CN114709083A - Modified graphene composite material and supercapacitor - Google Patents
Modified graphene composite material and supercapacitor Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a modified graphene composite material and a supercapacitor, wherein the preparation of the modified graphene composite material comprises the following steps: carrying out oxidation-reduction treatment on graphite to prepare graphene oxide powder; carrying out further modification treatment on the graphene oxide to obtain high specific surface graphene powder; the method comprises the following steps of (1) covalently linking parafuchsine to high-specific-surface graphene powder to obtain a modified graphene composite material; the supercapacitor obtained by assembling the working electrode prepared by taking the parafuchsine base @ high specific surface graphene composite material as an electrode material has higher specific capacitance and good cycle stability, and the capacitance retention rate is over 90% after 10000 cycles.
Description
Technical Field
The invention belongs to the technical field of new energy storage devices, particularly relates to a super capacitor, and more particularly relates to an organic modified graphene composite material, a preparation method of the composite material and the super capacitor.
Background
A supercapacitor is an electrical energy storage device, also known as an electrochemical capacitor, having a much higher charge-discharge power and cycle life than a secondary battery, also known as a gold capacitor or farad capacitor. From the point of view of the mechanism by which an ultracapacitor stores energy, it has three different types of capacitive behavior: electric double layer capacitors, pseudocapacitive capacitors and hybrid capacitors. Double layer capacitance is obtained from the accumulation of different electrostatic charges at the electrode electrolyte interface, pseudocapacitance is due to the occurrence of a rapid and reversible surface redox process, and hybrid capacitors utilize both mechanisms to meet the requirements of high energy density and high power density.
The main components of the super capacitor are double electrodes, electrolyte, a diaphragm, a current collector and the like. The electrode material is used as the most important component of the super capacitor and is a key factor for determining the performance of the super capacitor, and the structure and the components of the electrode material can directly influence the capacity, the service life and the rate performance of the super capacitor. The main electrode materials of the super capacitor comprise: metal oxides, carbon materials, and conductive polymers. The carbon material is easy to obtain, has various shapes, long service life and high cost performance, and is the first choice of electrode materials. The carbon materials currently applied to carbon-based supercapacitors mainly include: carbon aerogels, activated carbon, carbon nanotubes, graphene, and the like.
Graphene as a novel two-dimensional nano material is prepared from carbon atoms sp2The hybridized single-layer honeycomb crystal has optical, electrical, mechanical and thermodynamic properties superior to those of the traditional material, and the electron mobility can reach 2.0 multiplied by 105cm2·V-1·s-1. However, since graphene itself has a structure having a large specific surface area and van der waals force, it is very likely to be agglomerated, and thus the properties of the graphene composite material cannot be sufficiently exhibited. Graphene is chemically inert, so that the compatibility with a solvent is poor, the graphene is difficult to disperse in a plurality of solvents, and the application range of graphene is limited.
Disclosure of Invention
The invention aims to provide a modified graphene composite material and a super capacitor, and the prepared super capacitor has high specific capacitance and good cycle stability.
The purpose of the invention can be realized by the following technical scheme:
a modified graphene composite material comprising the steps of:
carrying out oxidation-reduction treatment on graphite to prepare graphene oxide powder;
carrying out further modification treatment on the graphene oxide to obtain high specific surface graphene powder;
and (3) covalently linking the parafuchsin base to the graphene powder with the high specific surface area to obtain the modified graphene composite material.
Further, the oxidation-reduction treatment comprises the following steps: (1) under the ice bath condition, 200ml of 98% concentrated sulfuric acid and 30-50ml of 85% concentrated phosphoric acid are added into a flask placed in the ice bath, the mixture is stirred by a magnetic stirrer until the mixture is uniformly mixed, the rotating speed is reduced, 10g of high-purity graphite ultrafine powder is slowly added, after the mixture is completely added, the rotating speed is kept for stirring for 40-50min, the rotating speed is reduced, and 10-15g of oxidant K is added2FeO4Adding into the graphite solution within 20-30min, removing ice bath, continuously stirring at room temperature for oxidizing for 4-5h, and cooling to < 5 deg.C after stirring;
(2) 500ml of 5-10% hydrogen peroxide solution is prepared and placed in an ice bath, after the solution in the step (1) is cooled, the solution is slowly poured into the hydrogen peroxide solution to stop the oxidation reaction, the solution is stirred for 2-3 hours after being poured completely, after centrifugal separation, 1000ml of 5% dilute hydrochloric acid is adopted for washing, then purified water is used for washing to be neutral, and the graphene oxide powder is obtained after freeze drying.
