CN118016453B - Compact graphene-based composite film and preparation method and application thereof - Google Patents
Compact graphene-based composite film and preparation method and application thereof Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims description 4
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of carbon nano materials, in particular to a compact graphene-based composite film, and a preparation method and application thereof. According to the invention, the compact graphene-based composite film is prepared by combining two hydrothermal reactions and a vacuum filtration process, the embedded carbon quantum dots prevent graphene nano sheets from self-stacking, and carbonized sodium alginate enhances the interlayer effect of graphene, so that the conductivity, compressive strength and specific surface area of the film are obviously improved. When the film is used as an electrode, the film has a smooth ion migration channel, good flexibility and hydrophilicity, has ultrahigh power performance and high compression resistance when being tested in a two-electrode system, solves the technical problem that the film prepared by the prior art cannot be compatible with high surface area, high density, high conductivity, high mechanical strength and high porosity, can be used for an energy storage unit of compression-resistant electronic equipment, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a compact graphene-based composite film, and a preparation method and application thereof.
Background
The deepest pressure of the seabed is about 110 MPa, and pressure-resistant electronic equipment is needed when deep sea military engineering, underwater detectors, oil reservoir monitoring and other operations are carried out. Electrochemical capacitors are one of the promising electrochemical energy storage device devices for their high power density, fast charge and long life, powering high voltage electronic devices and affecting the service life and effectiveness of the electronic devices in high voltage environments. The electrode material is a core component of the electrochemical capacitor, and plays a decisive role in the performances of power, energy, frequency response and the like of the whole device. Carbon materials are widely used in electrochemical capacitors because of their high conductivity, high specific surface area, good chemical stability, and the like. In general, the density of the carbon electrode material is low (< 0.8 g cm -3), the operation is easy to damage under high pressure, the stability is poor, the long-time stable operation is difficult, the integration of the electrochemical capacitor and the electronic device, especially the flexible electronic device, is not facilitated, and the use under the extremely high pressure environment is not facilitated.
In the prior art, a dense carbon electrode material is prepared by evaporating and inducing a shrinkage graphene hydrogel so as to improve the mechanical strength of the electrode material. However, due to random physical stacking (contact by Van der Waals force) of the graphene nano sheets, the compact electrode material still cannot meet the requirements of deep sea pressure-resistant electronic equipment due to weak interaction, small compressive strength, low conductivity and poor power among the graphene nano sheets.
It is found that various carbon-based nano materials such as carbon nano particles, carbon nano tubes, carbon nano fibers, other nano particles, nano sheets and the like are embedded into the graphene film by adopting the modes of mechanical mixing, vacuum filtering and the like, so that irreversible self-stacking among the graphene nano sheets can be effectively reduced, and then an ion migration channel is optimized to improve the capacity of the electrode material. However, the intercalation mode of the physical mixing type weakens the interlayer interaction between graphene nano sheets, and further leads to the reduction of the mechanical strength and the electrical conductivity of the graphene composite material, so that the development of the porous carbon electrode material with high surface area, high density, high electrical conductivity and high mechanical strength is very important for preparing a high-power electrochemical energy storage device with high compression resistance.
Disclosure of Invention
In order to solve the problems in the prior art, one of the purposes of the invention is to provide a preparation method of a compact graphene-based composite film, and the prepared composite film has good flexibility, conductivity, hydrophilicity, high mechanical strength, high porosity, high specific surface area and volume specific capacity by adopting two hydrothermal reactions and vacuum filtration processes. The prepared material is used as an electrode material of an electrochemical capacitor and has ultrahigh power and high compression resistance.
