CN115472443A - Method for loading graphene quantum dots on graphite paper by hydrothermal method and application of method in preparation of planar micro supercapacitor - Google Patents
Method for loading graphene quantum dots on graphite paper by hydrothermal method and application of method in preparation of planar micro 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
- H01G11/84—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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- 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
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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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- Electric Double-Layer Capacitors Or The Like (AREA)
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 the aspect of preparing a planar miniature supercapacitor, and belongs to the field of preparation of wearable energy storage devices. According to the preparation method, 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 supercapacitor.
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 the aspect of preparing a planar miniature supercapacitor, and belongs to the field of preparation of wearable energy storage devices.
Background
With the rapid development of electronic information technology, internet of things and wearable intelligent devices, people have higher requirements on flexible, miniature and portable electronic equipment (man-machine interaction systems, implantable medical monitoring modules and emergency energy sources for extreme environments). The micro 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 cycle stability, excellent charge and discharge rate and easy large-scale patterning preparation, and becomes one of the most potential micro energy storage devices of the next generation.
The preparation of the micro super capacitor usually uses platinum, gold, silver, copper, nickel and conductive polymer as current collectors, the intrinsic physical properties of the metal current collectors greatly limit the flexibility of the device, and the current collectors of the conductive polymer usually have poor conductivity and expensive material cost and are difficult to meet the requirements of practical application. The graphite paper is formed by stacking and rolling high-temperature expanded desulfurized graphite flakes, and has the advantages of small sheet resistance, good flexibility and low cost, and is an ideal material for a current collector.
Most of the current research on micro supercapacitors uses a complex physical or chemical synthesis method (self-assembly, electrodeposition, chemical polymerization, gas phase synthesis, etc.) to load high-quality active substances (transition metal oxides, two-dimensional/three-dimensional carbon materials, organic/inorganic metal framework composites) on a current collector to improve the energy density of the device as a whole. Most of the preparation methods have complex flow, high equipment requirement and toxic monomers, and the large-scale preparation of the miniature super capacitor is greatly limited. The graphene quantum dots are used as a quasi-zero-dimensional material, and the anisotropic movement of electrons in the graphene quantum dots is limited, so that the quantum confinement effect is particularly remarkable, and the graphene quantum dots have many unique electrical and optical properties. The graphene quantum dots have small sizes and abundant edge defects, and can provide a large number of redox sites. The material is used for an electrode material, the energy density of an energy storage device can be further improved under the condition of not changing the mass load of the device, and a new thought is provided for realizing a high-performance planar micro super capacitor.
Therefore, a preparation method for rapidly preparing a high-performance flexible planar micro supercapacitor by using graphene quantum dots is needed 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 quickly load a flexible electrode on the graphite paper, has low active substance loading thickness, and cannot block an ion transmission channel to cause rapid attenuation of capacity and rate capability.
The invention also provides a method for preparing the miniature super capacitor by cutting the graphene quantum dot-loaded graphite paper by laser, which can realize the rapid preparation of the graphite paper-based interdigital electrode with narrower electrode spacing under the setting of the optimal laser cutting parameters (power and scanning speed) so as to construct the high-performance planar miniature super capacitor.
The technical scheme adopted by the invention 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, adjusting the pH of the system to be neutral to obtain a graphene quantum dot solution; s2 graphite paper pretreatment
Preparing a pretreatment liquid with the concentration of 20mM-50mM by using a nitrogen source and water, immersing the graphite paper in the pretreatment liquid, placing the graphite paper in a polytetrafluoroethylene container for hydrothermal treatment at the hydrothermal temperature of 150-180 ℃ for 60-120 minutes, washing and drying to obtain pretreated graphite paper;
s3 hydrothermal method for depositing graphene quantum dots
Immersing the graphite paper pretreated in the step S2 in the graphene quantum dot solution of the step S1, placing the graphite paper in a hydrothermal kettle for hydrothermal treatment at the hydrothermal temperature of 100-180 ℃ for 60-180 minutes, and cleaning the graphite paper with water and ethanol to remove unreacted residual solution to obtain the graphite paper loaded with the graphene quantum dots.