Further, the further modification treatment comprises the following steps: weighing 1g of graphene oxide powder and 100ml of purified water, adding into a beaker, putting into an ultrasonic instrument for ultrasonic treatment for 20-30min, taking out and placing; weighing 30-50mgK2FeO4Adding into the above solution, continuing to put into an ultrasonic instrument for ultrasonic dispersion until the solution is completely dissolved, then adding the mixed solution into a polytetrafluoroethylene reaction kettle, reacting at the temperature of 180 ℃ and 200 ℃ for 12-15 h, pouring the product into 300ml of dilute hydrochloric acid with the concentration of 5-8% for soaking overnight after the reaction is finished, and then washing with purified water until the solution is in the middleAnd (4) carrying out freeze drying to obtain the graphene powder with the high specific surface.
Further, the covalent linkage comprises the following steps:
(1) weighing 1g of high specific surface area graphene powder, pouring the high specific surface area graphene powder into a round-bottom flask, adding 800-1000ml of dichloromethane solvent, and placing the mixture into an ultrasonic instrument for ultrasonic dispersion for 20-30min to obtain dispersion liquid;
(2) dissolving 200mg of DCC and 25-40mg of DMAP in 20ml of dichloromethane solution, slowly dripping into the dispersion liquid in the step (1), and continuing ultrasonic treatment for 20-30min to obtain a mixed solution;
(3) dissolving 200-250mg of parafuchsine in 20ml of dichloromethane solution, adding the parafuchsine dichloromethane solution into the mixed solution, putting the mixed solution into a water bath oscillator, oscillating for reaction for 4-6h at room temperature, taking out for suction filtration, soaking a filter cake in dichloromethane for suction filtration again, repeating for 3-5 times, washing with purified water, centrifuging, and freeze-drying to obtain the parafuchsine @ high-specific surface graphene composite material, namely the modified graphene composite material.
The supercapacitor comprises a working electrode prepared from an electrode material, wherein the electrode material is the parafuchsine-base @ high specific surface graphene composite material.
Further, the preparation method of the electrode material comprises the following steps: mixing and grinding 80-110 parts of parafuchsine base @ high-specific surface graphene composite material and 5-20 parts of conductive agent acetylene black, adding the ground powder into 0.5ml of Nafion solution with the mass fraction of 0.25-0.5%, then carrying out ultrasonic dispersion uniformly, measuring 6-10ul of dispersed liquid, dropwise adding the dispersed liquid onto the surface of a glassy carbon electrode with the diameter of 1cm, and drying to obtain the working electrode.
And packaging the dried working electrodes serving as the anode and the cathode of the supercapacitor and dimethyl carbonate solution serving as electrolyte to obtain the symmetrical supercapacitor.
Compared with the prior art, the invention has the beneficial effects that:
1) the oxidation-reduction treatment of the graphite adopts K2FeO4As oxidizing agents, in acidityUnder the condition, the oxidation capacity of the graphene is higher than that of potassium permanganate, and the graphene can be oxidized at low temperature, so that a large number of oxygen-containing functional groups (such as-OH, -COOH and the like) are arranged on the graphene, the graphene layer spacing is increased, and K is2FeO4The composite oxidizing agent has stronger oxidizing ability, is a green oxidizing agent, and is more efficient and more environment-friendly compared with other oxidizing agents.
2) Through further research, under the condition of adopting a hydrothermal method, K2FeO4The specific surface area, K, of the graphene oxide can be further improved2FeO4The carbon atoms on the graphene structure are directly oxidized and completely consumed, and then an inner hole is formed. Like this, the mesh porous structure has then been formed to the face hole in the graphite alkene structure and the off-plate hole between the layer, makes electrode material like this after, and electrolyte ion can directly get into the inside of high specific surface graphite alkene, and then can obtain higher specific capacitance.
