CN113921293B - Flexible asymmetric super capacitor and preparation method thereof - Google Patents
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- 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
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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
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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
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- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses a flexible asymmetric super capacitor and a preparation method thereof, and belongs to the technical field of capacitors. The flexible asymmetric supercapacitor comprises raw materials including an anode film, a cathode film and a gel electrolyte; the anode film and the cathode film are both films obtained by compounding carbonized cellulose and graphene or carbon nano tubes; MnO is loaded on the surface of the anode film 2 Particles; and polypyrrole particles are loaded on the surface of the cathode film. Compared with the traditional supercapacitor, the flexible asymmetric supercapacitor prepared by the invention has higher energy density and cycle stability, has high mechanical stability and flexibility, has small influence on electrochemical performance when deformed under the action of external force, and is expected to be widely applied to wearable electronic products.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a flexible asymmetric super capacitor and a preparation method thereof.
Background
The super capacitor is different from a traditional chemical energy storage device, is an energy storage device which is arranged between a traditional capacitor and a battery and has special performance, and mainly stores electric energy by electric double layers and redox pseudocapacitance charges. The flexible supercapacitor has the advantages of high power density, quick charge and discharge and long cycle life of the supercapacitor, has excellent mechanical flexibility, can adapt to various scenes, and has wide application prospects in portable and miniature electronic equipment. However, the traditional electrode materials are mainly metal-based materials and conductive polymers, the preparation process is complex and high in cost, and the excellent electrochemical performance, flexibility and mechanical stability are difficult to combine, so that the development of a novel flexible supercapacitor remains a great challenge.
Cellulose is one of the most abundant natural renewable high-molecular polymers in nature, has abundant surface groups (hydroxyl) and high mechanical flexibility, and has potential application in the aspect of flexible electrode materials of wearable equipment. However, cellulose is not conductive and has weak electrochemical performance, and how to apply cellulose to a flexible supercapacitor enables the flexible supercapacitor to have excellent electrochemical performance, flexibility and mechanical stability, so that the cellulose is a technical problem to be solved in the field of capacitors.
Disclosure of Invention
The invention aims to provide a flexible asymmetric supercapacitor and a preparation method thereof, which are used for solving the problems in the prior art and enabling the flexible supercapacitor to have excellent electrochemical performance, flexibility and mechanical stability.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a flexible asymmetric supercapacitor, which comprises raw materials including an anode film, a cathode film and a gel electrolyte;
the anode film and the cathode film are both films obtained by compounding carbonized cellulose and graphene or carbon nano tubes;
MnO is loaded on the surface of the anode film 2 Particles;
polypyrrole particles are loaded on the surface of the cathode film.
Further, the gel electrolyte is PVA/H 2 SO 4 A gel electrolyte.
The invention also provides a preparation method of the flexible asymmetric supercapacitor, which comprises the following steps:
and 4, coating a layer of gel electrolyte between the anode film and the cathode film to obtain the flexible asymmetric supercapacitor.
Further, the cellulose material in step 1 is one of cotton fiber, microcrystalline cellulose and carboxymethyl cellulose; the inert gas is nitrogen or argon.
Further, in step 1, the carbonization treatment specifically includes: heating from room temperature to 400-500 ℃ at a heating rate of 2-5 ℃/min, and keeping the temperature for 1-2 h; and then continuously heating to 800-1000 ℃ at the heating rate of 5-10 ℃/min, and preserving the heat for 1-2 h.
Further, in step 2, the carbon material is graphene or carbon nanotubes.
Further, in step 2, the carbon material dispersion liquid includes N, N-dimethylformamide, tannic acid, hydrazine hydrate, and water.
Further, the mass-to-volume ratio of the N, N-dimethylformamide, the tannic acid, the hydrazine hydrate and the water in the carbon material dispersion liquid is 70-100 mL: 30-50 mg: 10-20 mg: 5-15 mL.
Further, in the step 2, the temperature of the hydrothermal reaction is 80-100 ℃ and the time is 2-4 h.
Further, in step 3, electrodeposition is performed in a three-electrode system, with the film as a working electrode, a platinum electrode as a counter electrode, and a calomel electrode as a reference electrode.
