CN111540612B - Preparation method of organic/inorganic composite super capacitor - Google Patents

Preparation method of organic/inorganic composite super capacitor Download PDF

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CN111540612B
CN111540612B CN202010386347.XA CN202010386347A CN111540612B CN 111540612 B CN111540612 B CN 111540612B CN 202010386347 A CN202010386347 A CN 202010386347A CN 111540612 B CN111540612 B CN 111540612B
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CN111540612A (en
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赵瑨云
梁松
张根延
李泽彪
胡家朋
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WUYISHAN BIKONG ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd.
Wuyi University
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Wuyi University
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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
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Abstract

The invention provides a preparation method of an organic/inorganic composite super capacitor, which comprises the following steps: with SiO2Preparing a nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite positive electrode material by taking the microsphere as a template; preparing a nano-pore carbon fiber negative electrode material by thermally induced phase separation combined with carbon thermal reduction; preparing PVA/KOH gel solution; packaging the organic/inorganic composite super capacitor; the organic/inorganic composite super capacitor obtained by the invention has the advantages of low cost, simple process, good conductivity, good cycling stability, excellent thermal stability and the like, and has good industrial application prospect.

Description

Preparation method of organic/inorganic composite super capacitor
Technical Field
The invention relates to a preparation method of an organic/inorganic composite super capacitor, belonging to the field of composite materials and electrochemistry.
Background
In the 21 st century, the traditional energy can not meet the needs of people, and the search and development of sustainable energy become a hot spot of scientific research. As a novel energy storage device, the super capacitor has the advantages of high power density, long cycle life, high energy density, high charging and discharging speed, high efficiency, no maintenance, environmental friendliness and the like, so that the super capacitor has a strong application prospect in the development of new energy.
The performance of the super capacitor mainly depends on the electrode of a core component of the super capacitor, and the electrode has the characteristics of high specific capacity, high power, long cycle service life and the like. Common electrode materials mainly comprise three types including carbon-based materials, transition metal oxides and conductive polymer materials. Each of the three materials has its advantages and disadvantages. For example, the carbon-based material has a large specific surface area and high conductivity, however, in order to obtain an electric double layer structure, the pore structure must be larger than 2nm, whereas the carbon-based material of a high specific surface area is mostly composed of micropores (< 2nm), and thus the effective pore structure is greatly reduced, and its actually used specific capacity is about 10% of its theoretical capacity. Transition metal oxides and conductive polymer materials have the advantages of high specific capacity, high energy density and the like, but the transition metal oxides and the conductive polymer materials have small specific surface area and low conductivity, so that the wide application of the transition metal oxides and the conductive polymer materials is limited. How to compound the carbon-based material with the transition metal oxide and the conductive polymer to prepare the composite super capacitor becomes a hot point of scientific research. For example, Shen et al synthesized NiCo by a two-step synthesis2S4Loading the nano sheet to nitrogen-doped foam Carbon (CNF) to obtain NiCo2S4the/CNF composite electrode material. NiCo due to its multicomponent character and three-dimensional structure2S4The specific capacitance of the/CNF composite electrode is up to 877F/g under the condition that the current density is 20A/g, and the energy density reaches 45.5wh/kg (Shen L, et al, NiCo)2S4Nanosheets grow on Nitrogen-dot Carbon Foams as an Advanced electrodes for supercapacitors. adv. energy Mater,2015,5, 1400977). Chen et al utilize porous SiO2(SBA-15) is taken as a template, an ordered porous carbon tube (SBA-C) is prepared, and finally NiCoS nanosheets are loaded on the ordered porous carbon tube by a hydrothermal method to obtain a NiCoS @ SBA-C shell-core structure. When the current density is 1A/g, the specific capacitance reaches 1757F/g, and when the current density is increased to 20A/g, the specific capacitance still keeps 79.68 percent of the original specific capacitance, and the cyclic use performance is good. The energy density and power density of asymmetric supercapacitors prepared with NiCoS @ SBA-C as the anode and SBA-C as the cathode were 38.8Wh/kg and 800W/kg, respectively (Chen Y, et Al, Synthesis of porous NiCoS nano sheets with Al free on ordered mesoporous carbon for high-performance supercapacitors. chem.,2020,384,123)。
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of an organic/inorganic composite supercapacitor.
