CN113690061B - Carbon-based supercapacitor electrode and laser-acid modification synergistic preparation method and application thereof - Google Patents
Carbon-based supercapacitor electrode and laser-acid modification synergistic preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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Abstract
The invention provides a carbon-based supercapacitor electrode and a laser-acid modification synergistic preparation method and application thereof, and belongs to the technical field of supercapacitors. According to the invention, the high-quality graphene, porous carbon-based supercapacitor electrode doped with atomic nitrogen (or phosphorus or sulfur) is obtained by processing the acid-modified polyimidazole polymer substrate material by laser. Compared with the prior art that the quality of graphene or the porosity of graphene is simply improved, the processing method is simple, the conditions are mild, the problems that the quality of graphene, the porosity of porous graphene and the doping atomic weight of a carbon-based supercapacitor electrode are improved are solved at one time, and the highest specific surface capacitance of 149mF/cm can be realized2And a maximum energy density of 20.7. mu. Wh/cm2The energy storage effect of (2).
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a carbon-based super capacitor electrode and a laser-acid modification synergistic preparation method and application thereof.
Background
The super capacitor is used as a good electric energy storage device, becomes one of key electrical devices for solving sustainable green energy storage, and is widely applied to the fields related to energy requirements, such as motor vehicle battery stacks, secondary energy collection, power grid architecture energy distribution and the like. The capacitors have the characteristics of quick charge and discharge and large capacitance, and play a great role in energy distribution and energy storage. In order to ensure that the super capacitor can realize large-capacity storage, in addition to developing an electrolyte capable of enhancing ion diffusion, the super capacitor electrode with a good energy storage effect (namely, the super capacitor has high specific surface area (specific volume) capacitance, high energy density and power density) is developed, and becomes a hot spot in recent super capacitor technology development.
The carbon-based composite material is used as a supercapacitor electrode, and particularly the carbon-based composite material mainly containing graphene and graphene oxide is widely applied to supercapacitor equipment due to the characteristics of good conductivity, material processability and multi-dimensional material processing. In order to obtain a carbon-based supercapacitor electrode with good energy storage capacity, a carbon-based composite material with a porous and nano structure is developed to improve the capacity of a supercapacitor for storing charges.
The Laser induced graphene technology (Laser induced graphene) is one of the main technologies for preparing porous graphene and is also one of the main preparation processes for porous carbon-based supercapacitors. Compared with the traditional carbon-based composite material electrode processing means (such as high-temperature calcination, chemical vapor graphene deposition or high-temperature oxidation reduction and the like), the processing process is simple, certain polymers (hereinafter collectively referred to as precursors) are subjected to laser processing in a room-temperature environment, and laser energy generates free radicals to generate carbon rearrangement in the laser processing process to obtain the carbonized material, so that the one-step molding of the carbon-based composite material mainly comprising graphene and taking the laser processing surface as the surface and the carbonized graphene, the porous carbon structure and the polymer substrate as the arrangement sequence is realized. A large amount of polymer monomers are used as precursor materials, such as polybenzimidazole or polyetheretherketone, but the energy storage performance of the supercapacitor electrode obtained by the precursor materials and the technical route is poor, and the high-efficiency and stable energy storage performance of the supercapacitor is difficult to realize, such as low specific surface area capacitance and low energy density, and the method is a technical barrier for restricting the application of the laser-induced graphene technology-synthesized carbon-based composite material in the supercapacitor.
Disclosure of Invention
The invention aims to provide a carbon-based supercapacitor electrode and a laser-acid modification synergistic preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a carbon-based supercapacitor electrode by laser-acid modification synergy, which comprises the following steps:
mixing the imidazole polymer base material with an acid solution, and carrying out acid modification to obtain an acid-modified imidazole polymer base material;
and (3) performing laser irradiation on the acid-modified polyimidazole polymer substrate material to obtain the carbon-based supercapacitor electrode.
Preferably, the base material of the polyimidazole polymer is polybenzimidazole.
Preferably, the form of the base material of the imidazole polymer is a film material, a block material, a fiber or a fiber fabric.
Preferably, the acid in the acid solution comprises sulfuric acid and/or phosphoric acid.