Further, in step 3, when the film is an anode electrode material: the electrolyte contains 0.3 to0.6M Mn(CH 3 COO) 2 And 0.3 to 0.6M Na 2 SO 4 An anode constant current deposition method is adopted, and the current density is 5-10 mA cm -2 The deposition time is 800-1000 s, and compact MnO with a layer deposited on the surface is obtained 2 An anodic film of particles;
when the film is a cathode electrode material: 0.1-0.2M pyrrole and 0.3-0.5M H 2 SO 4 The pyrrole monomer is electropolymerized on the film by the electrolyte solution, and the deposition current density is 10-20 mA cm -2 And the deposition time is 100-300 s, and the cathode film with a layer of polypyrrole (PPy) particles formed by microsphere aggregation deposited on the surface is obtained.
In the initial stage of the electrodeposition process, the electrochemical performance is not obviously improved due to less active particles deposited on the surface of the electrode material; along with the increase of the deposition time, the specific capacity value of the electrode is improved; as the deposition time continues to increase, the deposited active particles clog the ion transport channels, thereby degrading electrochemical performance. Therefore, the deposition time of the anode film is preferably set to be 800-1000 s, and the deposition time of the cathode film is preferably set to be 100-300 s.
The technical conception of the invention is as follows:
cellulose has poor electrochemical performance, conductivity and capacitance performance of the cellulose can be improved through carbonization, but the requirement of a commercial capacitor on high energy density is still difficult to meet. Therefore, the mode of assembling the asymmetric super capacitor is adopted, the cellulose carbon material electrode is replaced by the cellulose electrode with the pseudo-capacitance energy storage characteristic, the potential windows of the two electrodes are fully utilized, the integral voltage window of the device is widened, and the energy density of the super capacitor is obviously improved.
The invention discloses the following technical effects:
(1) the experimental raw materials are low in price and easy to obtain, belong to renewable materials, can realize high-value utilization of biomass, and simultaneously expand the application of the biomass in the field of energy storage. The method has simple process, is suitable for industrial large-scale production, and has good industrial application prospect.
(2) The invention discloses a flexible asymmetric super capacitorCompared with the traditional super capacitor, the super capacitor has higher energy density and cycle stability at 1mA cm -2 The area specific capacitance under the current density is up to 1.383F cm -2 At 0.5mW cm -2 Has an energy density of 192.08 [ mu ] Wh cm at a power density of -2 The capacity retention rate can still reach 90.12% after 10000 cycles of charge and discharge. In addition, the flexible asymmetric supercapacitor prepared by the invention has high mechanical stability and flexibility, is less influenced by electrochemical properties when deformed under the action of external force, and is expected to be widely applied to wearable electronic products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a photograph of a sample of a carbonized cellulose/graphene film obtained in example 1;
FIG. 2 is a scanning electron micrograph of a carbonized cellulose/graphene thin film obtained in example 1;
FIG. 3 is a scanning electron microscope image of the anode thin film material and the cathode thin film material prepared in example 1; wherein, a is an anode film material, and b is a cathode film material;
FIG. 4 is a Cyclic Voltammetry (CV) curve of the flexible asymmetric supercapacitor made in example 1;
FIG. 5 is a constant current charge and discharge (GCD) curve of the flexible asymmetric supercapacitor made in example 1;
FIG. 6 is the specific capacitance of the flexible asymmetric supercapacitor made in example 1 at different current densities;
FIG. 7 shows the capacity retention of the flexible asymmetric supercapacitor made in example 1 after 10000 cycles;
fig. 8 shows the capacity retention of the flexible asymmetric supercapacitor made in example 1 during 500 bending folds.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The term "room temperature" as used herein means 20 to 25 ℃ unless otherwise specified.
The raw materials used in the examples of the present invention are all available from commercially available sources unless otherwise specified.
Example 1
when the film is an anode electrode material: the electrolyte contains 0.5M Mn (CH) 3 COO) 2 And 0.5M Na 2 SO 4 By anode constant current deposition method with current density of 10mA cm -2 The deposition time is 900s, and compact MnO with a layer deposited on the surface is obtained 2 An anodic film of particles;
when the film is a cathode electrode material: with 0.1M pyrrole and 0.5M H 2 SO 4 The electrolytic solution is used for electropolymerizing pyrrole monomer onto the film, and the deposition current density is 15mA cm -2 The deposition time is 200s, and a layer of microspheres aggregated on the surface is obtainedA cathode film of formed polypyrrole (PPy) particles.
