CN118026155A - Graphene-based electrode material and preparation method and application thereof - Google Patents
Graphene-based electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
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- 238000011282 treatment Methods 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
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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
- H01G11/84—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention provides a graphene-based electrode material, and a preparation method and application thereof, and belongs to the technical field of electrode materials. According to the preparation method, the wet graphite oxide film is subjected to flame plasma induction treatment, and the action among graphene oxide sheets is controlled by utilizing the hydrogen bond action between water molecules and oxygen-containing functional groups in the graphite oxide, so that the graphite oxide film is not fully peeled into flaky reduced graphene oxide by gas generated by decomposition in the flame plasma induced decomposition process, and a reduced graphene oxide porous net-shaped film is formed. The method provided by the invention is simple to operate, low in consumption and high in efficiency, and can be suitable for preparing the reduced graphene oxide porous reticular film material in a large scale. In addition, the prepared electrode material has a porous network structure, so that the capacity of the graphene-based electrode material can be effectively improved, and the prepared material has good conductivity, high specific capacitance and long cycle service life when used for super capacitors.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a graphene-based electrode material, and a preparation method and application thereof.
Background
In recent years, with the increasing demand of new energy mobile devices, the demand of fast-charging new energy storage devices with high power density, high energy density and long service life is also increasing. The super capacitor has the advantages of quick charge, high power and long service life, and is considered as a new energy storage device with great development potential. Graphene-based materials, particularly reduced graphene oxide, are more widely used in the construction of supercapacitors due to the combination of large specific surface area, high conductivity, and more defects and active sites.
At present, the traditional preparation method of the supercapacitor electrode is that reduced graphene oxide and the like are ground into paste with a binder and the like, and then two pieces of foam nickel are pressed together, and the method has the defect that the conductivity between graphene sheets is poor; the binder is non-conductive, reducing conductivity; the morphology of the graphene can be damaged during grinding, so that the performance of the electrode is reduced; in the charge and discharge process, the volume of the powdery reduced graphene oxide expands in the use process due to irregular accumulation, so that the service life of the powdery reduced graphene oxide is obviously reduced; and the weak interaction between the lamellar layers of the lamellar reduced graphene oxide leads to insufficient establishment of a conductive network, so that shedding and charge transfer are blocked, and the energy storage capacity of the lamellar reduced graphene oxide is reduced.
In addition, the common preparation methods of the reduced graphene oxide are a hydrothermal method, a solvothermal method, a high-temperature thermal decomposition method, a chemical reduction method, a flame method, a microwave method and the like. However, the existing method has the problems of complicated and time-consuming preparation process, special equipment, incapacity of mass production, toxic reaction reagent, high-temperature and high-pressure process, poor performance of preparing reduced graphene oxide, high cost and the like.
Therefore, there is still a need to develop a preparation method of graphene-based electrode materials, which is simple to operate, efficient, capable of mass production and excellent in electrochemical performance.
Disclosure of Invention
The invention aims to provide a graphene-based electrode material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a graphene-based electrode material, which comprises the following steps:
(1) Carrying out wetting treatment on the graphite oxide film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1) to obtain the graphene-based electrode material.
Preferably, the oxygen atom content of the graphite oxide in the graphite oxide film in the step (1) is 25 to 30at.%.
Preferably, the thickness of the graphite oxide film in the step (1) is 10 to 40 μm.
Preferably, the method of the wetting treatment in the step (1) includes: and standing the graphite oxide film in a steam environment until the graphite oxide film absorbs water to be saturated, so as to obtain the wet graphite oxide film.
Preferably, the temperature of the water vapor environment is 25-50 ℃.
Preferably, the time of the standing is 0.5 to 5 hours.
Preferably, the method of flame plasma induction treatment in the step (2) includes: the graphite oxide film is contacted with the outer flame of the flame.
Preferably, the time of said contacting is < 3s.
The invention also provides the graphene-based electrode material prepared by the preparation method of the technical scheme, and the graphene-based electrode material is of a porous network structure.
The invention also provides application of the graphene-based electrode material in serving as a working electrode of the supercapacitor.
