CN112713008A - Carbon-based composite electrode material and preparation method thereof - Google Patents
Carbon-based composite electrode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
Abstract
The invention relates to the technical field of electrode materials, in particular to a carbon-based composite electrode material and a preparation method thereof. Because the specific surface area of the carbon-based material is higher, the conductive polymer is attached to the surface of the carbon-based material in the form of the conductive polymer nanowire array, the active area of the conductive polymer is greatly increased, the capacitance of the carbon-based composite electrode material is further increased, and the charge-discharge cycle stability is good.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a carbon-based composite electrode material and a preparation method thereof.
Background
The rapid increase of global energy consumption and the destruction of traditional fossil energy to the environment pose serious challenges to human health, energy safety and global environment. Therefore, the development of green and renewable energy conversion and storage devices is an important issue for human beings. As a novel green energy storage device, the super capacitor has the advantages of high specific energy of a battery and high specific power of a traditional physical capacitor, has huge application value and market potential in the fields of electric automobiles, hybrid fuel automobiles, special trucks, electric power, railways, communication, national defense, consumer electronics and the like, plays an irreplaceable role of the battery and the traditional capacitor, and is widely concerned by countries in the world.
The electrode material is the key for determining the performance of the supercapacitor, and the carbon-based composite electrode material is concerned by a plurality of researchers due to excellent electrical, physical and chemical properties of the carbon-based composite electrode material. However, the carbon-based composite electrode material in the prior art has unsatisfactory capacitance, and the preparation method is relatively complex, thus being not beneficial to popularization and application.
Disclosure of Invention
Based on the carbon-based composite electrode material and the preparation method thereof, the carbon-based composite electrode material has high specific capacity, and the preparation method is simple and easy to operate.
A carbon-based composite electrode material comprises a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of poly (ethylenedioxythiophene) and polyacetylene.
According to the carbon-based composite electrode material, the specific surface area of the carbon-based material is high, and the conductive polymer is attached to the surface of the carbon-based material in the form of the conductive polymer nanowire array, so that the active area of the conductive polymer is greatly increased, the capacitance of the carbon-based composite electrode material is further increased, and the charge-discharge cycle stability is good.
In one embodiment, the mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.5-1: 2 to 6.
In one embodiment, the mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.7-0.8: 4 to 6.
In one embodiment, the mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
60 to 90 percent of carbon-based material,
10 to 40 percent of conductive polymer.
In one embodiment, the carbon-based material is graphene and/or graphene oxide; and/or the presence of a gas in the gas,
the graphene or graphene oxide is a granular material with the grain diameter of 0.01-2 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
preparing electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen, wherein the electrolyte is an aqueous solution of a conductive polymer, a doping agent and an oxidizing agent;
cleaning the carbon-based material;
dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, carrying out electrochemical reaction, and generating a conductive polymer nanowire array on the surface of the carbon-based material.
In one embodiment, in the electrochemical reaction, the temperature of the electrolyte is raised to 45-50 ℃ from room temperature at a temperature raising rate of 1-5 ℃/min.
In one embodiment, the current density of the electrochemical reaction is 0.05-2m.Acm-2The potential is 0.6-1.2V, and the energizing time is 1-3 hours.
In one embodiment, the concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are: 0.01-0.1mol.L-10.02 to 1mol.L of the conductive polymer-10.01 to 1mol.L of the dopant-1An oxidizing agent of (1).
In one embodiment, the dopant is a mixture of beta-naphthalene sulfonic acid and perchloric acid; and/or the doping agent is mixed with the following components in a mass ratio of 1: 1 to 3 of a mixture of beta-naphthalenesulfonic acid and perchloric acid.
In one embodiment, the oxidizing agent is ammonium persulfate or ferric chloride.