And 4, step 4: preparing a flexible asymmetric supercapacitor: at 20mL of 1.0M H 2 SO 4 Adding 2g of polyvinyl alcohol (PVA), and placing in a water bath at 95 ℃ to stir vigorously for 1H until the solution is completely clarified to form PVA/H 2 SO 4 Gel electrolyte, a layer of compact MnO is deposited on the surface prepared in the step 3 2 Uniformly coating a layer of PVA/H on the surfaces of the anode film of the particles and the cathode film with a layer of polypyrrole (PPy) particles formed by the aggregation of microspheres deposited on the surface 2 SO 4 And gel electrolyte is pressed together, so that the gel electrolyte forms a layer of diaphragm between the two electrode films to form the integrated flexible asymmetric super capacitor.
Fig. 1 shows a photograph of a sample of the carbonized cellulose/graphene film obtained in step 2 of this example. As can be seen from fig. 1, the carbonized cellulose/graphene film prepared in this embodiment has a smooth surface, can be bent and folded to 180 ° without damage, and has very high flexibility.
The scanning electron micrograph of the carbonized cellulose/graphene film obtained in step 2 of this example is shown in fig. 2. As can be seen from fig. 2, a large number of wrinkles exist on the surface of the carbonized cellulose/graphene film, which can provide more active sites for electrodeposition.
The scanning electron microscope images of the anode thin film material and the cathode thin film material prepared in step 3 of this embodiment are shown in fig. 3; wherein, a is anode film material, and b is cathode film material. As can be seen from FIG. 3, a layer of dense MnO is deposited on the surface of the anode film material 2 Particles, MnO 2 The nano particles have higher specific surface area and pseudocapacitance, and are beneficial to the permeation and transmission of electrolyte; a layer of polypyrrole (PPy) particles formed by aggregation of microspheres is deposited on the surface of the cathode film material, and the PPy particles are beneficial to reducing the internal resistance of the capacitor electrode.
The electrochemical performance of the flexible asymmetric supercapacitor prepared in the embodiment was tested in a three-electrode system:
the Cyclic Voltammetry (CV) curve of the flexible asymmetric supercapacitor made in this example is shown in fig. 4;as can be seen from FIG. 4, the CV curve is approximately rectangular in shape, with a pair of weak redox peaks being generated in the rectangle, primarily due to the MnO deposited 2 The result is. As the scan rate increased, the current response increased without any significant change in the shape of the CV curve, indicating that the flexible asymmetric supercapacitor prepared in this example had lower resistance and good rate performance.
The constant current charging and discharging (GCD) curve of the flexible asymmetric supercapacitor prepared in this embodiment is shown in fig. 5; as can be seen from FIG. 5, the GCD curves are both triangular and linear, indicating that the flexible asymmetric supercapacitor has high reversibility and good capacitance characteristics.
The specific capacitance of the flexible asymmetric supercapacitor manufactured by the embodiment under different current densities is shown in fig. 6; as can be seen from FIG. 6, at 1mA cm -2 The area specific capacitance under the current density is up to 1.383F cm -2 At 0.5mW cm -2 Has an energy density of 192.08 [ mu ] Wh cm at a power density of -2 。
The flexible asymmetric super capacitor prepared by the embodiment is 1A g -1 Has a mass specific capacitance of 125.7F g -1 At 5A g -1 Has a mass specific capacitance of 102.5F g at a current density of (2) -1 At 10A g -1 Has a mass specific capacitance of 93F g at a current density of (3) -1 。
The capacitance retention rate of the flexible asymmetric supercapacitor prepared in the embodiment after 10000 cycles is shown in fig. 7, wherein insets are constant current charge and discharge curves of 1-5 times and 9996-10000 times; as can be seen from fig. 7, after the flexible asymmetric supercapacitor prepared in this embodiment is cyclically charged and discharged for 10000 times, the capacitance retention rate is still as high as 90.12%, and the flexible asymmetric supercapacitor has very high capacitance stability.