Preferably, when the acid in the acid solution is phosphoric acid, the mass concentration of the acid solution is 0-85% and is not 0; when the acid in the acid solution is sulfuric acid, the mass concentration of the acid solution is 0-50% and is not 0; when the acid in the acid solution is sulfuric acid and phosphoric acid, the mass concentration of the sulfuric acid and the mass concentration of the phosphoric acid are 0-65% and not 0 independently, and the mass percentage ratio of the phosphoric acid to the sulfuric acid is 1 (0.1-10).
Preferably, the acid modification time is 20-120 h.
Preferably, the laser used for laser irradiation is a carbon dioxide laser, the wavelength of the carbon dioxide laser is 10.6 microns, and the wave number is 900-1500 cm-1The power of the laser irradiation is 1-40W, the scanning speed is 1-12 inch/s, and the image density is 200-1000 PPI.
The invention provides the carbon-based supercapacitor electrode prepared by the preparation method in the technical scheme.
The invention provides application of the carbon-based supercapacitor electrode in the technical scheme in a supercapacitor.
The invention provides a method for preparing a carbon-based supercapacitor electrode by laser-acid modification synergy, which comprises the following steps: mixing the imidazole polymer base material with an acid solution, and carrying out acid modification to obtain an acid-modified imidazole polymer base material; and (3) performing laser irradiation on the acid-modified polyimidazole polymer substrate material to obtain the carbon-based supercapacitor electrode. According to the invention, the quality of graphene on the surface of the carbon-based material and the porous graphene structure are improved through the synergistic processing effect of laser and acid modification, so that the problems of small specific capacitance and low energy density of the carbon-based supercapacitor electrode in the application process of the supercapacitor electrode and further limited energy storage effect are solved. According to the invention, the high-quality graphene, porous carbon-based supercapacitor electrode doped with atomic nitrogen (or phosphorus or sulfur) is obtained by processing the acid-modified polyimidazole polymer substrate material by laser. Firstly, the input energy in a processing system is changed by regulating and controlling the energy parameter of laser processing, so that the quality of surface graphene is controlled, and secondly, the imidazole polymer substrate material is more easily attacked by free radicals generated by laser due to the absorption effect of imidazole groups on hydrogen ions in acid molecules in the acid modification process, and compared with the imidazole polymer substrate material which is not subjected to acid modification, the carbonization degree of the imidazole polymer substrate material is more obvious. In addition, the acid molecules can easily absorb laser energy to generate more free radical promoting reactions, and can synthesize volatile gas to generate pores and take away energy while promoting the generation of the free radicals, so that the carbon-based supercapacitor electrode with different porosities can be processed by adjusting the concentration of the acid molecules; meanwhile, the amount of heteroatoms of different acidic molecules participating in the free radical reaction generated by laser is different, so that the heteroatom doping amount of the final carbon-based supercapacitor electrode is influenced. Therefore, the invention can realize the cooperative processing of laser and acid modification, in the process of energy storage, graphene generated by laser processing in the carbon-based supercapacitor electrode has the functions of electric conduction and energy storage, and the non-carbonized polymer substrate has the function of promoting ion transmission, particularly proton transmission, so that the specific capacitance and energy density of the carbon-based supercapacitor electrode can be improved, and the energy storage effect of the supercapacitor can be further improved.
Compared with the problems of simply improving the graphene quality or the graphene porosity and the like in the prior art, the processing method provided by the invention has the advantages that the processing method is simple, the condition is mild, and the problems of improving the graphene quality, the porous graphene porosity and the doping atomic weight of the carbon-based supercapacitor electrode are solved at one time (see the specification for details).
