CN111292967B - Preparation method of all-solid-state supercapacitor positive electrode material - Google Patents
Preparation method of all-solid-state supercapacitor positive electrode material Download PDFInfo
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- CN111292967B CN111292967B CN202010096075.XA CN202010096075A CN111292967B CN 111292967 B CN111292967 B CN 111292967B CN 202010096075 A CN202010096075 A CN 202010096075A CN 111292967 B CN111292967 B CN 111292967B
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- polyaniline
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 156
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 86
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- 238000001035 drying Methods 0.000 claims abstract description 23
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- 238000001914 filtration Methods 0.000 claims abstract description 18
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of an all-solid-state supercapacitor positive electrode material, which comprises the steps of performing surface modification on hollow mesoporous silica spheres, adding the hollow mesoporous silica spheres into a hydrochloric acid solution, stirring the mixture into a uniform mixed solution, moving the mixed solution into an ice bath kettle, stirring the mixed solution, slowly adding ammonium persulfate, adding the obtained composite material into a potassium permanganate solution, stirring the mixture, slowly dropwise adding concentrated sulfuric acid, heating and stirring the mixture for 1 to 1.5 times, and finally filtering, washing and drying the mixture to obtain the electrode material. The advantages are that: the manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material has a sandwich structure, and the structure clamps polyaniline between the manganese dioxide and the hollow mesoporous silica; the composite material has the advantages of higher specific surface area, larger pore diameter, higher capacitance, lower internal resistance and excellent cycling stability.
Description
Technical Field
The invention belongs to the field of energy materials, and particularly relates to a preparation method of a manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor positive electrode material.
Background
A supercapacitor is a new type of electrochemical energy storage device between a conventional rechargeable battery and a conventional electrostatic capacitor. It has a greater energy density than a conventional electrostatic capacitor, a greater power density than a conventional rechargeable battery, and a shorter charging time, a higher charging efficiency, and a greater number of cycles of the supercapacitor. Therefore, the super capacitor is a novel chemical power source capable of high-power charging and discharging.
Supercapacitors can be divided into three categories according to different energy storage mechanisms: electric double layer capacitors, faraday pseudocapacitors, and hybrid capacitors. Among them, the electric double layer capacitor is a device that stores energy using an electric double layer formed between an electrode and an electrolyte, i.e., electrostatic charges on the surface of the electrode can adsorb oppositely charged ions in the electrolyte to form an electric double layer having opposite charges. The charge and discharge of the double electric layer capacitor are physical processes, the performance is stable, and the cycle life is long. The Faraday pseudocapacitance is that on the two-dimensional or quasi-two-dimensional space of electrode surface or body phase, the electroactivity substance is undergone the process of underpotential deposition so as to produce high reversible chemical adsorption/desorption or oxidation/reduction reaction and produce capacitance related to electrode charging potential. The process of storing charges by the faraday pseudocapacitance includes not only storage on an electric double layer but also storage of charges in an electrode by redox reaction of ions in an electrolyte in an electrode active material. The hybrid capacitor is an energy storage device between a super capacitor and a secondary battery, namely, one electrode adopts a traditional battery electrode and stores and converts energy through electrochemical reaction; while the other pole stores energy through an electric double layer, primarily as a power source. The combination of the two can generate higher working voltage, so that the energy density of the hybrid capacitor is far greater than that of the double-electric-layer capacitor, and the energy storage mechanisms of the anode and the cathode are different in the charging and discharging process, so that the hybrid capacitor has double characteristics. The hybrid capacitor has the performance advantages of large energy density, high power density, high charge-discharge rate, long service life and the like.
The electrolyte can be divided into two categories, namely an aqueous supercapacitor and an organic supercapacitor, according to the type of the electrolyte. Further, there may be classified into a symmetrical supercapacitor and an asymmetrical supercapacitor according to whether the types of active materials are the same. Finally, the electrolyte can be classified into a solid electrolyte supercapacitor and a liquid electrolyte supercapacitor according to the state of the electrolyte.
