CN105869903B - Graphene preparation method - Google Patents
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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
-
- 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
-
- 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
-
- 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 provides a preparation method of graphene. According to the invention, graphene oxide and an oil phase are mixed to obtain a graphene oxide emulsion, so that the self-assembly of graphene oxide sheet layers on an emulsion interface is realized, meanwhile, the characteristic of gas generation through citric acid high-temperature hydrolysis is utilized, a hollow and porous graphene ball structure is prepared by a hydrothermal method, the structure is favorable for the diffusion and transmission of electrolyte ions, the ball structure is used as a conductive network, the agglomeration and stacking of the graphene sheet layers are inhibited, an internal cross-linked ball structure is constructed and used as a conductive network to be favorable for the transmission of electrons, the interface resistance is effectively reduced, and the specific capacity, the multiplying power and the cycle performance of the supercapacitor are improved. The graphene provided by the invention is stable in structure, has a high specific surface area and high conductivity, and can be applied to a super capacitor. The preparation method has simple process, easy control of the reaction process, less equipment investment, no need of being carried out under the vacuum high-pressure condition and capability of realizing large-scale production.
Description
Technical Field
The invention relates to graphene for a supercapacitor, and in particular relates to a preparation method of a graphene ball with a hollow and porous structure for the supercapacitor.
Background
The super capacitor has the characteristics of high power density, rapid charge and discharge, million secondary long cycle life, safety, reliability and the like, and has wide application prospect in the fields of rail transit, national defense, aerospace and the like. However, the rapid development of the super capacitor is restricted by the defect of low energy density of the super capacitor, and the energy density of the commercial activated carbon super capacitor is only 5-7 Wh kg-1. Therefore, in order to meet the increasing demand of the super capacitor, it is one of the development trends in the new energy field to develop a light super capacitor having high energy density, power density and good cycle stability.
Graphene is a graphite-exfoliated two-dimensional crystal composed of a layer of carbon atoms, has a two-dimensional periodic honeycomb lattice structure composed of carbon six-membered rings, and is a basic unit for constructing other-dimensional carbonaceous materials (such as zero-dimensional fullerene, one-dimensional carbon nanotubes and three-dimensional graphite). Due to the unique two-dimensional structure and the perfect crystal structure of graphene, graphene has high electrical conductivity, high mechanical strength, high thermal conductivity and peculiar optical properties, and is widely applied to information devices such as transistors. In the fields of nano composite materials, batteries, super capacitors and the like, the assembly form between two-dimensional planar graphene layers is particularly important. At present, porous graphene not only has the excellent properties of graphene, but also has the characteristics of high specific surface area, excellent conductivity, rich pore structure and the like, and becomes an ideal electrode material of a supercapacitor.
At present, due to pi-pi action, van der waals force and hydrophobicity, graphene prepared by the conventional redox method is easy to agglomerate and stack, so that infiltration and ion diffusion of electrolyte are inhibited, and the specific surface area of a material is remarkably reduced.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of graphene spheres with hollow and porous structures for a supercapacitor. The graphene obtained by the invention has a hollow and porous graphene internal cross-linked spherical structure, is beneficial to the diffusion and transmission of electrolyte ions, improves the transmission of electrons, obviously reduces the interface resistance, and improves the specific capacity, the multiplying power and the cycle performance of the super capacitor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphene and carbon nanotube composite macroscopic body has a porous structure.
A method of preparing graphene, the method comprising the steps of:
1) preparing a graphene oxide emulsion: mixing the graphene oxide solution and citric acid in proportion, and carrying out ultrasonic treatment for 0.5-2 h; adding the oil phase, and stirring to obtain a graphene oxide emulsion;
2) preparing a precursor: heating the emulsion obtained in the step 1) at 180-200 ℃ for 0.5-5 h to obtain a precursor;
3) preparing graphene: freeze-drying the precursor in the step 2); reacting for 1-5 h at 650-1000 ℃ in an inert atmosphere; washing with water, and drying to obtain the product.
Further, the concentration of the graphene oxide in the step 1) is 0.1-5 mg mL < -1 >.
Further, in the step 1), the oil phase is one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate and isopropyl methacrylate.
Further, the mass ratio of the graphene oxide to the citric acid in the step 1) is 1: (0.1-5).
Further, the volume ratio of the graphene oxide to the oil phase in the step 1) is 1: (0.05-5).
Further, the volume ratio of the graphene oxide to the oil phase is 1: 0.2.
further, the stirring time in the step 1) is 5-20 min.
Further, in the step 3), the reaction is carried out for 2 hours at 800 ℃ under nitrogen.
Further, the graphene obtained in the step 3) is of a hollow and porous spherical structure.
Furthermore, the graphene oxide adopted by the invention is prepared from crystalline flake graphite by a Hummer method.