Drawings
FIG. 1 is a specific capacity curve diagram of carbon-based composite electrode materials of example 2 and comparative examples 1-2 of the present invention;
FIG. 2 is a graph of cyclic voltammetry performance of carbon-based composite electrode materials of example 2 and comparative examples 1 to 2 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a carbon-based composite electrode material which comprises a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylene dioxythiophene and polyacetylene.
According to the carbon-based composite electrode material, the specific surface area of the carbon-based material is high, the conductive polymer is attached to the surface of the carbon-based material in the form of the conductive polymer nanowire array, and the nanowires of the conductive polymer are arranged into the orderly nanowire array, so that the active area of the conductive polymer is greatly increased, the capacitance of the carbon-based composite electrode material is further increased, and the charge-discharge cycle stability is good.
In one embodiment, the mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.5-1: 2 to 6, excellent adhesion forming effect and stability, and excellent capacitance. Preferably, the mass ratio of the mixture of the polyethylenedioxythiophene to the polyacetylene is 0.7-0.8: 4 to 6.
In one embodiment, the mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
60 to 90 percent of carbon-based material,
10 to 40 percent of conductive polymer.
The carbon-based material is selected from graphene and/or graphene oxide, and further, the graphene or graphene oxide is a granular material with the grain diameter of 0.01-2 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: preparing electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen, wherein the electrolyte is an aqueous solution of a conductive polymer, a doping agent and an oxidizing agent.
The electrolyte is prepared by adding the conductive polymer, the dopant and the oxidant into water in proportion and stirring the mixture evenly.
The time of introducing oxygen is 10-30 min, the electrolyte is stirred and dispersed, dissolved oxygen in the electrolyte is increased to promote subsequent oxidation reaction, and oxygen introduction is stopped during electrochemical reaction.
In one embodiment, the concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are: 0.01-0.1mol.L-10.02 to 1mol.L of the conductive polymer-10.01 to 1mol.L of the dopant-1An oxidizing agent of (1).
The dopant is a mixture of beta-naphthalenesulfonic acid and perchloric acid; preferably, the dopant is selected from the group consisting of 1: 1 to 3 of a mixture of beta-naphthalenesulfonic acid and perchloric acid.
The oxidant is ammonium persulfate or ferric chloride.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, carrying out electrochemical reaction, and generating a conductive polymer nanowire array on the surface of the carbon-based material.
In the electrochemical reaction, the temperature of the electrolyte is increased from room temperature to 45-50 ℃ at the temperature increase rate of 1-5 ℃/min.
The current density of the electrochemical reaction is 0.05-2m.Acm-2The potential is 0.6-1.2V, and the energizing time is 1-3 hours.
The preparation method of the carbon-based composite electrode material has the advantages of uncomplicated process, simple operation, less adopted components, difficult interference by impurities and good preparation effect.
The following is an example description.
Example 1
The carbon-based composite electrode material of the embodiment includes a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylenedioxythiophene and polyacetylene.
Nanowires of conducting polymers are displayed as ordered nanowire arrays.
The mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
61 percent of the carbon-based material,
39% of conductive polymer.
The mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 1: 6.
the carbon-based material is graphene particles with the particle size of 0.01-0.1 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: the method comprises the steps of putting a conductive polymer, a doping agent and an oxidizing agent into water in proportion, uniformly stirring to obtain an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen for 30min, wherein the electrolyte is an aqueous solution of the conductive polymer, the doping agent and the oxidizing agent.
The concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.05mol.L-10.1mol.L of the conductive polymer-1And 0.1mol.L of-1An oxidizing agent of (1).
The doping agent is 1: 1 β -naphthalenesulfonic acid and perchloric acid.
The oxidant is ferric chloride.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing carbon-based material in electrolyte, using the carbon-based material as a working electrode and using a platinum sheet as a counter electrodeTaking a saturated calomel electrode as a reference electrode, heating the temperature of the electrolyte to 45 ℃ from room temperature at a heating rate of 2 ℃/min, and carrying out electrochemical reaction, wherein the current density of the electrochemical reaction is 0.05m.Acm-2And generating a conductive polymer nanowire array on the surface of the carbon-based material to obtain the carbon-based composite electrode material, wherein the potential is 1.0V, and the electrifying time is 1 hour.