3) Further research is carried out on the basis of the high-specific-surface graphene powder, the paracanthrin with the stereo C4 structure is connected to the high-specific-surface graphene through covalent reaction, the three-dimensional graphene composite material shown in figures 2 and 4 can be obtained, the structure is loose, the specific surface area is high, micropores, mesopores and macropores simultaneously exist in the three-dimensional graphene composite material, and the porous structure provides a shortcut for the transmission of electrolyte ions and reduces the transmission resistance of the electrolyte.
4) The super capacitor has high specific capacitance and good cycle stability, and the capacitance retention rate is over 90 percent after 10000 cycles.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced 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 the drawings without creative efforts.
Fig. 1 is a preparation flow chart of a vice fuchsin base @ high specific surface area graphene composite material according to the invention;
fig. 2 is a three-dimensional structure diagram of a partial segment of a parafuchsine @ high specific surface graphene composite material according to the present invention;
FIG. 3 is a partially sectioned view of an infrared spectrum of high specific surface area graphene, sub-fuchsin @ high specific surface area graphene composite material and sub-fuchsin in sequence from bottom to top;
fig. 4 is a TEM image of high specific surface area graphene;
fig. 5 is an SEM image of a parafuchsin base @ high specific surface graphene composite.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of graphene oxide
Under the ice bath condition, adding 200ml of concentrated sulfuric acid (98%) and 30-50ml of concentrated phosphoric acid (85%) into a flask placed in the ice bath, stirring by a magnetic stirrer until the concentrated sulfuric acid and the concentrated phosphoric acid are uniformly mixed, reducing the rotating speed, slowly adding 10g of high-purity graphite ultrafine powder, after the high-purity graphite ultrafine powder is completely added, keeping the rotating speed to continue stirring for 40min, reducing the rotating speed, and adding 14g K2FeO4Adding into the graphite solution within 30min, removing ice bath, continuously stirring at room temperature for oxidizing for 5h, and cooling to less than 5 deg.C after stirring;
500ml of 10% hydrogen peroxide solution is prepared and placed in an ice bath, after the solution is cooled, the hydrogen peroxide solution is slowly poured into the ice bath to terminate the oxidation reaction, the hydrogen peroxide solution is stirred for 2 hours after all the hydrogen peroxide solution is poured into the ice bath, after centrifugal separation, 1000ml of 5% dilute hydrochloric acid is adopted for washing, then purified water is used for washing until the solution is neutral, and the graphene oxide powder is obtained after freeze drying.
As described in the background art, although graphene has optical, electrical, mechanical and thermodynamic properties superior to those of conventional materials, graphene has a structure with huge specific surface area and van der waals force, and thus is very easy to agglomerate, so that the properties of the graphene composite material cannot be fully exerted. Therefore, in order to solve the problem, firstly, the research and development team of the company firstly carries out oxidation treatment on graphite, and the invention selects K2FeO4As oxidizing agent, under acidic conditions, K2FeO4The oxidation capability is stronger, the standard electrode potential is 2.2V, the standard electrode potential of potassium permanganate is 1.67V, even under the low-temperature condition, the graphene can be oxidized, so that a large number of oxygen-containing functional groups (such as-OH, -COOH and the like) are arranged on the graphene, the graphene layer interval is further increased, and K is2FeO4The composite oxidizing agent has stronger oxidizing ability, is a green oxidizing agent, and is more efficient and more environment-friendly compared with other oxidizing agents.
Example 2
Preparation of high specific surface area graphene powder
Weighing 1g of graphene oxide powder and 100ml of purified water, adding into a beaker, putting into an ultrasonic instrument for ultrasonic treatment for 30min, taking out and placing; weigh 50mg K2FeO4Adding the solution into the solution, continuously placing the solution into an ultrasonic instrument for ultrasonic dispersion until the solution is completely dissolved, then adding the mixed solution into a polytetrafluoroethylene reaction kettle, reacting for 15 hours at the temperature of 200 ℃, pouring the product into 300ml of dilute hydrochloric acid with the concentration of 5% for soaking overnight after the reaction is finished, then washing the product to be neutral by purified water, and obtaining the graphene powder with the high specific surface area after freeze drying.