The invention provides a preparation method of a graphene-based electrode material, which comprises the following steps: carrying out wetting treatment on the graphite oxide film to obtain a wet graphite oxide film; and performing flame plasma induction treatment on the wet graphite oxide film to obtain the graphene-based electrode material. According to the invention, firstly, the graphite oxide film is subjected to wetting treatment, so that on one hand, the flexibility of the graphite oxide film is changed, the graphite oxide film is flexible and foldable, and on the other hand, water molecules can be intercalated between graphene oxide sheets in the graphite oxide through hydrogen bonding, and the interaction between the graphene oxide sheets is changed; and because the specific heat capacity of water is large, the existence of water molecules can well absorb part of heat generated in the decomposition process of the graphene oxide sheets, so that the gas generated by decomposition is cooled, the expansion pressure of the gas is reduced, and the stripping capacity of the decomposed gas to the reduced graphene oxide sheets is further reduced. According to the preparation method, the wet graphite oxide film is subjected to flame plasma induction treatment, and the action among graphene oxide sheets is controlled by utilizing the hydrogen bond action between water molecules in the wet graphite oxide and oxygen-containing functional groups in the graphite oxide, so that the graphene oxide film is not fully peeled into flake-shaped reduced graphene oxide by gas generated by decomposition in the flame plasma induced decomposition process, and a porous net-shaped reduced graphene oxide film is formed.
The method provided by the invention is simple to operate, low in consumption and high in efficiency, and can be suitable for preparing the reduced graphene oxide porous reticular film material in a large scale. In addition, the prepared electrode material has a porous network structure, so that the capacity of the graphene-based electrode material can be effectively improved, the problem that high-performance reduced graphene oxide is difficult to produce in a large-scale manner in the prior art is solved, and the prepared material is good in conductivity, high in specific capacitance and long in cycle service life when used for super capacitors. The example results show that the graphene-based electrode material prepared by the invention has the following characteristics: ① The specific capacitance is ultrahigh and is 230-280F/g; ② The cycle service life is long, and the 10000 circles of capacity is kept to be more than 90%; ③ Good conductivity and charge transfer impedance <1 omega.
Drawings
FIG. 1 is an optical photograph of a graphene-based electrode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a graphene-based electrode material prepared according to example 1 of the present invention;
FIG. 3 is an XPS spectrum of a graphene-based electrode material prepared in example 1 of the present invention;
FIG. 4 is a Raman spectrum of the graphene-based electrode material prepared in example 1 of the present invention;
FIG. 5 is an optical photograph of the reduced graphene oxide powder electrode material prepared in comparative example 1 of the present invention;
fig. 6 is an SEM image of the reduced graphene oxide powder electrode material prepared in comparative example 1 of the present invention;
FIG. 7 is an XPS spectrum of a reduced graphene oxide powder electrode material prepared in comparative example 1 of the present invention;
FIG. 8 is a Raman spectrum of the reduced graphene oxide powder electrode material prepared in comparative example 1 of the present invention;
FIG. 9 is a GCD graph at a current density of 1A/g for graphene-based electrode material prepared in example 1 of the present invention;
FIG. 10 is a GCD graph at a current density of 1A/g for the reduced graphene oxide powder electrode material prepared in comparative example 1 of the present invention;
FIG. 11 is a graph showing the specific capacitance of the graphene-based electrode material prepared in example 1 of the present invention and the reduced graphene oxide powder electrode material prepared in comparative example 1;
FIG. 12 is an EIS diagram of a graphene-based electrode material prepared in example 1 of the present invention;
FIG. 13 is an EIS diagram of a reduced graphene oxide powder electrode material prepared in comparative example 1 of the present invention;
Fig. 14 is a graph showing cycle life comparison of the graphene-based electrode material prepared in example 1 of the present invention and the reduced graphene oxide powder electrode material prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of a graphene-based electrode material, which comprises the following steps:
(1) Carrying out wetting treatment on the graphite oxide film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1) to obtain the graphene-based electrode material.
The invention carries out wetting treatment on the graphite oxide film to obtain the wet graphite oxide film.
In the present invention, the oxygen atom content of the graphite oxide in the graphite oxide film is preferably 25 to 30at.%, more preferably 28 to 30at.%. In the present invention, the thickness of the graphite oxide film is preferably 10 to 40. Mu.m, more preferably 10 to 20. Mu.m. When the graphite oxide is adopted, the oxygen-containing functional group and the water molecule have proper hydrogen bonding effect, so that the graphene-based electrode material is more beneficial to control to have a three-dimensional network structure.
