellent synergistic effect of the nano materials with different dimensions is combined to obtain the high-performance flexible electrode. And tested for performance as a supercapacitor electrode. The multidimensional assembled conductive polymer nanoparticle/vanadium pentoxide nanowire/carbon nanosheet composite film electrode and the preparation and application thereof have not been reported so far.
In one implementation, the mass ratio of the 1-dimensional vanadium pentoxide nanowires to the 2-dimensional carbon nanosheets is 1: 1.
Further, the 0-dimensional conductive polymer nanoparticles account for 2-50% of the total mass of the composite film electrode.
In one implementation, the 0-dimensional conductive polymer nanoparticles are polyethylenedioxythiophene-polystyrene nanoparticles
In one implementation, the diameter distribution of the 1-dimensional vanadium pentoxide nanowires is 10-100 nm.
In one implementation, the 2-dimensional carbon nanosheets have a thickness distribution ranging from 1nm to 10 nm.
The technical scheme of the invention also provides a method for preparing the multi-dimensional assembled composite film electrode, which is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a 1-dimensional vanadium pentoxide nanowire by a hydrothermal method;
step two, preparing a 2-dimensional carbon nano sheet dispersion solution, adding brown 1-dimensional vanadium pentoxide nanowire solid powder, simultaneously adding an anionic surfactant, and preparing the 1-dimensional vanadium pentoxide nanowire/2-dimensional carbon nano sheet mixed dispersion solution under the ultrasonic action;
adding a 0-dimensional conductive polymer nanoparticle solution into the 1-dimensional vanadium pentoxide nanowire/2-dimensional carbon nanosheet mixed dispersion solution to obtain a 0-dimensional conductive polymer nanoparticle 1-dimensional/vanadium pentoxide nanowire/2-dimensional carbon nanosheet ternary mixed dispersion solution;
and step four, placing the 0-dimensional conductive polymer nanoparticle 1-dimensional/vanadium pentoxide nanowire/2-dimensional carbon nanosheet ternary mixed dispersion solution into a solvent filter, performing vacuum filtration, and repeatedly washing with water and ethanol to remove the surfactant to prepare the flexible self-supporting composite film electrode.
In one implementation, the hydrothermal method for preparing 1-dimensional vanadium pentoxide in the first step is to take ammonium metavanadate as a precursor, add a non-ionic surfactant, and react for 24 hours at 120-160 ℃ in a reaction kettle to obtain brown 1-dimensional vanadium pentoxide nanowire solid powder with the diameter of 10-100 nm.
Further, the nonionic surfactant is P123.
In one implementation, the process of preparing the 2-dimensional carbon nanosheet dispersed solution in step two is: firstly, oxidizing natural graphite by using a Hummers method, then ultrasonically stripping to form an oxidized 2-dimensional carbon nanosheet, then adding a reducing agent hydrazine hydrate, heating, reducing and reacting for 2 hours, cooling, and centrifuging under the condition of 10000r/min to remove a small amount of agglomerated graphite fine particles to obtain 0.1-5 mg/mL of black 2-dimensional carbon nanosheet dispersion liquid.
In one implementation, the anionic surfactant is sodium dodecyl benzene sulfonate or sodium deoxycholate.
In one embodiment, the flexible self-supporting composite thin film electrode prepared in the fourth step is circular and has a thickness of 10-100 microns.
The technical scheme of the invention also provides an application of the multi-dimensional assembled composite film electrode, which is characterized in that: the composite film electrode can be used for preparing a solid flexible super capacitor, two composite film electrodes with the same area are placed in the middle of the composite film electrode, a solid electrolyte is placed in the middle of the composite film electrodes to form a sandwich structure in an electrode-electrolyte-electrode form, metal foils are connected to the two electrodes respectively to serve as connecting wires of a positive electrode and a negative electrode, then a polymer film is adopted as a packaging material on the outer layer of the sandwich structure, and epoxy resin or silicon rubber is cured and packaged to obtain the solid flexible super capacitor; wherein the solid electrolyte is a polymer gel electrolyte. Further, the polymer gel electrolyte is sodium sulfate-polyvinyl alcohol.
In one implementation, the area of the electrode in the obtained solid-state flexible supercapacitor is 1-5cm2The capacity is 10-300F/g.