The capacitance retention rate of the flexible asymmetric supercapacitor prepared in the embodiment in 500 bending and folding processes is shown in fig. 8; as can be seen from fig. 8, the capacitance retention rate is still higher than 80% after 500 folding processes, which indicates that the flexible asymmetric supercapacitor prepared in this embodiment has both mechanical stability and capacitance stability.
Example 2
The same as in example 1 except that the graphene oxide in step 2 was replaced with carbon nanotubes.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. The capacitance value is slightly lower than that of the embodiment 1 through CV and GCD test analysis; at 1mA cm -2 Has an area specific capacitance of 1.08F cm at a current density -2 At 0.5mW cm -2 Power density of 150.41 μ Wh cm -2 。
Example 3
The same as in example 1, except that the carbonization temperature in step 1 was raised to 1000 ℃ and the amount of the carbonized cellulose added in step 2 was 20 mg.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. At 1mA cm -2 Has an area specific capacitance of 1.41F cm at a current density of -2 At 0.5mW cm -2 Power density of 195.78 μ Wh cm -2 。
Example 4
Same as example 1, except that MnO was deposited in step 3 2 The time for the particles was 450s and the time for the deposition of the polypyrrole particles was 100 s.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. At 1mA cm -2 Has an area specific capacitance of 1.21F cm at a current density of -2 At 0.5mW cm -2 Power density of 170.52 μ Wh cm -2 。
Example 5
The same as in example 1, except that the filter paper in step 1 was replaced with microcrystalline cellulose and the amount of the carbonized cellulose added in step 2 was 20 mg.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. At 1mA cm -2 Has an area specific capacitance of 1.31F cm at a current density of -2 At 0.5mW cm -2 Power density ofDegree of 190.8. mu. Wh cm -2 。
Example 6
Same as example 1 except that the filter paper in step 1 was replaced with carboxymethyl cellulose and MnO was deposited in step 3 2 The time for the pellets was 1500s and the time for deposition of the polypyrrole pellets was 400 s.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. At 1mA cm -2 Has an area specific capacitance of 0.85F cm at a current density of -2 At 0.5mW cm -2 Power density of 110.56 μ Wh cm -2 。
Example 7
The same as in example 1, except that the hydrothermal reaction in step 2 was carried out at a temperature of 80 ℃ for 4 hours; in step 3, when the film is an anode electrode material: the electrolyte contains 0.3MMn (CH) 3 COO) 2 And 0.3M Na 2 SO 4 Current density of 8mA cm -2 The deposition time is 1000 s; when the film is a cathode electrode material: with 0.2M pyrrole and 0.3M H 2 SO 4 The pyrrole monomer is electropolymerized on the film by the electrolyte solution, and the deposition current density is 20mA cm -2 The deposition time was 300 s.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. At 1mA cm -2 Has an area specific capacitance of 1.226F cm at a current density of -2 At 0.5mW cm -2 Power density of 165.88 μ Wh cm -2 。
Example 8
The same as example 1, except that the hydrothermal reaction in step 2 was carried out at 100 ℃ for 2 hours; in step 3, when the film is an anode electrode material: the electrolyte contains 0.6M Mn (CH) 3 COO) 2 And 0.6M Na 2 SO 4 The current density is 5mA cm -2 The deposition time is 800 s; when the film is a cathode electrode material: with 0.15M pyrrole and 0.4M H 2 SO 4 The pyrrole monomer is electropolymerized on the film by the electrolyte solution, and the current density is depositedIs 10mA cm -2 The deposition time was 100 s.
As a result: the electrode material and the flexible asymmetric supercapacitor prepared by the embodiment also have very high flexibility. At 1mA cm -2 Has an area specific capacitance of 1.15F cm at a current density of -2 At 0.5mW cm -2 Power density of 154.26. mu. Wh cm -2 。
Comparative example 1
The same as example 1, except that step 3 was omitted and the carbonized cellulose/graphene film obtained in step 2 was directly passed through PVA/H 2 SO 4 The gel is assembled into a flexible symmetrical super capacitor.
As a result: the electrode material prepared by the comparative example and the flexible symmetrical supercapacitor also have very high flexibility. After the cyclic voltammetry test and analysis, all the curves are approximately rectangular and symmetrical, have an energy storage mechanism with the double-electric-layer capacitance characteristic and are 1mA cm -2 Has an area specific capacitance of only 0.621F cm at a current density of -2 At 0.5mW cm -2 Has an energy density of 95.05 [ mu ] Wh cm at a power density of -2 Much lower than in example 1.
