CN113479872A - Preparation method of nitrogen-doped three-dimensional porous graphene hydrogel electrode material, electrode and application thereof - Google Patents
Preparation method of nitrogen-doped three-dimensional porous graphene hydrogel electrode material, electrode and application thereof Download PDFInfo
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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
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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
-
- 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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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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
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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 belongs to the technical field of preparation of graphene supercapacitor electrode materials, and particularly relates to a preparation method of a nitrogen-doped three-dimensional porous graphene hydrogel electrode material, and an electrode and application thereof. The technical method of the invention is as follows: adding urea and hydrogen peroxide into a graphene oxide aqueous solution, performing ultrasonic homogenization, adopting a preparation process of a one-step hydrothermal reaction method, and performing freeze drying to obtain the nitrogen-doped three-dimensional porous graphene hydrogel. And uniformly mixing the active substance, the binder and the conductive carbon black according to a certain proportion, and tabletting to prepare the electrode. The electrode material prepared by the invention has larger specific capacitance and has wide application prospect in the fields of sewage treatment and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of graphene supercapacitor electrode materials, and particularly relates to a preparation method of a nitrogen-doped three-dimensional porous graphene hydrogel electrode material, and an electrode and application thereof.
Background
At present, 97% of the global water resource distribution is seawater and 3% of fresh water, while the surface fresh water available for human is only 0.3%, with the development of industry, the fresh water resource is polluted year by year, about one tenth of the population in the world can not obtain clean drinking water, and people are prompted to realize how to reasonably utilize the fresh water resource and the importance of sewage treatment. Nowadays, relatively mature desalination technologies mainly include Reverse Osmosis (RO), Electrodialysis (EDI), multi-stage flash evaporation (MSF), etc., but these technologies have some disadvantages in large-scale commercial application, the membrane cost in RO and EDI is high, and MSF requires high energy consumption and low efficiency, so that the development of a low-cost, low-energy consumption, high-efficiency and environment-friendly water treatment technology is the key to solve the shortage of fresh water resources. The Capacitive Deionization (CDI) technology is a desalination technology developed based on a super capacitor, adopts symmetrical active materials as electrodes, and positive and negative ions in a solution are correspondingly adsorbed to the surfaces of a negative electrode and a positive electrode under the action of an electrostatic field, so that desalination is realized, and the technology has low energy consumption (generally, the voltage applied to each pair of electrodes is less than 1.2V), and has no chemical reagent pollution.
Electrode materials have been studied mainly on carbon-based materials, comprising: activated carbon, carbon aerogels, carbon nanotubes, ordered mesoporous carbon, graphene, and the like. Preparing electrodes by using activated carbon such as M Aslan and the like and a binder according to a mass ratio of 9:1, and testing that the charging efficiency is 86% and the desalting capacity is 13.1mg in capacitive deionization; vafakhah and the like adopt hydrothermal reaction to prepare the ferric ferrocyanide/reduced graphene oxide aerogel electrode, the desalination capacity of the electrode reaches 30mg/g, and the electrode still has higher desalination stability after 100 times of cyclic adsorption. Han and the like utilize nitrogen and phosphorus co-doping to prepare the three-dimensional graphene electrode, the specific surface area is 567.14m2/g, the specific capacitance reaches 177.19F/g, the desalination capacity is 20.93mg/g, and meanwhile, the dopant is also favorable for regulating and controlling the pore size distribution. However, at present, hydrogen peroxide etching and nitrogen source doping are cooperatively used to modify graphene oxide, wherein the concentration of hydrogen peroxide is extremely low, and a one-step hydrothermal reaction method is adopted to prepare the three-dimensional porous graphene hydrogel electrode, which is not reported yet. The invention provides the preparation method of the carbon electrode, which is simple to operate, low in cost and environment-friendly, and the prepared electrode has excellent electrochemical performance.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-doped three-dimensional porous graphene hydrogel electrode material for a supercapacitor, an electrode and application thereof, wherein the preparation method is simple to operate, low in price and environment-friendly.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of a nitrogen-doped three-dimensional porous graphene hydrogel electrode material comprises the following steps:
(1) dropwise adding the aqueous hydrogen peroxide solution into the graphene oxide aqueous suspension solution, uniformly stirring, then adding urea, and uniformly stirring to obtain a uniform aqueous solution;
(2) and (3) carrying out hydrothermal reaction on the uniform aqueous solution obtained in the step (2) to obtain hydrogel, and then carrying out freeze drying treatment on the hydrogel to obtain the nitrogen-doped three-dimensional porous graphene hydrogel electrode material.