The technical scheme of the invention has the following remarkable advantages:
(1) the composite film electrode integrates the excellent characteristics of nano materials with different dimensions such as 0 dimension, 1 dimension and 2 dimension, combines the excellent conductivity and flexibility of a conductive polymer, the pseudo-capacitance characteristic of vanadium pentoxide and the good conductivity and stability of a carbon material, and shows higher capacitance capacity (300F/g) and cycle stability when being applied to a super capacitor electrode material;
(2) when the self-supporting composite film electrode is applied to a super capacitor electrode, additional conductive additives and high-molecular binders are not needed, and the self-supporting composite film electrode can be directly used as an electrode. On one hand, the preparation process of the electrode is simplified, and on the other hand, the loading capacity of active ingredients is improved; meanwhile, as no binder is adopted, the transmission of electrons in the electrode is improved, which is beneficial to improving the rate capability of the super capacitor;
(3) the composite film electrode has good bending resistance, and can be used as a flexible electrode to prepare a bending-resistant solid flexible supercapacitor.
The flexible supercapacitor based on the conductive polymer nanoparticle/vanadium pentoxide nanowire/carbon nanosheet composite film electrode prepared by the method provided by the invention is subjected to electrochemical test. The two electrode terminals of the flexible supercapacitor are connected to an electrochemical tester (VMP3, French Bio-logic company) tester, the voltage is scanned from 0V to 1V by cyclic voltammetry, namely, a certain voltage scanning rate is set, then the scanning speed returns to 0V, and the scanning area is recorded, so that the capacitor capacity can be calculated. The method for testing the capacity retention rate comprises the following steps: the method comprises the steps of charging from 0V to 1V under the charging and discharging current with the current density of 1-50A/g by adopting a constant-current charging and discharging method, then discharging to 0V under the same current, setting 5000 charging and discharging cycles, and obtaining the capacitance value through each cycle. Through this series of capacitance values, the retention ratio of the battery capacity can be obtained.
Detailed Description
The technical solution of the present invention will be further described with reference to the following examples:
example 1
The method for preparing the multi-dimensional assembled composite film electrode comprises the following steps:
1) vanadium pentoxide nanowires: 0.6g of ammonium metavanadate and 1g P123 g of ammonium metavanadate are added into 50mL of water, hydrochloric acid is added to adjust the pH value to be 2, and the mixture is stirred for 12 hours at normal temperature to be completely dissolved in the water to form an orange-red precursor solution. Then transferred to a reaction kettle to react for 24 hours at 120 ℃. After cooling, a yellowish brown suspension was obtained. Centrifugally cleaning with deionized water for three times, and then placing the mixture into a vacuum drying oven to be dried for 24 hours under a vacuum-pumping environment at 80 ℃. And obtaining dry vanadium pentoxide nanowire solid powder, wherein the diameter distribution range of the vanadium pentoxide nanowire is 10-50 nm.
2) Two-dimensional carbon nanosheet dispersion: first, natural graphite is oxidized into oxidized two-dimensional carbon nanosheets by the Hummers method. The procedure was to mix 5g of flake natural graphite with 3g of sodium nitrate and add to 120mL of concentrated sulfuric acid. After stirring in an ice bath and slowly adding 15g of potassium permanganate, the reaction was carried out for 2 hours, 300mL of deionized water was added to the reaction solution, the temperature was raised to 100 ℃ (solution boiling) and the reaction was continued for 30 minutes. Then, 100mL of deionized water was further added to the reaction solution to dilute the reaction solution, and 15mL of a hydrogen peroxide solution (30 wt%) was added to neutralize the unreacted potassium permanganate. After 30 minutes, the mixture is filtered while hot and repeatedly washed with deionized water for 3 to 5 times. And (3) placing the graphite oxide solution in probe ultrasound, and performing ultrasonic treatment for 1h under the power of 200W to obtain the peeled oxidized two-dimensional carbon nanosheet. Determining the mass concentration by a constant volume method (namely measuring a certain volume of solution, drying and weighing), and diluting to 1 mg/mL. Then adding a reducing agent hydrazine hydrate, heating to 95 ℃, and carrying out reduction reaction for 4 hours. And after cooling to room temperature, centrifuging under the condition of 10000r/min to remove a small amount of agglomerated two-dimensional carbon nanosheet fine particles in the obtained reaction solution, and diluting with constant volume to obtain 0.5mg/mL black two-dimensional carbon nanosheet dispersion liquid.
25mg of vanadium pentoxide nanowires are added into 50mL of 0.5mg/mL two-dimensional carbon nanosheet dispersion solution, and 75mg of NaDBS is added to assist in dispersion. Firstly carrying out water bath ultrasound for 10 minutes to fully dissolve the surfactant, then putting the surfactant in probe ultrasound, and carrying out ultrasound for 60 minutes under the power of 200W to form a vanadium pentoxide/carbon nano-sheet binary mixed dispersion solution.
