CN112441583B - Preparation method and application of gelatin-based porous carbon electrode material - Google Patents
Preparation method and application of gelatin-based porous carbon electrode material Download PDFInfo
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- CN112441583B CN112441583B CN202011556295.2A CN202011556295A CN112441583B CN 112441583 B CN112441583 B CN 112441583B CN 202011556295 A CN202011556295 A CN 202011556295A CN 112441583 B CN112441583 B CN 112441583B
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
Abstract
The invention relates to a preparation method and application of a gelatin-based porous carbon electrode material. The preparation method comprises the following steps: adding 3.75g of gelatin into a 100ml beaker, adding 50ml of deionized water, swelling at room temperature for 30min, transferring into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved; adding 1ml of glutaraldehyde into the solution in a water bath at 40 ℃, stirring at the temperature for 40min, standing at room temperature for 28min, and then carrying out freeze drying; carbonizing the dried sample under the protection of argon, and then activating the sample at 600-800 ℃ by using KOH; washing the obtained activated product with a dilute acid solution, then washing the activated product with distilled water to be neutral, and drying to finally obtain the gelatin-based porous carbon electrode material. The preparation process is simple and has controllability; the prepared gelatin-based porous carbon electrode material has the advantages of stable structure, excellent electrochemical performance, good cycle performance, high specific capacitance and the like, and is very suitable for being applied to the field of supercapacitors as an electrode material.
Description
Technical Field
The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method and application of a gelatin-based porous carbon electrode material.
Background
Gelatin is a colorless or light yellow transparent sheet or powder, the main component of which is protein, and contains a small amount of water and inorganic salt, and molecular chains contain abundant amino, hydroxyl, carboxyl and other functional groups, and the gelatin is easily soluble in hot water and hardly soluble in cold water. Xu et al, a gelatin-based carbon material prepared by pre-carbonizing gelatin and then activating with NaOH, has a specific capacitance of 382F/g at a current density of 0.05A/g under two-electrode test conditions, and a retention rate of 94% after 2500 cycles at a current density of 0.45A/g, indicating good cycling stability (Xu, b.; Hou, s.; Cao, g.; Wu, F.; Yang, y.J. Mater. Chem. 2012,22, 19088-)), Yi et al, which compound gelatin and CNT, then pre-carbonize and activate to obtain specific surface area 1992 m 2 Activated carbon material (Yi, B.; Chen, X.; Zeng, B.; Guo, K.; Wan, Z.; Qian, Q.; Yan, H.; Chen, J. Gelatin-based activated carbon with carbon nanotubes as a frame for electric double-layer catalysts).J. Porous Mater.2012,19, 37-44.); fan and the like compound gelatin and graphite oxide by a hydrothermal method and then activate the gelatin and the graphite oxide to obtain 252F with the specific capacitance when the current density is 1A/g under the three-electrode test conditionActivated carbon material (Fan, H.; Shen, W. Gelatin-based microporous carbon sheets as high performance supercapacitors electrodes).ACS Sustainable Chem. Eng. 2016,4,1328-1337.）。
Chinese patent document CN105097291A discloses a method for preparing a nitrogen and boron co-doped gelatin-based two-dimensional carbon sheet, comprising the following steps: (1) adding gelatin and boric acid into 50-100 ml of deionized water, and stirring for 4-12 h at 60-80 ℃; (2) stirring the mixed solution obtained in the step (1) at 70-95 ℃ to evaporate water until the mixed solution is completely dried; (3) preserving the heat of the product obtained in the step (2) at 800-1100 ℃ for 1-5 h in an inert atmosphere; (4) and (4) refluxing the product obtained in the step (3) for 90-240 min by using boiling water, separating out the two-dimensional carbon sheet, and performing vacuum drying at 80-100 ℃ for 12h to obtain the nitrogen-boron co-doped gelatin-based two-dimensional carbon sheet. However, when the nitrogen-boron co-doped gelatin-based two-dimensional carbon sheet obtained by the method is used as an electrode material, the specific capacitance is low, and 1mol/L H is used 2 SO 4 As an electrolyte, the specific capacitance is only 330F/g when the constant current discharge current density is 100 mA/g.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a gelatin-based porous carbon electrode material with high specific capacitance and good cycle performance.