Drawings
FIG. 1 is a schematic diagram of the reaction of polybenzimidazole material in the laser processing of the present invention;
FIG. 2 is a flow chart of the present invention for preparing carbon-based supercapacitor electrodes by acid modification and laser synergy of polybenzimidazole materials;
FIG. 3 is a Raman spectrum (a) and a corresponding G/D intensity ratio variation graph (b) of the carbon-based materials prepared in examples 1 to 3 and comparative example 1;
FIG. 4 is a BET specific surface area graph of carbon-based supercapacitor electrodes prepared in example 1 and comparative example 1;
FIG. 5 is an infrared spectrum of an acid-modified polybenzimidazole, a raw material polybenzimidazole and phosphoric acid prepared in examples 1 to 3 and comparative example 1;
FIG. 6 is a graph showing the change in specific capacitance of a symmetrical supercapacitor constructed from the carbon-based supercapacitor electrodes prepared in examples 1 to 4;
FIG. 7 is a BET partial pressure plot (a) and a corresponding histogram (b) of specific surface area for carbon-based supercapacitor electrodes prepared in examples 5-7 and comparative example 1;
FIG. 8 is a charge-discharge curve of an asymmetric micro-supercapacitor formed by the carbon-based supercapacitor electrodes prepared in examples 5 to 7;
fig. 9 is a specific capacitance test chart of the supercapacitors constructed of the carbon-based materials prepared in comparative example 1 and comparative example 2.
Detailed Description
The invention provides a method for preparing a carbon-based supercapacitor electrode by laser-acid modification synergy, which comprises the following steps:
mixing the imidazole polymer base material with an acid solution, and carrying out acid modification to obtain an acid-modified imidazole polymer base material;
and (3) performing laser irradiation on the acid-modified polyimidazole polymer substrate material to obtain the carbon-based supercapacitor electrode.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, the base material of the imidazole polymer is mixed with an acid solution for acid modification, so as to obtain the base material of the acid-modified imidazole polymer. In the invention, the acid modified imidazole material has a certain proton exchange performance, can promote the transmission of hydrogen ions, and improves the energy storage efficiency. According to the invention, by using the polyimidazole polymer substrate material, acid molecules stably exist in a molecular chain segment of the polymer material in the acid modification process, and the problems that most of subsequent laser energy is taken away by the acid molecules, the generated free radicals are difficult to influence the polymer substrate, even the carbon rearrangement process is hindered, and the formation of the carbon-based material is influenced are avoided.
In the invention, the base material of the polyimidazole polymer is preferably polybenzimidazole; the form of the base material of the polyimidazole polymer is preferably a membrane material, a block material, a fiber or a fiber fabric. The method for preparing the polybenzimidazole fiber or fiber fabric is not particularly limited in the present invention, and the polybenzimidazole fiber or fiber fabric can be prepared by a process well known in the art.
In the present invention, the preparation process of the polybenzimidazole membrane material or polybenzimidazole bulk material preferably comprises: mixing polybenzimidazole powder with an organic solvent, and heating and dissolving under stirring to obtain a homogeneous-phase polybenzimidazole solution; and uniformly coating the polybenzimidazole solution on a flat plate, volatilizing the organic solvent, cooling and stripping to obtain the polybenzimidazole film material or block material.
In the present invention, the organic solvent preferably includes one or more of dimethyl sulfoxide (DMSO), N Dimethylformamide (DMF), N dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); when the organic solvent is one of the above, the invention has no special limitation on the proportion of different organic solvents, and any proportion can be used.
The process of mixing the polybenzimidazole powder with the organic solvent is not particularly limited in the present invention, and the mixing may be performed according to a process well known in the art. In the invention, the heating and dissolving temperature is preferably 50-120 ℃, and more preferably 60 ℃; the time is preferably 2 to 7 hours, and more preferably 4 hours.
The process of uniformly coating the flat plate is not particularly limited, and the process is carried out according to the process known in the field; the plate is not particularly limited in the present invention, and any plate known in the art may be used. In the invention, the volatilizing of the organic solvent is preferably carried out under normal pressure, the volatilizing temperature is preferably 60-120 ℃, more preferably 70 ℃, and the volatilizing time is preferably 6-26 h, more preferably 24 h.
The cooling and peeling processes are not particularly limited in the present invention and may be performed according to processes well known in the art. The invention has no special limitation on the size of the membrane material or the block material obtained by stripping, and can be adjusted according to the actual requirement.
The polybenzimidazole powder is dissolved by an organic solvent and is evaporated for recrystallization to form a rich self-crosslinking structure and a film material or a block material, thereby overcoming the problems of high difficulty in direct acid treatment, difficult molding and difficult laser processing of the powder material.