Example 2
The carbon-based composite electrode material of the embodiment includes a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylenedioxythiophene and polyacetylene.
Nanowires of conducting polymers are displayed as ordered nanowire arrays.
The mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
68 percent of carbon-based material,
32% of conductive polymer.
The mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.7: 5.
the carbon-based material is graphene oxide particles with the particle size of 0.5-1 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: the method comprises the steps of putting a conductive polymer, a doping agent and an oxidizing agent into water in proportion, uniformly stirring to obtain an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen for 15min, wherein the electrolyte is an aqueous solution of the conductive polymer, the doping agent and the oxidizing agent.
The concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.01mol.L-10.5mol.L of the conductive polymer-1And 1mol.L of a dopant-1An oxidizing agent of (1).
The doping agent is 1: 2 β -naphthalenesulfonic acid and perchloric acid.
The oxidant is ammonium persulfate.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, heating the temperature of the electrolyte to 50 ℃ from room temperature at a heating rate of 2.5 ℃/min, and carrying out electrochemical reaction, wherein the current density of the electrochemical reaction is 2m.Acm-2And generating a conductive polymer nanowire array on the surface of the carbon-based material to obtain the carbon-based composite electrode material, wherein the potential is 0.8V, and the electrifying time is 3 hours.
Example 3
The carbon-based composite electrode material of the embodiment includes a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylenedioxythiophene and polyacetylene.
Nanowires of conducting polymers are displayed as ordered nanowire arrays.
The mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
the carbon-based material accounts for 73%,
27% of conductive polymer.
The mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.8: 4.
the carbon-based material is graphene oxide particles with the particle size of 1.5-2 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: the method comprises the steps of putting a conductive polymer, a doping agent and an oxidizing agent into water in proportion, uniformly stirring to obtain an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen for 10min, wherein the electrolyte is an aqueous solution of the conductive polymer, the doping agent and the oxidizing agent.
The concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.1mol.L-10.5mol.L of the conductive polymer-1And 1mol.L of a dopant-1An oxidizing agent of (1).
The doping agent is 1: 3 β -naphthalenesulfonic acid and perchloric acid.
The oxidant is ammonium persulfate.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, heating the temperature of the electrolyte to 50 ℃ from room temperature at a heating rate of 5 ℃/min, and carrying out electrochemical reaction, wherein the current density of the electrochemical reaction is 1.0m.Acm-2And generating a conductive polymer nanowire array on the surface of the carbon-based material to obtain the carbon-based composite electrode material, wherein the potential is 1.2V, and the electrifying time is 1 hour.
Example 4
The carbon-based composite electrode material of the embodiment includes a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylenedioxythiophene and polyacetylene.
Nanowires of conducting polymers are displayed as ordered nanowire arrays.
The mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.5: 5.
the mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
the carbon-based material accounts for 77%,
23% of conductive polymer.
The carbon-based material is graphene oxide particles with the particle size of 1-1.5 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: the method comprises the steps of putting a conductive polymer, a doping agent and an oxidizing agent into water in proportion, uniformly stirring to obtain an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen for 10min, wherein the electrolyte is an aqueous solution of the conductive polymer, the doping agent and the oxidizing agent.
The concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.03mol.L-10.5mol.L of the conductive polymer-1And 1mol.L of a dopant-1An oxidizing agent of (1).
The doping agent is 1: 1 β -naphthalenesulfonic acid and perchloric acid.
The oxidant is ammonium persulfate.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, heating the temperature of the electrolyte to 48 ℃ from room temperature at a heating rate of 4 ℃/min, and carrying out electrochemical reaction, wherein the current density of the electrochemical reaction is 0.1m.Acm-2And generating a conductive polymer nanowire array on the surface of the carbon-based material to obtain the carbon-based composite electrode material, wherein the potential is 1V, and the electrifying time is 3 hours.
