CN115472443B - Method for loading graphene quantum dots on graphite paper by hydrothermal method and application of method in aspect of preparing planar miniature supercapacitor - Google Patents
Method for loading graphene quantum dots on graphite paper by hydrothermal method and application of method in aspect of preparing planar miniature supercapacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 132
- 239000010439 graphite Substances 0.000 title claims abstract description 132
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 20
- 238000011068 loading method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 239000003990 capacitor Substances 0.000 claims abstract description 26
- 238000003698 laser cutting Methods 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 53
- 239000002096 quantum dot Substances 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000011245 gel electrolyte Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002608 ionic liquid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
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- 238000012545 processing Methods 0.000 claims description 9
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
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- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 238000010330 laser marking Methods 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
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- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of a miniature energy storage device, in particular to a method for loading graphene quantum dots on graphite paper by a hydrothermal method and application of the method in preparation of a planar miniature super capacitor, and belongs to the field of preparation of wearable energy storage devices. According to the invention, the graphene quantum dots are uniformly loaded on the graphite paper by using a hydrothermal method, and then the patterned interdigital electrode is rapidly prepared by combining laser cutting for preparing the miniature super capacitor.
Description
Technical Field
The invention relates to a preparation method of a miniature energy storage device, in particular to a method for loading graphene quantum dots on graphite paper by a hydrothermal method and application of the method in preparation of a planar miniature super capacitor, and belongs to the field of preparation of wearable energy storage devices.
Background
With the rapid development of electronic information technology, the internet of things and wearable intelligent devices, people have put forward higher requirements on flexible, miniature and portable electronic equipment (man-machine interaction systems, implanted medical monitoring modules and extreme environment standby emergency energy sources). The miniature super capacitor as a two-dimensional plane energy storage device gets rid of the problems of large volume and poor flexibility of the traditional energy storage unit, has the advantages of ultra-long cycling stability, excellent charge and discharge rate and easiness in large-scale patterning preparation, and becomes one of the most potential miniature energy storage devices of the next generation.
The preparation of the miniature super capacitor generally takes platinum, gold, silver, copper, nickel and conductive polymers as current collectors, the flexibility of the device is greatly limited by the intrinsic physical characteristics of the metal current collectors, and the conductive polymer current collectors are generally poor in conductivity and high in material cost, so that the requirements of practical application are difficult to meet. The graphite paper is formed by stacking and rolling high-temperature expanded desulfurized graphite sheets, and has the advantages of small sheet resistance, good flexibility and low cost, and is used as an ideal material of a current collector.
At present, most of the research on micro super-capacitors uses complex physical or chemical synthesis methods (self-assembly, electrodeposition, chemical polymerization, vapor synthesis methods and the like) to load high-quality active substances (transition metal oxides, two-dimensional/three-dimensional carbon materials and organic/inorganic metal framework compounds) on current collectors so as to improve the energy density of the whole device. The preparation method has the advantages of complex flow, high equipment requirement and toxic majority of monomers, and greatly limits the large-scale preparation of the miniature super capacitor. The graphene quantum dot is used as a quasi-zero-dimensional material, and the movement of electrons in the graphene quantum dot is limited, so that the quantum limiting effect is particularly remarkable, and the graphene quantum dot has a plurality of unique electrical and optical properties. The graphene quantum dots have smaller size and abundant edge defects, and can provide a large number of redox sites. The high-performance planar micro super capacitor is used for electrode materials, the energy density of the energy storage device can be further improved under the condition that the mass load of the device is not changed, and a new thought is provided for realizing the high-performance planar micro super capacitor.
Therefore, a preparation method for rapidly preparing the high-performance flexible planar micro supercapacitor by using the graphene quantum dots is required to be designed so as to meet the energy storage requirement of small electronic equipment.
Disclosure of Invention
The invention aims to provide a method for loading graphene quantum dots on graphite paper by a hydrothermal method, which can rapidly load a flexible electrode on the graphite paper, has low active substance loading thickness, and cannot obstruct an ion transmission channel to cause abrupt attenuation of capacity and rate performance.
The invention also provides a method for preparing the miniature supercapacitor by cutting the graphene quantum dot-loaded graphite paper by laser, which can realize rapid preparation of the graphite paper-based interdigital electrode with a narrower electrode spacing under the setting of optimal laser cutting parameters (power and scanning speed) so as to construct the high-performance planar miniature supercapacitor.
