CN112479187A - Improved self-supporting nitrogen-doped porous graphene for supercapacitor and preparation method thereof - Google Patents
Improved self-supporting nitrogen-doped porous graphene for supercapacitor 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
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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
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor, which comprises the steps of bonding nickel powder, aluminum powder and copper powder into a block by utilizing the strong adsorbability and cohesiveness of polydopamine, thermally decomposing a polydopamine precursor wrapped around the nickel powder, the aluminum powder and the copper powder under the high-temperature condition, generating a nitrogen-doped graphene material under the catalytic action of the nickel, the aluminum and the copper, and simultaneously ensuring the porosity of the graphene by using nano holes formed after the nano nickel powder, the aluminum powder and the copper powder in the block are removed to obtain high-quality nitrogen-doped graphene, wherein the thickness of the obtained nitrogen-doped graphene material is about 8-12 layers, the nitrogen content is more than 15%, and the specific surface area is 1800m2More than g. The technical proposal has the advantages of less required equipment, simple and easy preparation method, easy control of the reaction process,The method has the advantages of low danger, low cost, mass production and easy large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to improved self-supporting nitrogen-doped porous graphene for a supercapacitor and a preparation method thereof.
Background
The super Capacitor, also called as an electric Double-Layer Capacitor (electric Double-Layer Capacitor), is a novel energy storage device, and has the characteristics of short charging time, long service life, good temperature characteristic, energy conservation, environmental protection and the like. The super capacitor has wide application. The power balance power supply is used as a power balance power supply of the hoisting device and can provide power with super-large current; the battery is used as a vehicle starting power supply, has higher starting efficiency and reliability than the traditional battery, and can completely or partially replace the traditional battery; the energy used as the traction energy of the vehicle can produce an electric automobile, replace the traditional internal combustion engine and transform the existing trolley bus; the laser weapon can be used for military purposes to ensure the smooth starting of tank vehicles, armored vehicles and other war vehicles (particularly in cold winter) and is used as a pulse energy source of the laser weapon. Supercapacitors can be classified into electric double layer capacitors and pseudocapacitors according to the charge-discharge mechanism. The double-electric-layer capacitor mainly uses carbon-based materials, and the electrode materials of the pseudo capacitor mainly comprise transition metal oxides and conducting polymers. Along with the higher requirements of electronic products on power supply equipment, self-supporting supercapacitor materials without adding any binder and conductive agent are receiving more and more extensive attention and research. The two-dimensional graphene paper is a relatively ideal integral and self-supporting supercapacitor electrode material due to good conductivity and relatively high specific surface area, but in practical application, the effective area for forming an electric double layer is reduced due to the accumulation of graphene sheet layers. Therefore, it was investigated whether modification thereof could overcome this drawback. Ruoff et al, in Graphene-Based ultracapacapactors, firstly applied chemically modified Graphene materials to supercapacitor electrode materials, however, found that the specific capacitance values of both aqueous and organic electrolytes are low, and the analysis of the chemical modified Graphene materials is considered to cause the main reason that the mass specific capacitance is not ideal: the chemically modified graphene electrode material prepared by reduction is agglomerated again, so that the effective specific surface area of the chemically modified graphene electrode material is greatly reduced, and a large amount of electrolyte ions cannot be adsorbed. In addition, the electrical properties of the original carbon material are relatively weak, so far, the carbon-based energy source materials are all doped nano carbon materials, namely heteroatom-doped carbon materials. This is because the doped hetero atoms, particularly nitrogen atoms, not only can provide lone-pair electrons, but also can change the spin density and charge density of carbon atoms to have a high spin density. Meanwhile, electrons can be contributed to the nitrogen atom from adjacent carbon atoms, and the electrons can also be fed back to the pz orbit of the carbon atom through the nitrogen atom, so that the electrical property of the carbon atom is improved. Most of the existing graphene nitrogen doping methods adopt a method of doping nitrogen atoms into the crystal lattice of graphene by high temperature or arc discharge in a gas phase system, but the methods need professional equipment such as a high vacuum system and the like, and also need high-risk hydrogen, corrosive ammonia gas and the like, so that the preparation conditions are harsh, the cost is high, the risk is high, and the porosity of the graphene cannot be guaranteed, so that the method is not suitable for large-scale production. Therefore, the development of a rapid, green and simple synthesis method of N-doped porous graphene is still a research hotspot at present.