In the technology of graphene oxide, research teams find that K is obtained under the condition of a hydrothermal method2FeO4The specific surface area of graphene oxide can be further increased, as shown in FIG. 1, K2FeO4Stone made of stoneThe carbon atoms on the graphene structure are directly oxidized and completely consumed, thereby forming the internal pores (shown in fig. 4). Like this, the mesh porous structure has then been formed to the out-of-plane hole between the face hole of graphene construction and the layer, makes electrode material back like this, and electrolyte ion can directly get into the inside of high specific surface graphite alkene, and then can obtain higher specific capacitance.
Example 3
Preparation of parafuchsine @ high specific surface graphene composite material
Weighing 1g of high specific surface area graphene powder, pouring the high specific surface area graphene powder into a round-bottom flask, adding 1000ml of dichloromethane solvent, and placing the mixture into an ultrasonic instrument for ultrasonic dispersion for 30min to obtain dispersion liquid;
dissolving 200mg of DCC and 40mg of DMAP in 20ml of dichloromethane solution, slowly dripping into the dispersion liquid, and continuing ultrasonic treatment for 20min to obtain a mixed solution;
dissolving 200mg of parafuchsine in 20ml of dichloromethane solution, adding the parafuchsine dichloromethane solution into the mixed solution, putting the mixed solution into a water bath oscillator, oscillating for 5 hours at room temperature, taking out and filtering, soaking a filter cake with dichloromethane for carrying out suction filtration again, repeatedly carrying out suction filtration for 3-5 times, washing with purified water, centrifuging, and freeze-drying to obtain the parafuchsine @ high-specific surface graphene composite material;
in order to obtain an electrode material with higher capacitance, further research is carried out on the basis of high specific surface graphene powder, and the parafuchsine alkali with a stereo C4 structure is connected to the high specific surface graphene through covalent reaction, so that the three-dimensional graphene composite material shown in the figures 2 and 5 can be obtained, the structure is loose, the specific surface area is higher, micropores, mesopores and macropores simultaneously exist in the three-dimensional graphene composite material, and the porous structure provides a shortcut for the transmission of electrolyte ions and reduces the transmission resistance of the electrolyte.
The infrared spectrometer is BRUKER ALPHA type produced by Germany manufacturer, and as shown in FIG. 3, the graphene with high specific surface area is 3400cm-1The strong absorption peak at the left and right parts is caused by-OH stretching vibration, and the sub fuchsin @ high specific surface area graphene composite material is 3500cm-1And 1700cm-1Strong absorption peaks at left and rightIt is a-CONH-characteristic absorption peak.
Example 4
Preparation of super capacitor
A super capacitor comprises a working electrode prepared from an electrode material, and the preparation method of the working electrode comprises the following steps: mixing and grinding 5mg of parafuchsine-high specific surface graphene composite material and 0.8mg of conductive agent acetylene black, adding the ground powder into 0.5ml of Nafion solution with the mass fraction of 0.35%, then carrying out ultrasonic dispersion uniformly, measuring 6-10ul of dispersion liquid, dropwise adding the dispersion liquid onto the surface of a glassy carbon electrode with the diameter of 1cm, and drying to obtain the working electrode.
And packaging the dried working electrodes serving as the anode and the cathode of the supercapacitor and dimethyl carbonate solution serving as electrolyte to obtain the symmetrical supercapacitor.
Example 5
A working electrode is made of the graphene oxide powder prepared in the embodiment 1 according to the preparation method of the embodiment 4, the working electrode is used as a positive electrode and a negative electrode of the supercapacitor, and the working electrode and a dimethyl carbonate solution are used as electrolyte to be packaged, so that the symmetrical supercapacitor is obtained.
Example 6
A supercapacitor is prepared by preparing the high-specific-surface-area graphene powder prepared in the embodiment 2 into a working electrode according to the preparation method in the embodiment 4, using the working electrode as a positive electrode and a negative electrode of the supercapacitor, and packaging the working electrode and a dimethyl carbonate solution as an electrolyte to obtain a symmetrical supercapacitor.