The technical scheme adopted for solving the technical problems is as follows:
a method for loading graphene quantum dots on graphite paper by a hydrothermal method comprises the following steps:
s1 graphene quantum dot solution preparation
Carrying out heat treatment on citric acid, wherein the heating temperature is 150-210 ℃, the heating time is 15-45 minutes, and when the solution is changed from transparent to orange, regulating the pH value of the system to be neutral, so as to obtain graphene quantum dot solution; s2 graphite paper pretreatment
Preparing pretreatment liquid with the concentration of 20mM-50mM by using a nitrogen source and water, immersing graphite paper in the pretreatment liquid, placing the graphite paper in a polytetrafluoroethylene container for carrying out hydrothermal treatment, washing and drying the graphite paper at the hydrothermal temperature of 150-180 ℃ for 60-120 minutes to obtain pretreated graphite paper;
s3 hydrothermal method for depositing graphene quantum dots
Immersing the graphene quantum dot solution subjected to S2 pretreatment in the graphene quantum dot solution subjected to S1, placing the graphene quantum dot solution in a hydrothermal kettle for hydrothermal treatment, wherein the hydrothermal temperature is 100-180 ℃, the hydrothermal time is 60-180 minutes, and washing with water and ethanol to remove unreacted residual solution, so as to obtain the graphene quantum dot-loaded graphene paper.
According to the invention, a hydrothermal method is utilized, graphene quantum dots are directly introduced into the surface of the graphite paper in situ by a one-step method, and the high-performance graphite paper electrode is rapidly prepared. The method does not need complex and complicated chemical synthesis process, has low material requirement (the material is widely and easily obtained and does not contain toxic precursor substances), has low equipment requirement, and can rapidly prepare the miniature super capacitor with better flexibility, easy modularization integration and excellent chemical property. Has very wide application prospect for developing the wearable portable flexible planar energy storage device.
Through pretreatment, nitrogen elements are introduced into the graphite paper, so that the graphene quantum dots can be combined with the nitrogen elements on the graphite paper in situ in a hydrogen bond mode, and the graphene quantum dot active substances can be introduced into the graphite paper later.
Preferably, the thickness of the graphite paper is 50-200 mu m, and the purity of graphite is 50% -99%.
Preferably, S1 is adjusted by sodium hydroxide to adjust the pH of the system by: sodium hydroxide solution with a concentration of 5-20mg/ml was added dropwise with vigorous stirring until the pH of the solution was neutral.
Preferably, the nitrogen source is selected from one or more of ammonia water, urea and nitric acid.
In S1, the heat treatment temperature and time influence the cracking degree of the precursor substances and the formation of graphene quantum dots, and the optimized conditions are that the temperature is set to be 190-210 ℃ and the heat treatment time is 35-45 minutes.
In S3, introducing a hydrothermal method into the graphene quantum dots, wherein the reaction temperature and the reaction time influence the loading capacity of the graphene quantum dots, and the optimized conditions are that the hydrothermal temperature is controlled at 150-160 ℃ and the hydrothermal time is controlled at 90-120 minutes. The hydrothermal temperature is too low, the graphene quantum dots are difficult to combine with a nitrogen source on the surface of the graphite paper, the hydrothermal temperature is too high, hydrogen bonds between the graphene paper quantum dots and nitrogen elements are broken at high temperature, and the loading capacity of the graphene quantum dots is reduced. The hydrothermal time is controlled to be 90-120 minutes, the hydrothermal effect of the solvent can expand the graphite paper, and the stacked structure of the graphite paper layers is damaged. The irreversible damage of the graphite paper electrode is caused, and the overall energy density of the device and the flexibility of the device are reduced. The hydrothermal time is too low, the loading amount of the graphene quantum dots is low, and the electrochemical performance of the graphite paper electrode is difficult to effectively improve.
A method for preparing a miniature supercapacitor by cutting graphite paper loaded with graphene quantum dots by laser comprises the following steps:
(1) Patterned micro supercapacitor electrode prepared by cutting graphite paper by laser
Placing the graphite paper prepared by the method of claim 1 under a laser emitter (the laser emitter comprises a carbon dioxide marking machine, a fiber laser marking machine and a purple marking machine), setting proper fiber power and laser scanning speed, and cutting the graphite paper to prepare a patterned planar flexible interdigital electrode;
(2) Preparation and coating of gel electrolyte
Preparing gel electrolyte, uniformly coating the gel electrolyte on the interdigital electrode area, and standing at room temperature to solidify the gel electrolyte;
(3) Packaging miniature super capacitor
And packaging to obtain the miniature super capacitor.