The preparation method of the graphite oxide film is not particularly limited, and the graphite oxide film with the required thickness can be formed by adopting a conventional method.
The preparation method of the graphite oxide is not particularly limited, and the graphite oxide is prepared by a conventional method. In the present invention, the preparation method of the graphite oxide is preferably a Hummers method, STANDENMAIER method or a Brodie method.
In the present invention, the method of the wetting treatment preferably includes: and standing the graphite oxide film in a steam environment until the graphite oxide film absorbs water to be saturated, so as to obtain the wet graphite oxide film. The invention wets the graphite oxide film by utilizing the water vapor, so that water molecules can fully enter between the graphite oxide film layers, the graphite oxide film can be fully wetted, and the graphite oxide film can not be scattered.
In the present invention, the temperature of the water vapor atmosphere is preferably 25 to 50 ℃, more preferably 30 to 45 ℃. In the present invention, the time for the standing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours. The present invention can sufficiently wet the graphite oxide film under the above conditions.
The apparatus for forming the vapor atmosphere is not particularly limited, and the atmosphere may be filled with vapor to wet the graphite oxide film. In the invention, the device for forming the water vapor environment is preferably a sealing groove for distributing water at the bottom. By adopting the device, the environment full of water vapor can be formed in the sealing groove through water evaporation.
After the wet graphite oxide film is obtained, the wet graphite oxide film is subjected to flame plasma induction treatment to obtain the graphene-based electrode material.
In the present invention, the method of flame plasma induction treatment comprises: the graphite oxide film is contacted with the outer flame of the flame.
In the present invention, the time of the contact is preferably less than 3s. In the present invention, when the contact time is in the above range, the graphene oxide film can be formed into a porous mesh-like reduced graphene oxide film without being sufficiently peeled off into a sheet-like reduced graphene oxide by the gas generated by the decomposition in the flame plasma-induced decomposition process.
In the present invention, the flame preferably includes a flame generated by combustion of ethanol, methanol or acetone. According to the invention, the flame generated by the solvent is used as flame plasma, so that the wet graphite oxide film can be rapidly induced to be fully reduced into the reduced graphene oxide, and the hydrogen bond action of water molecules in the wet graphite oxide film and oxygen-containing functional groups in the graphite oxide film can be utilized, so that the graphene oxide sheet is not fully stripped into the sheet-shaped reduced graphene oxide by the gas generated by decomposition in the flame plasma induced decomposition process, and the porous net-shaped reduced graphene oxide film is formed.
According to the preparation method, the wet graphite oxide film is subjected to flame plasma induction treatment, and the action among graphene oxide sheets is controlled by utilizing the hydrogen bond action between water molecules in the wet graphite oxide and oxygen-containing functional groups in the graphite oxide, so that the graphene oxide film is not fully stripped into reduced graphene oxide sheets by gas generated by decomposition in the flame plasma induced decomposition process, and a porous net-shaped reduced graphene oxide film is formed. The method provided by the invention is simple to operate, low in consumption and high in efficiency, and can be suitable for preparing the reduced graphene oxide porous reticular film material in a large scale.
The invention also provides the graphene-based electrode material prepared by the preparation method. In the invention, the graphene-based electrode material is in a porous network structure.
The invention also provides application of the graphene-based electrode material in serving as a working electrode of the supercapacitor.
In the invention, the application method of the graphene-based electrode material in the working electrode of the supercapacitor preferably comprises the following steps: and placing the graphene-based electrode material between two pieces of foam nickel, and pressing to obtain the working electrode. The pressing pressure and time are not particularly limited, and the pressing pressure and time can be adjusted according to the needs. In the present invention, the pressing pressure is preferably 8Mpa, and the pressing time is preferably 10min.