A preparation method of an organic/inorganic composite super capacitor comprises the following steps:
s1, preparing a positive plate;
s2, preparing a negative plate;
s3, preparing a PVA/KOH gel solution;
s4, bonding one surface of the positive plate and one surface of the negative plate through PVA/KOH gel solution, and then respectively bonding one PET substrate on the other surface of the positive plate and the other surface of the negative plate through PVA/KOH gel solution to form the organic/inorganic composite super capacitor;
the preparation method of the positive plate comprises the following steps:
after absolute ethyl alcohol, ammonia water and distilled water are mixed evenly, tetraethyl orthosilicate is added, and after reaction, SiO is obtained through centrifugation and washing2Microspheres;
subjecting the SiO2Adding the microspheres into a mixed solution of ethylenediamine and carbon tetrachloride, uniformly dispersing, performing reflux reaction at 80-100 ℃, filtering, washing and drying a product, and soaking the product in a zinc chloride solution for activation;
heating the activated product to 600-800 ℃ at the speed of 10-15 ℃/min under the protection of nitrogen, and reacting to obtain nitrogen-doped carbon @ SiO2Microspheres;
the nitrogen is doped with carbon @ SiO2Soaking the microspheres in a mixed solution of hydrofluoric acid and ammonium fluoride to remove SiO2Obtaining nitrogen-doped carbon hollow microspheres;
uniformly mixing the nitrogen-doped carbon hollow microspheres with aniline, p-phenylenediamine, hydrochloric acid and sodium dodecyl sulfate, then dropwise adding an ammonium persulfate solution, and reacting at the temperature of 2-5 ℃ to obtain a nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound;
mixing the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound, acetylene black and PTFE in absolute ethyl alcohol, performing ultrasonic dispersion, coating on the surface of foamed nickel, drying, and tabletting to obtain the positive plate;
the preparation method of the negative plate comprises the following steps:
dissolving polyacrylonitrile and tetrabutyl titanate in an N, N' -dimethylformamide/glacial acetic acid mixed solvent, and stirring and dissolving at 50 ℃ to obtain a precursor solution;
freezing the precursor solution at-40 to-20 ℃ for 120-160 min, putting the precursor solution into distilled water to remove the solvent, and freeze-drying to obtain PAN/TiO2A nanofiber;
mixing the PAN/TiO2Under the protection of argon, heating the nano-fibers from normal temperature to 250-300 ℃, preserving heat for 120-150 min, heating the nano-fibers from 250-300 ℃ to 1000-1200 ℃, preserving heat for 120-180 min, introducing chlorine, reacting for 120-180 min, introducing argon after the reaction is finished, and naturally cooling to normal temperature to obtain the nano-porous carbon fibers;
mixing the nano-pore carbon fiber, acetylene black and PTFE in absolute ethyl alcohol, uniformly dispersing, coating on foamed nickel, drying at 60 ℃ in vacuum for 6 hours, and then pressing under the pressure of 10MPa to obtain the negative plate.
Preferably, the SiO is2The mass ratio of the microspheres to the ethylenediamine to the carbon tetrachloride is (0.5-1): (1-2): (10-20).
Preferably, the concentration of the zinc chloride solution is 2-3 mol/L.
Preferably, the mass ratio of the nitrogen-doped carbon hollow microsphere to the aniline to the p-phenylenediamine is (1-1.5): (1-2): (0.05-0.1).