In order to achieve the above purpose, the invention adopts the following technical scheme that the preparation method of the compact graphene-based composite film comprises the following steps:
Step 1, dissolving carbon quantum dots with the particle size of 2-8 nm and graphene oxide in deionized water, and uniformly mixing by ultrasonic to obtain a mixed solution 1, wherein the total concentration of the carbon quantum dots and the graphene oxide in the mixed solution 1 is 0.01-0.1 g/L;
Step 2, placing the mixed solution 1 into an autoclave, and carrying out hydrothermal treatment at 180-210 ℃ for 3-8 h to obtain a colloidal solution of the reduced graphene oxide/carbon quantum dot composite nano-sheet;
Step 3, adding 1-10 g/L sodium alginate solution into the colloid solution, wherein the mass ratio of the carbon quantum dots, graphene oxide and sodium alginate in the sodium alginate solution in step 1 is (2-20): 10 (4-6), stirring uniformly, and standing to obtain a mixed solution 2;
Step 4, taking the mixed solution 2, carrying out vacuum suction filtration, and heating and drying solid matters on a filter membrane to obtain a reduced graphene oxide/carbon quantum dot/sodium alginate composite film;
and 5, placing the reduced graphene oxide/carbon quantum dot/sodium alginate composite film in a high-pressure reaction kettle, adding deionized water into the high-pressure reaction kettle, sealing the high-pressure reaction kettle, and cooling after hydrothermal treatment at 180-210 ℃ for 3-8 h to obtain the compact graphene-based composite film with the thickness of 0.65-4 mu m.
As the preparation method of the compact graphene-based composite film, the following is further improved:
Preferably, the preparation method of the carbon quantum dots in the step 1 is as follows: adding a carbon source into 1-3 mol/L sodium hydroxide solution, wherein the weight ratio of the carbon source to the sodium hydroxide solution is 1:50, then placing the mixture into a high-pressure reaction kettle for reaction at 180-210 ℃ for 3-8 h, filtering the reaction product, centrifugally separating out solid matters, removing impurities from the solid matters, and drying to obtain the carbon quantum dots.
Preferably, the carbon source is a bio-based material.
Preferably, the manufacturer of the graphene oxide in the step 1 is single-layer graphene oxide manufactured by Shenzhen city constant navigation technology limited company.
Preferably, the pore size of the filter membrane used for vacuum filtration in step 4 is 0.1 microns or 0.22 microns.
Preferably, the temperature of the filter membrane and the solid materials heated and dried after the suction filtration in the step 4 is 80-120 ℃.
Preferably, the mass of deionized water in the high-pressure reaction kettle in the step 5 is 100-1000 times of the mass of the reduced graphene oxide/carbon quantum dot/sodium alginate composite film.
The second object of the invention is to provide a dense graphene-based composite film prepared by the preparation method of any one of the dense graphene-based composite films.
The invention further provides an application of the compact graphene-based composite film to an electrochemical capacitor, the prepared compact graphene-based composite film is cut to be used as a positive electrode material and a negative electrode material, a platinum sheet is used as a current collector, the current collector, an NKK-MPF30AC-100 diaphragm and electrolyte are assembled together, and then the electrochemical capacitor is obtained after packaging is carried out by using a PET film.
As the application of the compact graphene-based composite film to an electrochemical capacitor, the application of the compact graphene-based composite film to the electrochemical capacitor is further improved:
Preferably, the compact graphene-based composite film is cut into a round shape or a square shape, wherein the round shape is one of diameters of 1 cm, 1.5 cm, 2.5 cm, 3 cm, 3.5 cm, 4 cm, 4.5 cm, 5 cm, 5.5 cm, 6 cm and 6.5 cm, and the square shape is one of side lengths of 1 cm, 1.5 cm, 2.5 cm, 3 cm, 3.5 cm, 4 cm and 4.5 cm.
Preferably, the electrolyte is one of sulfuric acid solution, phosphoric acid solution, potassium hydroxide solution, sodium hydroxide solution, lithium sulfate solution, sodium sulfate solution, potassium sulfate solution, sodium chloride solution, potassium chloride solution and lithium chloride solution, and the concentration is 0.5-6 mol/L.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a preparation method of a compact graphene-based composite film, which combines two processes of hydrothermal reaction and vacuum suction filtration, and specifically comprises the following steps:
Firstly, small-size and rigid carbon quantum dots are selected to be mixed with graphene oxide nano sheets, and the carbon quantum dots are embedded between graphene sheets, so that self-stacking of the graphene nano sheets is avoided, and an ion transport path is optimized. Through the first hydrothermal reaction, strong bonds, such as chemical bonds, are constructed between the carbon quantum dots and the graphene nanoplatelets so as to improve the compressive strength and the electrical conductivity of the high-graphene composite film.