Preferably, the power of the laser cutting is set to be 200-350W, the scanning speed is 20-50Hz, and the processing speed is 300-600 mm/s. The laser power has a great influence on the formation resolution of the pattern, so that the optimized condition is that the laser cutting power is set to be 330-350W, the scanning speed is 30-35Hz, and the processing speed is 350-400 mm/s.
Preferably, the gel electrolyte is selected from lithium chloride (LiCl) system, sulfuric acid (H 2 SO 4 ) One of carboxymethyl cellulose (CMC) and ionic liquid electrolytes.
Preferably, the LiCl-based electrolyte is prepared by adding 2-4g of polyvinyl alcohol (PVA) to 20-50ml of a solution containing 1-5M LiCl, and stirring at 70-100deg.C for 6 hours until the PVA is completely dissolved;
H 2 SO 4 the preparation process of the electrolyte comprises adding 2-4-g H into 20-40ml water 2 SO 4 (98%) and 2-4g PVA, stirred at 95℃for 6 hours to form a uniform gel electrolyte;
the CMC electrolyte is prepared through adding 2-3g carboxymethyl cellulose and 1-2g sodium sulfate into 20-30ml water and stirring at 70-85 deg.c for 3 hr to obtain stable electrolyte;
the ionic liquid electrolyte is prepared by dissolving 1-2g polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in 8-10ml acetone, heating to 50-60deg.C, and adding 10-20g ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate (EMIMBF) after half an hour 4 ) Or 1-butyl-3-methylimidazole hexafluorophosphate (BMIMPF) 6 ) Stirring at 50 ℃ for 1 hour to obtain the uniform ionic liquid gel electrolyte.
Preferably, the packaging method is as follows: copper foil is connected to two sides of the electrode, and conductive silver paste is dripped into a contact area between the electrode and the copper foil to enhance the electrical contact performance; subsequently, the micro supercapacitor was packaged on both sides with polyimide tape.
According to the method, the electrode with high capacitance performance is prepared by directly carrying out hydrothermal graphene quantum dots on the graphite paper through a one-step method, and relevant experimental parameters of uniformly loading the graphene quantum dots on the graphite paper are explored through regulating and controlling the quality, hydrothermal time and hydrothermal temperature of a graphene quantum dot solution precursor. And then, a laser cutting machine is used for regulating and controlling laser parameters and laser frequency, and the interdigital electrode is prepared through a photoetching technology, has fine interdigital electrode patterns, can reach the micron level at intervals, and has higher definition. And then, coating the prepared gel electrolyte on the interdigital electrode, and packaging to finish the preparation of the planar micro supercapacitor. The miniature energy storage device prepared by the method can be used as a planar electrochemical energy storage device for continuously supplying power to a small wearable flexible electronic device, and the flexible device prepared by the method can be further integrated in series-parallel connection for use, so that the use scene is greatly widened.
Compared with the prior art, the invention has the following characteristics:
(1) The special preparation process can simply load active substances (graphene quantum dots) on the graphite paper by a one-step method, so that the high-performance flexible electrode is prepared, the operation is simple and convenient, the preparation process is greatly shortened, and the used precursor substance citric acid has no biotoxicity;
(2) The graphite paper loaded with the active substances is cut Cheng Dianji by laser, is used for an energy storage device (mainly a miniature super capacitor) after being coated with electrolyte, and can be used for rapidly and massively preparing patterned graphite paper-based electrodes by laser cutting, so that the method is simple, the requirement on operation equipment is low, and the requirements of future mass production can be met;
(3) Because a layer of active substance can be additionally loaded on the graphite paper, the electrochemical performance (such as capacity, discharge time and the like) of the composite graphite paper electrode for the energy storage device is further improved, and the prepared miniature super capacitor has the advantages of good flexibility, higher capacitance and long cycle service life, and can meet the application requirements of various scenes.