Preferably, the graphene oxide in the step (1) is prepared by using crystalline flake graphite as a raw material through a Hummers method.
Preferably, the concentration of the graphene oxide aqueous suspension solution in the step (1) is 1.5mg/mL-3.5 mg/mL; specifically, the graphene oxide is obtained by adding deionized water into graphene oxide according to a proportion and performing ultrasonic dispersion for 1-2 h.
Preferably, the concentration of the aqueous hydrogen peroxide solution in the step (1) is 1mg/mL to 3mg/mL, and the mass ratio of the hydrogen peroxide to the graphene oxide is (0.05 to 0.1): 1.
preferably, the stirring speed in the step (1) is 1000rpm-1500rpm, and the stirring time is 10min-20 min.
Preferably, the mass ratio of the urea to the graphene oxide in the step (1) is (5-10): 1, the stirring speed is 2000rpm-2500rpm, and the stirring time is 30min-60 min.
Preferably, the hydrothermal reaction time in the step (2) is 8-12h, and the temperature is 120-180 ℃.
An electrode comprises the nitrogen-doped three-dimensional porous graphene hydrogel electrode material prepared by the method.
Specifically, the preparation method comprises the following steps: the nitrogen-doped three-dimensional porous graphene hydrogel electrode material prepared by the method is uniformly mixed with a binder and conductive carbon black to prepare slurry, the slurry is pressed on foamed nickel through pressure, and the electrode is obtained after vacuum drying.
Preferably, the mass ratio of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material to the binder to the conductive carbon black is 8:1:1, wherein the binder is PTFE, the thickness of the nickel foam is 2mm, and the coating area is 1cm2The pressure of tabletting is 10MPa, the time is 20S, the vacuum drying temperature is 80 ℃, and the time is 12 h.
The electrode is mainly used in the field of water treatment desalination and has higher desalination efficiency.
Compared with the prior art, the invention has the following beneficial effects:
the method creatively adds hydrogen peroxide and a nitrogen source into a hydrothermal reaction kettle at the same time, and adopts a one-step method to prepare the nitrogen-doped three-dimensional porous graphene oxide hydrogel electrode material. Compared with pure heteroatom doping, the hydrogen peroxide etches the graphene sheet layer to form a porous structure, and the graphene oxide is modified in cooperation with nitrogen doping, so that two-dimensional pores are formed, an ion transmission path is increased, the folding degree of the graphene sheet layer is increased, the defect structure is obvious, and the electrochemical performance of the electrode material is improved. Compared with the prior art, the concentration of the hydrogen peroxide used in the invention is extremely low, the potential safety hazard and the environmental pollution are greatly reduced in the industrialization process, and meanwhile, the preparation process method of the electrode material is simple.
The nitrogen-doped three-dimensional porous graphene oxide hydrogel electrode material prepared by the invention has outstanding performance advantages, abundant pore structure and graphene structure defects in the field of water treatment desalination, provides a rapid ion transmission and transfer channel, increases active sites for ion storage, and improves ion adsorption efficiency and storage capacity.
Drawings
Fig. 1 is a photograph of a nitrogen-doped three-dimensional porous graphene hydrogel electrode material in example 1;
FIG. 2 is TEM images of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material in example 1 at different magnification;
FIG. 3 is a cyclic voltammogram of the nitrogen-doped three-dimensional porous graphene electrode of example 1 at different scan rates, with an electrolyte of 6M KOH aqueous solution;
fig. 4 is a constant current charge-discharge curve of the nitrogen-doped three-dimensional porous graphene electrode in example 1 at a current density of 1A/g, and the electrolyte is 6M KOH aqueous solution;
fig. 5 is an XPS spectrum of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material in example 1;
FIG. 6 is a desalination performance curve of the nitrogen-doped three-dimensional porous graphene electrode in example 1, wherein the NaCl concentration in the solution is 100 mg/L.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
example 1
The method comprises the following steps: weighing 120mg of graphene oxide, and adding the graphene oxide into 60mL of deionized water for ultrasonic dispersion for 1 h;
step two: weighing 1.0g of hydrogen peroxide with the mass fraction of 30%, adding 100mL of deionized water, and preparing 3mg/mL of hydrogen peroxide aqueous solution;
step three: weighing 5mL of the aqueous hydrogen peroxide solution obtained in the step II, adding the aqueous hydrogen peroxide solution obtained in the step (1) into the aqueous graphene oxide solution obtained in the step (1), and stirring at 1500rpm for 15 min;
step four: 1.2g of urea is weighed and added into the aqueous solution in the third step, the stirring speed is 2000rpm, and the stirring is carried out for 30 min;
step five: pouring the aqueous solution obtained in the fourth step into a 100mL hydrothermal reaction kettle, heating at 180 ℃ for 12h, and freeze-drying to obtain the nitrogen-doped three-dimensional porous graphene hydrogel electrode material;
step six: and D, uniformly mixing the nitrogen-doped three-dimensional porous graphene hydrogel electrode material obtained in the step five with a binder (PTFE) and conductive carbon black according to a mass ratio (8:1:1) to prepare slurry, pressing the slurry on foamed nickel through pressure, and drying the foamed nickel in vacuum to obtain the electrode.
