CN114121502A - Ultraviolet curing graphene supercapacitor and preparation method thereof - Google Patents
Ultraviolet curing graphene supercapacitor and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000001723 curing Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000000016 photochemical curing Methods 0.000 claims abstract description 24
- 238000001259 photo etching Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
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- 238000010146 3D printing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 57
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
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- 239000012298 atmosphere Substances 0.000 description 9
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/84—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
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Abstract
The invention discloses an ultraviolet curing graphene supercapacitor and a preparation method thereof, wherein a photocuring material can be directly printed by using an ultraviolet curing process to prepare a graphene electrode, the electrode is placed at a high temperature to endow the electrode with conductivity, and finally, the high-performance supercapacitor can be obtained through simple assembly. The preparation method not only expands the application field of the photoetching/photocuring process, can prepare the graphene electrode with high purity and high resolution, but also can prepare the electrode with small characteristic size, and increases the energy density of the super capacitor; the further preparation of a more complex electrode structure reduces the transmission efficiency of electrons and ions and increases the power density of the capacitor, and the preparation method has great significance for improving the performance of the super capacitor and quickly preparing the super capacitor.
Description
Technical Field
The invention belongs to the technical field of printed circuits, and particularly relates to an ultraviolet curing graphene supercapacitor and a preparation method thereof.
Background
The photocuring additive manufacturing technology has wide application in life and industrial production due to the advantages of high efficiency, high resolution, and capability of forming complex structures, but has little application in electronic printing because the photocurable material cannot conduct electricity. The graphene is a two-dimensional material with high conductivity and large specific surface area, and is very suitable for serving as an electrode material of a supercapacitor. At present, the preparation methods of the graphene supercapacitor mainly comprise the following two methods, and the traditional MEMS (micro electro mechanical system) process is complex, has more working procedures, and is high in cost and long in time when being prepared in large batch. The extrusion additive manufacturing process faces the problem of large characteristic dimension of the electrode structure, so that the capacitance performance is low, and the power density of the super capacitor is limited by the simple electrode structure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an ultraviolet curing graphene supercapacitor and a preparation method thereof, so as to solve the problem that the graphene supercapacitor preparation process in the prior art is difficult to be applied to graphene supercapacitors.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of an ultraviolet curing graphene supercapacitor comprises the following steps:
step 1, placing photo-curable modified graphene oxide in a solvent, and stirring to obtain a graphene solution A;
step 2, adding a photoinitiator into the graphene solution A, and continuously stirring to obtain a process solution B;
step 3, placing the process solution B in a vacuum chamber with the pressure of-1 to-0.5 MPa, stirring to remove bubbles to obtain a photocuring graphene solution, and performing ultraviolet curing on the photocuring graphene solution or performing 3D printing to obtain a three-dimensional graphene electrode or an interdigital electrode;
the ultraviolet light curing process comprises the following steps: coating a photocuring graphene solution on the surface of a substrate, drying the substrate, then attaching a film to the substrate, placing a mask on the film, placing the mask in a photoetching machine for ultraviolet curing, and then placing the substrate attached with the film in a developing solution to obtain a three-dimensional graphene electrode or an interdigital electrode;
the 3D printing is SLA or DLP;
step 4, placing the three-dimensional graphene electrode or the interdigital electrode in a tubular furnace, and heating to obtain the three-dimensional graphene electrode or the interdigital electrode with electric conductivity;
and 5, combining the three-dimensional graphene electrode or the interdigital electrode with an electrolyte to form the graphene supercapacitor.
The invention is further improved in that:
preferably, in the process solution B, by mass, the solvent is 80-95 parts, the photo-curable modified graphene oxide is 1-10 parts, and the photoinitiator is 1-5 parts.
Preferably, in the step 1, the stirring speed is 100-500r/min, and the stirring time is 5-30 min.
Preferably, in step 1, the solvent is one or more of deionized water, ultrapure water, ethanol and trifluoroethanol.
Preferably, in the step 2, the stirring speed is 100-500r/min, and the stirring time is 10-60 min.
Preferably, in step 2, the photoinitiator is one or a mixture of 819, 184, TPO, ITX, or 907.
Preferably, in the step 3, in the ultraviolet curing process, the drying temperature is 70-100 ℃, and the drying time is 5-10 min.