Drawings
Fig. 1 is a TEM image of a graphene quantum dot solution prepared by using citric acid as a precursor material in example 1, wherein a is a high-resolution TEM image of graphene quantum dots, and b is a size distribution diagram of the prepared graphene quantum dots;
FIG. 2 is an SEM image of the surface morphology of the pretreated graphite paper of example 1, wherein a is the untreated graphite paper and b is the pretreated graphite paper;
fig. 3 is an SEM image of graphene quantum dot solution prepared by taking citric acid as a precursor substance in example 1, loaded on graphite paper after hydrothermal method, a is an SEM image of non-loaded graphene quantum dots on the graphite paper, and b is an SEM image of the rear surface of the graphene quantum dots loaded on the graphite paper;
fig. 4 is an SEM image of the graphene quantum dot loaded after pretreatment with nitric acid as a nitrogen source in comparative example 1;
fig. 5 is an SEM image of graphene quantum dot solution prepared by using graphene oxide as a precursor material in comparative example 2 loaded on graphite paper after hydrothermal method;
FIG. 6 is a surface SEM image of graphene quantum dots supported on graphite paper using electrodeposition in comparative example 3;
FIG. 7 is a graphical representation of laser cut micro supercapacitors of comparative example 4 without pre-treated graphite paper;
FIG. 8 shows electrochemical performance-constant current charge-discharge curves (GCD) of planar micro supercapacitors coated with lithium chloride aqueous gel electrolyte in application example 1, wherein the different curves represent current densities of 25, 30, 50, 75. Mu. Acm, respectively -2 Is a charge-discharge curve of (2);
FIG. 9 is an electrochemical performance-long cycle curve of a planar micro supercapacitor coated with a lithium chloride aqueous gel electrolyte in application example 1;
fig. 10 is a graph showing electrochemical performance-constant current charge-discharge (GCD) of a lithium chloride (LiCl) aqueous electrolyte and an ionic liquid electrolyte for a micro supercapacitor according to application example 2.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The laser lithography machine used in the following examples was the severe laser marking machine QJ-01.
Graphite paper purchased from Jiangsu Xianfeng nanometer Limited company, the thickness of the graphite paper is 50 mu m, and the purity is 99%.
Example 1
The preparation method of the graphene quantum dot loaded on the graphite paper comprises the following specific steps:
(1) Preparation of graphene Quantum dot solution
2g of precursor citric acid was weighed into a beaker, the beaker was placed at 200 ℃ for 5 minutes, after which the solid powder melted, after 30 minutes the citric acid turned into a liquid state and the color turned from pale yellow to orange. The beaker was taken out and 100mL of 10mg mL was added dropwise thereto -1 Sodium hydroxide solution and stirring vigorously to make the pH value of the system neutral. A TEM image of a graphene quantum dot solution prepared by using citric acid as a precursor is shown in fig. 1.
(2) Pretreatment of graphite paper
The pretreatment method of the hydrothermal pretreatment graphite paper comprises the following specific steps:
0.06g of urea is weighed into a beaker, 50ml of deionized water is added, untreated graphite paper is immersed into the solution after the urea is dissolved, and then the solution containing the graphite paper is transferred into a polytetrafluoroethylene hydrothermal kettle. After the hydrothermal kettle is treated for 2 hours at 180 ℃, the graphite paper is taken out, and is repeatedly washed with ethanol and deionized water for 3 times. SEM comparison of the surface morphology of the graphite paper before and after pretreatment is shown in fig. 2.
(3) Graphene quantum dot loaded by hydrothermal method
50ml of the prepared graphene quantum dot solution is added into a polytetrafluoroethylene bottle containing graphite paper with the purity of 99%, the polytetrafluoroethylene bottle is placed into a hydrothermal kettle, the hydrothermal kettle is placed into a baking oven with the temperature of 150 ℃ and heated for 1.5 hours, after the hydrothermal kettle is at room temperature, the graphite paper is taken out, deionized water and ethanol are repeatedly washed for 3 times, and then the graphite paper is dried and used for subsequent laser cutting of the flexible electrode. The SEM image of the surface morphology of the graphite paper loaded with the graphene quantum dots by hydrothermal method is shown in figure 3.