According to the invention, a hydrothermal method is utilized, graphene quantum dots are directly introduced in situ on the surface of graphite paper by a one-step method, and the high-performance graphite paper electrode is rapidly prepared. The method does not need complex and tedious chemical synthesis process, has low requirements on materials (the materials are wide and easy to obtain and do not contain toxic precursor substances), has low equipment requirements, and can quickly prepare the micro supercapacitor which has better flexibility, is easy to modularize and integrate and has excellent chemical performance. The wearable portable flexible planar energy storage device has a very wide application prospect in development.
After 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 subsequent introduction of more graphene quantum dot active substances on the graphite paper is facilitated.
Preferably, the thickness of the graphite paper is 50-200 μm, and the purity of the graphite is 50% -99%.
Preferably, S1 is adjusted to system pH by sodium hydroxide by: dropwise adding sodium hydroxide solution with the concentration of 5-20mg/ml under vigorous stirring until the pH of the solution is neutral.
Preferably, the nitrogen source is selected from one or more of ammonia, urea and nitric acid.
In S1, the cracking degree of a precursor substance and the formation of graphene quantum dots are influenced by the heat treatment temperature and the heat treatment time, 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, a hydrothermal method is introduced into the graphene quantum dots, the load capacity of the graphene quantum dots is influenced by the reaction temperature and the reaction time, and the optimized conditions are that the hydrothermal temperature is controlled to be 150-160 ℃, and the hydrothermal time needs to be controlled to be 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 graphite paper quantum dots and a nitrogen element are damaged by high temperature, and the loading capacity of the graphene quantum dots is reduced. The hydrothermal time is controlled to be 90-120 minutes, the time is too long, the thermal effect of the solvent can expand the graphite paper, and the stacked structure of the graphite paper layer by layer is damaged. The graphite paper electrode is irreversibly damaged, and the overall energy density and flexibility of the device are reduced. The hydrothermal time is too low, the loading capacity 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 graphene quantum dot-loaded graphite paper 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 light marking machine), setting proper 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 an interdigital electrode area, and standing at room temperature to solidify the interdigital electrode area;
(3) Packaged 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 patterning, and therefore, the conditions after optimization are that the laser cutting power is set between 330 and 350W, the scanning speed is 30 to 35Hz, and the processing speed is 350 to 400 mm/sec.
Preferably, the gel electrolyte is selected from the group consisting of lithium chloride (LiCl) system, sulfuric acid (H) 2 SO 4 ) Is one of carboxymethyl cellulose (CMC) or ionic liquid electrolyte.
Preferably, the LiCl-based electrolyte is prepared by adding 2-4g of polyvinyl alcohol (PVA) into 20-50ml of a solution containing 1-5M LiCl, and stirring at 70-100 deg.C for 6 hours until the PVA is completely dissolved;
H 2 SO 4 the electrolyte is prepared by adding 2-4g H into 20-40ml water 2 SO 4 (98%) and 2-4g PVA, stirred at 95 ℃ for 6 hours to form a homogeneous gel electrolyte;
the CMC electrolyte is prepared by adding 2-3g of carboxymethyl cellulose and 1-2g of sodium sulfate into 20-30ml of water, and stirring for 3 hours at 70-85 ℃ to prepare a stable electrolyte;
the ionic liquid electrolyte is prepared by dissolving 1-2g polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in 8-10ml acetone, heating to 50-60 deg.C for half an hour, and adding 10-20g ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF) 4 ) Or 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF) 6 ) And stirring the mixture for 1 hour at 50 ℃ to obtain a uniform ionic liquid gel electrolyte.
Preferably, the packaging method comprises the following steps: connecting copper foils at two sides of the electrode, and dripping conductive silver paste in a contact area of the electrode and the copper foils to enhance the electric contact performance; subsequently, the micro-supercapacitor was encapsulated on both sides with polyimide tape.