In the present invention, the acid in the acid solution preferably includes sulfuric acid and/or phosphoric acid; when the acid in the acid solution is phosphoric acid, the mass concentration of the acid solution is preferably 0-85% but not 0, more preferably 0.5-70%, and even more preferably 0.85-30%; when the acid in the acid solution is sulfuric acid, the mass concentration of the acid solution is 0-50% but not 0, and more preferably 20-40%; when the acid in the acid solution is sulfuric acid and phosphoric acid, the mass concentration of the sulfuric acid and the phosphoric acid is preferably 0-65% and not 0 independently, more preferably 10-50%, and the mass percentage ratio of the phosphoric acid to the sulfuric acid is preferably 1 (0.1-10), more preferably 1 (1-8). According to the invention, the generation amount of free radicals in the subsequent laser irradiation process is controlled by adjusting the concentration of acid molecules, the number of acid molecules embedded in a high-molecular chain segment is controlled by using different acid modification concentrations, and under the same laser irradiation processing condition, the higher the acid concentration is, the more laser energy can be taken away by the acid molecules in the modified polybenzimidazole material, so that the energy for carbonization is reduced, the degree of carbon atom rearrangement is reduced, and the quality of conductive graphene in the carbon-based supercapacitor electrode is reduced.
In the invention, the mixing mode of the base material of the imidazole polymer and the acid solution is preferably dipping mixing, the dosage ratio of the acid solution to the base material of the imidazole polymer is not specially limited, and the base material of the imidazole polymer is completely dipped in the acid solution.
In the invention, the time for modifying the acid is preferably 20-120 h, and more preferably 50-80 h. In the acid modification process, hydrogen ions in the acidic molecules modify macromolecular imidazole groups of the polybenzimidazole to form positive electric centers, and the acidic molecules are coated, so that the acidic molecules are embedded into macromolecular chain segments and coexist in the polybenzimidazole material in the forms of the positive electric centers and acid radical anions.
After the acid modification is completed, the method preferably further comprises the steps of flatly spreading the obtained material, removing redundant water and redundant acid on the surface by means of ventilation drying at the temperature of 30-100 ℃, and removing floating acid which is not removed in the drying process by means of a paper towel after drying to obtain the acid-modified polyimidazole polymer base material.
After the acid modified polyimidazole base material is obtained, the acid modified polyimidazole base material is subjected to laser irradiation to obtain the carbon-based supercapacitor electrode. In the invention, the laser used for laser irradiation is preferably carbon dioxide laser, the wavelength of the carbon dioxide laser is preferably 10.6 μm, and the wave number is preferably 900-1500 cm-1The power of the laser irradiation is preferably 1-40W, more preferably 2-30W, and further preferably 3-10W; the scanning speed is preferably 1-12 inch/s, and the image density is preferably 200-1000 PPI; the environment for laser irradiation is preferably a normal-temperature normal-pressure air environment. The equipment used for the laser irradiation is not particularly limited, and is selectedBy means of laser irradiation equipment known in the art.
In the laser irradiation process, free radicals are generated by the absorption effect of acid molecules embedded in the polymer chain segments on laser energy, so that carbon atoms are rearranged on the surface and inside of the polybenzimidazole polymer material, a carbon-based material is obtained, and the laser acid modification cooperative processing is realized. Taking phosphoric acid and a polybenzimidazole material as an example, as shown in fig. 1, during laser irradiation, laser energy ionizes air molecules to generate free radicals, spontaneous free radical reaction is utilized to generate collision of chemical bonds for molecular rearrangement, the carbon rearrangement process of the polybenzimidazole material is realized, and acidic molecules break the chemical bonds by absorbing the laser energy to generate more free radicals to promote the carbon rearrangement process; in addition, the carbon rearrangement reaction is easier to occur with free radicals due to the increase of active hydrogen sites of the modified polybenzimidazole material, and the carbon rearrangement process is promoted. Meanwhile, small molecule gas such as water molecules and the like generated by the free radical reaction can form pores inside the carbon-based material, so that the porosity of the material is improved.