And secondly, sodium alginate is introduced as a connecting material in a hydrothermal carbonization mode, so that the hydrothermal carbonization temperature is low, inert gas protection is not needed, the method is economical and cheap, and the carbonization process is mild and controllable. The adjacent reduced graphene oxide/carbon quantum dot composite nano sheets are connected in a chemical bond mode after sodium alginate carbonization, the interlayer effect of the reduced graphene oxide/carbon quantum dot composite nano sheets is enhanced, materials are tightly connected, and carbon quantum dots are supported among the graphene nano sheets, so that the materials can be kept stable in a high-pressure environment, the electron transfer and the ion migration are extremely affected, and the conductivity of the graphene film is improved. In the hydrothermal carbonization process, due to the protection effect of water, oxygen-containing functional groups exposed on the surfaces of the reduced graphene oxide/carbon quantum dot composite nano-sheet and sodium alginate derived carbon are not reduced, and the film has good hydrophilicity, and the hydrophilic contact angle is stabilized below 10 degrees. Meanwhile, the film is gradually contracted by carbonization of sodium alginate, densification is realized, the density of the material is very high (> 1.5 g/cm 3), high pores and specific surface area (246.6 m 2/g of specific surface area under the density of 1.9 g/cm 3) can be maintained under high density, and the prepared dense graphene-based composite film can be applied to electrode materials of electrochemical capacitors, and can obtain high volume specific capacitance of 309F/cm 3.
2) The compact graphene-based composite film prepared by the invention is tightly connected with materials, has an all-carbon integrated conductive network, greatly improves the conductivity (2510S/m) and is higher than the conductivity (411S/m) of a pure graphene film, and the composite film is applied to electrode materials of electrochemical capacitors, so that the maximum power of the electrochemical capacitors can reach 12307W/cm 3, and is superior to the traditional aluminum electrolytic capacitors. The hydrophilicity is good, the frequency response performance of the aluminum electrolytic capacitor in the water system electrolyte is improved, and the rapid frequency response speed of the aluminum electrolytic capacitor can replace the aluminum electrolytic capacitor in certain fields. The prepared graphene-based compact composite film is used as an electrode material of an electrochemical capacitor, and the electrochemical capacitor (1 mol/L sulfuric acid electrolyte) can obtain high-frequency response performance (lower than 30 ms) under the condition of obtaining high volume specific capacity of 247-309F/cm 3, which is superior to the performance of the existing similar electrode material.
3) The maximum elastic modulus of the compact graphene-based composite film prepared by the invention is 803 MPa, and the material is used as an electrode material of an electrochemical capacitor, and has a high capacitance retention rate of 74% under the ultra-high pressure of 360 MPa, so that the material can be possibly applied to the electrode material of a storage unit (about 110 and MPa of the maximum pressure at the bottom of the sea) of a deep sea detector. The compact graphene-based composite film prepared by the invention has good flexibility, and when the bending radius is 0.5 cm, the bending angle can reach 180 degrees. The material is used as an electrode material of an electrochemical capacitor, so that the electrochemical capacitor can keep almost 100% of capacity under the angle, and 89.1% of capacity still exists after 3000 bending tests, and therefore, the prepared compact graphene-based composite film can be applied to the electrochemical capacitor and is convenient for other electronic equipment to be well integrated together.
Drawings
FIG. 1 is a flow chart of the preparation of a dense graphene-based composite film according to the present invention.
Fig. 2 is a transmission electron microscope image of the reduced graphene oxide/carbon quantum dot composite nanoplatelets prepared in step 1 of example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the dense graphene-based composite film prepared in example 2.
Fig. 4 is a schematic diagram of ion transport when the rGO thin film prepared in comparative example 2 and the dense graphene-based composite thin film prepared in example 2 are used as electrode materials of electrochemical capacitors.
FIG. 5 shows performance tests of the films obtained in comparative examples 1 to 2 and examples 1 to 2, wherein (a) is an N 2 adsorption-desorption curve and (b) is a pore size distribution.
Fig. 6 is an energy density and power density diagram of an assembled electrochemical capacitor when the films prepared in comparative examples 1 to 2 and examples 2 to 3 are used as electrode materials of the electrochemical capacitor.
FIG. 7 is a diagram of a stress resistance test apparatus.
FIG. 8 (a) shows specific capacitances at different pressures when the films prepared in example 2 and comparative example 2 are used as electrode materials of electrochemical capacitors; (b) When the film obtained in example 2 was used as an electrode material for an electrochemical capacitor, the film had cycle stability (constant current charge and discharge of 32 mA/cm 2) at 180 MPa g.