Comparative example 2
The same as example 1 except that MnO was electrodeposited only on the surface of the anode thin film in step 3 2 Nano particles, cathode film without any treatment, two electrode film materials are passed through PVA/H 2 SO 4 The gel is assembled into the flexible asymmetric super capacitor.
As a result: the electrode material prepared by the comparative example and the flexible asymmetric supercapacitor also have very high flexibility. The capacitance value is lower than that of the embodiment 1 through CV and GCD test analysis; at 1mA cm -2 Has an area specific capacitance of only 0.98F cm at current density -2 At 0.5mW cm -2 Has an energy density of 120.35 [ mu ] Wh cm at a power density of -2 。
Comparative example 3
The same as example 1, except that in step 3, the anode film is not treated, PPy is deposited on the surface of the cathode film, and the two electrode film materials are passed through PVA/H 2 SO 4 And assembling the gel into the flexible asymmetric supercapacitor.
As a result: the electrode material prepared by the comparative example and the flexible asymmetric supercapacitor also have very high flexibility. The capacitance value is lower than that of the embodiment 1 through CV and GCD test analysis; at 1mA cm -2 Has an area specific capacitance of only 0.87F cm at current density -2 At 0.5mW cm -2 Has an energy density of 110.56 [ mu ] Wh cm at a power density of -2 。
Comparative example 4
As a result: the electrode material and the flexible symmetrical supercapacitor prepared by the comparative example have good flexibility, and are basically consistent with those in the example 1. The capacitance value is far lower than that of the embodiment 1 through CV and GCD test analysis; at 1mA cm -2 Specific area capacitance under current density ofIs 0.57F cm -2 At 0.5mW cm -2 Has an energy density of 67.39. mu. Wh cm at a power density of -2 The capacity retention after 10000 cycles was only 70.58%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A flexible asymmetric super capacitor is characterized in that the raw materials comprise an anode film, a cathode film and a gel electrolyte;
the anode film and the cathode film are both films obtained by compounding carbonized cellulose and graphene or carbon nano tubes;
MnO is loaded on the surface of the anode film 2 Particles;
polypyrrole particles are loaded on the surface of the cathode film;
the preparation method of the flexible asymmetric supercapacitor comprises the following steps:
step 1, carbonizing a cellulose material in an inert gas atmosphere, and cooling and grinding the carbonized cellulose material after carbonization to obtain carbonized cellulose;
step 2, adding the carbonized cellulose into the carbon material dispersion liquid, carrying out hydrothermal reaction, and then carrying out vacuum filtration to obtain a film;
step 3, performing electrodeposition on the film to respectively obtain surface deposition MnO 2 Anode film of the particles and cathode film of polypyrrole particles deposited on the surface;
and 4, coating a layer of gel electrolyte between the anode film and the cathode film to obtain the flexible asymmetric supercapacitor.
2. The flexible asymmetric supercapacitor according to claim 1, wherein the gel electrolyte is PVA/H 2 SO 4 Gel electricityAnd (4) decomposing the materials.
3. The flexible asymmetric supercapacitor according to claim 1, wherein in step 1, the cellulose material is one of cotton fiber, microcrystalline cellulose and carboxymethyl cellulose; the inert gas is nitrogen or argon.
4. The flexible asymmetric supercapacitor according to claim 1, wherein in step 2, the carbon material is graphene or carbon nanotubes.
5. The flexible asymmetric supercapacitor according to claim 1, wherein in the step 2, the carbon material dispersion liquid comprises N, N-dimethylformamide, tannic acid, hydrazine hydrate and water.
6. The flexible asymmetric supercapacitor according to claim 1, wherein in the step 2, the temperature of the hydrothermal reaction is 80-100 ℃ and the time is 2-4 h.
7. The flexible asymmetric supercapacitor according to claim 1, wherein in step 3, electrodeposition is performed in a three-electrode system, and the thin film is used as a working electrode, a platinum electrode is used as a counter electrode, and a calomel electrode is used as a reference electrode.
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