According to the invention, the laser energy absorption degree is regulated and controlled by regulating the laser irradiation energy input and the acid modification concentration, so that the electrode quality and the porosity of different carbon-based supercapacitors are regulated and controlled, and the cooperative processing of laser and acid molecules is realized.
After the laser irradiation is finished, the carbon-based supercapacitor electrode is obtained preferably without any treatment.
Fig. 2 is a flow chart of the preparation of the carbon-based supercapacitor electrode by using the acid modification-laser synergy of the polybenzimidazole material, as shown in fig. 2, the polybenzimidazole material is soaked for acid modification, acidic molecules are embedded into the polybenzimidazole material to obtain the acid-modified polybenzimidazole material, then laser processing is carried out, the acidic molecules absorb laser energy, the free radical reaction is enhanced, and carbon rearrangement is carried out to obtain the carbon-based supercapacitor electrode for the supercapacitor electrode.
The method realizes the graphene quality, the porous graphene porosity and the heteroatom for energy storage in the carbon-based supercapacitor electrode through the laser power and acid modification cooperative processing controlPrecise control of the doping content (hereinafter referred to as the amount of hetero atoms). For controlling the quality of graphene in the carbon-based supercapacitor electrode, the ratio of characteristic peak G/D of the carbon-based supercapacitor electrode product under a Raman spectrum can be controlled to be 0.8-1.3 by controlling the acid modification concentration and the laser power, so that the precise regulation of graphite, multilayer graphene (3 layers to 10 layers) and single-layer/few-layer graphene is obtained, and the regulation and control effect on the conductivity of the electrode is achieved. For controlling the porosity of the porous graphene, the embedding amount of acidic molecules in the polybenzimidazole material can be controlled through the acid modification concentration, and the acid modification degree of the polybenzimidazole material is regulated and controlled; acid molecules embedded in the material and the modified polybenzimidazole material are triggered to generate free radicals through laser processing, and when carbon rearrangement occurs to form graphene, micromolecule volatile gas is generated in gaps of graphene layers to play a role in pore forming, so that the porosity and the specific surface area inside the carbon-based supercapacitor electrode are further improved. In the laser processing process, the laser power is controlled, the energy density input to the polybenzimidazole material is adjusted, the carbon rearrangement degree is controlled, and the generation of small molecular gas in the carbon rearrangement process is generated, so that the regulation and control of the porosity and the specific surface area in the carbon-based material are realized, the coordinated processing with acid modification is achieved, the energy storage space of the carbon-based supercapacitor electrode is expanded or reduced, and the regulation and control space of the specific surface area can reach 20.2-1073 m2(ii) in terms of/g. For the amount of the heteroatom, the amount of the heteroatom participating in carbon rearrangement can be influenced by regulating the amount of the acidic molecule embedded in the polybenzimidazole material and the laser power through acid modification, so that the regulation of the amount of the heteroatom of the rearranged graphene is realized; the doped phosphoric acid can affect the 2-10% content change (X-ray electron spectrum (XPS) total atomic weight) of heteroatom phosphorus in the graphene and the 0.5-2.5% content change of heteroatom N, and the doped sulfuric acid can affect the change of graphene heteroatom sulfur and the content change of heteroatom N, so that the electrochemical process in the charging and discharging process inside the supercapacitor is controlled, and the capacitance performance of the supercapacitor is potentially improved. From the viewpoint of the performance of the super capacitor: the carbon-based supercapacitor electrode is prepared by changing the quality, porosity and doping elements of graphene in a carbon-based material through laser irradiation and acid modification concentration regulationThe content is divided, so that the processed graphene has the functions of electric conduction and energy storage. Because the acid modified polybenzimidazole material substrate which is not carbonized partially has the function of promoting ion transmission, particularly proton transmission, the migration and exchange of protons in electrolyte can be promoted, and the acid modified polybenzimidazole material substrate is particularly obvious in acid electrolyte and can realize the highest specific surface capacitance of 149mF/cm2And a maximum energy density of 20.7. mu. Wh/cm2The energy storage effect of (2).
The invention provides the carbon-based supercapacitor electrode prepared by the preparation method in the technical scheme.