Fig. 9 is a graph showing a change in capacitance retention rate of 3000 bending tests at a bending angle of 180 ° when the film prepared in example 2 was used as an electrode material for an electrochemical capacitor.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
Preparation example 1
The preparation example provides a preparation method of carbon quantum dots, which specifically comprises the following steps:
Adding peanut shells into 3 mol/L sodium hydroxide solution, wherein the weight ratio of the peanut shells to the sodium hydroxide solution is 1:50, then placing the peanut shells and the sodium hydroxide solution in a high-pressure reaction kettle to react at 160 ℃ for 5 h, obtaining reaction liquid, filtering reaction products, centrifugally separating out solid matters, removing impurities from the solid matters, and drying the solid matters to obtain the carbon quantum dots. The particle size is 2-8 nm.
Example 1
The embodiment provides a preparation method of a compact graphene-based composite film, the preparation flow is shown in fig. 1, and the preparation method specifically comprises the following steps:
step 1, dissolving carbon quantum dots with the particle size of 2-8 nm and graphene oxide prepared in preparation example 1 in deionized water, and uniformly mixing by ultrasonic to obtain a mixed solution 1, wherein the total concentration of the carbon quantum dots and the graphene oxide in the mixed solution 1 is 0.05 g/L; hydrothermal treatment is carried out on the mixed solution 1 in an autoclave at 180 ℃ for 3 h to obtain a colloidal solution of the reduced graphene oxide/carbon quantum dot composite nano-sheet;
Step 2, adding 2 g/L sodium alginate solution into the colloid solution, wherein the volume ratio of the colloid solution to the sodium alginate solution is 280:2, and the mass ratio of carbon quantum dots in the carbon quantum dot solution in step 1 to graphene oxide to sodium alginate in the sodium alginate solution in step 2 is 4:10:4, and standing for more than 5 hours after uniformly stirring to obtain a mixed solution 2;
Step 3, taking 0.28L of mixed solution 2, carrying out suction filtration by using a filter membrane with the aperture of 0.1 micron to obtain a solid with uniform thickness, and heating and drying the filter membrane and the solid on the surface at the temperature of 90 ℃ to obtain a reduced graphene oxide/carbon quantum dot/sodium alginate composite film;
And 4, placing the reduced graphene oxide/carbon quantum dot/sodium alginate composite film in a high-pressure reaction kettle, simultaneously adding deionized water into the high-pressure reaction kettle, wherein the mass of the deionized water is 100 times that of the reduced graphene oxide/carbon quantum dot/sodium alginate composite film, and then sealing the film at 185 ℃ for secondary hydrothermal treatment to obtain the compact graphene-based composite film 1, wherein the thickness of the film is 2.6 mu m.
Example 2
The embodiment provides a preparation method of a compact graphene-based composite film, and the specific steps refer to embodiment 1, and the differences are that: in the step 2, adding 2 g/L sodium alginate solution into the colloid solution, wherein the volume ratio of the colloid solution to the sodium alginate solution is 280:3, the mass ratio of the carbon quantum dots to the graphene oxide in the step 1 to the sodium alginate in the sodium alginate solution in the step 2 is 4:10:6, stirring uniformly, and standing for more than 5 hours to obtain the mixed solution 2.
Finally, the dense graphene-based composite film 2 is prepared, and the thickness of the film is 2.6 mu m.
Example 3
The embodiment provides a preparation method of a compact graphene-based composite film, and the specific steps refer to embodiment 1, and the differences are that: adding 2 g/L sodium alginate solution into the colloid solution in the step 2, wherein the volume ratio of the colloid solution to the sodium alginate solution is 280:3, and the mass ratio of the carbon quantum dots to the graphene oxide in the step 1 to the sodium alginate in the sodium alginate solution in the step 2 is 4:10:6, uniformly stirring, and standing for more than 5 hours to obtain a mixed solution; and 3, taking 0.07L of the mixed solution 2, and carrying out suction filtration by using a filter membrane with the pore diameter of 0.1 micrometer to obtain a solid with uniform thickness.
Finally, the compact graphene-based composite film 3 is prepared, and the thickness of the film is 0.65 mu m.