Example 5
The carbon-based composite electrode material of the embodiment includes a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylenedioxythiophene and polyacetylene.
Nanowires of conducting polymers are displayed as ordered nanowire arrays.
The mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
the carbon-based material accounts for 83 percent,
17% of conductive polymer.
The mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.7: 6.
the carbon-based material is graphene oxide particles with the particle size of 1-2 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: the method comprises the steps of putting a conductive polymer, a doping agent and an oxidizing agent into water in proportion, uniformly stirring to obtain an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen for 20min, wherein the electrolyte is an aqueous solution of the conductive polymer, the doping agent and the oxidizing agent.
The concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.1mol.L-11mol.L of the conductive polymer-1And 0.02mol.L of-1An oxidizing agent of (1).
The doping agent is 1: 3 β -naphthalenesulfonic acid and perchloric acid.
The oxidant is ferric chloride.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, heating the temperature of the electrolyte to 50 ℃ from room temperature at a heating rate of 5 ℃/min, and carrying out electrochemical reaction, wherein the current density of the electrochemical reaction is 1.5m.Acm-2And generating a conductive polymer nanowire array on the surface of the carbon-based material to obtain the carbon-based composite electrode material, wherein the potential is 1.2V, and the electrifying time is 2 hours.
Example 6
The carbon-based composite electrode material of the embodiment includes a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylenedioxythiophene and polyacetylene.
Nanowires of conducting polymers are displayed as ordered nanowire arrays.
The mass contents of the carbon-based material and the conductive polymer in the carbon-based composite electrode material are respectively as follows:
89% of the carbon-based material,
11% of conductive polymer.
The mass ratio of the mixture of the polyethylenedioxythiophene and the polyacetylene is 0.6: 6.
the carbon-based material is graphene oxide particles with the particle size of 0.8-1 mu m.
The preparation method of the carbon-based composite electrode material is a template-free electrochemical method and comprises the following steps:
s100: the method comprises the steps of putting a conductive polymer, a doping agent and an oxidizing agent into water in proportion, uniformly stirring to obtain an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen for 15min, wherein the electrolyte is an aqueous solution of the conductive polymer, the doping agent and the oxidizing agent.
The concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.05mol.L-10.5mol.L of the conductive polymer-1And 0.01mol.L-1An oxidizing agent of (1).
The doping agent is 1: 1 β -naphthalenesulfonic acid and perchloric acid.
The oxidant is ferric chloride.
S200: cleaning the carbon-based material, ultrasonically cleaning the carbon-based material by using water, and then drying the carbon-based material.
S300: dispersing a carbon-based material in an electrolyte, taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, heating the temperature of the electrolyte to 46 ℃ from room temperature at a heating rate of 4 ℃/min, and carrying out electrochemical reaction, wherein the current density of the electrochemical reaction is 0.5m.Acm-2And generating a conductive polymer nanowire array on the surface of the carbon-based material to obtain the carbon-based composite electrode material, wherein the potential is 0.8V, and the electrifying time is 2 hours.
Comparative example 1
A carbon-based composite electrode material was prepared in substantially the same manner as in example 2, except that: the conductive polymer is only polyethylene dioxythiophene and does not contain polyacetylene.
Comparative example 2
A carbon-based composite electrode material was prepared in substantially the same manner as in example 2, except that: the conductive polymer is only polyacetylene and does not contain polyethylenedioxythiophene.
Performance testing
The carbon-based composite electrode materials of example 2 and comparative examples 1-2 were tested using the following methods:
cyclic voltammetry was used to test the cyclic voltammetry performance of the carbon-based composite electrode material, and the results are shown in fig. 1.
The electrochemical capacity performance of the carbon-based composite electrode material is shown in fig. 2.