The invention provides application of the carbon-based supercapacitor electrode in the technical scheme in a supercapacitor. The method for applying the carbon-based supercapacitor electrode to the supercapacitor is not particularly limited, and the carbon-based supercapacitor electrode can be applied according to a method well known in the art.
In the present invention, the supercapacitor preferably includes a three-electrode type supercapacitor, a planar supercapacitor, a counter electrode supercapacitor or a micro supercapacitor, and further includes a symmetric supercapacitor and an asymmetric supercapacitor included in the counter electrode supercapacitor or the micro supercapacitor. The invention has no special limitation on the components and the construction method of the supercapacitors with different configurations, and the supercapacitors with components well known in the art can be used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Pouring commercial polybenzimidazole powder into a stirring kettle containing an organic solvent DMF and DMSO in a volume ratio of 1:4, raising the temperature of the stirring kettle to 80 ℃, and heating and dissolving for 6 hours to obtain a polybenzimidazole solution; uniformly coating the polybenzimidazole solution on a flat plate, treating for 24 hours at 80 ℃ under the normal pressure condition, volatilizing the solvent, cooling and stripping to obtain a polybenzimidazole membrane material;
soaking the polybenzimidazole membrane material in a phosphoric acid solution with the mass concentration of 0.85% for 50h, carrying out acid modification, flattening and unfolding the obtained material, carrying out ventilation drying at 50 ℃ to remove redundant water and redundant acid on the surface, and removing floating acid which is not removed in the drying process by using a paper towel after drying to obtain an acid-modified polybenzimidazole material;
the acid modified polybenzimidazole material is subjected to laser irradiation with the laser power of 2W, the laser is carbon dioxide laser with the wavelength of 10.6 mu m, and the wave number is 1000cm-1And the scanning speed of laser irradiation is 10inch/s, the image density is 400PPI, and the carbon-based supercapacitor electrode is obtained.
Example 2
The only difference from example 1 is: the phosphoric acid solution had a mass concentration of 30% and the same procedure as in example 1 was repeated.
Example 3
The only difference from example 1 is: the phosphoric acid solution had a mass concentration of 70%, and the procedure was otherwise the same as in example 1.
Example 4
The only difference from example 1 is: the phosphoric acid solution had a mass concentration of 50% and the same procedure as in example 1 was repeated.
Example 5
Pouring commercial polybenzimidazole powder into a container containing organic solvents DMF and DMAC, wherein the volume fraction ratio of the organic solvents DMF to the DMAC is 1: 2, raising the temperature of the stirring kettle to 70 ℃, and heating and dissolving for 4 hours to obtain a polybenzimidazole solution; uniformly coating the polybenzimidazole solution on a flat plate, treating for 20 hours at 100 ℃ under normal pressure, volatilizing the solvent, cooling and stripping to obtain a polybenzimidazole membrane material;
soaking the polybenzimidazole membrane material in a phosphoric acid solution with the mass concentration of 0.85% for 50h, carrying out acid modification, then flatly spreading the obtained material, and removing floating acid which is not removed in the drying process by using a paper towel after carrying out ventilation drying at 50 ℃ to obtain an acid-modified polybenzimidazole material;
the acid modified polybenzimidazole material is subjected to laser irradiation with the laser power of 2W and the laser wavelength of 10.6 μm carbon dioxide laser with wave number of 1000cm-1And the scanning speed of laser irradiation is 6inch/s, the image density is 800PPI, and the carbon-based supercapacitor electrode is obtained.
Example 6
The only difference from example 5 is that: the phosphoric acid solution had a mass concentration of 30% and the same procedure as in example 5 was repeated.
Example 7
The only difference from example 5 is that: the phosphoric acid solution had a mass concentration of 70%, and the procedure was otherwise the same as in example 5.