According to the invention, firstly, an electrode with high capacitive performance is prepared by directly carrying out hydrothermal treatment on graphene quantum dots on graphite paper through a one-step method, and relevant experimental parameters of the graphene quantum dots uniformly loaded on the graphite paper are explored by regulating the quality, hydrothermal time and hydrothermal temperature of a precursor of a graphene quantum dot solution. Then, a laser cutting machine is utilized to regulate and control laser parameters and laser frequency, and an interdigital electrode is prepared by a photoetching technology, has fine patterns, achieves the interdigital interval at the micron level 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 to continuously supply power to a small wearable flexible electronic device, and the flexible device prepared by the method can be further used in a series-parallel connection integrated manner, 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 load active substances (graphene quantum dots) on the graphite paper simply and conveniently by one step, so that the high-performance flexible electrode is prepared, the operation is simple and convenient, the preparation flow is greatly shortened, and the used precursor substance citric acid has no biological toxicity;
(2) The graphite paper loaded with the active substances is cut into electrodes by laser, the electrodes are coated with electrolytes and then are used for energy storage devices (mainly micro supercapacitors), and the patterned graphite paper-based electrodes can be rapidly prepared in a large scale by laser cutting, so that the method is simple, has low requirements on operating equipment, and can meet the requirements of future large-scale production;
(3) Because a layer of active substance can be additionally loaded on the graphite paper, the electrochemical performance (such as capacity, discharge time and other performances) of the composite graphite paper electrode for the energy storage device is further improved, and the prepared micro super capacitor has 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 substance in example 1, wherein a is a high resolution TEM image of the graphene quantum dot, and b is a size distribution diagram of the prepared graphene quantum dot;
FIG. 2 is SEM images of the surface morphology of the graphite paper in example 1 before and after pretreatment, wherein a is the graphite paper without pretreatment, and b is the graphite paper after pretreatment;
fig. 3 is an SEM image of a graphene quantum dot solution prepared by using citric acid as a precursor substance in example 1, which is loaded on graphite paper through a hydrothermal method, a is an SEM image of an unloaded graphene quantum dot on graphite paper, and b is an SEM image of a rear surface of graphite paper loaded with a graphene quantum dot;
FIG. 4 is an SEM image of the loaded graphene quantum dots after pretreatment in comparative example 1 with nitric acid as a nitrogen source;
fig. 5 is an SEM image of the graphene quantum dot solution prepared by using graphene oxide as a precursor substance in comparative example 2, which is loaded on graphite paper after a hydrothermal method;
FIG. 6 is a surface SEM image of graphene quantum dots loaded on graphite paper by an electrodeposition method in comparative example 3;
FIG. 7 is a schematic representation of a laser cut miniature supercapacitor made from graphite paper in comparative example 4 without pretreatment;
FIG. 8 is the electrochemical performance-constant current charge and discharge curves (GCD) of the planar micro supercapacitor coated with lithium chloride aqueous gel electrolyte of application example 1, wherein the different curves represent current densities of 25, 30, 50, 75 μ Acm, respectively -2 Charge and discharge coil of (2)A wire;
FIG. 9 is an electrochemical performance-long cycle curve of the planar micro-supercapacitor coated with lithium chloride aqueous gel electrolyte in application example 1;
fig. 10 is a graph showing electrochemical performance-constant current charge and discharge curves (GCD) of a lithium chloride (LiCl) aqueous electrolyte and an ionic liquid electrolyte in the micro supercapacitor in application example 2.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the invention is not limited to the following examples, and that any changes and/or modifications may be made to the invention as described herein.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used 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 is a sharp laser marker QJ-01.
The graphite paper is purchased from Jiangsu Xiancheng nanometer Limited company, the thickness of the graphite paper is 50 μm, 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
Weighing 2g of precursor citric acid in a beaker, placing the beaker at 200 ℃, melting the solid powder after 5 minutes, and converting the citric acid into liquid after 30 minutes, wherein the color is changed from light yellow to orange. The beaker was taken out, and 100mL, 10mg mL, was dropwise added thereto -1 Sodium hydroxide solution and stirring vigorously to make the pH value of the system neutral. A TEM image of the 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 graphite paper before hydrothermal comprises the following specific steps:
weighing 0.06g of urea in a beaker, adding 50ml of deionized water, immersing untreated graphite paper in the solution after the urea is dissolved, and transferring the solution containing the graphite paper to a polytetrafluoroethylene hydrothermal kettle. After the hydrothermal kettle is treated for 2 hours at 180 ℃, the graphite paper is taken out and repeatedly washed for 3 times by ethanol and deionized water. SEM comparison of the surface appearance of the graphite paper before and after pretreatment is shown in figure 2.