Furthermore, the graphene provided by the invention mainly starts from graphene oxide; because the surface of the graphene oxide contains a large number of oxygen-containing functional groups and has a good hydrophilic effect, researches show that the graphene cluster has certain hydrophobicity, so that the performance of the graphene oxide is close to that of an amphiphilic block copolymer.
Furthermore, the graphene oxide emulsion is obtained by mixing the graphene oxide with the oil phase, so that the self-assembly of the graphene oxide sheet layer on the emulsion interface is realized, meanwhile, the characteristic that citric acid is hydrolyzed at high temperature to generate gas is utilized, the hollow and porous graphene ball is prepared by a hydrothermal method, and the high-temperature annealing is further carried out, so that the conductivity of the material is improved.
Further, the prepared graphene is applied to a super capacitor.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
1. according to the technical scheme provided by the invention, the graphene oxide emulsion is obtained by mixing the graphene oxide and the oil phase, the self-assembly of a graphene oxide sheet layer on an emulsion interface is realized, meanwhile, the characteristic that citric acid is hydrolyzed at high temperature to generate gas is utilized, the hollow and porous graphene ball is prepared by a hydrothermal method, and the high-temperature annealing is further carried out, so that the conductivity of the material is improved.
2. The hollow and porous structure constructed by the technical scheme provided by the invention is beneficial to diffusion and transmission of electrolyte ions, the graphene spherical structure is used as a conductive network, agglomeration and stacking of graphene sheet layers are inhibited, and meanwhile, the internal cross-linked spherical structure is constructed as a conductive network and is beneficial to transmission of electrons, so that the interface resistance is effectively reduced, and the specific capacity, the multiplying power and the cycle performance of the supercapacitor are improved.
3. The graphene prepared by the method is stable in structure, has high specific surface area and high conductivity, and can be applied to a super capacitor.
4. The preparation method has simple process, easy control of the reaction process, less equipment investment, no need of being carried out under the vacuum high-pressure condition and capability of realizing large-scale production.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a scanning electron micrograph of graphene prepared in example 1;
FIG. 2 is a cyclic voltammogram of the graphene prepared in example 1 at a sweep rate of 25mV s-1;
FIG. 3 is a constant current charge and discharge curve of graphene prepared in example 1 at a current density of 1A g-1.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
Taking 100mL of graphene oxide aqueous solution with the concentration of 3mg mL-1, adding 100mg of citric acid, and carrying out ultrasonic treatment for 1 h; according to the volume ratio of the graphene solution to the oil phase of 1: 0.2, adding methyl methacrylate, and stirring for 20min to prepare a graphene oxide emulsion; heating the emulsion at 180 ℃ for 3h to obtain a precursor; freeze-drying the precursor, and then reacting for 2 hours at 800 ℃ in a nitrogen environment; and (4) taking the reaction product, repeatedly washing with deionized water, and drying to obtain the graphene material.
Scanning Electron Microscope (SEM) detection is performed on the graphene prepared in this embodiment, as shown in fig. 1, it can be known that the graphene is a porous and internal cross-linked spherical structure, which is favorable for diffusion and transmission of an electrolyte, and the internal cross-linked layered structure is used as a conductive network to be favorable for transmission of electrons.
Respectively weighing 80mg of graphene prepared in the embodiment, 10mg of conductive agent Super P and 10mg of binder PVDF, putting the graphene, the conductive agent Super P and the binder PVDF into an agate mortar for grinding, dropwise adding N-methylpyrrolidone NMP, grinding into a slurry state, uniformly coating the slurry on foamed nickel, drying at 120 ℃ for 4 hours, pressing into pole pieces under the pressure of 10MPa, wherein the loading capacity of active substances of each pole piece is 3-5 mg; taking out two pole pieces with equal mass as the positive pole and the negative pole of the super capacitor, assembling the super capacitor into a CR2032 button cell by taking the ionic liquid as electrolyte and the glass fiber membrane as a diaphragm, and testing the electrochemical performance of the electrode material; as shown in fig. 2, the cyclic voltammetry curve of the graphene electrode material prepared in this example at a sweep rate of 25mV/s shows that the material exhibits better electric double layer capacitance characteristics as shown in fig. 2. And then, performing a constant current charge and discharge test, and as shown in fig. 3, it can be known that the graphene has a specific capacity of 150F/g at a current density of 1A/g.
Example 2
Taking 100mL of graphene oxide aqueous solution with the concentration of 0.5mg mL-1, adding 50mg of citric acid, and carrying out ultrasonic treatment for 1.5 h; according to the volume ratio of the graphene solution to the oil phase of 1: 0.5, adding ethyl methacrylate, and stirring for 15min to prepare a graphene oxide emulsion; heating the emulsion at 190 ℃ for 1h to obtain a precursor; freeze-drying the precursor, and then reacting for 3 hours at 900 ℃ in a nitrogen environment; and (4) taking the reaction product, repeatedly washing with deionized water, and drying to obtain the graphene material.