According to the energy storage principle of the super capacitor, the energy storage of the capacitor mainly depends on the electrode material, so that it is very important to further develop the electrode material with high capacity and good performance. At present, there are three main categories of supercapacitors: conductive polymer materials (polyaniline, polypyrrole, polythiophene, and the like), metal oxide materials (manganese dioxide, nickel oxide, and cobalt oxide), and carbon-based materials (porous carbon, carbon nanotubes, graphene, and the like).
Among these materials, the conductive polymer has the advantages of higher working voltage, lighter weight, good corrosion resistance, good electron transport capability, good plasticity, easy processing, low cost, environmental friendliness and the like. However, polyaniline causes volume expansion and contraction during charging and discharging, so that the cycling stability of the material is poor. Currently, in order to improve the problem, many researchers compound polyaniline and a carbon material to prepare a supercapacitor electrode material. For example, chinese patent publication No. CN108010750A discloses a method for preparing an ultra-thin wall multi-stage porous carbon/polyaniline supercapacitor electrode material, which comprises using pitch and an additive as raw materials, adding a certain amount of styrene to mix, and placing into an atmosphere furnace for carbonization to obtain the ultra-thin wall multi-stage porous carbon; and then adding the porous carbon into an ethanol solution for ultrasonic dispersion, moving the porous carbon into a constant-temperature low-temperature reaction bath, adding an ammonium persulfate solution into the mixed solution, and finally washing with water, washing with alcohol and drying to obtain the ultrathin-wall multistage porous carbon/polyaniline compound. The preparation method of the polyaniline graft modified silicon dioxide composite electrode material for the supercapacitor, which is disclosed in the Chinese patent publication No. CN106565971A, comprises the steps of dispersing nano-silica in a hydroxylation solution in a novel stirring manner to prepare hydroxyl-rich nano-silica; dispersing modified nano silicon dioxide containing active reaction groups in an acidic aqueous solution, and adding aniline after ultrasonic dispersion. Dispersing an oxidant in an acidic aqueous solution, refrigerating, dropwise adding the mixture into a mixed solution of aniline and modified nano-silica containing active reaction groups, washing the mixed solution with water and absolute ethyl alcohol once until filtrate is colorless, and drying in vacuum to obtain the composite electrode material for the supercapacitor. Chinese patent publication No. CN102924715A discloses a method for preparing a double-mesoporous ordered mesoporous carbon/polyaniline nanowire, which comprises the steps of using ordered mesoporous carbon with silica nanoparticles embedded on the carbon wall as a carrier, growing a polyaniline nanowire array from the inside to the outside of a pore channel of the carbon by a chemical oxidation polymerization method, and finally removing the silica by hydrofluoric acid to obtain the double-mesoporous ordered mesoporous carbon/polyaniline nanowire hierarchical composite material. Polyaniline is widely applied to electrode materials of super capacitors due to the advantages of good conductivity, high electrochemical activity, easiness in synthesis and the like, however, mechanical degradation and electrochemical performance attenuation of electrodes are caused due to volume expansion and contraction in the charging and discharging processes, so that the application of polyaniline in super capacitors is limited, and the cycle life is shortened. If the technical problem of volume expansion and contraction of polyaniline in the charging and discharging process can be solved, the cycle life of the polyaniline can be greatly prolonged. Therefore, the preparation of the polyaniline supercapacitor electrode composite material with high specific capacity and high cycling stability is extremely important.
Manganese dioxide has rich resources, low cost and high specific capacitance (1370F g)-1) And the like, but the lattice structure is unstable in the electrochemical reaction process, so that the performance of the material is deteriorated, the continuous exertion of the electrochemical performance of the material is influenced, and in addition, the specific capacitance of the material in practical application is far lower than the theoretical capacity due to the poor conductivity of the material. In order to improve the above problems, some researchers have tried to prepare an electrode material by compounding manganese dioxide with a carbon-based material. For example, the preparation method of the enteromorpha activated carbon composite manganese dioxide supercapacitor electrode material disclosed in chinese patent publication No. CN108400018A includes carbonizing enteromorpha at high temperature to obtain enteromorpha carbon, mixing the obtained enteromorpha carbon with potassium permanganate and sulfuric acid to perform chemical wet heat reaction, and finally washing, suction filtering and drying to obtain the composite material. The preparation method of the ordered mesoporous carbon loaded manganese dioxide shell-core nanobelt for the electrode material of the supercapacitor, which is disclosed in the Chinese patent publication No. CN110136977A, comprises the steps of taking an ordered mesoporous molecular sieve as a template, filling carbon, carbonizing and removing the template to obtain the mesoporous carbon molecular sieve with ordered internal pore channels, and finally taking the molecular sieve as a raw material to construct the carbon loaded manganese dioxide shell-core type material in situ.