Performance testing
(1) Specific surface area
The invention adopts a scanning electron microscope of S4800 model produced by Hitachi, Japan to test the structure; the specific surface area of the working electrode materials prepared in examples 1, 2 and 3 was measured by using an american maculometer, and is shown in table 1:
(2) electrical Performance testing
The cycling performance of the supercapacitors prepared in examples 4-6 at a current density of 1A/g, the specific capacitance results of the discharge measurements are shown in Table 2:
from the above, the super capacitor of the invention has high specific capacitance and good cycle stability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (6)
1. A modified graphene composite material is characterized by comprising the following steps:
carrying out oxidation-reduction treatment on graphite to prepare graphene oxide powder;
carrying out further modification treatment on the graphene oxide to obtain high specific surface graphene powder;
and (3) covalently linking the parafuchsin base to the graphene powder with the high specific surface area to obtain the modified graphene composite material.
2. The modified graphene composite material of claim 1, wherein the redox treatment comprises the following steps: (1) under the ice bath condition, 200ml of 98% concentrated sulfuric acid and 30-50ml of 85% concentrated phosphoric acid are added into a flask placed in the ice bath, the mixture is stirred by a magnetic stirrer until the mixture is uniformly mixed, the rotating speed is reduced, 10g of high-purity graphite ultrafine powder is slowly added, after the mixture is completely added, the rotating speed is kept for stirring for 40-50min, the rotating speed is reduced, and 10-15g of oxidant K is added2FeO4Adding into the graphite solution within 20-30min, removing ice bath, continuously stirring at room temperature for oxidizing for 4-5h, and cooling to < 5 deg.C after stirring;
(2) 500ml of 5-10% hydrogen peroxide solution is prepared and placed in an ice bath, after the solution in the step (1) is cooled, the solution is slowly poured into the hydrogen peroxide solution to stop the oxidation reaction, the solution is stirred for 2-3 hours after being poured completely, after centrifugal separation, 1000ml of 5% dilute hydrochloric acid is adopted for washing, then purified water is used for washing to be neutral, and the graphene oxide powder is obtained after freeze drying.
3. The modified graphene composite material of claim 1, wherein the further modification treatment comprises the following steps: weighing 1g of graphene oxide powder and 100ml of purified water, adding into a beaker, putting into an ultrasonic instrument for ultrasonic treatment for 20-30min, taking out and placing; weighing 30-50mg K2FeO4Adding the solution into the solution, continuously placing the solution into an ultrasonic instrument for ultrasonic dispersion until the solution is completely dissolved, then adding the mixed solution into a polytetrafluoroethylene reaction kettle, reacting at the temperature of 180 ℃ and 200 ℃ for 12-15 h, pouring the product into 300ml of dilute hydrochloric acid with the concentration of 5-8% for soaking overnight after the reaction is finished, then washing the product to be neutral by purified water, and obtaining the graphene powder with the high specific surface area after freeze drying.
4. The modified graphene composite material of claim 1, wherein the covalent linkage comprises the following steps:
(1) weighing 1g of high specific surface area graphene powder, pouring the high specific surface area graphene powder into a round-bottom flask, adding 800-1000ml of dichloromethane solvent, and placing the mixture into an ultrasonic instrument for ultrasonic dispersion for 20-30min to obtain dispersion liquid;
(2) dissolving 200mg of DCC and 25-40mg of DMAP in 20ml of dichloromethane solution, slowly dripping into the dispersion liquid in the step (1), and continuing ultrasonic treatment for 20-30min to obtain a mixed solution;
(3) dissolving 200-250mg of parafuchsine in 20ml of dichloromethane solution, adding the parafuchsine dichloromethane solution into the mixed solution, putting the mixed solution into a water bath oscillator, oscillating for reaction for 4-6h at room temperature, taking out for suction filtration, soaking a filter cake in dichloromethane for suction filtration again, repeating for 3-5 times, washing with purified water, centrifuging, and freeze-drying to obtain the parafuchsine @ high-specific surface graphene composite material, namely the modified graphene composite material.