Example 3
Taking 100mL of 4mg mL-1 graphene oxide aqueous solution, adding 200mg of citric acid, and carrying out ultrasonic treatment for 0.5 h; according to the volume ratio of the graphene solution to the oil phase of 1: 2, adding methyl methacrylate, and stirring for 5min to prepare a graphene oxide emulsion; heating the emulsion at 200 ℃ for 0.5h to obtain a precursor; freeze-drying the precursor, and then reacting for 1h at 1000 ℃ in a nitrogen environment; and (4) taking the reaction product, repeatedly washing with deionized water, and drying to obtain the graphene material.
Example 4
Taking 100mL of graphene oxide aqueous solution with the concentration of 2mg mL-1, adding 200mg of citric acid, and carrying out ultrasonic treatment for 1.5 h; according to the volume ratio of the graphene solution to the oil phase of 1: 3, adding n-butyl methacrylate, and stirring for 10min to prepare a graphene oxide emulsion; heating the emulsion at 185 ℃ for 2h to obtain a precursor; freeze-drying the precursor, and then reacting for 3 hours at 700 ℃ in a nitrogen environment; and (4) taking the reaction product, repeatedly washing with deionized water, and drying to obtain the graphene material.
Example 5
Taking 100mL of graphene oxide aqueous solution with the concentration of 1mg mL-1, adding 300mg of citric acid, and carrying out ultrasonic treatment for 2 h; according to the volume ratio of the graphene solution to the oil phase of 1: 3.5, adding n-propyl methacrylate, and stirring for 15min to prepare graphene oxide emulsion; heating the emulsion at 195 ℃ for 4h to obtain a precursor; freeze-drying the precursor, and then reacting for 3 hours at 850 ℃ in a nitrogen environment; and (4) taking the reaction product, repeatedly washing with deionized water, and drying to obtain the graphene material.
Example 6
Taking 100mL of graphene oxide aqueous solution with the concentration of 0.1mg mL-1, adding 50mg of citric acid, and carrying out ultrasonic treatment for 1 h; according to the volume ratio of the graphene solution to the oil phase of 1: 0.1, adding isopropyl methacrylate, and stirring for 8min to prepare a graphene oxide emulsion; heating the emulsion at 195 ℃ for 1h to obtain a precursor; freeze-drying the precursor, and then reacting for 3.5 hours at 900 ℃ in a nitrogen environment; and (4) taking the reaction product, repeatedly washing with deionized water, and drying to obtain the graphene material.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (3)
1. A graphene preparation method is characterized by comprising the following steps:
1) preparing a graphene oxide emulsion: carrying out ultrasonic treatment on a mixture prepared by a graphene oxide solution and citric acid according to a proportion for 0.5-2 h; adding the oil phase, mixing and stirring to prepare emulsion;
2) preparing a precursor: heating the emulsion obtained in the step 1) at 180-200 ℃ for 0.5-5 h to obtain a precursor;
3) preparing graphene: freeze-drying the precursor in the step 2); reacting for 2 hours at 800 ℃ in a nitrogen atmosphere; washing and drying to obtain a product;
the concentration of the graphene oxide in the step 1) is 0.1-5 mg mL-1；
The oil phase in the step 1) is one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate and isopropyl methacrylate;
the mass ratio of the graphene oxide to the citric acid in the step 1) is 1: (0.1-5);
the volume ratio of the graphene oxide to the oil phase in the step 1) is 1: 0.2;
the graphene obtained in the step 3) is of a hollow porous spherical structure.
2. The preparation method according to claim 1, wherein the stirring time in the step 1) is 5 to 20 min.
3. Use of the graphene of claim 1 for the preparation of a supercapacitor.
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| CN106449129B (en) * | 2016-09-29 | 2018-03-27 | 成都新柯力化工科技有限公司 | A kind of ultracapacitor graphene self-assembling electrode material and preparation method |
| CN107082420B (en) * | 2017-04-27 | 2019-06-28 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method and supercapacitor of graphene powder |
| CN107942572B (en) * | 2017-11-17 | 2020-12-04 | 深圳市华星光电技术有限公司 | Color film substrate and preparation method of black matrix material |
| CN115180616B (en) * | 2022-08-11 | 2023-04-11 | 深圳一个烯材科技有限公司 | Nano-porous graphene material |
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| CN104167298A (en) * | 2014-07-28 | 2014-11-26 | 复旦大学 | Graphene-protein derived carbon supercapcaitor material and preparation method thereof |
| CN104733695A (en) * | 2015-03-27 | 2015-06-24 | 浙江大学 | Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application |
| CN105131596A (en) * | 2015-09-14 | 2015-12-09 | 江南大学 | Preparation method of graphene/polyaniline composite hollow microspheres |
| CN105293476A (en) * | 2015-11-16 | 2016-02-03 | 复旦大学 | Preparation method of large-size graphene oxide or graphene |
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