The preparation method for loading polyaniline and manganese dioxide on the surface of the carbon material or the nano silicon dioxide is simple, green and environment-friendly. The prepared composite material has higher specific capacity and energy density and is widely applied to the fields of electronic products, electric bicycles, electric automobiles and the like. However, the bonding force between manganese dioxide and carbon and the bonding force between polyaniline and carbon are weak, and the polyaniline and carbon are easy to fall off in the long-term charge and discharge process, so that the cycle stability is reduced; meanwhile, the specific capacitance of the carbon material is low, and some carbon materials such as carbon nanotubes and graphene also have the problems of high cost, complex preparation process and the like. And the traditional solid nano silicon dioxide material has low specific surface area, extremely high resistivity, is not beneficial to charge transmission and storage, has weak binding force with polyaniline, and seriously influences the stability of the material. Therefore, the method has the advantages of simple preparation method, low cost, stable structure and large specific surface area, and is of great significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor positive electrode material with high specific capacity and excellent cycle performance.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of an all-solid-state supercapacitor positive electrode material comprises the following steps:
1) carrying out surface modification on the hollow mesoporous silica spheres:
adding hollow mesoporous silica spheres into a toluene solution containing 3-aminopropyltriethoxysilane, performing ultrasonic treatment for 30-50 minutes, performing reflux treatment for 6-8 hours, washing the mixed solution after the reflux treatment, and drying to obtain modified hollow mesoporous silica spheres;
2) preparing a polyaniline/hollow mesoporous silica sphere composite material:
adding the modified hollow mesoporous silica spheres and aniline monomer into a hydrochloric acid solution, stirring to obtain a uniform mixed solution, transferring the mixed solution into an ice bath kettle, stirring for 10-12 hours, slowly adding ammonium persulfate, continuously stirring for 20-24 hours, filtering, washing with deionized water and absolute ethyl alcohol, and drying;
3) preparing a manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material:
adding the prepared polyaniline/hollow mesoporous silica sphere composite material into a potassium permanganate aqueous solution, uniformly stirring, slowly dropwise adding concentrated sulfuric acid to control the pH value to be 2-5, heating the mixed solution to 80-90 ℃, continuously stirring for 1-1.5 hours, and finally filtering, washing and drying to obtain the electrode material.
The mass ratio of the hollow mesoporous silica spheres in the step 1) to the 3-aminopropyltriethoxysilane is 2.2-3.8, the toluene solution concentration of the 3-aminopropyltriethoxysilane is 0.07-0.1mol/L, and the reflux temperature is 95-120 ℃.
3. The method for preparing the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the ultrasonic power in the step 1) is 750-900W.
The molar ratio of the aniline monomer to the ammonium persulfate in the step 2) is (0.8-1.2): (1-1.5); the modified hollow mesoporous silica spheres and the aniline monomer have a mass ratio of (0.8-1.6): (1.6-3.6); the concentration of the hydrochloric acid solution is 0.8-1.2 mol/L; the dropping speed of the ammonium persulfate is 0.03-0.08 mL/min.
The stirring speed in the step 2) is 800-.
The mass ratio of the potassium permanganate to the polyaniline/hollow mesoporous silica sphere composite material in the step 3) is (20-25): (0.8-1.5).
The stirring speed in the step 3) is 500-800 rpm.
The manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material obtained in the step 3) is used as an asymmetric all-solid-state supercapacitor positive electrode material:
uniformly mixing a manganese dioxide/polyaniline/hollow mesoporous silica ball composite material with acetylene black and polyvinylidene fluoride, dispersing the mixture in 1-methyl 2-pyrrolidone, and stirring for 2-6 hours to form stable suspension; and coating the suspension on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, and performing vacuum drying at 40-80 ℃ for 8-12 hours to obtain the positive electrode plate of the supercapacitor.
The mass ratio of the manganese dioxide/polyaniline/hollow mesoporous silica ball composite material to the acetylene black and the polyvinylidene fluoride is (7.5-8.5): (0.8-1.2): (0.8-1.2); the mass ratio of the 1-methyl 2-pyrrolidone to the manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material is (7.5-8.5): (0.8-1.2); the thickness of the mixture coated on the nickel foam was 300-600 μm.
Coating commercial activated carbon on (1.4-1.8) cm multiplied by (1.4-1.8) cm of foamed nickel, drying for 8-12 hours in vacuum at 40-80 ℃ to obtain a super capacitor negative electrode plate, assembling an asymmetric all-solid-state super capacitor by using a super capacitor positive electrode plate prepared by using a manganese dioxide/polyaniline/hollow mesoporous silica ball composite material as a raw material and using polyvinyl alcohol-potassium hydroxide gel as a working electrolyte, and performing electrochemical energy storage application.
Compared with the prior art, the invention has the beneficial effects that:
the manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material prepared by the simple chemical method has a sandwich structure, and the structure is used for clamping polyaniline between the manganese dioxide and the hollow mesoporous silica; the composite material has the advantages of high specific surface area, large aperture, high capacitance, low internal resistance and excellent cycling stability, and the capacitance preservation rate of an electrode plate prepared from the composite material is up to 113.0 percent after 3000 cycling stability tests; when the composite material is assembled into an all-solid-state asymmetric supercapacitor, the capacitance value is only reduced by 0.2% after 5000 times of cycle stability tests compared with that before the tests, and meanwhile, the supercapacitor has higher energy density and power density.
The hollow mesoporous silica spheres can provide carriers for polyaniline and manganese dioxide, can effectively improve the agglomeration phenomenon of the polyaniline and the manganese dioxide, can well improve the structural collapse phenomenon of the polyaniline in the charging and discharging processes, and can fully play the synergistic effect of the polyaniline and the manganese dioxide, so that the specific capacitance of the composite material is further improved, and the cycle stability of the composite material is increased. The electric quantity, the circulation stability, the energy density and the power density of the super capacitor are greatly improved, and the requirements of people in daily life can be met.
The manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material prepared by the invention has the following advantages:
1. has better conductivity, higher specific surface area, higher specific capacitance and excellent cycling stability.
2. The method has the advantages of simple and efficient synthesis method, low cost, high sample yield and the like, and has good application prospect.
3. Under the current density of 4A/g, the specific capacitance reaches 428.6F/g and the good cycle stability is that the specific capacitance reaches 485.7F/g after 3000-cycle constant current charging and discharging, and the specific capacitance retention rate is 113.0%.
The manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material prepared by the invention is used as a positive electrode material, commercial activated carbon is used as a negative electrode material, polyvinyl alcohol-potassium hydroxide gel is used as a working electrolyte to assemble the asymmetric all-solid-state supercapacitor, the voltage window is up to 1.6V, and the specific capacitance is up to 248.5F/g under the current density of 1A/g; when the power density is 800W/kg, the energy density is 88.4 Wh/kg; even when the power density is 8.0kW/kg, the energy density is still as high as 24.4 Wh/kg; and after 5000 cycles of charge and discharge at the current density of 1A/g, the capacity of the lithium ion battery still keeps 97.7 percent of the initial capacity.
Drawings
Fig. 1 is a scanning electron micrograph of a manganese dioxide/polyaniline/hollow mesoporous silica sphere composite.