Comparative example 1
(1) Preparation of graphene Quantum dot solution
As described in example 1, 2g of precursor citric acid was weighed into a beaker, and after 5 minutes the solid powder melted and after 30 minutes the citric acid turned liquid and the colour changed from pale yellow to orange. The beaker was taken out and 100mL of 10mg mL was added dropwise thereto -1 Sodium hydroxide solution and stirring vigorously to make the pH value of the system neutral.
(2) Pretreatment of graphite paper
The method comprises the following specific steps of:
50ml of a 6M nitric acid solution was prepared, the untreated graphite paper was immersed in the nitric acid solution, and then the nitric acid solution containing the graphite paper was transferred to a polytetrafluoroethylene hydrothermal kettle. After the hydrothermal kettle is treated for 2 hours at 180 ℃, the graphite paper is taken out, and is repeatedly washed for 3 times by ethanol and deionized water.
(3) Graphene quantum dot loaded by hydrothermal method
In the same manner as in example 1, 50ml of the prepared graphene quantum dot solution was added to a polytetrafluoroethylene bottle containing 99% purity graphite paper, and the polytetrafluoroethylene bottle was placed in a hydrothermal kettle, and the hydrothermal kettle was placed in a 150 ℃ oven and heated for 1.5 hours, after the hydrothermal kettle was brought to room temperature, the graphite paper was taken out, repeatedly washed with deionized water and ethanol for 3 times, and then dried for subsequent laser cutting of the flexible electrode.
And an SEM image of the surface morphology of the graphite paper hydrothermally loaded with the graphene quantum dots by the nitrogen nitrate source is shown in figure 4.
Comparative example 2
Uniformity contrast of graphene quantum dot solutions prepared from different precursors deposited on graphite paper:
(1) Preparation of graphene Quantum dot solution
Deionized water and 30% hydrogen peroxide are mixed according to the weight ratio of 1:100 was formulated into 50ml of a solution, and then 50mg of Graphene Oxide (GO) powder was added to the above solution and stirred for half an hour. The mixture was then transferred to an autoclave lined with teflon, which was autoclaved, placed in an oven at 170 ℃ for 5h, and then cooled naturally to room temperature.
(2) Pretreatment of graphite paper
0.06g of urea was weighed into a beaker, 50ml of deionized water was added, after the urea was dissolved, the urea solution was added to a polytetrafluoroethylene hydrothermal kettle, and untreated graphite paper was placed therein. After the hydrothermal kettle is treated for 2 hours at 180 ℃, the graphite paper is taken out, and is repeatedly washed for 3 times by ethanol and deionized water.
(2) Graphene quantum dot loaded solution by hydrothermal method
Adding 50ml of graphene oxide quantum dot solution prepared by taking graphene oxide as a precursor into a polytetrafluoroethylene bottle containing graphite paper with the purity of 99%, placing the polytetrafluoroethylene bottle into a hydrothermal kettle, placing the hydrothermal kettle into a 160 ℃ oven, heating for 3 hours, taking out the graphite paper after the hydrothermal kettle is at room temperature, and repeatedly washing with deionized water and ethanol for 3 times to remove unreacted solution. The SEM morphology chart of graphene quantum dot solution loaded graphite paper prepared by using graphene oxide as a precursor is shown in figure 5.
It can be seen that the graphene quantum dot solutions prepared from different precursor substances are deposited on graphite paper to different degrees after being subjected to hydrothermal treatment, and the deposition uniformity has a larger influence on the capacitance performance of the subsequently prepared miniature super capacitor. Comparative example 3 electrodeposition method of graphene Quantum dots Supported on graphite paper
Graphite paper is used as a working electrode, platinum is used as a counter electrode, and the graphene quantum dot suspension prepared in example 1 is used as an electrolyte. The deposition condition is 10V direct current, the deposition time is 360 seconds, and the reaction is stopped when the deposition liquid is changed from light yellow to orange yellow. And then, carrying out mild cleaning on the prepared graphite paper electrode by using deionized water to remove redundant graphene quantum dot solution. An SEM image of the surface morphology of the electrodeposited graphite paper is shown in FIG. 6.
Comparative example 4
Graphite paper (a commercially available product) which is not pretreated by a nitrogen source is directly used for preparing the flexible interdigital electrode by laser cutting, the laser power is set to be 350W, the scanning speed is 20Hz, and the processing speed is 500 mm/s. Graphite paper which is not treated by nitrogen elements, graphite sheets are tightly stacked, and the precision of subsequent laser processing is affected. A digital photo of the graphite paper interdigital electrode after laser cutting is shown in figure 7.