FIG. 1 is a photograph of a three-dimensional graphene hydrogel electrode material prepared from graphene oxide, a nitrogen source and hydrogen peroxide by a one-step hydrothermal reaction method, wherein the material is in a fluffy three-dimensional columnar shape; as shown in fig. 2, the graphene sheet layer is in a corrugated state, and the hole is formed in the middle of the sheet layer, so that the synergistic modification of nitrogen doping and hydrogen peroxide etching is obvious; FIG. 3 is a plot of cyclic voltammograms at different scan rates, showing that as the scan rate increases, the area of the plot increases; as shown in FIG. 4, the GCD curve at the current density of the electrode material 1A/g shows a symmetrical triangular shape and shows typical double-layer capacitance behavior, and the specific capacitance of the test is 290F/g; XPS of fig. 5 shows that the nitrogen source was successfully doped in graphene oxide; FIG. 6 shows the desalination performance of the electrode material in a capacitive deionization system, and the desalination efficiency is 51.2% at 30 min.
Example 2
The method comprises the following steps: weighing 120mg of graphene oxide, and adding the graphene oxide into 60mL of deionized water for ultrasonic dispersion for 1 h;
step two: weighing 0.8g of hydrogen peroxide with the mass fraction of 30%, adding 100mL of deionized water, and preparing 2.4mg/mL of hydrogen peroxide aqueous solution;
step three: weighing 5mL of the aqueous hydrogen peroxide solution obtained in the step II, adding the aqueous hydrogen peroxide solution obtained in the step (1) into the aqueous graphene oxide solution obtained in the step (1), and stirring at 1500rpm for 15 min;
step four: 1.2g of urea is weighed and added into the aqueous solution in the third step, the stirring speed is 2000rpm, and the stirring is carried out for 30 min;
step five: pouring the aqueous solution obtained in the fourth step into a 100mL hydrothermal reaction kettle, heating at 180 ℃ for 12h, and freeze-drying to obtain the nitrogen-doped three-dimensional porous graphene hydrogel electrode material;
step six: and D, uniformly mixing the nitrogen-doped three-dimensional porous graphene hydrogel electrode material obtained in the step five with a binder (PTFE) and conductive carbon black according to a mass ratio (8:1:1) to prepare slurry, pressing the slurry on foamed nickel through pressure, and drying the foamed nickel in vacuum to obtain the electrode.
Example 3
The method comprises the following steps: weighing 120mg of graphene oxide, and adding the graphene oxide into 60mL of deionized water for ultrasonic dispersion for 1 h;
step two: weighing 0.5g of hydrogen peroxide with the mass fraction of 30%, adding 100mL of deionized water, and preparing 1.5mg/mL of hydrogen peroxide aqueous solution;
step three: weighing 5mL of the aqueous hydrogen peroxide solution obtained in the step II, adding the aqueous hydrogen peroxide solution obtained in the step (1) into the aqueous graphene oxide solution obtained in the step (1), and stirring at 1500rpm for 15 min;
step four: 1.2g of urea is weighed and added into the aqueous solution in the third step, the stirring speed is 2000rpm, and the stirring is carried out for 30 min;
step five: pouring the aqueous solution obtained in the fourth step into a 100mL hydrothermal reaction kettle, heating at 180 ℃ for 12h, and freeze-drying to obtain the nitrogen-doped three-dimensional porous graphene hydrogel electrode material;
step six: and D, uniformly mixing the nitrogen-doped three-dimensional porous graphene hydrogel obtained in the step five with a binder (PTFE) and conductive carbon black according to a mass ratio (8:1:1) to prepare slurry, pressing the slurry on foamed nickel through pressure, and drying the foamed nickel in vacuum to obtain the electrode.