Preferably, the mass ratio of the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite to the acetylene black to the PTFE is 8: 1: 1.
preferably, the mass ratio of the nanoporous carbon fibers, the acetylene black and the PTFE is 8: 1: 1.
preferably, the preparation method of the PVA/KOH gel solution comprises the following steps:
dissolving polyvinyl alcohol in distilled water, adding KOH aqueous solution, and dissolving by magnetic stirring to obtain PVA/KOH gel solution.
Preferably, in the PVA/KOH gel solution, the mass concentration of PVA is 3-6%, and the mass concentration of KOH is 8-10%.
The basic principle of the invention is as follows:
1. taking tetraethyl orthosilicate as a precursor, and obtaining SiO by hydrolyzing and condensing tetraethyl orthosilicate under alkaline conditions2And (3) microspheres. With SiO2Reacting ethylenediamine with carbon tetrachloride under reflux condition, drying to obtain black product, and soaking in ZnCl2Activating in solution, carbonizing to obtain nitrogen-doped carbon @ SiO2Removing SiO by washing with hydrofluoric acid2Obtaining the nitrogen-doped carbon hollow microsphere. Aniline and p-phenylenediamine are used as monomers, and nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite is obtained through copolymerization. And the composite is used as the positive electrode material of the super capacitor.
2. PAN (Polyacrylonitrile) is taken as a polymer, tetrabutyl titanate is taken as a precursor, and the PAN/TiO is obtained by a thermally induced phase separation method (freezing)2And (3) compounding the nano fibers. Mixing PAN/TiO2The composite nano-fiber converts PAN into C by low-temperature oxidation and high-temperature carbonization to obtain C/TiO2Composite nanofibers of C and TiO by carbothermic reduction2Reacting to form TiC; and finally, reacting TiC with chlorine to obtain the nanopore carbon fiber.
3. And (3) obtaining the organic/inorganic composite super capacitor by taking PVA/KOH gel as electrolyte, the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite as a positive electrode material and the nanopore carbon fiber as a negative electrode material.
Compared with the prior art, the invention has the following beneficial effects:
1. the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite is used as a positive electrode material, the carbon hollow microsphere provides a large specific surface area and good conductivity, and the polyaniline-p-phenylenediamine copolymer provides a large specific capacitance, so that the defect of low specific capacitance of a carbon-based material is overcome, and the specific capacitance of the electrode material is greatly improved.
2. The nitrogen-doped carbon hollow microsphere improves the active sites of the carbon hollow microsphere, so that the carbon hollow microsphere can show better performance when in oxygen.
3. The cathode material adopts the nano-pore carbon fiber, compared with the common carbon-based material, the material is the carbon fiber, the agglomeration of the nano-scale carbon-based material is overcome, and the fiber contains a large number of nano-pores, so that the specific surface area of the material is greatly improved.
4. The organic/inorganic composite super capacitor prepared by the invention has the characteristics of stable process, easy operation, low equipment dependence, no pollution and the like, is suitable for industrial large-scale production, and is expected to become an ideal super capacitor electrode material.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the preparation route of an organic/inorganic composite supercapacitor prepared according to the present invention;
FIG. 2 is a cross-sectional view of an organic/inorganic composite supercapacitor made in accordance with the present invention;
in the figure: 1. PET base plate, 2, gel layer, 3, positive plate, 4, negative plate.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a preparation method of an organic/inorganic composite supercapacitor, which specifically includes the following steps as shown in fig. 1:
preparation of positive plate
Adding 40g of absolute ethyl alcohol, 4g of ammonia water (mass concentration is 20-30%) and 150g of distilled water into a three-neck flask, and magnetically stirring for 10min to form a solution. Under the stirring condition will5g tetraethyl orthosilicate is dropwise added into the solution, magnetically stirred for 60min, centrifuged, washed and dried to obtain SiO2And (3) microspheres.
Take 0.8g SiO2Adding the microspheres into a mixed solution of 1.5g of ethylenediamine and 15g of carbon tetrachloride, and carrying out reflux reaction at 90 ℃ for 10 hours under magnetic stirring. After the reaction is finished, filtering, washing and drying the solid product. Soaking the dried product in ZnCl with the concentration of 2mol/L2Activating the solution for 6h, and drying for later use.