Application example 1
The electrochemical performance of the graphite paper for the energy storage device can be further improved by introducing graphene quantum dots on the graphite paper, and the graphite paper is used for preparing the flexible micro supercapacitor.
A method for preparing a water-based miniature super capacitor by cutting graphite paper through laser comprises the following specific steps:
the laser power parameter was set at 330W, the scan speed at 30Hz and the processing speed at 400 mm/s. The laser cutting machine is turned on for red light indication, the graphite paper with the uniform graphene quantum dots loaded is placed in the area indicated by the indicator lamp, and four sides of the graphite paper are pressed by tweezers, so that uneven electrode preparation caused by sample fluctuation in the laser process is avoided. And after finishing cutting, finishing the preparation of the interdigital electrode.
4.239g of lithium chloride (LiCl) powder was weighed into a beaker, 40ml of deionized water was added to the beaker, and stirred to prepare a uniform solution. Subsequently, 4g of polyvinyl alcohol powder was weighed, added to a beaker, and the beaker was heated to 85 ℃ and stirred continuously for 6 hours, and after the polyvinyl alcohol (PVA) was completely dissolved, a stable LiCl aqueous gel electrolyte was prepared. The electrolyte is uniformly coated on the graphite paper interdigital electrode, and after the electrolyte completely wets the electrode, the device is packaged by using the polyimide adhesive tape so as to be convenient for subsequent application. A constant current charge-discharge test chart of the assembled device is shown in figure 8. The long-cycle stability of charge and discharge is shown in figure 9.
Application example 2
The method for preparing the water-based micro supercapacitor by cutting the graphite paper by laser comprises the following specific steps of:
the laser power parameter was set at 305W, the scan rate at 30Hz, and the processing speed at 400 mm/s. According to the red light indication of the laser cutting machine, the graphite paper loaded with the graphene quantum dots is placed in the area indicated by the indication lamp, and four sides of the graphite paper are pressed by tweezers, so that uneven electrode preparation caused by sample fluctuation in the laser process is avoided. After cutting, the preparation of the interdigital electrode is completed.
2g of poly (vinylidene fluoride-co-hexafluoropropylene) powder was weighed into a beaker, 10ml of acetone was added to the beaker, stirred, and continuously stirred at 50℃to prepare a uniform transparent solution. Subsequently, 18g of an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) was weighed, added to a beaker, and stirred for 2 hours, followed by preparation of an ionic liquid gel polymer electrolyte. And uniformly coating the electrolyte on the interdigital electrode, and packaging to finish the preparation of the miniature super capacitor. A voltage window comparison graph of the ionic liquid gel electrolyte assembly device and the aqueous electrolyte assembly device is shown in fig. 10.
The gel electrolyte of different systems has great influence on the energy storage performance of the miniature super capacitor, the voltage window of the miniature super capacitor prepared by the water-based electrolyte is (0-0.8V) due to the fact that the theoretical water-splitting voltage is 1.23V, and the voltage window can be expanded to 3.6V by adopting the ionic gel electrolyte, so that the energy storage capacity of the device is greatly improved, and the practical application range of the device is widened.
Data analysis
Fig. 1 is a transmission electron microscope image of a graphene quantum dot solution prepared by taking citric acid as a precursor in example 1, and it can be seen from fig. a that the prepared graphene quantum dots are uniform in size, and most of particle sizes are distributed between 1 nm and 3nm in fig. b. The smaller graphene quantum dot size has rich edge sites, and the edges can gather more electrons and provide more redox active sites, so that the pseudocapacitance performance of the supercapacitor is improved.
Fig. 2 is a SEM comparison of the pretreatment and the post-pretreatment of the graphite paper of example 1, and fig. a is a graphite paper without pretreatment, and graphite sheets are closely packed together and are disadvantageous for subsequent laser cutting. And the graph b is the graphite paper subjected to pretreatment, partial tightly packed graphite sheets are puffed by the solvothermal effect in the pretreatment process, the subsequent laser cutting of the graphite paper is facilitated after the puffing, the laser processing precision is improved, and the interval between the interdigital electrodes is reduced. The device size can be reduced so that the integration capability of the device is improved on the same area substrate.