3) Ternary mixed dispersion solution: and adding 0.13mL of commercial conductive polymer nanoparticle water dispersion solution (PEDOT-PSS, model PH1000, Clevios company) with the mass fraction of 10% into the binary mixed solution, and uniformly mixing by ultrasonic for 1h to form 50mL of conductive polymer nanoparticle/vanadium pentoxide nanowire/carbon nanosheet ternary mixed dispersion solution. The conductive polymer comprises 13mg of conductive polymer nanoparticles, 25mg of vanadium pentoxide and 25mg of carbon nanosheets.
4) Assembling and preparing a film: selecting a nylon filter membrane (phi 35mm, pore diameter of 0.4 micron), placing 20mL of the mixed dispersion into a solvent filter for placing the filter membrane, carrying out vacuum filtration, and washing with water and ethanol for three times to remove the surfactant. Taking down the electrode, and airing the electrode in the air to obtain a circular composite film electrode (phi 35mm, the thickness is 40 microns), wherein the content of the conductive polymer accounts for 20%.
Example 2
A multi-dimensionally assembled composite thin film electrode was prepared according to the method of example 1. Except that the step 4) of mixing the dispersion solution process: 50mL of the mixed dispersion was placed in a solvent filter with a filter membrane and vacuum filtered, and washed three times with water and ethanol to remove the surfactant. Taking down the electrode, and airing the electrode in the air to obtain a circular composite film electrode (phi 35mm, the thickness is 100 microns), wherein the content of the conductive polymer accounts for 20%.
Example 3
A multi-dimensionally assembled composite thin film electrode was prepared according to the method of example 1. Except that step 3) ternary mixed dispersion solution: and adding 0.01mL of commercial conductive polymer nanoparticle water dispersion solution (PEDOT-PSS, model PH1000, Clevios company) with the mass fraction of 10% into the binary mixed solution, and uniformly mixing by ultrasonic for 1h to form 50mL of conductive polymer nanoparticle/vanadium pentoxide nanowire/carbon nanosheet ternary mixed dispersion solution. The conductive polymer comprises 1mg of conductive polymer nanoparticles, 25mg of vanadium pentoxide and 25mg of carbon nanosheets.
4) Assembling and preparing a film: selecting a nylon filter membrane (phi 35mm, pore diameter of 0.4 micron), placing 20mL of the mixed dispersion into a solvent filter for placing the filter membrane, carrying out vacuum filtration, and washing with water and ethanol for three times to remove the surfactant. Taking down the electrode, and airing the electrode in the air to obtain a circular composite film electrode (phi 35mm, the thickness is 30 microns), wherein the content of the conductive polymer accounts for 2 percent.
Example 4
A multi-dimensionally assembled composite thin film electrode was prepared according to the method of example 1. Except that step 3) ternary mixed dispersion solution: and adding 0.5mL of commercial conductive polymer nanoparticle water dispersion solution (PEDOT-PSS, model PH1000, Clevios company) with the mass fraction of 10% into the binary mixed solution, and uniformly mixing by ultrasonic for 1h to form 50mL of conductive polymer nanoparticle/vanadium pentoxide nanowire/carbon nanosheet ternary mixed dispersion solution. The conductive polymer comprises 50mg of conductive polymer nanoparticles, 25mg of vanadium pentoxide and 25mg of carbon nanosheets.
4) Assembling and preparing a film: selecting a nylon filter membrane (phi 35mm, pore diameter of 0.4 micron), placing 20mL of the mixed dispersion into a solvent filter for placing the filter membrane, carrying out vacuum filtration, and washing with water and ethanol for three times to remove the surfactant. Taking down the electrode, and airing the electrode in the air to obtain a circular composite film electrode (phi 35mm, the thickness is 30 microns), wherein the content of the conductive polymer accounts for 20%.
Example 5
A multi-dimensionally assembled composite thin film electrode was prepared according to the method of example 1.