And (3) drying the activated product, and placing the dried product in an atmosphere furnace under the nitrogen protection condition, wherein the nitrogen flow is 100 mu L/min. Heating the mixture from room temperature to 600 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 3h at the temperature to obtain the nitrogen-doped carbon @ SiO2And (3) microspheres. Nitrogen is doped with carbon @ SiO2Soaking the microspheres in 2mol/L hydrofluoric acid and 8mol/L ammonium fluoride solution for 2h, washing and drying to obtain the nitrogen-doped carbon hollow microspheres.
1.2g of nitrogen-doped carbon hollow microspheres, 1.5g of aniline, 0.07g of p-phenylenediamine, 10mL of hydrochloric acid with the concentration of 0.5mol/L and 1g of sodium dodecyl sulfate are added into a 250mL three-neck flask, and magnetic stirring is carried out at normal temperature to obtain a mixed solution. Under the condition of magnetic stirring, 20mL of ammonium persulfate solution with the concentration of 0.5mol/L is dropwise added into the mixed solution, the dropwise adding speed is 0.01mL/s, and after the dropwise adding is finished, the reaction is continued for 24 hours, and the reaction temperature is 2 ℃. And filtering the precipitate after the reaction is finished, repeatedly washing the precipitate with hydrochloric acid and acetone, and performing vacuum drying at 50 ℃ for 24 hours to obtain the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite.
Mixing a nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound, acetylene black and PTFE according to the weight ratio of 8: 1: 1 in absolute ethyl alcohol, ultrasonically dispersing for 40min, coating on foamed nickel, vacuum drying at 60 ℃ for 6h, and then pressing under the pressure of 10MPa to obtain the positive plate.
Second, preparation of negative plate
Dissolving 1.2g of PAN and 0.12g of tetrabutyl titanate in a mixed solvent of 20g N, N' -dimethylformamide and 0.5g of glacial acetic acid, and stirring and dissolving at 50 ℃ to obtain a precursor solution; freezing the precursor solution at-20 deg.C for 150min, adding into distilled water to remove solvent, and freeze drying to obtain PAN/TiO2A nanofiber; mixing PAN/TiO2And (2) under the protection of argon, heating the flow of argon to be 100 mu L/min from normal temperature to 250 ℃, preserving heat for 150min, heating the temperature from 250 ℃ to 1200 ℃, preserving heat for 180min, introducing chlorine, reacting for 180min, introducing the argon for protection after the reaction is finished, and naturally cooling to normal temperature to obtain the nanopore carbon fiber. Mixing the nano-porous carbon fiber, acetylene black and PTFE according to the weight ratio of 8: 1: 1 in absolute ethyl alcohol, ultrasonically dispersing for 40min, coating on foamed nickel, vacuum drying at 60 ℃ for 6h, and then pressing under the pressure of 10MPa to obtain the negative plate.
Preparation of PVA/KOH gel solution
Adding 4g of polyvinyl alcohol into 35g of distilled water, heating and stirring for dissolving, then adding 15g of KOH aqueous solution with the mass concentration of 30%, and magnetically stirring for dissolving to obtain PVA/KOH gel solution.
Preparation of organic/inorganic composite super capacitor
And after one surface of the positive plate and one surface of the negative plate are bonded through the PVA/KOH gel solution, respectively bonding one PET substrate on the other surface of the positive plate and the other surface of the negative plate through the PVA/KOH gel solution to form the organic/inorganic composite supercapacitor. The structure is as shown in fig. 2, a layer of gel layer 2 is clamped between the positive plate 3 and the negative plate 4, the surfaces of the positive plate 3 and the negative plate 4 are respectively covered with a layer of gel layer 2, and the surfaces of the two adhesive layers 2 are respectively covered with a layer of PET substrate 1.