Fig. 3 is an SEM image of graphene quantum dot solution-supported graphite paper prepared by using citric acid as a precursor in example 1. As shown in the graph a, the surface of the graphite paper on which the graphene quantum dots are not deposited is smooth, and in the graph b, the graphene quantum dots on the graphite paper are uniformly loaded after hydrothermal treatment, and the graphene quantum dots are uniform in size and have no aggregation and cross-linked linear structures. The uniform load of the graphene quantum dots is beneficial to the formation of a good conductive path of the graphite paper electrode, and the rate capability and the cycling stability of the electrode are improved.
FIG. 4 is a graph of comparative example 1 using nitric acid as the nitrogen source for pretreatment of graphite paper. Compared with urea as a pretreatment substance, the graphene quantum dots loaded on the graphite paper are less in distribution after nitric acid treatment and are difficult to uniformly deposit on the graphite paper, so that the graphene quantum dots are unfavorable for the subsequent use of the graphene paper in an energy storage device and the electrochemical performance of the graphene paper is improved.
Fig. 5 is an SEM image of graphene quantum dot solution-supported graphite paper prepared by using graphene oxide as a precursor in comparative example 2. After hydrothermal treatment, the graphene quantum dots are aggregated into a mass substance on the graphite paper, the specific surface area of the aggregated graphene quantum dots is greatly reduced, edge defect sites are reduced, and oxidation-reduction reaction of the electrode is not facilitated, so that the energy density of the device is reduced. And the distribution is scattered, and the load uniformity is poor. It is seen that graphene quantum dots prepared with graphene oxide as a carbon source are not suitable for uniform deposition on graphite paper.
Fig. 6 is a graph showing that in comparative example 3, graphene quantum dots are loaded on graphite paper by an electrodeposition method, the graphite paper is used as a working electrode in the electrodeposition method, and after 10V of direct current is applied, a large amount of bubbles are generated on the graphite paper to expand the graphite paper, so that the shape retention of the graphite paper is lost, and the graphite paper is unfavorable for subsequent laser cutting into interdigital electrodes. And the graphene quantum dots loaded by the electrodeposition method are poor in distribution uniformity on the graphite paper, and the graphene quantum dots are gathered into larger spheres in some areas, so that the graphene quantum dots are less loaded, and the capacity performance of the miniature supercapacitor is not improved.
Fig. 7 is a graph of a graphite paper laser cut without pretreatment in comparative example 4, and it can be seen from the graph that the laser machining precision is poor, a large amount of residual graphite fragments exist at the edge of the device, the definition between the interdigital fingers is poor, and the two electrodes are contacted due to the low machining precision, so that the assembled device is short-circuited. The poor electrode morphology is unfavorable for the subsequent formation of the miniature energy storage device, and has no application value.
Fig. 8 is a constant current charge-discharge curve of different current densities for the micro supercapacitor assembled using aqueous lithium chloride (LiCl) as an electrolyte in application example 1. The curve shows the excellent area capacitance performance of the device, and the quasi-triangle shape also shows that the device has better theoretical super capacitor rapid charge and discharge capability.
Fig. 9 is a long-cycle stability curve of the micro supercapacitor assembled using aqueous lithium chloride (LiCl) as an electrolyte in application example 1. It can be seen that the device maintained 80% capacity after 10000 charge-discharge cycles. The ultra-high cycle stability greatly improves the service life of the device, and can be used as a chargeable energy device to meet the application under the condition of multiple scenes.