(3) Graphene quantum dot loaded by hydrothermal method
Adding 50ml of prepared graphene quantum dot solution into a polytetrafluoroethylene bottle containing graphite paper with the purity of 99%, placing the polytetrafluoroethylene bottle into a hydrothermal kettle, placing the hydrothermal kettle in an oven at 150 ℃, heating for 1.5 hours, taking out the graphite paper after the hydrothermal kettle is cooled to room temperature, repeatedly washing the graphite paper with deionized water and ethanol for 3 times, and drying the graphite paper for subsequent laser cutting of the flexible electrode. An SEM image of the surface morphology of the graphite paper with the hydrothermal graphene quantum dots is shown in the attached figure 3.
Comparative example 1
(1) Preparation of graphene quantum dot solution
2g of citric acid precursor was weighed into a beaker as described in example 1, the beaker was placed at 200 ℃ for 5 minutes, the solid powder was melted, and after 30 minutes, the citric acid turned into liquid and changed from light yellow to orange. The beaker was taken out, and 100mL, 10mg mL, was dropwise added 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 steps:
50ml 6M nitric acid solution is prepared, untreated graphite paper is immersed in the nitric acid solution, and then the nitric acid solution containing the graphite paper is transferred to a polytetrafluoroethylene hydrothermal kettle. After the hydrothermal kettle is treated at 180 ℃ for 2 hours, the graphite paper is taken out and repeatedly washed with ethanol and deionized water for 3 times.
(3) Graphene quantum dot loaded by hydrothermal method
The same procedure as described in example 1 was followed, 50ml of the prepared graphene quantum dot solution was added to a teflon bottle containing 99% pure graphite paper, the teflon bottle was placed in a hydrothermal kettle, the hydrothermal kettle was placed in an oven at 150 ℃ and heated for 1.5 hours, after the hydrothermal kettle was brought to room temperature, the graphite paper was taken out, washed repeatedly with deionized water and ethanol 3 times, and dried for subsequent laser cutting of the flexible electrode.
An SEM image of the surface morphology of the graphite paper hydrothermally loaded with graphene quantum dots by a nitric acid nitrogen source is shown in an attached figure 4.
Comparative example 2
Uniformity comparison of graphene quantum dot solutions prepared from different precursors deposited on graphite paper:
(1) Preparation of graphene quantum dot solution
Mixing deionized water and 30% hydrogen peroxide according to the weight ratio of 1:100 are compounded into 50ml solution, then 50mg of Graphene Oxide (GO) powder is added into the solution, and the mixture is stirred for half an hour. The mixture was then transferred to an autoclave lined with teflon, placed in an oven at 170 ℃ for 5h, and then allowed to cool naturally to room temperature.
(2) Pretreatment of graphite paper
Weighing 0.06g of urea in a beaker, adding 50ml of deionized water, adding the urea solution into a polytetrafluoroethylene hydrothermal kettle after the urea is dissolved, and adding untreated graphite paper into the kettle. After the hydrothermal kettle is treated at 180 ℃ for 2 hours, the graphite paper is taken out and repeatedly washed with ethanol and deionized water for 3 times.
(2) Graphene quantum dot solution loaded by hydrothermal method
Adding 50ml of graphene quantum dot solution prepared by taking graphene oxide as a precursor into a polytetrafluoroethylene bottle containing 99% graphite paper, putting the polytetrafluoroethylene bottle into a hydrothermal kettle, placing the hydrothermal kettle in a drying oven at 160 ℃, heating for 3 hours, taking out the graphite paper after the hydrothermal kettle is cooled to room temperature, repeatedly washing for 3 times by using deionized water and ethanol, and removing unreacted solution. An SEM (scanning electron microscope) morphology of graphene quantum dot solution loaded graphite paper prepared by using graphene oxide as a precursor is shown in an attached figure 5.