The voltage window of the organic/inorganic composite supercapacitor prepared in example 1 was 1.7V. The electrochemical performance of the electrochemical material is excellent within the voltage range of 0-1.7V, the corresponding specific capacitance and energy density of the electrochemical material can respectively reach 102.1F/g and 38.1Wh/kg, and the electrochemical material has good cycle performance.
Example 2
Preparation of positive electrode material
Adding 40g of absolute ethyl alcohol, 4g of ammonia water (mass concentration is 20-30%) and 150g of distilled water into a three-neck flask, and magnetically stirring for 10min to form a solution. Adding 5g tetraethyl orthosilicate into the solution drop by drop under the stirring condition, magnetically stirring for 60min, centrifuging, washing and dryingTo obtain SiO2And (3) microspheres.
Taking 1g of SiO2Adding the microspheres into a mixed solution of 1.2g of ethylenediamine and 12g of carbon tetrachloride, and carrying out reflux reaction at 95 ℃ for 8 hours under magnetic stirring. After the reaction is finished, filtering, washing and drying the solid product. Soaking the dried product in ZnCl with the concentration of 2.5mol/L2Activating the solution for 5h, and drying for later use.
And (3) drying the activated product, and placing the dried product in an atmosphere furnace under the nitrogen protection condition, wherein the nitrogen flow is 120 mu L/min. Heating from room temperature to 650 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 4h at the temperature to obtain the nitrogen-doped carbon @ SiO2And (3) microspheres. Nitrogen is doped with carbon @ SiO2Soaking the microspheres in 2mol/L hydrofluoric acid and 8mol/L ammonium fluoride solution for 2h, washing and drying to obtain the nitrogen-doped carbon hollow microspheres.
1g of nitrogen-doped carbon hollow microspheres, 1.2g of aniline, 0.05g of p-phenylenediamine, 10mL of hydrochloric acid with the concentration of 0.6mol/L and 1.2g of sodium dodecyl sulfate are added into a 250mL three-neck flask, and magnetic stirring is carried out at normal temperature to obtain a mixed solution. Under the condition of magnetic stirring, 20mL of ammonium persulfate solution with the concentration of 0.5mol/L is dropwise added into the mixed solution, the dropwise adding speed is 0.02mL/s, and after the dropwise adding is finished, the reaction is continued for 24 hours, and the reaction temperature is 3 ℃. And filtering the precipitate after the reaction is finished, repeatedly washing the precipitate with hydrochloric acid and acetone, and performing vacuum drying at 50 ℃ for 24 hours to obtain the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite.
Mixing a nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound, acetylene black and PTFE according to the weight ratio of 8: 1: 1 in absolute ethyl alcohol, ultrasonically dispersing for 40min, coating on foamed nickel, vacuum drying at 60 ℃ for 6h, and then pressing under the pressure of 10MPa to obtain the positive plate.
Preparation of cathode material
Dissolving 1g of PAN and 0.11g of tetrabutyl titanate in a mixed solvent of 20g N, N' -dimethylformamide and 0.5g of glacial acetic acid, and stirring and dissolving at 50 ℃ to obtain a precursor solution; freezing the precursor solution at-30 deg.C for 120min, adding into distilled water to remove solvent, and freeze drying to obtain PAN/TiO2A nanofiber; mixing PAN/TiO2Nanofibers under argon shield, argonHeating the solution from normal temperature to 250 ℃ for 150min, heating the solution from 250 ℃ to 1100 ℃ for 180min, introducing chlorine gas, reacting for 180min, introducing argon gas for protection after the reaction is finished, and naturally cooling the solution to normal temperature to obtain the nanopore carbon fiber. Mixing the nano-porous carbon fiber, acetylene black and PTFE according to the weight ratio of 8: 1: 1 in absolute ethyl alcohol, ultrasonically dispersing for 40min, coating on foamed nickel, vacuum drying at 60 ℃ for 6h, and then pressing under the pressure of 10MPa to obtain the negative plate.