The prepared electrode material has a porous network structure, so that the capacity of the graphene-based electrode material can be effectively improved, the problem that high-performance reduced graphene oxide is difficult to produce in a large-scale manner in the prior art is solved, and the prepared material has good conductivity, high specific capacitance and long cycle service life when used for super capacitors.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of graphene-based electrode material comprises the following steps:
(1) Preparation of graphite oxide film by Hummers method in chemical exfoliation method: weighing 1g of crystalline flake graphite and 0.5g of sodium nitrate, placing the crystalline flake graphite and 0.5g of sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding magneton, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate, adding the potassium permanganate into a reactor, continuing stirring for 1H, transferring the reactor into a water bath at 35 ℃ after the reaction is finished, continuing stirring for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into an oil bath at 98 ℃, continuing stirring for 15min, sequentially adding 140mL of distilled water and 30% of H 2O2 mL of the mass percentage, centrifuging after the reaction system is finally bright yellow, sequentially washing the solution into neutrality by using 500mL of hydrochloric acid with the mass percentage of 5% of HCl and distilled water, placing the solution on the surface of a surface dish, and drying to prepare a graphite oxide (oxygen atom content is 25-30 at%) film with the thickness of 10-20 mu m;
Placing the prepared graphite oxide film on the surface of a foam plate floating on the water surface, keeping the water temperature at 25 ℃, and sealing and standing the whole water tank for 3 hours by using a preservative film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1), wherein the method comprises the following steps: and placing the wet graphite oxide film on the surface of the porous metal net, then moving the wet graphite oxide film into a flame zone, immediately removing the flame zone after the wet graphite oxide film turns black from brown, and obtaining the graphene-based electrode material in the whole process of less than 3 s.
Example 2
A preparation method of graphene-based electrode material comprises the following steps:
(1) Preparation of graphite oxide by STANDENMAIER method in chemical stripping method: weighing 17.5mL of concentrated sulfuric acid and 9mL of concentrated nitric acid into a 250mL flask, and stirring for 15min; 1g of graphite was weighed and slowly added to the flask; after stirring evenly, adding 11g of potassium chlorate and reacting for 96 hours; washing with 800mL of distilled water, washing with 5% diluted hydrochloric acid, washing with distilled water to be neutral, placing on the surface of a surface dish, and drying to obtain a graphite oxide (with the oxygen atom content of 25-30 at%) film with the thickness of 10-20 mu m;
Placing the prepared graphite oxide film on the surface of a foam plate floating on the water surface, keeping the water temperature at 50 ℃, and sealing and standing the whole water tank for 0.5h by utilizing a preservative film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1), wherein the method comprises the following steps: and placing the wet graphite oxide film on the surface of the porous metal net, then moving the wet graphite oxide film into a flame zone, immediately removing the flame zone after the wet graphite oxide film turns black from brown, and obtaining the graphene-based electrode material in the whole process of less than 3 s.
Example 3
A preparation method of graphene-based electrode material comprises the following steps:
(1) Graphite oxide was prepared by Hummers method in chemical exfoliation: weighing 1g of crystalline flake graphite and 0.5g of sodium nitrate, placing the crystalline flake graphite and 0.5g of sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding magneton, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate, adding the potassium permanganate into a reactor, continuing stirring for 1H, transferring the reactor into a water bath at 35 ℃ after the reaction is finished, continuing stirring for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into an oil bath at 98 ℃, continuing stirring for 15min, sequentially adding 140mL of distilled water and 30% of H 2O2 mL of the mass percentage, centrifuging after the reaction system is finally bright yellow, sequentially washing the solution into neutrality by using 500mL of hydrochloric acid with the mass percentage of 5% of HCl and distilled water, placing the solution on the surface of a surface dish, and drying to prepare a graphite oxide (oxygen atom content is 25-30 at%) film with the thickness of 15-20 mu m;
placing the prepared graphite oxide film on the surface of a foam plate floating on the water surface, keeping the water temperature at 40 ℃, and sealing and standing the whole water tank for 1h by using a preservative film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1), wherein the method comprises the following steps: and placing the wet graphite oxide film on the surface of the porous metal net, then moving the wet graphite oxide film into a flame zone, immediately removing the flame zone after the wet graphite oxide film turns black from brown, and obtaining the graphene-based electrode material in the whole process of less than 3 s.