Different step 2) two-dimensional carbon nanosheet dispersion: first, natural graphite is oxidized into oxidized two-dimensional carbon nanosheets by the Hummers method. The procedure was to mix 5g of flake natural graphite with 3g of sodium nitrate and add to 120mL of concentrated sulfuric acid. After stirring in an ice bath and slowly adding 15g of potassium permanganate, the reaction was carried out for 4 hours, 300mL of deionized water was added to the reaction solution, the temperature was raised to 100 ℃ (solution boiling) and the reaction was continued for 30 minutes. Then, 100mL of deionized water was further added to the reaction solution to dilute the reaction solution, and 15mL of a hydrogen peroxide solution (30 wt%) was added to neutralize the unreacted potassium permanganate. After 30 minutes, the mixture is filtered while hot and repeatedly washed with deionized water for 3 to 5 times. And (3) placing the graphite oxide solution in probe ultrasound, and performing ultrasonic treatment for 2h under the power of 200W to obtain the peeled oxidized two-dimensional carbon nanosheet. The mass concentration is determined by a constant volume method (namely, a certain volume of solution is measured, and the solution is weighed after being dried), and is diluted to 0.1 mg/mL. Then adding a reducing agent hydrazine hydrate, heating to 95 ℃, and carrying out reduction reaction for 4 hours. And after cooling to room temperature, centrifuging under the condition of 10000r/min to remove a small amount of agglomerated two-dimensional carbon nanosheet fine particles in the obtained reaction solution, and diluting with constant volume to obtain 0.1mg/mL black two-dimensional carbon nanosheet dispersion liquid. The thickness was 1nm as characterized by atomic force microscopy.
Example 6
A vanadium nitride-based porous nanowire-two-dimensional carbon nanosheet composite electrode was prepared according to the method of example 1. Different step 3) two-dimensional carbon nanosheet dispersion: first, natural graphite is oxidized into oxidized two-dimensional carbon nanosheets by the Hummers method. The procedure was to mix 5g of flake natural graphite with 3g of sodium nitrate and add to 120mL of concentrated sulfuric acid. After stirring in an ice bath and slowly adding 15g of potassium permanganate, the reaction was carried out for 4 hours, 300mL of deionized water was added to the reaction solution, the temperature was raised to 100 ℃ (solution boiling) and the reaction was continued for 30 minutes. Then, 100mL of deionized water was further added to the reaction solution to dilute the reaction solution, and 15mL of a hydrogen peroxide solution (30 wt%) was added to neutralize the unreacted potassium permanganate. After 30 minutes, the mixture is filtered while hot and repeatedly washed with deionized water for 3 to 5 times. And (3) placing the graphite oxide solution in probe ultrasound, and performing ultrasonic treatment for 4 hours at the power of 200W to obtain the peeled oxidized two-dimensional carbon nanosheet. Determining the mass concentration by a constant volume method (namely measuring a certain volume of solution, drying and weighing), and diluting to 5 mg/mL. Then adding a reducing agent hydrazine hydrate, heating to 95 ℃, and carrying out reduction reaction for 4 hours. And after cooling to room temperature, centrifuging under the condition of 10000r/min to remove a small amount of agglomerated two-dimensional carbon nanosheet fine particles in the obtained reaction solution, and diluting with constant volume to obtain 5mg/mL black two-dimensional carbon nanosheet dispersion liquid. The thickness was 0.5nm as characterized by atomic force microscopy.
Application example 1
This example illustrates the use of the self-supporting composite flexible film prepared in the above examples to further prepare solid state flexible supercapacitors. The specific process comprises the following steps: the composite film electrode prepared in example 1 was cut into a rectangular electrode film of 1cm by 2.5cm, two sheets of such electrodes were used, and a gel polymer electrolyte was applied between the two sheets of electrodes to form a sandwich structure (electrode-electrolyte-electrode), and a small piece of copper foil was connected to the back of each of the two sheets of electrodes as a connecting wire for the positive and negative electrodes. And then, adopting a Polyester (PET) film as a packaging material on the outer layer of the sandwich structure, and curing and packaging with room-temperature silicon rubber. The specific capacitance of the prepared solid flexible capacitor is 300F/g through constant current charge and discharge tests. 10000 cycles of continuous constant current charging and discharging are carried out, the cycling stability is tested, and the capacity retention rate of the capacitor is found to be 96%.
Comparative example 1
A flexible capacitor was fabricated by the method of example 7, except that the composite film of example 3 was used as an electrode, and the fabricated solid flexible capacitor had a specific capacitance of 150F/g as measured by constant current charge and discharge.
Comparative example 2
A flexible capacitor was fabricated by the method of example 7, except that the composite film of example 4 was used as an electrode, and the fabricated solid flexible capacitor had a specific capacitance of 260F/g as measured by constant current charge and discharge. 10000 cycles of continuous constant current charging and discharging are carried out, the cycling stability is tested, and the capacity retention rate of the capacitor is found to be 65%.