Example 4
The embodiment provides a preparation method of a compact graphene-based composite film, and the specific steps refer to embodiment 1, and the differences are that: in the step 2, adding 2 g/L sodium alginate solution into the colloid solution, wherein the volume ratio of the colloid solution to the sodium alginate solution is 280:3, the mass ratio of the carbon quantum dots to the graphene oxide in the step 1 to the sodium alginate in the sodium alginate solution in the step 2 is 20:10:6, stirring uniformly, and standing for more than 5 hours to obtain the mixed solution 2.
Finally, the compact graphene-based composite film 4 is prepared, and the thickness of the film is 4 mu m.
Example 5
The embodiment provides a preparation method of a compact graphene-based composite film, and the specific steps refer to embodiment 1, and the differences are that: in the step 2, adding 2 g/L sodium alginate solution into the colloid solution, wherein the volume ratio of the colloid solution to the sodium alginate solution is 280:2, the mass ratio of the carbon quantum dots to the graphene oxide in the step 1 to the sodium alginate in the sodium alginate solution in the step 2 is 2:10:4, stirring uniformly, and standing for more than 5 hours to obtain the mixed solution 2.
Finally, the dense graphene-based composite film 5 is prepared, and the thickness of the film is 3 mu m.
Comparative example 1
The comparative example provides a preparation method of a compact reduced graphene oxide/carbon quantum dot composite film, and the specific steps refer to the embodiment 2, and the difference is that 2 g/L sodium alginate solution is not added in the step 2, and the operation of the step 3 is directly carried out.
Finally, the compact reduced graphene oxide/carbon quantum dot composite film is prepared and is marked as an rGO/CQDs film, and the thickness of the film is 3.1 mu m.
Comparative example 2
The comparative example provides a preparation method of a reduced graphene oxide film, which comprises the following specific steps:
And 1, taking a graphene oxide solution with the concentration of 0.05L and 2 g/L, adding deionized water to dilute the total concentration to 0.05 g/L, uniformly mixing by ultrasonic, and then placing the mixture in an autoclave to carry out hydrothermal treatment at 180 ℃ for 3 hours to obtain a colloidal solution of the reduced graphene oxide nano-sheet.
And 2, adding water into the colloid solution to dilute to 0.2 g/L, carrying out suction filtration by using a filter membrane with the aperture of 0.1 micrometer to obtain a solid with uniform thickness, heating and drying the filter membrane and the solid on the surface at the temperature of 90 ℃ to obtain a reduced graphene oxide film, namely an rGO film, wherein the thickness of the film is 2.6 micrometers.
Example 6
The compact graphene-based composite films 1-5, the rGO/CQDs film prepared in comparative example 1 and the rGO film prepared in comparative example 2 are respectively cut into circles with diameters of 1 cm, and are used as positive electrode materials and negative electrode materials of an electrochemical capacitor, a platinum sheet is used as a current collector, sulfuric acid of 1 mol/L is used as electrolyte, and the electrochemical capacitor is prepared by assembling with NKK-MPF30AC-100 membrane produced in Japan and packaging with PET film.
FIG. 1 is a flow chart of the preparation of the dense graphene-based composite film, and the specific flow chart is as follows: firstly, preparing a mixed solution of carbon quantum dots and graphene oxide, uniformly mixing by ultrasonic, and then placing the mixed solution in an autoclave for hydrothermal reaction to obtain a reduced graphene oxide/carbon quantum dot composite nano-sheet colloidal solution; and adding sodium alginate solution into the colloid solution, uniformly mixing, standing, preparing a reduced graphene oxide/carbon quantum dot/sodium alginate composite film by using a vacuum suction filtration mode, marking the reduced graphene oxide/carbon quantum dot/sodium alginate composite film as an rGO/CQDs/SA composite film, placing the composite film into a high-pressure reaction kettle, adding enough deionized water, sealing for secondary hydrothermal reaction, and connecting adjacent rGO/CQDs composite nano sheets by using a chemical bond mode after sodium alginate carbonization to obtain a compact graphene-based composite film, and marking the compact graphene-based composite film as an rGO/CQDs/SADC composite film.
Fig. 2 is a transmission electron microscope image of the reduced graphene oxide/carbon quantum dot composite nanoplatelets prepared in step 1 of example 1. As can be seen from fig. 2, the carbon quantum dots having the particle size of 2 to 8 nm are uniformly supported on the reduced graphene oxide nanoplatelets.