The graphene quantum dot solution prepared from different precursor substances is deposited on the graphite paper in different uniform degrees after being hydrothermally treated, and the deposition uniformity has great influence on the capacitance performance of the subsequently prepared micro supercapacitor. Comparative example 3 electro-deposition method for loading graphene quantum dots 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 solution is changed from light yellow to orange yellow. And then, carrying out mild cleaning on the prepared graphite paper electrode by using deionized water, and removing redundant graphene quantum dot solution. The SEM image of the surface topography of the graphite paper after electrodeposition is shown in the attached figure 6.
Comparative example 4
Graphite paper (a commercial product) which is not subjected to nitrogen source pretreatment 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. The graphite sheets of the graphite paper which is not treated by the nitrogen element are tightly stacked, so that the precision of subsequent laser processing is influenced. The 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 used for the energy storage device can be further improved by introducing the graphene quantum dots on the graphite paper, and the graphite paper can be used for preparing the flexible micro super capacitor.
A method for preparing a water system micro super capacitor by cutting graphite paper with laser comprises the following specific steps:
the laser power parameter was set to 330W, the scanning speed was 30Hz, and the processing speed was 400 mm/sec. Turning on a laser cutting machine for red light indication, placing the graphite paper uniformly loaded with the graphene quantum dots prepared in the embodiment 1 in an area indicated by an indicator lamp, and pressing four sides of the graphite paper by using tweezers to avoid uneven electrode preparation caused by sample fluctuation in a laser process. And after 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 homogeneous solution. Subsequently, 4g of polyvinyl alcohol powder is weighed and added into a beaker, the beaker is heated to 85 ℃, and after stirring is continuously carried out for 6 hours, stable LiCl aqueous gel electrolyte is prepared after polyvinyl alcohol (PVA) is completely dissolved. And uniformly coating the electrolyte on the graphite paper interdigital electrode, standing for 2 hours until the electrolyte completely wets the electrode, and packaging the device by using a polyimide adhesive tape to facilitate subsequent application. The constant current charge and discharge test pattern of the assembled device is shown in fig. 8. The charge and discharge long cycle stability is shown in figure 9.
Application example 2
The method for preparing the water system micro super capacitor by cutting graphite paper by laser comprises the following specific steps:
the laser power parameter was set at 305W, the scanning speed was 30Hz, and the processing speed was 400 mm/sec. 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 indicator light, and the four sides of the graphite paper are pressed by using tweezers, so that the phenomenon that the electrode preparation is uneven due to the fact that a sample fluctuates in the laser process is avoided. And finishing the preparation of the interdigital electrode after cutting.
2g of poly (vinylidene fluoride-co-hexafluoropropylene) powder is weighed into a beaker, 10ml of acetone is added into the beaker, stirred and continuously stirred at 50 ℃ to prepare uniform and transparent solution. Subsequently, 18g of the ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) was weighed and added to a beaker, and after stirring was continued for 2 hours, an ionic liquid gel polymer electrolyte was prepared. And uniformly coating the electrolyte on the interdigital electrode, and packaging to finish the preparation of the micro super capacitor. A voltage window comparison graph of the ionic liquid gel electrolyte assembly and the water-based electrolyte assembly is shown in fig. 10.
The gel electrolytes of different systems have great influence on the energy storage performance of the micro super capacitor, the voltage window of the prepared micro super capacitor is (0-0.8V) due to the theoretical water decomposition voltage of the water system electrolyte being 1.23V, and the voltage window can be expanded to 3.6V by adopting the ion gel electrolyte, so that the energy storage capacity of the device is greatly improved, and the actual 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 using 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 fig. b shows that most of the particle sizes are distributed between 1 nm and 3 nm. 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 before and after pretreatment of the graphite paper of example 1, wherein a is a graph of graphite paper without pretreatment, and graphite flakes are tightly stacked together and are not beneficial to subsequent laser cutting. And b, the picture b is the graphite paper after pretreatment, part of tightly stacked graphite flakes are expanded by the solvent heat effect in the pretreatment process, the subsequent laser cutting of the graphite paper is facilitated after the expansion, the laser processing precision is improved, and the distance between the interdigital electrodes is reduced. The size of the device can be reduced, so that the integration capability of the device is improved on the substrate with the same area.