Example 8
Pouring commercial polybenzimidazole powder into a container containing DMF, DMSO and DMAC in a mass fraction ratio of 1: 2: 2, putting the mixed organic solvent into a stirring kettle, and heating and dissolving for 4 hours at the temperature of 70 ℃ by lifting the temperature of the stirring kettle to obtain a polybenzimidazole solution; uniformly coating the polybenzimidazole solution on a flat plate, treating for 10 hours at 90 ℃ under the condition of normal pressure, volatilizing the solvent, cooling and stripping to obtain a polybenzimidazole membrane material;
soaking the polybenzimidazole membrane material in a uniformly mixed solution of 10 mass percent phosphoric acid solution and 10 mass percent sulfuric acid solution in a mass ratio of 1:1 for 60 hours for acid modification, flatly spreading the obtained material, and removing floating acid which is not removed in the drying process by using a paper towel after carrying out ventilation drying at 60 ℃ to obtain an acid-modified polybenzimidazole material;
the acid modified polybenzimidazole material is subjected to laser irradiation with the laser power of 5W, the laser is carbon dioxide laser with the wavelength of 10.6 mu m, and the wave number is 1000cm-1And the scanning speed of laser irradiation is 5inch/s, the image density is 300PPI, and the carbon-based supercapacitor electrode is obtained.
Comparative example 1
The only difference from example 1 is: the procedure of example 1 was repeated except that no acid modification was performed, i.e., no acid treatment was performed.
Comparative example 2
A carbon-based material was obtained by irradiating commercially available polyimide Paper (PI) with laser light in the same manner as in example 1.
Performance testing
1) Performing a raman test on the carbon-based materials prepared in examples 1 to 3 and comparative example 1, wherein the obtained spectra are shown in fig. 3, wherein a is a raman spectrum of the carbon-based materials prepared in examples 1 to 3 and comparative example 1, and b is a G/D intensity ratio variation graph corresponding to a; as can be seen from a in FIG. 3, all the spectra have obvious graphene characteristics, but comparing the G/D intensity ratios of the carbon-based supercapacitor electrodes obtained under different phosphoric acid concentrations in b in FIG. 3, the ratio of the G/D peak of the carbon-based supercapacitor electrode generated by the phosphoric acid modified polybenzimidazole materials prepared in examples 1-3 through laser irradiation is higher than that of the carbon-based supercapacitor electrode prepared in comparative example 1. According to the characteristic of the spectrogram peak of the graphene characteristic, the higher the G/D ratio is, the fewer the graphene layers are, and the more obvious the conductive property is. It is shown that the concentration of phosphoric acid affects the quality of graphene in the carbon-based material, and the lower the concentration of phosphoric acid, the better the quality of graphene.
2) BET specific surface area tests were performed on the carbon-based supercapacitor electrodes prepared in example 1 and comparative example 1, and the results are shown in fig. 4; as shown in fig. 4, the specific surface area of the carbon-based material modified by phosphoric acid is much larger than that of the carbon-based material without phosphoric acid treatment, wherein the specific surface area of the graphene treated by 0.85% phosphoric acid concentration is 1073m2And g, showing that the existence of the phosphoric acid influences the structure of the internal pores of the carbon-based supercapacitor electrode, and the specific surface area in the material can be increased.
3) The acid-modified polybenzimidazole prepared in examples 1 to 3 and comparative example 1, the polybenzimidazole as a raw material and a concentrated phosphoric acid liquid sold in the market are subjected to infrared test, and the obtained result is shown in a figure 5; as can be seen from FIG. 5, the polybenzimidazole material treated with different phosphoric acid concentrations is 900-1500 cm in the wavelength range of carbon dioxide laser-1The absorption peak in the wave number is higher, which indicates that the laser energy can be absorbed by phosphoric acid with any concentration, and the absorption degree of the laser energy is more obvious with the increase of the concentration of the phosphoric acid.