Claims (14)

1. A multi-dimensional assembled composite film electrode is characterized in that: the composite film electrode is formed by microscopically interweaving and assembling three materials, namely 0-dimensional conductive polymer nano-particles, 1-dimensional vanadium pentoxide nanowires and 2-dimensional carbon nano-sheets to form an interpenetrating network, so that a flexible self-supporting film is formed;
the preparation method of the multi-dimensional assembled composite film electrode comprises the following steps:
step one, preparing a 1-dimensional vanadium pentoxide nanowire by a hydrothermal method;
step two, preparing a 2-dimensional carbon nano sheet dispersion solution, adding brown 1-dimensional vanadium pentoxide nanowire solid powder, simultaneously adding an anionic surfactant, and preparing the 1-dimensional vanadium pentoxide nanowire/2-dimensional carbon nano sheet mixed dispersion solution under the ultrasonic action;
adding a 0-dimensional conductive polymer nanoparticle solution into the 1-dimensional vanadium pentoxide nanowire/2-dimensional carbon nanosheet mixed dispersion solution to obtain a 0-dimensional conductive polymer nanoparticle 1-dimensional/vanadium pentoxide nanowire/2-dimensional carbon nanosheet ternary mixed dispersion solution;
and step four, placing the 0-dimensional conductive polymer nanoparticle 1-dimensional/vanadium pentoxide nanowire/2-dimensional carbon nanosheet ternary mixed dispersion solution into a solvent filter, performing vacuum filtration, and repeatedly washing with water and ethanol to remove the surfactant to prepare the flexible self-supporting composite film electrode.
2. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the mass ratio of the 1-dimensional vanadium pentoxide nanowire to the 2-dimensional carbon nanosheet is 1: 1.
3. A multi-dimensional assembled composite thin film electrode according to claim 1 or 2, wherein: the 0-dimensional conductive polymer nanoparticles account for 2-50% of the total mass of the composite film electrode.
4. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the 0-dimensional conductive polymer nanoparticles are polyethylene dioxythiophene-polystyrene nanoparticles.
5. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the diameter distribution of the 1-dimensional vanadium pentoxide nanowires is 10-100 nm.
6. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the thickness distribution of the 2-dimensional carbon nanosheets is 1 nm-10 nm.
7. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: in the step one, the hydrothermal method for preparing the 1-dimensional vanadium pentoxide takes ammonium metavanadate as a precursor, and adds the nonionic surfactant to react for 24 hours at 120-160 ℃ in a reaction kettle to obtain the brown 1-dimensional vanadium pentoxide nanowire solid powder with the diameter of 10-100 nm.
8. The multi-dimensionally assembled composite thin film electrode of claim 7, wherein: the nonionic surfactant is P123.
9. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the process for preparing the 2-dimensional carbon nanosheet dispersion solution in the second step is as follows: firstly, oxidizing natural graphite by using a Hummers method, then ultrasonically stripping to form an oxidized 2-dimensional carbon nanosheet, then adding a reducing agent hydrazine hydrate, heating, reducing and reacting for 2 hours, cooling, and centrifuging under the condition of 10000r/min to remove a small amount of agglomerated graphite fine particles to obtain 0.1-5 mg/mL of black 2-dimensional carbon nanosheet dispersion liquid.
10. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the anionic surfactant is sodium dodecyl benzene sulfonate or sodium deoxycholate.
11. The multi-dimensionally assembled composite thin film electrode of claim 1, wherein: the flexible self-supporting composite thin film electrode prepared in the step four is circular, and the thickness of the flexible self-supporting composite thin film electrode is 10-100 micrometers.
12. Use of a multi-dimensionally assembled composite thin-film electrode according to claim 1, wherein: the composite film electrode can be used for preparing a solid flexible super capacitor, two composite film electrodes with the same area are placed in the middle of the composite film electrode, a solid electrolyte is placed in the middle of the composite film electrodes to form a sandwich structure in an electrode-electrolyte-electrode form, metal foils are connected to the two electrodes respectively to serve as connecting wires of a positive electrode and a negative electrode, then a polymer film is adopted as a packaging material on the outer layer of the sandwich structure, and epoxy resin or silicon rubber is cured and packaged to obtain the solid flexible super capacitor; wherein the solid electrolyte is a polymer gel electrolyte.
13. Use of a multi-dimensionally assembled composite thin-film electrode according to claim 12, wherein: the polymer gel electrolyte is sodium sulfate-polyvinyl alcohol.
14. Use of a multi-dimensionally assembled composite thin-film electrode according to claim 12, wherein: the area of the electrode in the obtained solid flexible super capacitor is 1-5cm2The capacity is 10-300F/g.
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