Fig. 3 is an SEM image of graphene quantum dot solution-supported graphite paper prepared using citric acid as a precursor in example 1. As shown in the drawing a, the surface of the graphite paper without the deposited graphene quantum dots is smooth, while in the drawing b, it can be seen that the graphene quantum dots on the graphite paper are uniformly loaded and have uniform size without agglomeration and cross-linking to form a linear structure after the hydrothermal treatment. The uniform load of the graphene quantum dots is beneficial to forming a good conductive path for the graphite paper electrode, and the rate capability and the cycling stability of the electrode are improved.
FIG. 4 shows the use of nitric acid as a nitrogen source for pretreating graphite paper in comparative example 1. Compared with urea as a pretreatment substance, SEM shows that graphene quantum dots loaded on graphite paper are less distributed after nitric acid treatment, and are difficult to uniformly deposit on the graphite paper, so that the graphene quantum dots are not beneficial to being subsequently used for an energy storage device and improving the electrochemical performance of the energy storage device.
Fig. 5 is an SEM image of graphene quantum dot solution-supported graphite paper prepared using graphene oxide as a precursor in comparative example 2. After hydrothermal treatment, the graphene quantum dots are aggregated on the graphite paper into a bulk substance, the specific surface area of the aggregated graphene quantum dot group is greatly reduced, the number of edge defect sites is reduced, and the 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. Therefore, the graphene quantum dots prepared by taking the graphene oxide as the carbon source are not suitable for being uniformly deposited on the graphite paper.
Fig. 6 is an illustration showing that in comparative example 3, graphene quantum dots are loaded on graphite paper by an electrodeposition method, in the electrodeposition method, the graphite paper is used as a working electrode, and after a direct current of 10V is applied, a large number of bubbles are generated on the graphite paper, so that the graphite paper is expanded and loses shape retention, and the interdigital electrode is not beneficial to subsequent laser cutting. And the graphene quantum dots loaded by the electrodeposition method are poor in distribution uniformity on graphite paper, some graphene quantum dots are gathered into larger small spheres in some regions, and the graphene quantum dots are less in load, so that the improvement of the capacitance performance of the miniature supercapacitor is not facilitated.
Fig. 7 is a real object diagram of the graphite paper which has not been subjected to the laser cutting in the comparative example 4, and it can be seen from the diagram that the laser processing precision is poor, a large amount of residual graphite fragments exist at the edge of the device, the inter-finger definition is poor, and the two electrodes are in contact due to the low processing precision between the electrodes, so that the assembled device is short-circuited. The poor electrode morphology is not beneficial to the subsequent formation of a micro energy storage device, and has no application value.
FIG. 8 is a constant current charge and discharge curve of a micro supercapacitor assembled with 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-triangular shape also shows that the device has better theoretical super capacitor rapid charge and discharge capacity.
FIG. 9 is a long cycle stability curve of a micro supercapacitor assembled with aqueous lithium chloride (LiCl) as an electrolyte in application example 1. It can be seen that the device retains 80% of its capacity after 10000 charge-discharge cycles. The ultrahigh cycle stability greatly prolongs the service life of the device, and the device can be used as a rechargeable energy device to meet the application under multi-scene conditions.
FIG. 10 is a graph showing a comparison of voltage windows of devices assembled using an ionic liquid electrolyte and aqueous lithium chloride (LiCl) as an electrolyte in application example 2. The gel electrolytes of different systems have great influence on the energy storage performance of the micro super capacitor, the voltage window of the prepared micro super capacitor is (0-0.8V) due to the theoretical water decomposition voltage of the water system electrolyte being 1.23V, the voltage window can be expanded to 3.5V by adopting the ion gel electrolyte, the energy storage capacity of the device is greatly improved, the wider voltage window is beneficial to the device to output higher working voltage, and the actual application range of the device is widened.