Preparation of PVA/KOH gel solution
Adding 5g of polyvinyl alcohol into 35g of distilled water, heating and stirring for dissolving, then adding 15g of KOH aqueous solution with the mass concentration of 30%, and magnetically stirring for dissolving to obtain PVA/KOH gel solution.
Preparation of organic/inorganic composite super capacitor
And after one surface of the positive plate and one surface of the negative plate are bonded through the PVA/KOH gel solution, respectively bonding one PET substrate on the other surface of the positive plate and the other surface of the negative plate through the PVA/KOH gel solution to form the organic/inorganic composite supercapacitor.
The voltage window of the organic/inorganic composite supercapacitor prepared in example 2 was 1.7V. The electrochemical performance of the composite material is excellent within the voltage range of 0-1.7V, the corresponding specific capacitance and energy density of the composite material can respectively reach 98.4F/g and 40.2Wh/kg, and the composite material has good cycle performance.
Example 3
Preparation of positive plate
Adding 40g of absolute ethyl alcohol, 4g of ammonia water (mass concentration is 20-30%) and 150g of distilled water into a three-neck flask, and magnetically stirring for 10min to form a solution. Adding 5g tetraethyl orthosilicate into the solution drop by drop under the stirring condition, magnetically stirring for 60min, centrifuging, washing and drying to obtain SiO2And (3) microspheres.
Take 1.2g of SiO2Adding the microspheres into a mixed solution of 1g of ethylenediamine and 15g of carbon tetrachloride, and carrying out reflux reaction for 10 hours at 90 ℃ under magnetic stirring. After the reaction is finished, filtering, washing and drying the solid product. Soaking the dried product in a solution with a concentration of 2mol/LZnCl2Activating the solution for 5h, and drying for later use.
And (3) drying the activated product, and placing the dried product in an atmosphere furnace under the nitrogen protection condition, wherein the nitrogen flow is 100 mu L/min. Heating from room temperature to 650 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 4h at the temperature to obtain the nitrogen-doped carbon @ SiO2And (3) microspheres. Nitrogen is doped with carbon @ SiO2Soaking the microspheres in 2mol/L hydrofluoric acid and 8mol/L ammonium fluoride solution for 2h, washing and drying to obtain the nitrogen-doped carbon hollow microspheres.
1.4g of nitrogen-doped carbon hollow microspheres, 1g of aniline, 0.08g of p-phenylenediamine, 10mL of hydrochloric acid with the concentration of 0.7mol/L and 1.4g of sodium dodecyl sulfate are added into a 250mL three-neck flask, and magnetic stirring is carried out at normal temperature to obtain a mixed solution. Under the condition of magnetic stirring, 20mL of ammonium persulfate solution with the concentration of 0.8mol/L is dropwise added into the mixed solution, the dropwise adding speed is 0.01mL/s, and after the dropwise adding is finished, the reaction is continued for 24 hours, and the reaction temperature is 2 ℃. And filtering the precipitate after the reaction is finished, repeatedly washing the precipitate with hydrochloric acid and acetone, and performing vacuum drying at 50 ℃ for 24 hours to obtain the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite.
Mixing a nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound, acetylene black and PTFE according to the weight ratio of 8: 1: 1 in absolute ethyl alcohol, performing ultrasonic dispersion for 40min, coating on foamed nickel, performing vacuum drying at 60 ℃ for 6h, and then pressing a sheet under the pressure of 10MPa to obtain the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite cathode material.