The technical scheme of the invention is as follows:
according to the invention, the preparation method of the gelatin-based porous carbon electrode material comprises the following steps:
(1) adding gelatin into a beaker filled with deionized water, and standing at normal temperature for 30 min;
(2) putting the gelatin solution obtained in the step (1) into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved;
(3) adding 0.5-2.5 ml of glutaraldehyde into the step (2), magnetically stirring for 40min, and standing for 28min at normal temperature;
(4) freeze-drying the product obtained in the step (3);
(5) carbonizing the product obtained in the step (4) at 300 ℃ for 1h under the protection of argon;
(6) immersing the carbon material obtained in the step (5) in KOH solution at 55 DEG ℃ Drying for 24 hours, activating for 1-3 hours at 600-800 ℃ under the protection of argon, and naturally cooling to room temperature; wherein the mass ratio of the carbon material to KOH is 1: 0.5-1: 3;
(7) washing the product obtained in the step (6) with a dilute acid solution, and then washing with distilled water to be neutral;
(8) and (4) drying the product obtained in the step (7) at 55 ℃ for 24h to obtain the gelatin-based porous carbon electrode material.
According to the present invention, it is preferable that the mass of gelatin in step (1) is 3.75 g.
According to the present invention, it is preferred that glutaraldehyde is added in an amount of 1ml in step (2).
According to the present invention, it is preferred that the activation temperature in the step (6) is 700 ℃.
According to the present invention, it is preferable that the mass ratio of the carbon material to KOH in the step (6) is 1: 1.
According to the present invention, it is preferred that the activation time in step (6) is 1 hour.
An application of a gelatin-based porous carbon electrode material for an electrode material of a super capacitor.
The technical advantages of the invention are as follows:
(1) the preparation method is simple in preparation process and controllable, and the specific surface area and the pore structure of the carbon material can be controlled by controlling the proportion of the pre-carbonized product and KOH.
(2) The gelatin-based porous carbon electrode material prepared by the invention has the advantages of stable structure, excellent electrochemical performance, good cycle performance, high specific capacitance and the like.
Drawings
Fig. 1 is a transmission electron microscope image of the gelatin-based porous carbon electrode material prepared in example 1 of the present invention.
Fig. 2 is a constant current charge-discharge diagram of the gelatin-based porous carbon electrode material prepared in example 1 of the present invention.
Fig. 3 is a cyclic voltammogram of the gelatin-based porous carbon electrode material prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying drawings, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
adding 3.75g of gelatin into a 100ml beaker, adding 50ml of deionized water, swelling for 30min at room temperature, transferring into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved; adding 1ml of glutaraldehyde into the solution in a water bath at 40 ℃, stirring at the temperature for 40min, standing at room temperature for 28min for continuous crosslinking, and freeze-drying the obtained product; preserving the heat of the dried sample at 300 ℃ for 1h in an argon atmosphere;
immersing the pre-carbonized product in KOH solution at 55 deg.C ℃ Drying for 24h, activating for 1h at 700 ℃ under the protection of argon, and naturally cooling to room temperature; wherein the mass ratio of the carbon material to KOH is 1: 1;
washing with dilute hydrochloric acid solution, and then washing with distilled water to be neutral; and drying the obtained product at 55 ℃ for 24h to obtain the gelatin-based porous carbon electrode material.
By adopting a three-electrode system, 2mol/L sulfuric acid solution is used as electrolyte, and when the mass load is 13.76mg, the specific capacitance measured at 1A/g is 390F/g, the specific capacitance measured at 10A/g is 234F/g, and the stability is better.
The transmission electron microscope image of the gelatin-based porous carbon electrode material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the final product is a porous sheet-like structure.
As shown in FIG. 2, the constant current charging and discharging of the gelatin-based porous carbon electrode material prepared in this example shows that, as shown in FIG. 2, the specific capacitance measured at 0.5A/g is 447F/g, the specific capacitance measured at 1A/g is 390F/g, the specific capacitance measured at 5A/g is 286F/g, and the specific capacitance measured at 10A/g is 234F/g, which is better in stability.
Example 2:
adding 3.75g of gelatin into a 100ml beaker, adding 50ml of deionized water, swelling for 30min at room temperature, transferring into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved; adding 1.5ml of glutaraldehyde into the solution in a water bath at 40 ℃, stirring for 40min at the temperature, standing for 28min at room temperature for continuous crosslinking, and then carrying out freeze drying on the obtained product; preserving the temperature of the dried sample at 300 ℃ for 1h under the argon atmosphere;
immersing the pre-carbonized product in KOH solution at 55 deg.C ℃ Drying for 24h, activating for 1h at 700 ℃ under the protection of argon, and naturally cooling to room temperature; wherein the mass ratio of the carbon material to KOH is 1: 1;
washing with dilute hydrochloric acid solution, and then washing with distilled water to be neutral; and drying the obtained product at 55 ℃ for 24h to obtain the gelatin-based porous carbon electrode material.