FIG. 2 is a graph showing electrochemical performance test curves of an asymmetric all-solid-state supercapacitor
FIG. 2 (a) is a cyclic voltammogram of an asymmetric all-solid-state supercapacitor at different sweep rates with a voltage window of 0-1.6V; (b) the constant current charging and discharging curve diagram of the asymmetric all-solid-state super capacitor under different current densities is shown; (c) the capacity retention rate curve diagram of 5000 times of cyclic charge and discharge of the asymmetric all-solid-state supercapacitor under the current density of 4A/g; (d) is a power density versus energy density graph of an asymmetric all-solid-state supercapacitor.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
The preparation method of the all-solid-state supercapacitor positive electrode material comprises the following steps:
A) 0.9g of hollow mesoporous silica spheres and 0.4g of 3-aminopropyltriethoxysilane are dissolved in 25mL of toluene, the mixed solution is subjected to ultrasonic treatment for 30 minutes at the ultrasonic power of 800W, then the mixed solution is refluxed at 110 ℃ for 6 hours, and the reflux treatment is that the mixed solution is filled into a three-neck flask with a condensing device and then is placed into an oil bath pot for heating. And finally filtering, washing and drying.
B) And B), dissolving 0.3g of the hollow mesoporous silica spheres treated in the step A) and 0.6g of aniline monomer in 240mL of hydrochloric acid solution with the concentration of 1mol/L, stirring to obtain a uniform mixed solution, moving the mixed solution to an ice bath kettle, stirring for 10 hours at the stirring speed of 850rpm, slowly dropwise adding 200mL of aqueous solution containing 1.47g of ammonium persulfate into the mixed solution at the dropwise adding speed of 0.05mL/min, and continuously stirring the mixed solution in an ice bath at the same stirring speed for 24 hours. And finally, filtering, washing and drying to obtain the polyaniline/hollow mesoporous silica sphere composite material.
C) And B), dissolving 0.1g of the polyaniline/hollow mesoporous silica sphere composite material obtained in the step B) and 2.5g of potassium permanganate in 100mL of deionized water, stirring for 10 minutes at the stirring speed of 650rpm, then dropwise adding a small amount of sulfuric acid into the mixed solution, controlling the pH value of a reaction system to be 3.8-4.2, then transferring the mixed solution into a water bath kettle at the temperature of 80 ℃, continuously stirring for 1 hour at the stirring speed of 650rpm, and finally filtering, washing and drying to obtain the manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor anode material.
D) Taking 0.08g of the manganese dioxide/polyaniline/hollow mesoporous silica ball composite material obtained in the step C), 0.01g of acetylene black and 0.01g of polyvinylidene fluoride to be dissolved in 0.8g of 1-methyl 2-pyrrolidone to form uniform suspension, then coating the suspension on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, controlling the thickness of the mixture coated on the foamed nickel to be 600 mu m, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the positive pole piece of the supercapacitor; coating 0.08g of commercial activated carbon on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, and performing vacuum drying at 40-80 ℃ for 8-12 hours to obtain a cathode piece of the supercapacitor; and finally assembling the positive pole piece, the negative pole piece and the polyvinyl alcohol-potassium hydroxide gel working electrolyte into the asymmetric all-solid-state supercapacitor.
Example 2
The preparation method of the all-solid-state supercapacitor positive electrode material comprises the following steps:
A) dissolving 1.8g of hollow mesoporous silica spheres and 0.8g of 3-aminopropyltriethoxysilane in 50mL of toluene, carrying out ultrasonic treatment on the mixed solution for 30 minutes at the ultrasonic power of 800W, refluxing the mixed solution at 110 ℃ for 6 hours, and finally filtering, washing and drying.
B) And B), dissolving 0.6g of the hollow mesoporous silica spheres treated in the step A) and 1.2g of aniline monomer in 480mL of 1mol/L hydrochloric acid solution, stirring to obtain a uniform mixed solution, moving the mixed solution to an ice bath kettle, stirring for 10 hours at the stirring speed of 850rpm, slowly dropwise adding 200mL of an aqueous solution containing 2.94g of ammonium persulfate into the mixed solution at the dropwise adding speed of 0.05mL/min, and continuously stirring the mixed solution in an ice bath at the same stirring speed for 24 hours. And finally, filtering, washing and drying to obtain the polyaniline/hollow mesoporous silica sphere composite material.