(4) The carbon-based supercapacitor electrodes prepared in the embodiments 1 to 4 are made into interdigital miniature symmetrical supercapacitors, and the current density ranges of the obtained different supercapacitors at normal temperature and normal pressure are 0.05-1 mA/cm2The constant current charge and discharge test, the data obtained are shown in FIG. 6, and FIG. 6 showsIt is known that supercapacitors formed from carbon-based supercapacitor electrodes prepared at different phosphoric acid concentrations have a current density of 0.05mA/cm2The specific capacitance of the dielectric ceramic is up to 14.13mF/cm2The calculation shows that the energy density is as high as 1.96 mu Wh/cm2。
5) The BET specific surface area partial pressure test is performed on the carbon-based supercapacitor electrodes prepared in examples 5 to 7 and comparative example 1, and the obtained result is shown in fig. 7, wherein a is a BET partial pressure graph of the carbon-based supercapacitor electrodes prepared in examples 5 to 7 and comparative example 1, and b is a corresponding specific surface area histogram; as can be seen from fig. 7, as the concentration of phosphoric acid increases, the adsorption amount of the carbon-based material at the same partial pressure (P/P0) decreases (a in fig. 7), illustrating that the phosphoric acid regulates and influences the porosity of the carbon-based material processed by the laser processed polybenzimidazole material, and as the specific surface area calculated from the adsorption amount (b in fig. 7), as the concentration of phosphoric acid decreases, the specific surface area of the carbon-based material increases to 384.46m2And/g, consistent with the BET partial pressure chart conclusion, the specific surface can be regulated by changing the phosphoric acid variable under the synergistic processing mode of laser/phosphoric acid modification.
6) The carbon-based supercapacitor electrodes prepared in examples 5 to 7 were cut with 30W laser power, and combined with a copper bare electrode to form an interdigital micro supercapacitor to form an asymmetric micro supercapacitor, a specific capacitance test was performed, cyclic voltammetry scanning was performed at a voltage scan rate of 0.001 to 0.5V/s at normal temperature and pressure, and the obtained results are shown in fig. 8. As can be seen from FIG. 8, the specific capacitance of the asymmetric super capacitor is up to 149mF/cm2The calculation shows that the energy density is as high as 20.7 mu Wh/cm2。
8) The asymmetric supercapacitors constructed according to 6) above were subjected to the specific capacitance test on the carbon-based materials prepared in comparative example 1 and comparative example 2, and the capacitance performance calculated by scanning the cyclic voltammograms ranging from 0.001V/s to 5V/s at normal temperature and pressure was shown in fig. 9. As can be seen from FIG. 9, the capacitance of the capacitor (10 mF/cm) is symmetrical with respect to the processing of the acid-modified polybenzimidazole material2) Non-acid treated polybenzimidazole (4.48F/cm)2) And carbon-based material (1.36 mF/cm) made of pure polyimide material2) It is difficult to achieve 10mF/cm2High level of capacitive energy storage.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. A laser-acid modification synergistic preparation method of a carbon-based supercapacitor electrode comprises the following steps:
mixing the imidazole polymer base material with an acid solution, and carrying out acid modification to obtain an acid-modified imidazole polymer base material;
and (3) performing laser irradiation on the acid-modified polyimidazole polymer substrate material to obtain the carbon-based supercapacitor electrode.
2. The preparation method according to claim 1, wherein the base material of the polyimidazole-based polymer is polybenzimidazole.
3. The preparation method according to claim 2, wherein the form of the base material of the imidazole polymer is a film material, a block material, a fiber or a fiber fabric.
4. The method according to claim 1, wherein the acid in the acid solution comprises sulfuric acid and/or phosphoric acid.
5. The production method according to claim 4, wherein when the acid in the acid solution is phosphoric acid, the mass concentration of the acid solution is 0 to 85% and is not 0; when the acid in the acid solution is sulfuric acid, the mass concentration of the acid solution is 0-50% and is not 0; when the acid in the acid solution is sulfuric acid and phosphoric acid, the mass concentration of the sulfuric acid and the mass concentration of the phosphoric acid are 0-65% and not 0 independently, and the mass percentage ratio of the phosphoric acid to the sulfuric acid is 1 (0.1-10).
6. The preparation method according to claim 1, wherein the acid modification time is 20-120 h.
7. The production method according to claim 1, wherein the laser used for the laser irradiation is a carbon dioxide laser having a wavelength of 10.6 μm and a wave number of 900 to 1500cm-1The laser irradiation power is 1-40W, the scanning speed is 1-12 inch/s, and the image density is 200-1000 PPI.
8. The carbon-based supercapacitor electrode prepared by the preparation method of any one of claims 1 to 7.
9. Use of the carbon-based supercapacitor electrode of claim 8 in a supercapacitor.
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