Comparative example 1
The method comprises the following steps: weighing 120mg of graphene oxide, and adding the graphene oxide into 60mL of deionized water for ultrasonic dispersion for 1 h;
step two: weighing 1.2g of urea, adding the urea into the aqueous solution obtained in the step one, stirring at 2000rpm for 30 min;
step three: pouring the aqueous solution obtained in the step two into a 100mL hydrothermal reaction kettle, heating at 180 ℃ for 12h, and freeze-drying to obtain the nitrogen-doped three-dimensional graphene hydrogel;
step four: and (3) uniformly mixing the nitrogen-doped three-dimensional graphene hydrogel in the third step with a binder (PTFE) and conductive carbon black according to a mass ratio (8:1:1) to prepare slurry, pressing the slurry on foamed nickel under pressure, and drying the foamed nickel under vacuum to obtain the electrode.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped three-dimensional porous graphene hydrogel electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) dropwise adding the aqueous hydrogen peroxide solution into the graphene oxide aqueous suspension solution, uniformly stirring, then adding urea, and uniformly stirring to obtain a uniform aqueous solution;
(2) and (3) carrying out hydrothermal reaction on the uniform aqueous solution obtained in the step (2) to obtain hydrogel, and then carrying out freeze drying treatment on the hydrogel to obtain the nitrogen-doped three-dimensional porous graphene hydrogel electrode material.
2. The preparation method of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material according to claim 1, characterized in that: the graphene oxide in the step (1) is prepared by taking crystalline flake graphite as a raw material through a Hummers method.
3. The preparation method of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material according to claim 1, characterized in that: the concentration of the graphene oxide water suspension solution in the step (1) is 1.5mg/mL-3.5 mg/mL.
4. The preparation method of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material according to claim 1, characterized in that: the concentration of the aqueous hydrogen peroxide solution in the step (1) is 1mg/mL-3mg/mL, and the mass ratio of the hydrogen peroxide to the graphene oxide is (0.05-0.1): 1.
5. the preparation method of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material according to claim 1, characterized in that: the stirring speed in the step (1) is 1000-1500 rpm, and the stirring time is 10-20 min;
and/or the mass ratio of the urea to the graphene oxide in the step (1) is (5-10): 1, the stirring speed is 2000rpm-2500rpm, and the stirring time is 30min-60 min.
6. The preparation method of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material according to claim 1, characterized in that: the hydrothermal reaction time in the step (2) is 8-12h, and the temperature is 120-180 ℃.
7. An electrode, characterized by: the nitrogen-doped three-dimensional porous graphene hydrogel electrode material prepared by the preparation method of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material according to any one of claims 1 to 6.
8. The electrode of claim 7, wherein: the preparation method comprises the following steps: and uniformly mixing the nitrogen-doped three-dimensional porous graphene hydrogel electrode material with a binder and conductive carbon black to prepare slurry, pressing the slurry on foamed nickel under pressure, and drying the foamed nickel under vacuum to obtain the electrode.
9. The electrode of claim 7, wherein: the mass ratio of the nitrogen-doped three-dimensional porous graphene hydrogel electrode material to the binder to the conductive carbon black is 8:1:1, wherein the binder is PTFE, the thickness of the foamed nickel is 2mm, and the coating area is 1cm2The pressure of tabletting is 10MPa, the time is 20S, the vacuum drying temperature is 80 ℃, and the time is 12 h.
10. Use of an electrode according to claim 7, wherein: the electrode is used for desalination treatment in water.
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Cited By (2)
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| CN114496586A (en) * | 2022-02-18 | 2022-05-13 | 常州大学 | Nitrogen-doped three-dimensional graphene/MOF (Metal organic framework) derived carbon composite electrode material for capacitive deionization and preparation and application thereof |
| CN115259305A (en) * | 2022-07-22 | 2022-11-01 | 同济大学 | Nitrogen-doped graphene aerogel loaded ferrocene-polyaniline composite electrode and preparation method and application thereof |
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