FIG. 3 is a scanning electron microscope image of the dense graphene-based composite film prepared in example 2. As can be seen from fig. 3, the dense graphene-based composite film has a uniform thickness, a waveform texture shape, and a dense structure.
FIG. 4 is a schematic diagram of ion transport when rGO film prepared in comparative example 2 and dense graphene-based composite film prepared in example 2 (denoted rGO/CQDs/SADC composite film in the drawing) are used as electrode materials for electrochemical capacitors. As can be seen from fig. 4, in the rGO thin film, ion migration is hindered and power performance is reduced due to self-stacking of reduced graphene oxide nanoplatelets. In the compact graphene-based composite film of embodiment 2, carbon quantum dots are embedded between the reduced graphene oxide nano sheets, so that the reduced graphene oxide nano sheets are prevented from self-stacking, an ion diffusion channel is widened, high-efficiency transmission of ions is ensured, and a covalent bond constructed by sodium alginate derived carbon improves electron migration rate, thereby being beneficial to improving power performance.
Fig. 5 (a) to (b) show the adsorption and desorption curves and pore size distributions of N 2 of the films prepared in comparative examples 1 to 2 and examples 1 to 2, respectively. The test method is to measure nitrogen adsorption-desorption isotherms (degassing temperature: 120 ℃) by a full-automatic specific surface area porosity analyzer and calculate the specific surface area. As can be seen from fig. 5, the specific surface area and pore volume of the dense graphene-based composite film gradually increased with the increase of the amount of sodium alginate. When the mass ratio of raw material carbon quantum dots/graphene oxide/sodium alginate is 4:10:6 (example 2), the specific surface area and the pore capacity are increased to 246.6 m 2/g and 0.43 cm 3/g respectively, which are significantly higher than that of the rGO film of comparative example 2 (the specific surface area and the pore capacity are 27.8 m 2/g and 0.10 cm 3/g respectively).
Fig. 6 is an energy density and power density diagram of an assembled electrochemical capacitor when the films prepared in comparative examples 1 to 2 and examples 2 to 3 are used as electrode materials of the electrochemical capacitor. The testing method comprises the following steps: constant-current charge and discharge (the voltage window is 1V) are carried out through different current densities, and the energy density and the power density are calculated according to constant-current charge and discharge curves under different current densities. As can be seen from fig. 6, the ion transmission rate and specific surface area are increased by embedding carbon quantum dots in the thin film, and the energy density and power density are increased as compared with the rGO thin film (comparative example 2). Further, the adjacent reduced graphene oxide/carbon quantum dot composite nano sheets are connected into an integrated all-carbon conductive frame in a covalent bond mode through carbonization of sodium alginate, so that the conductivity of the film is improved while the high ion transmission rate is ensured, the specific surface area of sodium alginate-derived carbon is further improved, and therefore, the film prepared based on examples 2-3 is used as an electrode material of an electrochemical capacitor, and the energy density and the power density of the assembled electrochemical capacitor are further improved.
FIG. 7 is a diagram of a stress resistance test apparatus, the test steps being as follows: firstly, cutting a film sample into corresponding dimensions, assembling the film sample into a symmetrical electrochemical capacitor, then placing the symmetrical electrochemical capacitor under a hydraulic press to adjust the symmetrical electrochemical capacitor to corresponding pressure, and finally testing the electrochemical performance of the symmetrical electrochemical capacitor under specific pressure, such as a cyclic voltammogram, a constant-current charge-discharge curve and an electrochemical impedance spectrum. The parameters are as follows: sample size (circular film with diameter of 1 cm), electrolyte is 1 mol/L sulfuric acid solution, and test pressure is 0-360 MPa.
Fig. 8 (a) to (b) show specific capacities of the films prepared in example 2 and comparative example 2 as electrode materials of electrochemical capacitors at different pressures, respectively, and cyclic stability of the electrochemical capacitors prepared in example 2 at 180 MPa (constant current charge and discharge of 32 mA/cm 2). The testing method comprises the following steps: placing the mixture under a hydraulic press to adjust the pressure to 180 MPa; under the pressure, a cyclic constant current charge and discharge test is carried out at a current density of 32 mA/cm 2, and the specific capacitance under different charge and discharge times is calculated. As can be seen from fig. 8, the capacitor retention rate was 95.4% after 5 ten thousand constant current charge and discharge tests, which indicates that the capacitor can continuously and stably operate under high pressure.