Example 4
A preparation method of graphene-based electrode material comprises the following steps:
(1) Preparation of graphite oxide by the Brodie method in chemical stripping: weighing 2g of graphite powder, adding the graphite powder into 3mL of concentrated sulfuric acid containing 3g K 2S2O8 and 3g of P 2O5, heating at 80 ℃ for 6 hours, cooling to room temperature, diluting with distilled water, washing to be neutral, drying to obtain pre-oxidized graphite, weighing 1g of the obtained pre-oxidized graphite, adding the obtained pre-oxidized graphite into 46mL of concentrated sulfuric acid, adding 3g of potassium permanganate under the ice water bath condition, and reacting for 2 hours at 35 ℃; adding 46mL of distilled water after the reaction, slowly adding 280mL of distilled water and 5mL of 30% hydrogen peroxide, centrifuging while the mixture is hot, washing the mixture to be neutral by 500mL of 5% diluted hydrochloric acid and a large amount of distilled water, placing the mixture on the surface of a surface dish, and drying to obtain a graphite oxide (the oxygen atom content is 25-30 at%) film with the thickness of 15-20 mu m;
placing the prepared graphite oxide film on the surface of a foam plate floating on the water surface, keeping the water temperature at 25 ℃, and sealing and standing the whole water tank for 5 hours by using a preservative film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1), wherein the method comprises the following steps: and placing the wet graphite oxide film on the surface of the porous metal net, then moving the wet graphite oxide film into a flame zone, immediately removing the flame zone after the wet graphite oxide film turns black from brown, and obtaining the graphene-based electrode material in the whole process of less than 3 s.
Example 5
A preparation method of graphene-based electrode material comprises the following steps:
(1) Graphite oxide was prepared by Hummers method in chemical exfoliation: weighing 1g of crystalline flake graphite and 0.5g of sodium nitrate, placing the crystalline flake graphite and 0.5g of sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding magneton, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate, adding the potassium permanganate into a reactor, continuing stirring for 1H, transferring the reactor into a water bath at 35 ℃ after the reaction is finished, continuing stirring for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into an oil bath at 98 ℃, continuing stirring for 15min, sequentially adding 140mL of distilled water and 30% of H 2O2 mL of the mass percentage, centrifuging after the reaction system is finally bright yellow, sequentially washing the solution into neutrality by using 500mL of hydrochloric acid with the mass percentage of 5% of HCl and distilled water, placing the solution on the surface of a surface dish, and drying to prepare a graphite oxide (oxygen atom content is 25-30 at%) film with the thickness of 15-20 mu m;
Placing the prepared graphite oxide film on the surface of a foam plate floating on the water surface, keeping the water temperature at 25 ℃, and sealing and standing the whole water tank for 1h by using a preservative film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1), wherein the method comprises the following steps: and placing the wet graphite oxide film on the surface of the porous metal net, then moving the wet graphite oxide film into a flame zone, immediately removing the flame zone after the wet graphite oxide film turns black from brown, and obtaining the graphene-based electrode material in the whole process of less than 3 s.
Comparative example 1
A preparation method of graphene-based electrode material comprises the following steps:
(1) Graphite oxide was prepared by Hummers method in chemical exfoliation: weighing 1g of crystalline flake graphite and 0.5g of sodium nitrate, placing the crystalline flake graphite and 0.5g of sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98% and adding magneton, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate and adding the potassium permanganate into a reactor, continuing stirring for 1H, transferring the reactor into a water bath kettle with the temperature of 35 ℃ after the reaction is finished, continuing stirring for 30min, weighing 50mL of distilled water and adding the distilled water into the round-bottom flask, transferring the round-bottom flask into an oil bath with the temperature of 98 ℃, continuing stirring for 15min, sequentially adding 140mL of distilled water and 30% of H 2O2 mL of the mass percentage, centrifuging, sequentially washing the solution into neutrality by using 500mL of hydrochloric acid with the mass percentage of 5% of HCl and distilled water, placing the solution on the surface of a surface dish, and drying to prepare a graphite oxide (oxygen atom content of 25-30 at%) film with the thickness of 15-20 mu m, thus obtaining a graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the graphite oxide film obtained in the step (1), wherein the method comprises the following steps: and placing the graphite oxide film on the surface of the porous metal net, then transferring the graphite oxide film into a flame zone, immediately removing the flame zone after the graphite oxide film turns black from brown, and obtaining the reduced graphene oxide powder electrode material in the whole process of less than 3 s.
Application example 1
A preparation method of a working electrode comprises the following steps: 2mg of the graphene-based electrode material prepared in example 1 was placed between two pieces of foam nickel, and pressed under a pressure of 8Mpa for 10min to prepare a working electrode.
Application example 2
A preparation method of a working electrode comprises the following steps: 2mg of the graphene-based electrode material prepared in example 2 was placed between two pieces of foam nickel, and pressed under a pressure of 8Mpa for 10min to prepare a working electrode.