Second, preparation of negative plate
Dissolving 0.8g of PAN and 0.1g of tetrabutyl titanate in a mixed solvent of 20g N, N' -dimethylformamide and 0.5g of glacial acetic acid, and stirring and dissolving at 50 ℃ to obtain a precursor solution; freezing the precursor solution at-40 deg.C for 150min, adding into distilled water to remove solvent, and freeze drying to obtain PAN/TiO2A nanofiber; mixing PAN/TiO2The nanofiber is prepared by heating the argon flow to be 100 mu L/min from normal temperature to 250 ℃, preserving heat for 150min, heating the argon flow to be 1050 ℃ from 250 ℃ and preserving heat for 180min, introducing chlorine gas, reacting for 180min, introducing the argon for protection after the reaction is finished, and naturally cooling to normal temperature to obtain the nanofiber, wherein the argon flow is 100 mu L/min, the chlorine flow is 200 mu L/min, and the chlorine flow is introduced for protectionNanoporous carbon fibers. Mixing the nano-porous carbon fiber, acetylene black and PTFE according to the weight ratio of 8: 1: 1 in absolute ethyl alcohol, ultrasonically dispersing for 40min, coating on foamed nickel, vacuum drying at 60 ℃ for 6h, and then pressing under the pressure of 10MPa to obtain the negative plate.
Preparation of PVA/KOH gel solution
Adding 4g of polyvinyl alcohol into 35g of distilled water, heating and stirring for dissolving, then adding 15g of KOH aqueous solution with the mass concentration of 30%, and magnetically stirring for dissolving to obtain PVA/KOH gel solution.
Preparation of organic/inorganic composite super capacitor
And after one surface of the positive plate and one surface of the negative plate are bonded through the PVA/KOH gel solution, respectively bonding one PET substrate on the other surface of the positive plate and the other surface of the negative plate through the PVA/KOH gel solution to form the organic/inorganic composite supercapacitor.
The voltage window of the organic/inorganic composite supercapacitor prepared in example 3 was 1.7V. The electrochemical performance of the electrochemical capacitor is excellent within the voltage range of 0-1.7V, the corresponding specific capacitance and energy density of the electrochemical capacitor can respectively reach 104.8F/g and 40.9Wh/kg, and the electrochemical capacitor has good cycle performance.
Comparative example 1
The difference from the embodiment 1 is that ZnCl is not generated in the preparation process of the positive plate2Activating and keeping the rest conditions unchanged. The voltage window of the supercapacitor prepared in comparative example 1 was 1.7V. The corresponding specific capacitance and energy density were 77.2F/g and 30.1Wh/kg, respectively.
Comparative example 2
The difference from the embodiment 1 is that the positive plate in the fourth step adopts nitrogen-doped carbon hollow microspheres, and the other conditions are not changed. The voltage window of the supercapacitor prepared in comparative example 2 was 1.5V. The corresponding specific capacitance and energy density were 70.3F/g and 32Wh/kg, respectively.
Comparative example 3
The difference from the example 1 is that in the fourth step, the commercially available activated carbon is used as the negative electrode material, and the rest materials are unchanged. The voltage window of the supercapacitor prepared in comparative example 3 was 1.4V. The corresponding specific capacitance and energy density were 71.9F/g and 29.9Wh/kg, respectively.