Disclosure of Invention
In view of the above, the present invention provides an improved self-supporting nitrogen-doped porous graphene for a supercapacitor and a preparation method thereof, which can prepare the nitrogen-doped porous graphene with a higher specific surface area and a higher quality.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) sequentially dispersing 12-15g of nano nickel powder, 5-8g of nano aluminum powder and 10-12g of nano copper powder in 1500-2000mL of dopamine/Tris-HCl buffer solution with the concentration of 6-8mg/mL, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reaction for 3-4h, heating at 60 ℃ for 2-3h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor;
(2) taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking the coordination of nickel, aluminum and copper as a catalyst and a template, sintering at high temperature in an inert gas sintering furnace at the temperature of 1100-1300 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product;
(3) and (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene.
As a preferred embodiment, the buffer solution of dopamine/Tris-HCl in step (1) has a pH = 8.5; the pressure of the roller press is 0.5-0.6 Mpa.
As a preferable scheme, the purity of the nano nickel powder in the step (1) is more than or equal to 99%, and the average particle size is less than or equal to 0.5 μm.
As a preferable scheme, the purity of the nano aluminum powder in the step (1) is more than or equal to 99%, and the average particle size is less than or equal to 0.4 μm.
Preferably, the purity of the nano copper powder in the step (1) is more than or equal to 99 percent, and the average particle size is less than or equal to 0.3 mu m.
As a preferable scheme, the inert gas in the step (2) is argon or nitrogen with the purity of more than or equal to 99 percent.
In a preferable embodiment, the strong acid in step (3) is at least one of hydrochloric acid, nitric acid and perchloric acid.
An improved self-supporting nitrogen-doped porous graphene for a super capacitor is prepared by the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
the method comprises the steps of bonding the nickel powder, the aluminum powder and the copper powder into a block by utilizing the strong adsorbability and the caking property of the polydopamine, thermally decomposing a polydopamine precursor wrapped around the nickel powder, the aluminum powder and the copper powder under the high-temperature condition, generating a nitrogen-doped graphene material under the catalysis of the nickel, the aluminum and the copper, and simultaneously ensuring the porosity of the graphene by using nano holes formed after removing the nano nickel powder, the aluminum powder and the copper powder in the block to obtain the high-quality nitrogen-doped graphene, wherein the thickness of the obtained nitrogen-doped graphene material is about 8-12 layers, the nitrogen content is more than 15%, and the specific surface area is 1800m2More than g. The technical scheme has the advantages of less required equipment, simple and easy preparation method, easy control of reaction process, low risk, low cost, batch production and easy large-scale popularization and application.