Preferably, in step 3, the developing solution is an aqueous solution of sodium hydroxide with a mass concentration of 0.1-0.5%.
Preferably, in the step 4, the heating temperature in the tubular furnace is 250-1900 ℃, and the heating time is 1-6 h.
An ultraviolet light cured graphene supercapacitor prepared by the preparation method of any one of the ultraviolet light cured graphene supercapacitors.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of an ultraviolet curing graphene supercapacitor, which can be used for directly printing a photocuring material by using an ultraviolet curing process to prepare a graphene electrode, placing the electrode at a high temperature to endow the electrode with electric conductivity, and finally obtaining the high-performance supercapacitor through simple assembly. The preparation method not only expands the application field of the photoetching/photocuring process, can prepare the graphene electrode with high purity and high resolution, but also can prepare the electrode with small characteristic size, and increases the energy density of the super capacitor; the further preparation of a more complex electrode structure reduces the transmission efficiency of electrons and ions and increases the power density of the capacitor, and the preparation method has great significance for improving the performance of the super capacitor and quickly preparing the super capacitor.
Further, different drying temperatures exist in the ultraviolet curing process for different solvents.
Furthermore, the mass fraction of the sodium hydroxide aqueous solution as the developing solution is limited, so that the subsequent patterns can be displayed.
Further, the heating temperature of the tube furnace is limited because the hydroxyl groups in the graphene oxide start to decompose from 250 ℃, the hydroxyl groups are completely decomposed with time, the graphene has certain conductivity, and other groups are gradually decomposed with the increase of the temperature.
The invention also discloses an ultraviolet light curing graphene super capacitor, the prepared light curing graphene material can be used for preparing a high-purity and high-resolution graphene electrode, the high conductivity and the high specific surface area are realized, and the assembled graphene super capacitor has higher energy density and power density.
Drawings
FIG. 1 is a physical diagram of an interdigital electrode prepared in example 1;
FIG. 2 is a CV test graph of a graphene supercapacitor;
fig. 3 is a physical diagram of the interdigital electrode prepared by DLP printer printing.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
in the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly and encompass, for example, both fixed and removable connections; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The invention discloses a preparation method of an ultraviolet curing graphene supercapacitor, which specifically comprises the following steps:
the method comprises the following steps: placing the photo-curable modified graphene oxide in a beaker, adding the photo-curable modified graphene oxide into a solvent, and stirring for 5-30min at a rotation speed of 100-. Wherein the solvent is one or a mixture of deionized water, ultrapure water, ethanol and trifluoroethanol. The photo-curable modified graphene oxide mentioned in the present example is photo-curable modified graphene oxide prepared under application No. 201910318224X.
Step two: and (3) adding a photoinitiator into the graphene solution prepared in the step one, and stirring the mixture for 10-60min at the rotating speed of 100-500r/min to obtain a process solution B. Further, the photoinitiator is one or more of 819, 184, TPO, ITX or 907 mixed.
In the second step, the light-cured material in the process solution B comprises the following components in parts by weight:
| composition (I) | Mass fraction |
| Solvent(s) | 80 to 95 portions of |
| Graphene | 1-10 parts of |
| Photoinitiator | 1-5 parts of |
Step three: and (2) placing the process solution B prepared in the step two into a vacuum chamber with the pressure of-1 to-0.5 MPa to remove stirring bubbles to obtain slurry, coating the slurry on the surface of a substrate (one of quartz glass and Si sheets), drying the substrate on a hot plate at 70-100 ℃ for 5-10 minutes, obtaining the substrate attached with a film after the drying is completed, placing the substrate and a mask plate into a photoetching machine for ultraviolet curing, wherein the ultraviolet curing needs to etch the graphene completely, and placing the substrate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.1-0.5%, so that the graphene interdigital electrode can be obtained, or directly printing the three-dimensional graphene electrode or the interdigital electrode by using an SLA or DLP 3D printer.
Step four: and (3) placing the graphene electrode prepared in the third step into a tubular furnace, and maintaining the high temperature of 250-1900 ℃ for 1-6 hours under the vacuum/nitrogen/argon atmosphere to endow the electrode with conductivity, so as to obtain the electrode or the interdigital electrode with conductivity.
Step five: and combining the high-conductivity graphene electrode prepared in the fourth step with an electrolyte to form a graphene supercapacitor, wherein the electrolyte is one of sodium hydroxide, sodium sulfate, sulfuric acid or phosphoric acid.