Fig. 9 is a graph showing a change in capacitance retention rate of the film prepared in example 2 used as an electrode material of an electrochemical capacitor subjected to a bending test at 180 deg. for 3000 times. The testing method comprises the following steps: fixing the motor on a linear motor flat push panel, adjusting the nearest push distance of the motor to be 0.8 cm (ensuring the bending angle of a capacitor to be 180 degrees), and setting the push frequency to be 2 Hz (bending 2 times per second); bending test was performed at this frequency, and after 200 times of bending, charge and discharge test was performed at a current density of 32 mA/cm 2, and specific capacitances at different bending times were calculated. As can be seen from fig. 9, after 3000 bending tests, the capacitor retention rate is 89.1%, which indicates that the capacitor has good flexibility, can continuously and stably operate during bending deformation, and can be applied to electrochemical capacitors and be well integrated with other electronic devices.
The physical properties of the films prepared in examples and comparative examples and the properties used as electrode materials for electrochemical capacitors are shown in tables 1 and 2, respectively:
table 1 physical properties parameters of the films obtained in examples 1 to 2 and comparative examples 1 to 2
TABLE 2 Properties of the films prepared in examples 1 to 5 and comparative examples 1 to 2 as electrode materials for electrochemical capacitors
As can be seen from the test results in tables 1 and 2, the dense graphene-based composite films prepared in examples 1 and 2 have the advantages of high conductivity, large specific surface area, high pores, high density, high mechanical strength, good hydrophilicity and the like. The elastic modulus of the dense graphene-based composite films prepared in examples 1,2 and 3 was 762 MPa, 803, MPa and 796, MPa, while the elastic modulus of comparative example 2 was 441 and MPa. When the bending radius of the sample in example 2 is 0.5 cm, the bending angle can reach 180 degrees, and when the compact graphene-based composite film prepared in example 2 is used as an electrode material of an electrochemical capacitor, almost 100% of capacity is maintained at the angle, and 89.1% of capacity is still obtained after 3000 bending tests; based on the use of the dense graphene-based composite film prepared in example 2 as an electrode material for electrochemical capacitors, the electrochemical properties thereof were measured while applying pressure, and it was found that a high capacitance retention of 74% was maintained at a high pressure of 360 MPa, compared to the capacity without applying pressure. The dense graphene-based composite film prepared based on the embodiment 3 is used as an electrode material of an electrochemical capacitor, the maximum power of the corresponding electrochemical capacitor can reach 12307W/cm 3, the frequency response speed is extremely high, the minimum response time is lower than 10 ms, and the performance is at an international leading level. When the compact graphene-based composite film prepared based on the embodiments 1-5 is used as an electrode material of an electrochemical capacitor, the energy storage unit requirement of the deep sea detector can be met.
In summary, the preparation method of the compact graphene-based composite film is designed, the proportion of carbon quantum dots/graphene oxide and the hydrothermal temperature are regulated and controlled, the stably dispersed reduced graphene oxide/carbon quantum dot composite nano-sheet colloid solution is prepared, and the compact graphene-based composite film is prepared by further regulating and controlling the mixing proportion of the reduced graphene oxide/carbon quantum dot composite nano-sheet colloid solution and sodium alginate and the secondary hydrothermal temperature, so that the carbonization process is mild and the controllability is good, and the prepared composite film has the advantages of high conductivity, large specific surface area, high pores, high density, high mechanical strength, good hydrophilicity and the like. The prepared composite film is used as an electrode to be assembled into an electrochemical capacitor, and the electrochemical capacitor has excellent power performance, pressure resistance and bending stability through test, and can meet the requirement of an energy storage unit of a deep sea detector.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.