C) And B), dissolving 0.2g of the polyaniline/hollow mesoporous silica sphere composite material obtained in the step B) and 5.0g of potassium permanganate in 200mL of deionized water, stirring for 10 minutes at the stirring speed of 650rpm, then dropwise adding a small amount of sulfuric acid into the mixed solution, controlling the pH value of a reaction system to be about 4, then transferring the mixed solution into a water bath kettle at the temperature of 80 ℃, continuously stirring for 1 hour at the stirring speed of 650rpm, and finally filtering, washing and drying to obtain the manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor anode material.
D) Taking 0.08g of the manganese dioxide/polyaniline/hollow mesoporous silica ball composite material obtained in the step C), 0.01g of acetylene black and 0.01g of polyvinylidene fluoride to be dissolved in 0.8g of 1-methyl 2-pyrrolidone to form uniform suspension, then coating the suspension on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, controlling the thickness of the mixture coated on the foamed nickel to be 600 mu m, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the positive pole piece of the supercapacitor; coating 0.08g of commercial activated carbon on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, and performing vacuum drying at 40-80 ℃ for 8-12 hours to obtain a cathode piece of the supercapacitor; and finally assembling the positive pole piece, the negative pole piece and the polyvinyl alcohol-potassium hydroxide gel working electrolyte into the asymmetric all-solid-state supercapacitor.
Example 3
A) Dissolving 0.9g of hollow mesoporous silica spheres and 0.4g of 3-aminopropyltriethoxysilane in 25mL of toluene, carrying out ultrasonic treatment on the mixed solution for 30 minutes at the ultrasonic power of 800W, refluxing the mixed solution at 110 ℃ for 6 hours, and finally filtering, washing and drying.
B) And B), dissolving 0.3g of the hollow mesoporous silica spheres treated in the step A) and 0.6g of aniline monomer in 240mL of hydrochloric acid solution with the concentration of 1mol/L, stirring to obtain a uniform mixed solution, moving the mixed solution to an ice bath kettle, stirring for 10 hours at the stirring speed of 900rpm, slowly dropwise adding 200mL of aqueous solution containing 1.47g of ammonium persulfate into the mixed solution at the dropwise adding speed of 0.05mL/min, and continuously stirring the mixed solution in an ice bath at the same stirring speed for 24 hours. And finally, filtering, washing and drying to obtain the polyaniline/hollow mesoporous silica sphere composite material.
C) And B), dissolving 0.1g of the polyaniline/hollow mesoporous silica sphere composite material obtained in the step B) and 2.5g of potassium permanganate in 100mL of deionized water, stirring for 10 minutes at the stirring speed of 700rpm, then dropwise adding a small amount of sulfuric acid into the mixed solution, controlling the pH value of a reaction system to be about 4.5, then transferring the mixed solution into a water bath kettle at the temperature of 80 ℃, continuously stirring for 1 hour at the stirring speed of 700rpm, and finally filtering, washing and drying to obtain the manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor anode material.
D) Taking 0.08g of the manganese dioxide/polyaniline/hollow mesoporous silica ball composite material obtained in the step C), 0.01g of acetylene black and 0.01g of polyvinylidene fluoride to be dissolved in 0.8g of 1-methyl 2-pyrrolidone to form uniform suspension, then coating the suspension on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, controlling the thickness of the mixture coated on the foamed nickel to be 600 mu m, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the positive pole piece of the supercapacitor; coating 0.08g of commercial activated carbon on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, and performing vacuum drying at 40-80 ℃ for 8-12 hours to obtain a cathode piece of the supercapacitor; and finally assembling the positive pole piece, the negative pole piece and the polyvinyl alcohol-potassium hydroxide gel working electrolyte into the asymmetric all-solid-state supercapacitor.
Example 4
A) Dissolving 1.8g of hollow mesoporous silica spheres and 0.8g of 3-aminopropyltriethoxysilane in 50mL of toluene, carrying out ultrasonic treatment on the mixed solution for 30 minutes at the ultrasonic power of 800W, refluxing the mixed solution at 110 ℃ for 6 hours, and finally filtering, washing and drying.