FIG. 10 is a graph showing a comparison of voltage windows of an assembled device using an ionic liquid electrolyte and aqueous lithium chloride (LiCl) as electrolytes in application example 2. The gel electrolyte of different systems has great influence on the energy storage performance of the miniature super capacitor, the voltage window of the miniature super capacitor prepared by the water-based electrolyte is (0-0.8V) because the theoretical water-splitting voltage is 1.23V, and the voltage window can be expanded to 3.5V by adopting the ion gel electrolyte, so that the energy storage capacity of the device is greatly improved, the wider voltage window is beneficial to outputting higher working voltage of the device, and the practical application range of the device is widened.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The method for loading graphene quantum dots on the graphite paper by the hydrothermal method provided by the invention is described in detail above and the application of the hydrothermal method in the aspect of preparing the planar miniature super capacitor. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (6)
1. A method for loading graphene quantum dots on graphite paper by a hydrothermal method is characterized by comprising the following steps:
s1 graphene quantum dot solution preparation
Carrying out heat treatment on citric acid, wherein the heating temperature is 150-210 ℃, the heating time is 15-45 minutes, and when the solution is changed from transparent to orange, regulating the pH value of the system to be neutral, so as to obtain graphene quantum dot solution; the method for regulating the pH value of the system to be neutral comprises the following steps: dropwise adding 5-20mg/ml sodium hydroxide solution under vigorous stirring until the pH value of the solution is neutral;
s2 graphite paper pretreatment
Preparing pretreatment liquid with the concentration of 20mM-50mM by using a nitrogen source and water, immersing graphite paper in the pretreatment liquid, placing the graphite paper in a polytetrafluoroethylene container for carrying out hydrothermal treatment, washing and drying the graphite paper at the hydrothermal temperature of 150-180 ℃ for 60-120 minutes to obtain pretreated graphite paper; the nitrogen source is selected from one or more of ammonia water, urea and nitric acid;
s3 hydrothermal method for depositing graphene quantum dots
Immersing the graphene quantum dot solution subjected to S2 pretreatment in the graphene quantum dot solution subjected to S1, placing the graphene quantum dot solution in a hydrothermal kettle for hydrothermal treatment, wherein the hydrothermal temperature is 100-180 ℃, the hydrothermal time is 60-180 minutes, and washing with water and ethanol to remove unreacted residual solution, so as to obtain graphene quantum dot-loaded graphene paper;
the thickness of the graphite paper is 50-200 mu m, and the purity of graphite is 50% -99%;
the method for preparing the miniature super capacitor by cutting the graphite paper loaded with the graphene quantum dots through laser comprises the following steps:
(1) Patterned micro supercapacitor electrode prepared by cutting graphite paper by laser
Placing graphite paper loaded with graphene quantum dots under a laser emitter, setting proper optical fiber power and laser scanning speed, cutting the graphite paper, and preparing a patterned planar flexible interdigital electrode;
(2) Preparation and coating of gel electrolyte
Preparing gel electrolyte, uniformly coating the gel electrolyte on the interdigital electrode area, and standing at room temperature to solidify the gel electrolyte;
(3) Packaging miniature super capacitor
Packaging to obtain a miniature super capacitor;
the laser transmitter comprises a carbon dioxide marking machine, an optical fiber laser marking machine and a purple light marking machine.
2. The method according to claim 1, characterized in that:
s1, heat treatment is carried out at 190-210 ℃ for 35-45 minutes;
in S3, the hydrothermal temperature is controlled to be 150-160 ℃, and the hydrothermal time is controlled to be 90-120 minutes.
3. The method according to claim 1, wherein: the laser cutting power is set to be 200-350W, the scanning speed is 20-50Hz, and the processing speed is 300-600 mm/s.
4. The method according to claim 1, characterized in that: the gel electrolyte is selected from one of lithium chloride, sulfuric acid, carboxymethyl cellulose or ionic liquid electrolyte.
5. The method according to claim 1, characterized in that:
the LiCl electrolyte is prepared by adding 2-4-g polyvinyl alcohol into 20-50-ml LiCl solution containing 1-5M, stirring at 70-100deg.C for 6 hr until PVA is completely dissolved;
H 2 SO 4 the preparation process of the electrolyte comprises adding 2-4g H into 20-40ml water 2 SO 4 And 2-4g PVA, stirring at 95℃for 6 hours to form a uniform gel electrolyte;
the CMC electrolyte is prepared through adding 2-3g carboxymethyl cellulose and 1-2g sodium sulfate into 20-30ml water and stirring at 70-85 deg.c for 3 hr to obtain stable electrolyte;
the ionic liquid electrolyte is prepared through dissolving polyvinylidene fluoride-hexafluoropropylene in 8-10ml acetone, heating at 50-60 deg.c for half an hour, adding 1-ethyl-3-methylimidazole tetrafluoroborate or 1-butyl-3-methylimidazole hexafluorophosphate into ionic liquid in 10-20-g, and stirring at 50 deg.c for 1 hr to obtain homogeneous ionic liquid gel electrolyte.
6. The method according to claim 1, characterized in that: the laser cutting power is set to be 330-350W, the scanning speed is 30-35Hz, and the processing speed is 350-400 mm/s.
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