Application example 3
A preparation method of a working electrode comprises the following steps: 2mg of the graphene-based electrode material prepared in example 3 was placed between two pieces of foam nickel, and pressed under a pressure of 8Mpa for 10min to prepare a working electrode.
Application example 4
A preparation method of a working electrode comprises the following steps: 2mg of the graphene-based electrode material prepared in example 4 was placed between two pieces of foam nickel, and pressed under a pressure of 8Mpa for 10min to prepare a working electrode.
Application example 5
A preparation method of a working electrode comprises the following steps: 2mg of the graphene-based electrode material prepared in example 5 was placed between two pieces of foam nickel, and pressed under a pressure of 8Mpa for 10min to prepare a working electrode.
Comparative application example 1
A preparation method of a working electrode comprises the following steps: 2mg of the graphene-based electrode material prepared in comparative example 1 was placed between two pieces of foam nickel, and pressed under a pressure of 8Mpa for 10min to prepare a working electrode.
Test case
(1) Electrochemical performance test:
The working electrodes prepared in application examples 1 to 5 and comparative example 1 were respectively assembled into a three-electrode system, and the electrochemical properties thereof were tested, and the assembly method of the three-electrode system was as follows: the platinum sheet electrode is used as a counter electrode, the reference electrode is a saturated calomel electrode, the electrolyte solution is 2mol/LKOH aqueous solution, and the testing equipment is an Shanghai Chenhua 660E electrochemical workstation; the charge transfer impedance was obtained by an electrochemical impedance spectroscopy module (a.c. impedance) test in the Shanghai Chenhua 660E electrochemical workstation. Specific capacitance (Cs) was tested by a constant current charge-discharge module (Chronopotentiometry) in the Shanghai Chenhua 660E electrochemical workstation and calculated using the formula cs=it/mΔv, I, t, m, V of which represents discharge current (a), discharge time(s), active substance mass (g), potential difference (V), respectively, and the test results are shown in table 1:
TABLE 1 electrochemical performance test results of working electrodes prepared by application examples 1 to 5 and comparative example 1
| Sample of | Charge transfer impedance (omega) | Specific capacitance (F/g) |
| Application example 1 | ＜1 | 245～260 |
| Application example 2 | ＜1 | 235～243 |
| Application example 3 | ＜1 | 240～250 |
| Application example 4 | ＜1 | 230～240 |
| Application example 5 | ＜1 | 265～280 |
| Comparative example 1 | ＜1 | 180～200 |
(2) Topography testing
FIG. 1 is an optical photograph of graphene-based electrode material prepared in example 1;
FIG. 2 is an SEM image of a graphene-based electrode material prepared in example 1;
FIG. 3 is an XPS spectrum of the graphene-based electrode material prepared in example 1;
Fig. 4 is a Raman spectrum of the graphene-based electrode material prepared in example 1.
As can be seen from fig. 1, the graphene-based electrode material prepared in example 1 was a black, loose, uniform film-like material, which indicates that the film-like material was successfully prepared. As can be seen from fig. 2, the graphene-based electrode material prepared in example 1 is microscopically presented as a porous network structure composed of pleated tissue, indicating that the porous network structure was successfully fabricated. As can be seen from fig. 3, the graphene-based electrode material prepared in example 1 has a low oxygen content, and the oxygen content is 5.8at.% by quantitative analysis, which indicates that reduced graphene oxide is obtained after reduction treatment. As can be seen from fig. 4, the graphene-based electrode material structure prepared in example 1 contains a large number of carbon defects, which indicates that the prepared reduced graphene oxide has a large number of defect structures.
FIG. 5 is an optical photograph of the reduced graphene oxide powder electrode material prepared in comparative example 1;
Fig. 6 is an SEM image of the reduced graphene oxide powder electrode material prepared in comparative example 1;
FIG. 7 is an XPS spectrum of the reduced graphene oxide powder electrode material prepared in comparative example 1;
fig. 8 is a Raman spectrum of the reduced graphene oxide powder electrode material prepared in comparative example 1.
As can be seen from fig. 5, the reduced graphene oxide powder electrode material prepared in comparative example 1 has a black, loose, powdery structure. As can be seen from fig. 6, the reduced graphene oxide powder electrode material prepared in comparative example 1 has a pleated chiffon-like structure. As can be seen from fig. 7, the oxygen content of the reduced graphene oxide powder electrode material prepared from comparative example 1 was 6.2at.%. As can be seen from fig. 8, the reduced graphene oxide powder electrode material structure prepared in comparative example 1 contains a large number of carbon defects.