By adopting a three-electrode system, 2mol/L sulfuric acid solution is used as electrolyte, when the mass load is 9.52mg, the specific capacitance measured by 1A/g is 360F/g, the specific capacitance measured by 10A/g is 217F/g, and the stability is better.
Example 3:
adding 3.75g of gelatin into a 100ml beaker, adding 50ml of deionized water, swelling at room temperature for 30min, transferring into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved; adding 2ml of glutaraldehyde into the solution in a water bath at 40 ℃, stirring at the temperature for 40min, standing at room temperature for 28min for continuous crosslinking, and freeze-drying the obtained product; preserving the temperature of the dried sample at 300 ℃ for 1h under the argon atmosphere;
soaking the pre-carbonized product in KOH solution, drying at 55 ℃ for 24h, then activating at 700 ℃ for 1h under the protection of argon, and naturally cooling to room temperature; wherein the mass ratio of the carbon material to KOH is 1: 1;
washing with dilute hydrochloric acid solution, and then washing with distilled water to be neutral; and drying the obtained product at 55 ℃ for 24h to obtain the gelatin-based porous carbon electrode material.
By adopting a three-electrode system, 2mol/L sulfuric acid solution is used as electrolyte, and when the mass load is 2mg, the specific capacitance measured by 1A/g is 336F/g, the specific capacitance measured by 10A/g is 252F/g, and the stability is better.
Example 4:
adding 3.75g of gelatin into a 100ml beaker, adding 50ml of deionized water, swelling for 30min at room temperature, transferring into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved; adding 2.5ml of glutaraldehyde into the solution in a water bath at 40 ℃, stirring at the temperature for 40min, standing at room temperature for 28min to continue crosslinking, and freeze-drying the obtained product; preserving the temperature of the dried sample at 300 ℃ for 1h under the argon atmosphere;
immersing the pre-carbonized product in KOH solution at 55 deg.C ℃ Drying for 24h, activating for 1h at 700 ℃ under the protection of argon, and naturally cooling to room temperature; wherein the mass ratio of the carbon material to KOH is 1: 1;
washing with dilute hydrochloric acid solution, and then washing with distilled water to be neutral; and drying the obtained product at 55 ℃ for 24h to obtain the gelatin-based porous carbon electrode material.
By adopting a three-electrode system, 2mol/L sulfuric acid solution is used as electrolyte, when the mass load is 2.16mg, the specific capacitance measured by 1A/g is 338F/g, the specific capacitance measured by 10A/g is 217F/g, and the stability is better.
Claims (4)
1. A preparation method of a gelatin-based porous carbon electrode material comprises the following steps:
(1) adding 3.75g of gelatin into a beaker filled with deionized water, and standing for 30min at normal temperature;
(2) putting the gelatin solution obtained in the step (1) into a water bath kettle, and stirring at 40 ℃ until the gelatin is completely dissolved;
(3) adding 1mL of glutaraldehyde into the step (2), magnetically stirring for 40min, and standing at normal temperature for 28 min;
(4) freeze-drying the product obtained in the step (3);
(5) carbonizing the product obtained in the step (4) at 300 ℃ for 1h under the protection of argon;
(6) soaking the carbon material obtained in the step (5) in a KOH solution, drying for 24h at 55 ℃, then activating for 1-3 h at 600-800 ℃ under the protection of argon, and naturally cooling to room temperature; wherein the mass ratio of the carbon material to KOH is 1: 1;
(7) washing the product obtained in the step (6) with a dilute acid solution, and then washing with distilled water to be neutral;
(8) and (4) drying the product obtained in the step (7) at 55 ℃ for 24h to obtain the gelatin-based porous carbon electrode material.
2. The method for preparing a gelatin-based porous carbon electrode material as claimed in claim 1, wherein the activation temperature in the step (6) is 700 ℃.
3. The method for preparing a gelatin-based porous carbon electrode material as claimed in claim 1, wherein the activation time in step (6) is 1 h.
4. The use of the gelatin-based porous carbon electrode material obtained by the method for preparing a gelatin-based porous carbon electrode material according to claim 1, as an electrode material for a supercapacitor.
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| CN202011556295.2A CN112441583B (en) | 2020-12-25 | 2020-12-25 | Preparation method and application of gelatin-based porous carbon electrode material |
| PCT/CN2021/115764 WO2022134652A1 (en) | 2020-12-25 | 2021-08-31 | Preparation method for gelatin-based porous carbon electrode material, and application |
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