Comparative example 4
The difference from the embodiment 1 is that the electrolyte in the fourth step adopts 3mol/L KOH aqueous solution, the other conditions are not changed, and the voltage window of the finally obtained super capacitor is 1.4V. The corresponding specific capacitance and energy density can reach 95.1F/g and 26.1Wh/kg respectively.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (8)

1. A preparation method of an organic/inorganic composite super capacitor is characterized by comprising the following steps:
s1, preparing a positive plate;
s2, preparing a negative plate;
s3, preparing a PVA/KOH gel solution;
s4, bonding one surface of the positive plate and one surface of the negative plate through PVA/KOH gel solution, and then respectively bonding one PET substrate on the other surface of the positive plate and the other surface of the negative plate through PVA/KOH gel solution to form the organic/inorganic composite super capacitor;
the preparation method of the positive plate comprises the following steps:
after absolute ethyl alcohol, ammonia water and distilled water are mixed evenly, tetraethyl orthosilicate is added, and after reaction, SiO is obtained through centrifugation and washing2Microspheres;
subjecting the SiO2Adding the microspheres into a mixed solution of ethylenediamine and carbon tetrachloride, uniformly dispersing, performing reflux reaction at 80-100 ℃, filtering, washing and drying a product, and soaking the product in a zinc chloride solution for activation;
heating the activated product to 600-800 ℃ at the speed of 10-15 ℃/min under the protection of nitrogen, and reacting to obtain nitrogen-doped carbon @ SiO2Microspheres;
the nitrogen is doped with carbon @ SiO2Mixed solution of hydrofluoric acid and ammonium fluoride for microspheresSoaking and removing SiO2Obtaining nitrogen-doped carbon hollow microspheres;
uniformly mixing the nitrogen-doped carbon hollow microspheres with aniline, p-phenylenediamine, hydrochloric acid and sodium dodecyl sulfate, then dropwise adding an ammonium persulfate solution, and reacting at the temperature of 2-5 ℃ to obtain a nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound;
mixing the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer compound, acetylene black and PTFE in absolute ethyl alcohol, performing ultrasonic dispersion, coating on the surface of foamed nickel, drying, and tabletting to obtain the positive plate;
the preparation method of the negative plate comprises the following steps:
dissolving polyacrylonitrile and tetrabutyl titanate in an N, N' -dimethylformamide/glacial acetic acid mixed solvent, and stirring and dissolving at 50 ℃ to obtain a precursor solution;
freezing the precursor solution at-40 to-20 ℃ for 120-160 min, putting the precursor solution into distilled water to remove the solvent, and freeze-drying to obtain PAN/TiO2A nanofiber;
mixing the PAN/TiO2Under the protection of argon, heating the nano-fibers from normal temperature to 250-300 ℃, preserving heat for 120-150 min, heating the nano-fibers from 250-300 ℃ to 1000-1200 ℃, preserving heat for 120-180 min, introducing chlorine, reacting for 120-180 min, introducing argon after the reaction is finished, and naturally cooling to normal temperature to obtain the nano-porous carbon fibers;
mixing the nano-pore carbon fiber, acetylene black and PTFE in absolute ethyl alcohol, uniformly dispersing, coating on foamed nickel, drying at 60 ℃ in vacuum for 6 hours, and then pressing under the pressure of 10MPa to obtain the negative plate.
2. The method for preparing the organic/inorganic composite supercapacitor according to claim 1, wherein the SiO is2The mass ratio of the microspheres to the ethylenediamine to the carbon tetrachloride is (0.5-1): (1-2): (10-20).
3. The method for preparing the organic/inorganic composite supercapacitor according to claim 1, wherein the concentration of the zinc chloride solution is 2 to 3 mol/L.
4. The method for preparing the organic/inorganic composite supercapacitor according to claim 1, wherein the mass ratio of the nitrogen-doped carbon hollow microsphere to the aniline to the p-phenylenediamine is (1-1.5): (1-2): (0.05-0.1).
5. The method for preparing the organic/inorganic composite supercapacitor according to claim 1, wherein the mass ratio of the nitrogen-doped carbon hollow microsphere/polyaniline-p-phenylenediamine copolymer composite, acetylene black and PTFE is 8: 1: 1.
6. the method for preparing the organic/inorganic composite supercapacitor according to claim 1, wherein the mass ratio of the nanoporous carbon fibers, the acetylene black and the PTFE is 8: 1: 1.
7. the method for preparing the organic/inorganic composite supercapacitor according to claim 1, wherein the method for preparing the PVA/KOH gel solution comprises:
dissolving polyvinyl alcohol in distilled water, adding KOH aqueous solution, and dissolving by magnetic stirring to obtain PVA/KOH gel solution.
8. The method for preparing the organic/inorganic composite supercapacitor according to claim 7, wherein in the PVA/KOH gel solution, the mass concentration of PVA is 3 to 6%, and the mass concentration of KOH is 8 to 10%.
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