FIG. 9 is a graph of a constant current charge-discharge curve (GCD) at a current density of 1A/g for the graphene-based electrode material prepared in example 1;
FIG. 10 is a GCD graph at a current density of 1A/g for the reduced graphene oxide powder electrode material prepared in comparative example 1.
As can be seen from fig. 9, the GCD graph of the graphene-based electrode material prepared in example 1 at a current density of 1A/g shows a charge-discharge curve similar to an isosceles triangle, which illustrates the electric double layer energy storage behavior of the supercapacitor. As can be seen from fig. 10, the GCD graph of the reduced graphene oxide powder electrode material prepared from comparative example 1 also exhibits a charge-discharge curve approximating an isosceles triangle at a current density of 1A/g.
Fig. 11 is a graph showing the specific capacitance contrast of the graphene-based electrode material prepared in example 1 and the reduced graphene oxide powder electrode material prepared in comparative example 1. As can be seen from fig. 11, the graphene-based electrode material prepared in example 1 has significantly higher specific capacitance than the reduced graphene oxide powder electrode material prepared in comparative example 1, indicating that it has higher energy storage capacity.
FIG. 12 is an Electrochemical Impedance Spectroscopy (EIS) diagram of the graphene-based electrode material prepared in example 1;
fig. 13 is an EIS diagram of the reduced graphene oxide powder electrode material prepared in comparative example 1.
As can be seen from fig. 12, the EIS diagram of the graphene-based electrode material prepared in example 1 shows a very small semicircle in the high frequency region, which indicates that the charge transfer resistance is small, the charge transfer capability is strong, and the charge exchange is facilitated, thereby obtaining high electrochemical activity. As can be seen from fig. 13, the EIS diagram of the reduced graphene oxide powder electrode material prepared in comparative example 1 also shows a very small semicircle in the high frequency region, indicating that the electric charge transfer resistance is small, the electric charge transfer capability is strong, and the electric charge exchange is facilitated.
Fig. 14 is a graph showing cycle life comparison of the graphene-based electrode material prepared in example 1 and the reduced graphene oxide powder electrode material prepared in comparative example 1. As can be seen from fig. 14, the cycle life of the graphene-based electrode material prepared in example 1 was significantly better than that of the reduced graphene oxide electrode material prepared in comparative example 1.
From the detection results and the drawings, the method provided by the invention is simple to operate, high-efficiency and large-scale in production, and the prepared graphene-based electrode material has high activity, high specific capacitance, good conductivity and excellent cycle performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a graphene-based electrode material comprises the following steps:
(1) Carrying out wetting treatment on the graphite oxide film to obtain a wet graphite oxide film;
(2) And (3) performing flame plasma induction treatment on the wet graphite oxide film obtained in the step (1) to obtain the graphene-based electrode material.
2. The method for producing a graphene-based electrode material according to claim 1, wherein the oxygen atom content of graphite oxide in the graphite oxide film in the step (1) is 25 to 30at.%.
3. The method for producing a graphene-based electrode material according to claim 1, wherein the thickness of the graphite oxide film in the step (1) is 10 to 40 μm.
4. The method for preparing a graphene-based electrode material according to claim 1, wherein the wetting treatment in step (1) comprises: and standing the graphite oxide film in a steam environment until the graphite oxide film absorbs water to be saturated, so as to obtain the wet graphite oxide film.
5. The method for preparing graphene-based electrode material according to claim 4, wherein the temperature of the water vapor environment is 25-50 ℃.
6. The method for preparing a graphene-based electrode material according to claim 4, wherein the standing time is 0.5 to 5 hours.
7. The method for preparing graphene-based electrode material according to claim 1, wherein the method for flame plasma induction treatment in step (2) comprises: the graphite oxide film is contacted with the outer flame of the flame.
8. The method for preparing graphene-based electrode material according to claim 7, wherein the contact time is < 3s.
9. The graphene-based electrode material prepared by the preparation method according to any one of claims 1 to 8, wherein the graphene-based electrode material has a porous network structure.
10. Use of the graphene-based electrode material of claim 9 as a working electrode for a supercapacitor.
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