Detailed Description
The invention discloses a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor, which comprises the following steps:
(1) sequentially dispersing 12-15g of nano nickel powder, 5-8g of nano aluminum powder and 10-12g of nano copper powder in 1500-2000mL of dopamine/Tris-HCl buffer solution with the concentration of 6-8mg/mL, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reaction for 3-4h, heating at 60 ℃ for 2-3h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.5-0.6 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking the coordination of nickel, aluminum and copper as a catalyst and a template, sintering at high temperature in an inert gas sintering furnace at the temperature of 1100-1300 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is argon or nitrogen with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is at least one of hydrochloric acid, nitric acid and perchloric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
The invention is illustrated in more detail below in the following examples:
example 1:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) dispersing 12g of nano nickel powder, 7g of nano aluminum powder and 10g of nano copper powder in 1800mL of dopamine/Tris-HCl buffer solution with the concentration of 7mg/mL in sequence, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reaction for 3h, heating at 60 ℃ for 2h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.5 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking nickel, aluminum and copper as a catalyst and a template in a matching manner, sintering the solid precursor at a high temperature in an inert gas sintering furnace at 1100 ℃, and finally cooling the solid precursor to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is argon with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is hydrochloric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
Example 2:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) dispersing 15g of nano nickel powder, 5g of nano aluminum powder and 11g of nano copper powder in 1500mL of dopamine/Tris-HCl buffer solution with the concentration of 6mg/mL in sequence, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reaction for 4h, heating at 60 ℃ for 3h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.6 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking nickel, aluminum and copper as a catalyst and a template in a matching manner, sintering at high temperature in an inert gas sintering furnace at 1200 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is nitrogen with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is nitric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
Example 3:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) dispersing 13g of nano nickel powder, 8g of nano aluminum powder and 12g of nano copper powder in 1700mL of 8mg/mL dopamine/Tris-HCl buffer solution in sequence, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reacting for 3.5h, heating at 60 ℃ for 2.5h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.55 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking nickel, aluminum and copper as a catalyst and a template in a matching manner, sintering at a high temperature in an inert gas sintering furnace at 1300 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is argon with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is perchloric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
Example 4:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) sequentially dispersing 14g of nano nickel powder, 5.5g of nano aluminum powder and 10.5g of nano copper powder in 1600mL of dopamine/Tris-HCl buffer solution with the concentration of 6.8mg/mL, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reacting for 3.8h, heating at 60 ℃ for 2.4h, pressing into paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.58 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking nickel, aluminum and copper as a catalyst and a template in a matching manner, sintering at a high temperature in an inert gas sintering furnace at the temperature of 1150 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is nitrogen with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is hydrochloric acid and nitric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
Example 5:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) dispersing 15g of nano nickel powder, 6.5g of nano aluminum powder and 11.5g of nano copper powder in 2000mL of dopamine/Tris-HCl buffer solution with the concentration of 6.5mg/mL in sequence, carrying out ultrasonic oscillation for 2h, then mechanically stirring at room temperature for reaction for 3.2h, heating at 60 ℃ for 2.7h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.52 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking the coordination of nickel, aluminum and copper as a catalyst and a template, sintering at a high temperature in an inert gas sintering furnace at 1250 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is nitrogen with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is hydrochloric acid, nitric acid and perchloric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
Example 6:
a preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor comprises the following steps:
(1) dispersing 13g of nano nickel powder, 7.5g of nano aluminum powder and 11.8g of nano copper powder in 1900mL of dopamine/Tris-HCl buffer solution with the concentration of 7.5mg/mL in sequence, carrying out ultrasonic oscillation for 2h, then mechanically stirring at room temperature for reaction for 3.6h, heating at 60 ℃ for 2.8h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor; pH =8.5 for buffered dopamine/Tris-HCl solution; the pressure of the roller press is 0.54 Mpa. The purity of the nano nickel powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.5 mu m, the purity of the nano aluminum powder is more than or equal to 99 percent, the average grain diameter is less than or equal to 0.4 mu m, the purity of the nano copper powder is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
(2) Taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking nickel, aluminum and copper as a catalyst and a template in a matching manner, sintering at a high temperature in an inert gas sintering furnace at 1280 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product; the inert gas is argon with the purity of more than or equal to 99 percent.
(3) And (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene. The strong acid is hydrochloric acid.
The invention also discloses an improved self-supporting nitrogen-doped porous graphene for the super capacitor, which is prepared by adopting the preparation method of the improved self-supporting nitrogen-doped porous graphene for the super capacitor.
The specific surface area and specific capacity of the graphene prepared in each of the above embodiments were measured by N2 For the adsorbate, the adsorption isotherm of the graphene sheet at 77K was determined using an automatic adsorption apparatus (Micromeritics ASAP 2020M) and the specific surface area was determined.