5. A supercapacitor, comprising a working electrode prepared from an electrode material, wherein the electrode material comprises the parafuchsine @ high specific surface area graphene composite material according to claim 4.
6. The supercapacitor according to claim 5, wherein the method for preparing the working electrode comprises the following steps: mixing and grinding 80-110 parts of parafuchsine base @ high-specific surface graphene composite material and 5-20 parts of conductive agent acetylene black, adding the ground powder into 0.5ml of Nafion solution with the mass fraction of 0.25-0.5%, then carrying out ultrasonic dispersion uniformly, measuring 6-10ul of dispersed liquid, dropwise adding the dispersed liquid onto the surface of a glassy carbon electrode with the diameter of 1cm, and drying to obtain the working electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115083793A (en) * | 2022-08-11 | 2022-09-20 | 深圳市今朝时代股份有限公司 | Super capacitor electrode material and preparation method thereof |
| CN117265606A (en) * | 2023-10-12 | 2023-12-22 | 广州工程技术职业学院 | Electroplating solution for metal filter screen, metal filter screen and preparation method of metal filter screen |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015184815A1 (en) * | 2014-06-04 | 2015-12-10 | 福州大学 | Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof |
| WO2016029527A1 (en) * | 2014-08-30 | 2016-03-03 | 海安南京大学高新技术研究院 | Method for preparing paraffin microcapsule phase-change material modified by graphene oxide |
| CN105692602A (en) * | 2016-03-08 | 2016-06-22 | 上海大学 | Method for simply and rapidly preparing thin graphene |
| US20160244333A1 (en) * | 2015-02-24 | 2016-08-25 | Aruna Zhamu | Environmentally benign production of graphene materials |
| CN107840953A (en) * | 2017-11-13 | 2018-03-27 | 东华大学 | A kind of synthesis of rich nitrogen porous organic polymer |
| CN110660590A (en) * | 2019-10-21 | 2020-01-07 | 东华大学 | Nitrogen-containing carbon aerogel and preparation and application thereof |
| CN114014306A (en) * | 2021-12-15 | 2022-02-08 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
-
2022
- 2022-05-25 CN CN202210572409.5A patent/CN114709083B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015184815A1 (en) * | 2014-06-04 | 2015-12-10 | 福州大学 | Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof |
| WO2016029527A1 (en) * | 2014-08-30 | 2016-03-03 | 海安南京大学高新技术研究院 | Method for preparing paraffin microcapsule phase-change material modified by graphene oxide |
| US20160244333A1 (en) * | 2015-02-24 | 2016-08-25 | Aruna Zhamu | Environmentally benign production of graphene materials |
| CN105692602A (en) * | 2016-03-08 | 2016-06-22 | 上海大学 | Method for simply and rapidly preparing thin graphene |
| CN107840953A (en) * | 2017-11-13 | 2018-03-27 | 东华大学 | A kind of synthesis of rich nitrogen porous organic polymer |
| CN110660590A (en) * | 2019-10-21 | 2020-01-07 | 东华大学 | Nitrogen-containing carbon aerogel and preparation and application thereof |
| CN114014306A (en) * | 2021-12-15 | 2022-02-08 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
Non-Patent Citations (1)
| Title |
|---|
| KIYOUNG JO: "《Ultrathin Supercapacitor Electrode Based on Reduced Graphene》", 《AMERICAN CHEMICAL SOCIETY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115083793A (en) * | 2022-08-11 | 2022-09-20 | 深圳市今朝时代股份有限公司 | Super capacitor electrode material and preparation method thereof |
| CN115083793B (en) * | 2022-08-11 | 2022-11-29 | 深圳市今朝时代股份有限公司 | Super capacitor electrode material and preparation method thereof |
| CN117265606A (en) * | 2023-10-12 | 2023-12-22 | 广州工程技术职业学院 | Electroplating solution for metal filter screen, metal filter screen and preparation method of metal filter screen |
| CN117265606B (en) * | 2023-10-12 | 2024-04-26 | 广州工程技术职业学院 | Electroplating solution for metal filter screen, metal filter screen and preparation method of metal filter screen |
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