Example 1:
(1) synthetic photo-curable material
And (3) placing 60mg of the photo-curable modified graphene oxide in a beaker, adding 2g of deionized water, and stirring for 15min at a rotation speed of 200r/min so that the photo-curable modified graphene oxide is fully dissolved in the solvent.
20mg of photoinitiator 819 is added into the prepared photo-curable modified graphene oxide solution, and the mixture is stirred for 30min at the rotating speed of 200r/min, so that the graphene material with photo-curing performance is prepared.
(2) Preparation of graphene electrode
Placing the prepared photo-cured graphene material into a vacuum chamber with the pressure of-1 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 100 ℃ for 10 minutes, placing the quartz glass and a mask plate together into a photoetching machine for ultraviolet light curing after the photo-cured graphene material is completely dried, and then placing the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.3%, so that the graphene interdigital electrode can be obtained; the synthesis resulted in a patterned electrode pattern as shown in figure 1.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 850 ℃ for 3h under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled test super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
Placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 14.2g of sodium sulfate, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, and air-drying for 24h in the atmosphere to complete the assembly of the graphene supercapacitor.
The performance of the capacitor is measured by using the electrochemical workstation cyclic voltammetry, constant current and alternating current impedance, the test result of the cyclic voltammetry is shown in fig. 2, and the cyclic voltammetry still has a good rectangular-like shape under a higher scanning rate, which shows that the cyclic voltammetry can form a good double electric layer, has a larger capacitance performance and has a rapid charge and discharge performance from fig. 2.
Example 2
(1) Synthetic photo-curable material
And (3) placing 1 part of the photo-curable modified graphene oxide in a beaker, adding 80 parts of ultrapure water, and stirring for 20min at the rotating speed of 300r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
Adding 1 part of photoinitiator 184 into the prepared photo-curable modified graphene oxide solution, and stirring the mixture for 60min at the rotating speed of 100r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.9 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 90 ℃ for 5 minutes, putting the quartz glass and a mask plate into a photoetching machine for ultraviolet curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tube furnace, and maintaining the high temperature of 250 ℃ for 6 hours under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
Placing 14g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 14.2g of sodium sulfate, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, and air-drying for 24h in the atmosphere to complete the assembly of the graphene supercapacitor.
Example 3
(1) Synthetic photo-curable material
And 3 parts of the photo-curable modified graphene oxide is placed in a beaker, 85 parts of ethanol is added, and the mixture is stirred for 30min at the rotating speed of 100r/min, so that the photo-curable modified graphene oxide is fully dissolved in the solvent.
And adding 2 parts of photoinitiator TPO into the prepared photo-curable modified graphene oxide solution, and stirring the mixture for 40min at the rotating speed of 300r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.8 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 85 ℃ for 7 minutes, putting the quartz glass and a mask plate into a photoetching machine together for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tube furnace, and maintaining the high temperature of 500 ℃ for 4 hours under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 5.46ml of sulfuric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor.
Example 4
(1) Synthetic photo-curable material
And (3) placing 5 parts of the photo-curable modified graphene oxide in a beaker, adding 90 parts of trifluoroethanol, and stirring for 30min at a rotating speed of 100r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
Adding 1 part of photoinitiator into the prepared photo-curable modified graphene oxide solution, wherein the photoinitiator is a mixture of ITX and 907 according to a mass ratio of 2:1, and stirring the mixture for 20min at a speed of 400r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.7 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 80 ℃ for 8 minutes, putting the quartz glass and a mask plate into a photoetching machine together for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 1200 ℃ for 2h under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 5.46ml of sulfuric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor.
Example 5
(1) Synthetic photo-curable material
And (3) placing 10 parts of the photo-curable modified graphene oxide in a beaker, adding 95 parts of ultrapure water, and stirring for 5min at the speed of 500r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
Adding 5 parts of photoinitiator into the prepared photo-curable modified graphene oxide solution, wherein the photoinitiator is a mixture of ITX and 907 according to a mass ratio of 2:1, and stirring the mixture for 55min at a speed of 150r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.9 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 75 ℃ for 6 minutes, putting the quartz glass and a mask plate into a photoetching machine for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 1900 ℃ for 1h under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 6.8ml of phosphoric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor.