The specific capacity test method comprises the following steps: cutting self-supporting nitrogen-doped porous graphene into wafers with the diameter of 1cm, selecting two pieces with similar mass as electrode materials, using a glass fiber membrane as a diaphragm, and using 1M Na2SO4And (3) using the aqueous solution as an electrolyte, assembling a two-electrode super capacitor by using a Swagelok type battery, performing constant-current charge and discharge test, and measuring the specific capacity of the super capacitor under the current density of 100mA/g, wherein the voltage is 0.01-1.0V.
By the above tests, the data obtained are shown in table 1 below:
nitrogen content, specific surface area and electrochemical properties of the prepared activated graphene of the examples shown in table 1
As can be seen from Table 1, the nitrogen-doped porous graphene self-supporting supercapacitor electrode material prepared by the method is higher in nitrogen content, larger in specific surface area, higher in specific capacitance, more excellent in rate capability and better in cycling stability, and is very suitable for various fine electronic devices and the like.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (8)
1. A preparation method of improved self-supporting nitrogen-doped porous graphene for a supercapacitor is characterized by comprising the following steps: the method comprises the following steps:
(1) sequentially dispersing 12-15g of nano nickel powder, 5-8g of nano aluminum powder and 10-12g of nano copper powder in 1500-2000mL of dopamine/Tris-HCl buffer solution with the concentration of 6-8mg/mL, ultrasonically oscillating for 2h, mechanically stirring at room temperature for reaction for 3-4h, heating at 60 ℃ for 2-3h, pressing into a paste by using a roller press with the roller diameter of 45cm to obtain a sheet-shaped nitrogen-doped porous graphene precursor;
(2) taking polydopamine in the sheet-shaped nitrogen-doped porous graphene precursor prepared in the step (1) as a solid precursor, and taking the coordination of nickel, aluminum and copper as a catalyst and a template, sintering at high temperature in an inert gas sintering furnace at the temperature of 1100-1300 ℃, and finally cooling to room temperature in inert gas to obtain a nickel-aluminum-copper sheet body coated by a nitrogen-doped graphene product;
(3) and (3) putting the nickel-aluminum copper sheet body coated with the nitrogen-doped graphene product prepared in the step (2) into strong acid, etching away the nano nickel-aluminum copper powder template by using the acid, and repeatedly cleaning and drying in ultrapure water to obtain the self-supporting nitrogen-doped porous graphene.
2. The preparation method of the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to claim 1, characterized by comprising the following steps: the buffer solution of dopamine/Tris-HCl in the step (1) has pH = 8.5; the pressure of the roller press is 0.5-0.6 Mpa.
3. The preparation method of the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to claim 1, characterized by comprising the following steps: the purity of the nano nickel powder in the step (1) is more than or equal to 99 percent, and the average particle size is less than or equal to 0.5 mu m.
4. The preparation method of the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to claim 1, characterized by comprising the following steps: in the step (1), the purity of the nano aluminum powder is more than or equal to 99 percent, and the average particle size is less than or equal to 0.4 mu m.
5. The preparation method of the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to claim 1, characterized by comprising the following steps: the purity of the nano copper powder in the step (1) is more than or equal to 99 percent, and the average grain diameter is less than or equal to 0.3 mu m.
6. The preparation method of the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to claim 1, characterized by comprising the following steps: the inert gas in the step (2) is argon or nitrogen with the purity of more than or equal to 99 percent.
7. The preparation method of the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to claim 1, characterized by comprising the following steps: the strong acid in the step (3) is at least one of hydrochloric acid, nitric acid and perchloric acid.
8. The utility model provides an improved generation self-supporting nitrogen doping porous graphene for ultracapacitor system which characterized in that: the preparation method is adopted to prepare the improved self-supporting nitrogen-doped porous graphene for the supercapacitor according to any one of claims 1 to 7.
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| KR20220150138A (en) * | 2021-05-03 | 2022-11-10 | 서울대학교산학협력단 | Carbon sheet and porous catalyst comprising the same |
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