Test results show that the performance of the carbon-based composite electrode material in the embodiment 2 is superior to that of the comparative examples 1-2, and when the conductive polymer is a mixture of polyethylene dioxythiophene and polyacetylene, the carbon-based composite electrode material has good electrical performance, high specific capacity and stable charge-discharge cycle.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express one embodiment of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The carbon-based composite electrode material is characterized by comprising a carbon-based material and a conductive polymer attached to the carbon-based material, wherein the conductive polymer is attached to the surface of the carbon-based material in the form of a conductive polymer nanowire array, and the conductive polymer is a mixture of polyethylene dioxythiophene and polyacetylene.
2. The carbon-based composite electrode material as claimed in claim 1, wherein the mass ratio of the mixture of polyethylenedioxythiophene and polyacetylene is 0.5-1: 2 to 6.
3. The carbon-based composite electrode material as claimed in claim 2, wherein the mass ratio of the mixture of polyethylenedioxythiophene and polyacetylene is 0.7-0.8: 4 to 6.
4. The carbon-based composite electrode material according to claim 1, wherein the carbon-based material and the conductive polymer in the carbon-based composite electrode material are contained in the following amounts by mass:
60 to 90 percent of carbon-based material,
10 to 40 percent of conductive polymer.
5. The carbon-based composite electrode material according to claim 1, wherein the carbon-based material is graphene and/or graphene oxide; and/or the presence of a gas in the gas,
the graphene or graphene oxide is a granular material with the grain size of 0.01-2 mu m.
6. The method for preparing the carbon-based composite electrode material according to any one of claims 1 to 5, wherein the preparation method is a template-free electrochemical method comprising the steps of:
preparing an electrolyte, putting the electrolyte into an electrolytic cell, and introducing oxygen, wherein the electrolyte is an aqueous solution of a conductive polymer, a doping agent and an oxidizing agent;
cleaning the carbon-based material;
and dispersing the particles of the carbon-based material in the electrolyte, carrying out electrochemical reaction by taking the carbon-based material as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and generating a conductive polymer nanowire array on the surface of the carbon-based material.
7. The preparation method of the carbon-based composite electrode material according to claim 6, wherein in the electrochemical reaction, the temperature of the electrolyte is raised from room temperature to 45-50 ℃ at a temperature raising rate of 1-5 ℃/min.
8. Carbon-based composite electrode material according to claim 7 and use thereofThe preparation method is characterized in that the current density of the electrochemical reaction is 0.05-2m.Acm-2The potential is 0.6-1.2V, and the energizing time is 1-3 hours.
9. The carbon-based composite electrode material and the preparation method thereof according to claim 6, wherein the concentrations of the conductive polymer, the dopant and the oxidant in the electrolyte are respectively as follows: 0.01-0.1mol.L-10.02 to 1mol.L of the conductive polymer-10.01 to 1mol.L of the dopant-1An oxidizing agent of (1).
10. The carbon-based composite electrode material and the preparation method thereof according to claim 6, wherein the dopant is a mixture of β -naphthalenesulfonic acid and perchloric acid; and/or the oxidant is ammonium persulfate or ferric chloride.
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| US9552929B2 (en) * | 2013-07-15 | 2017-01-24 | Clemson University | Polymer-nanocarbon composites, methods of making composites, and energy storage devices including the composite |
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2020
- 2020-12-15 CN CN202011477611.7A patent/CN112713008A/en active Pending
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- 2021-03-12 WO PCT/CN2021/080382 patent/WO2022126875A1/en active Application Filing
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| CN102222565A (en) * | 2010-04-15 | 2011-10-19 | 国家纳米科学中心 | Carbon-based composite electrode material and preparation method thereof, and application of the carbon-based composite electrode material to super capacitor |
| CN101857191A (en) * | 2010-04-16 | 2010-10-13 | 华侨大学 | Flexible transduction/energy-storage nanodevice and preparation method |
| CN101887966A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon cathode material of lithium ion battery and preparation method thereof |
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