Claims (10)
1. The preparation method of the compact graphene-based composite film is characterized by comprising the following steps of:
Step 1, dissolving carbon quantum dots with the particle size of 2-8 nm and graphene oxide in deionized water, and uniformly mixing by ultrasonic to obtain a mixed solution 1, wherein the total concentration of the carbon quantum dots and the graphene oxide in the mixed solution 1 is 0.01-0.1 g/L;
Step 2, placing the mixed solution 1 into an autoclave, and carrying out hydrothermal treatment at 180-210 ℃ for 3-8 h to obtain a colloidal solution of the reduced graphene oxide/carbon quantum dot composite nano-sheet;
Step 3, adding 1-10 g/L sodium alginate solution into the colloid solution, wherein the mass ratio of the carbon quantum dots, graphene oxide and sodium alginate in the sodium alginate solution in step 1 is (2-20): 10 (4-6), stirring uniformly, and standing to obtain a mixed solution 2;
Step 4, taking the mixed solution 2, carrying out vacuum suction filtration, and heating and drying solid matters on a filter membrane to obtain a reduced graphene oxide/carbon quantum dot/sodium alginate composite film;
and 5, placing the reduced graphene oxide/carbon quantum dot/sodium alginate composite film in a high-pressure reaction kettle, adding deionized water into the high-pressure reaction kettle, sealing the high-pressure reaction kettle, and cooling after hydrothermal treatment at 180-210 ℃ for 3-8 h to obtain the compact graphene-based composite film with the thickness of 0.65-4 mu m.
2. The method for preparing a dense graphene-based composite film according to claim 1, wherein the method for preparing the carbon quantum dots in step 1 is as follows: adding a carbon source into 1-3 mol/L sodium hydroxide solution, wherein the weight ratio of the carbon source to the sodium hydroxide solution is 1:50, then placing the mixture into a high-pressure reaction kettle for reaction at 180-210 ℃ for 3-8 h, filtering the reaction product, centrifugally separating out solid matters, removing impurities from the solid matters, and drying to obtain the carbon quantum dots.
3. The method for preparing a dense graphene-based composite film according to claim 2, wherein the graphene oxide in step1 is a single-layer graphene oxide.
4. The method for producing a dense graphene-based composite membrane according to claim 1, wherein the pore size of the filter membrane used for vacuum filtration in step 4 is 0.1 μm or 0.22 μm.
5. The method for preparing a dense graphene-based composite film according to claim 1 or 4, wherein the temperature of the filter membrane and the solid after suction filtration in the step 4 is 80-120 ℃.
6. The method for preparing the dense graphene-based composite film according to claim 1, wherein the mass of deionized water in the high-pressure reaction kettle in the step 5 is 100-1000 times of the mass of the reduced graphene oxide/carbon quantum dot/sodium alginate composite film.
7. A dense graphene-based composite film produced by the production method of the dense graphene-based composite film according to any one of claims 1 to 6.
8. The application of the compact graphene-based composite film in an electrochemical capacitor, which is characterized in that the prepared compact graphene-based composite film is cut and used as a positive electrode material and a negative electrode material, a platinum sheet is used as a current collector, and the current collector, an NKK-MPF30AC-100 diaphragm and electrolyte are assembled together, and then the electrochemical capacitor is obtained after packaging by using a PET film.
9. The use of a dense graphene-based composite membrane according to claim 8, wherein the dense graphene-based composite membrane is cut to form a round shape or a square shape, the round shape having a diameter of one of 1cm, 1.5 cm, 2.5 cm, 3 cm, 3.5 cm, 4 cm, 4.5 cm, 5 cm, 5.5 cm, 6 cm, and 6.5 cm, and the square shape having a side length of one of 1cm, 1.5 cm, 2.5 cm, 3 cm, 3.5 cm, 4 cm, and 4.5 cm.
10. The application of the dense graphene-based composite film according to claim 8, wherein the electrolyte is one of sulfuric acid solution, phosphoric acid solution, potassium hydroxide solution, sodium hydroxide solution, lithium sulfate solution, sodium sulfate solution, potassium sulfate solution, sodium chloride solution, potassium chloride solution and lithium chloride solution, and the concentration is 0.5-6 mol/L.
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| CN116876109A (en) * | 2023-08-21 | 2023-10-13 | 哈尔滨工业大学 | Graphene composite fiber and preparation method thereof |
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| CN109137142A (en) * | 2018-07-26 | 2019-01-04 | 南京工业大学 | Carbon quantum dot-graphene fiber with dot-sheet structure and preparation and application thereof |
| CN112117436A (en) * | 2020-09-24 | 2020-12-22 | 北京化工大学 | Novel two-dimensional carbon composite flexible electrode of sodium ion battery and preparation method thereof |
| CN116013703A (en) * | 2023-02-08 | 2023-04-25 | 广东韩研活性炭科技股份有限公司 | Active carbon composite material for capacitor electrode and preparation method thereof |
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