In the present specification, the embodiments are described in a progressive manner, and each embodiment focuses on differences from other embodiments, and the same or similar parts between the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The method for loading graphene quantum dots on graphite paper by the hydrothermal method provided by the invention and the application of the method in the aspect of preparing the planar micro supercapacitor are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A method for loading graphene quantum dots on graphite paper by a hydrothermal method is characterized by comprising the following steps:
preparation of S1 graphene quantum dot solution
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, adjusting the pH of the system to be neutral to obtain a graphene quantum dot solution;
pretreatment of S2 graphite paper
Preparing a pretreatment solution with the concentration of 20mM-50mM by using a nitrogen source and water, immersing graphite paper in the pretreatment solution, placing the graphite paper in a polytetrafluoroethylene container, carrying out hydrothermal treatment for 60-120 minutes at the hydrothermal temperature of 150-180 ℃, washing, and drying to obtain pretreated graphite paper;
s3 hydrothermal method for depositing graphene quantum dots
Immersing the pretreated graphite paper in the S1 graphene quantum dot solution, placing the graphite paper in a hydrothermal kettle for hydrothermal treatment at 100-180 ℃ for 60-180 minutes, and cleaning the graphite paper with water and ethanol to remove unreacted residual solution to obtain the graphene quantum dot-loaded graphite paper.
2. The method of claim 1, wherein: the thickness of the graphite paper is 50-200 μm, and the purity of the graphite is 50-99%.
3. The method of claim 1, wherein: s1, adjusting the pH of a system by using sodium hydroxide, wherein the method comprises the following steps: dropwise adding sodium hydroxide solution with the concentration of 5-20mg/ml under vigorous stirring until the pH of the solution is neutral.
4. The method of claim 1, wherein: the nitrogen source is selected from one or more of ammonia, urea and nitric acid.
5. The method of claim 1, wherein:
in the S1, the heat treatment temperature is 190-210 ℃, and the heat treatment time is 35-45 minutes;
in S3, the hydrothermal temperature is controlled to be 150-160 ℃, and the hydrothermal time needs to be controlled to be 90-120 minutes.
6. A method for preparing a miniature supercapacitor by cutting graphene quantum dot-loaded graphite paper by laser is characterized by comprising 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 light marking machine), setting proper 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 an interdigital electrode area, and standing at room temperature to solidify the interdigital electrode area;
(3) Packaged miniature super capacitor
And packaging to obtain the miniature super capacitor.
7. The method of claim 6, wherein: 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.
8. The method of claim 6, wherein: the gel electrolyte is selected from lithium chloride (LiCl) system, sulfuric acid (H) 2 SO 4 ) Is one of carboxymethyl cellulose (CMC) or ionic liquid electrolyte.
9. The method of claim 6, wherein:
the LiCl electrolyte is prepared by adding 2-4g polyvinyl alcohol (PVA) into 20-50ml solution containing 1-5MLiCl, and stirring at 70-100 deg.C for 6 hr until PVA is completely dissolved;
H 2 SO 4 the electrolyte is prepared by adding 2-4g H into 20-40ml water 2 SO 4 (98%) and 2-4g of PVA, stirred at 95 ℃ for 6 hours to form a homogeneous gel electrolyte;
the CMC electrolyte is prepared by adding 2-3g of carboxymethyl cellulose and 1-2g of sodium sulfate into 20-30ml of water, and stirring for 3 hours at 70-85 ℃ to prepare a stable electrolyte;
the ionic liquid electrolyte is prepared by dissolving 1-2g polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in 8-10ml acetone, heating to 50-60 deg.C for half an hour, and adding 10-20g ionic liquid 1-ethyl-3-methylimidazoleAzole tetrafluoroborate (EMIMBF) 4 ) Or 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF) 6 ) And stirring the mixture for 1 hour at 50 ℃ to obtain the uniform ionic liquid gel electrolyte.
10. The method of claim 6, wherein: the laser cutting power is set between 330 and 350W, the scanning speed is 30 to 35Hz, and the processing speed is 350 to 400 mm/s.
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