Example 6
(1) Synthetic photo-curable material
And (3) placing 7 parts of the light-curable modified graphene oxide in a beaker, adding 83 parts of deionized water, and stirring for 8min at a rotation speed of 150r/min to fully dissolve the light-curable modified graphene oxide in the solvent.
4 parts of photoinitiator 819 is added into the prepared photo-curable modified graphene oxide solution, and the mixture is stirred for 55min at the rotating speed of 150r/min, so that the graphene material with photo-curing performance is prepared.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.9 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 75 ℃ for 6 minutes, putting the quartz glass and a mask plate into a photoetching machine for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tube furnace, and maintaining the high temperature of 350 ℃ for 5 hours under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 6.8ml of phosphoric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor.
Example 7
(1) Synthetic photo-curable material
And (3) placing 8 parts of the photo-curable modified graphene oxide in a beaker, adding 88 parts of ultrapure water, and stirring for 18min at the rotation speed of 250r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
Adding 2 parts of photoinitiator 184 into the prepared photo-curable modified graphene oxide solution, and stirring the mixture for 45min at the rotating speed of 350r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.8 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 95 ℃ for 5 minutes, putting the quartz glass and a mask plate into a photoetching machine together for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 600 ℃ for 4 hours under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 5.46ml of sulfuric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor. Example 8
(1) Synthetic photo-curable material
Placing 2 parts of the photo-curable modified graphene oxide in a beaker, adding 92 parts of ethanol, and stirring for 28min at a rotation speed of 350r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
Adding 3 parts of photoinitiator TPO into the prepared photo-curable modified graphene oxide solution, and stirring the mixture for 35min at the rotating speed of 450r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.7 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at 78 ℃ for 10 minutes, putting the quartz glass and a mask plate into a photoetching machine for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, so that the graphene interdigital electrode can be obtained.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 1500 ℃ for 3 hours under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 5.46ml of sulfuric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor.
Example 9
(1) Synthetic photo-curable material
Placing 6 parts of the photo-curable modified graphene oxide in a beaker, adding 86 parts of trifluoroethanol, and stirring for 25min at the rotation speed of 450r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
Adding 1 part of photoinitiator ITX and 907 part of photoinitiator into the prepared photo-curable modified graphene oxide solution, and stirring the mixture for 25min at the rotating speed of 250r/min to prepare the graphene material with photo-curing performance.
(2) Preparation of graphene electrode
And (2) putting the prepared photo-cured graphene material into a vacuum chamber with the pressure of-0.5 MPa to remove stirring bubbles, coating the photo-cured graphene material on quartz glass, drying the quartz glass on a hot plate at the temperature of 92 ℃ for 7 minutes, putting the quartz glass and a mask plate into a photoetching machine together for ultraviolet light curing after the photo-cured graphene material is completely dried, and putting the quartz glass and the mask plate into a developing solution, wherein the developing solution is a sodium hydroxide aqueous solution with the mass concentration of 0.5%, and thus the graphene interdigital electrode is obtained.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 1000 ℃ for 2h under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
And (2) placing 10g of polyvinyl alcohol in a 250ml beaker, adding 100ml of deionized water, stirring for 30min at 200r/min, adding 5.46ml of sulfuric acid, stirring for 30min at 200r/min, preparing a sodium sulfate gel electrolyte, dripping the electrolyte on the prepared graphene electrode, air-drying for 24h in the atmosphere, and finishing the assembly of the graphene supercapacitor.
Example 9
(1) Synthetic photo-curable material
Placing 6 parts of the photo-curable modified graphene oxide in a beaker, adding 86 parts of trifluoroethanol, and stirring for 25min at the rotation speed of 450r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
1 part of photoinitiator 819 is added into the prepared photo-curable modified graphene oxide solution, and the mixture is stirred for 25min at the rotating speed of 250r/min, so that the graphene material with photo-curing performance is prepared.
(2) Preparation of graphene electrode
And (3) placing the prepared photocuring graphene material into a vacuum chamber with the pressure of-0.5 MPa to remove stirring bubbles, and printing the slurry through an SLA printer to obtain the graphene electrode.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 1000 ℃ for 2h under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled test super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
Example 9
(1) Synthetic photo-curable material
Placing 6 parts of the photo-curable modified graphene oxide in a beaker, adding 86 parts of trifluoroethanol, and stirring for 25min at the rotation speed of 450r/min to fully dissolve the photo-curable modified graphene oxide in the solvent.
1 part of photoinitiator 819 is added into the prepared photo-curable modified graphene oxide solution, and the mixture is stirred for 25min at the rotating speed of 250r/min, so that the graphene material with photo-curing performance is prepared.
(2) Preparation of graphene electrode
The prepared photo-curing graphene material is placed in a vacuum chamber with the pressure of-0.5 MPa to remove stirring bubbles, the slurry is printed by a DLP printer to prepare a graphene electrode, and the prepared electrode is shown in figure 3.
And (3) placing the prepared graphene electrode in a tubular furnace, and maintaining the high temperature of 1000 ℃ for 2h under the nitrogen atmosphere to endow the electrode with conductivity.
(3) Assembled test super capacitor
And placing the prepared graphene interdigital electrode on a desktop, and dot-coating conductive silver paste to lead out a lead.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of an ultraviolet curing graphene supercapacitor is characterized by comprising the following steps:
step 1, placing photo-curable modified graphene oxide in a solvent, and stirring to obtain a graphene solution A;
step 2, adding a photoinitiator into the graphene solution A, and continuously stirring to obtain a process solution B;
step 3, placing the process solution B in a vacuum chamber with the pressure of-1 to-0.5 MPa, stirring to remove bubbles to obtain a photocuring graphene solution, and performing ultraviolet curing on the photocuring graphene or performing 3D printing to obtain a three-dimensional graphene electrode or an interdigital electrode;
the ultraviolet light curing process comprises the following steps: coating photocuring graphene on the surface of a substrate, drying the substrate, attaching a film to the substrate, placing a mask on the film, placing the mask in a photoetching machine for ultraviolet curing, and placing the substrate attached with the film in a developing solution after the ultraviolet curing is finished to obtain a three-dimensional graphene electrode or an interdigital electrode;
the 3D printing is SLA or DLP;
step 4, placing the three-dimensional graphene electrode or the interdigital electrode in a tubular furnace, and heating to obtain the three-dimensional graphene electrode or the interdigital electrode with electric conductivity;
and 5, combining the three-dimensional graphene electrode or the interdigital electrode with an electrolyte to form the graphene supercapacitor.
2. The method for preparing the ultraviolet curing graphene supercapacitor as claimed in claim 1, wherein in the process solution B, by mass, the solvent is 80-95 parts, the photo-curable modified graphene oxide is 1-10 parts, and the photoinitiator is 1-5 parts.
3. The method for preparing the ultraviolet curing graphene supercapacitor as claimed in claim 1, wherein in the step 1, the stirring speed is 100-500r/min, and the stirring time is 5-30 min.
4. The method for preparing the ultraviolet curing graphene supercapacitor according to claim 1, wherein in the step 1, the solvent is one or more of deionized water, ultrapure water, ethanol and trifluoroethanol.
5. The method for preparing the ultraviolet curing graphene supercapacitor as claimed in claim 1, wherein in the step 2, the stirring speed is 100-500r/min, and the stirring time is 10-60 min.
6. The method for preparing the ultraviolet curing graphene supercapacitor according to claim 1, wherein in the step 2, the photoinitiator is one or a mixture of 819, 184, TPO, ITX and 907.
7. The method for preparing the ultraviolet curing graphene supercapacitor according to claim 1, wherein in the step 3, the drying temperature is 70-100 ℃ and the drying time is 5-10 min in the ultraviolet curing process.
8. The method for preparing the ultraviolet curing graphene supercapacitor according to claim 1, wherein in the step 3, the developing solution is an aqueous solution of sodium hydroxide with a mass concentration of 0.1-0.5%.
9. The preparation method of the ultraviolet curing graphene supercapacitor according to claim 1, wherein in the step 4, the heating temperature in the tube furnace is 250-1900 ℃, and the heating time is 1-6 hours.
10. An ultraviolet light cured graphene supercapacitor prepared by the preparation method of the ultraviolet light cured graphene supercapacitor according to any one of claims 1 to 9.
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| US20120170171A1 (en) * | 2010-11-22 | 2012-07-05 | Woo Young Lee | Inkjet-printed flexible electronic components from graphene oxide |
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