B) And B), dissolving 0.6g of the hollow mesoporous silica spheres treated in the step A) and 1.2g of aniline monomer in 480mL of 1mol/L hydrochloric acid solution, stirring to obtain a uniform mixed solution, moving the mixed solution to an ice bath kettle, stirring for 10 hours at the stirring speed of 950rpm, slowly dropwise adding 200mL of an aqueous solution containing 2.94g of ammonium persulfate into the mixed solution at the dropwise adding speed of 0.05mL/min, and continuously stirring the mixed solution in an ice bath at the same stirring speed for 24 hours. And finally, filtering, washing and drying to obtain the polyaniline/hollow mesoporous silica sphere composite material.
C) And B), dissolving 0.2g of the polyaniline/hollow mesoporous silica sphere composite material obtained in the step B) and 5.0g of potassium permanganate in 200mL of deionized water, stirring for 10 minutes at the stirring speed of 750rpm, then dropwise adding a small amount of sulfuric acid into the mixed solution, controlling the pH value of a reaction system to be about 3.5, then transferring the mixed solution into a water bath kettle at the temperature of 80 ℃, continuously stirring for 1 hour at the stirring speed of 750rpm, and finally filtering, washing and drying to obtain the manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor anode material.
D) Taking 0.08g of the manganese dioxide/polyaniline/hollow mesoporous silica ball composite material obtained in the step C), 0.01g of acetylene black and 0.01g of polyvinylidene fluoride to be dissolved in 0.8g of 1-methyl 2-pyrrolidone to form uniform suspension, then coating the suspension on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, controlling the thickness of the mixture coated on the foamed nickel to be 600 mu m, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the positive pole piece of the supercapacitor; coating 0.08g of commercial activated carbon on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, and performing vacuum drying at 40-80 ℃ for 8-12 hours to obtain a cathode piece of the supercapacitor; and finally assembling the positive pole piece, the negative pole piece and the polyvinyl alcohol-potassium hydroxide gel working electrolyte into the asymmetric all-solid-state supercapacitor.
According to the invention, the hollow mesoporous silica spheres are used as a substrate material, the hollow mesoporous silica spheres have the characteristics of larger hollow cavity, controllable outer layer mesoporous structure, large specific surface area and the like, and then polyaniline and manganese dioxide are sequentially coated on the hollow mesoporous silica spheres respectively to prepare the manganese dioxide/polyaniline/hollow mesoporous silica sphere asymmetric all-solid-state supercapacitor anode material. The sandwich structure with the polyaniline in the middle can well inhibit the collapse of the super capacitor due to the volume expansion structure in the charging and discharging process, so that the electric quantity, the circulation stability, the energy density and the power density of the super capacitor are greatly improved, and the requirements of people in daily life can be met.
Claims (10)
1. The preparation method of the all-solid-state supercapacitor positive electrode material is characterized in that the all-solid-state supercapacitor positive electrode material has a sandwich structure, and polyaniline is sandwiched between manganese dioxide and hollow mesoporous silica spheres; the preparation method comprises the following steps:
1) carrying out surface modification on the hollow mesoporous silica spheres:
adding hollow mesoporous silica spheres into a toluene solution containing 3-aminopropyltriethoxysilane, performing ultrasonic treatment for 30-50 minutes, performing reflux treatment for 6-8 hours, washing the mixed solution after the reflux treatment, and drying to obtain modified hollow mesoporous silica spheres;
2) preparing a polyaniline/hollow mesoporous silica sphere composite material:
adding the modified hollow mesoporous silica spheres and aniline monomer into a hydrochloric acid solution, stirring to obtain a uniform mixed solution, transferring the mixed solution into an ice bath kettle, stirring for 10-12 hours, slowly adding ammonium persulfate, continuously stirring for 20-24 hours, filtering, washing with deionized water and absolute ethyl alcohol, and drying;
3) preparing a manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material:
adding the prepared polyaniline/hollow mesoporous silica sphere composite material into a potassium permanganate aqueous solution, uniformly stirring, slowly dropwise adding concentrated sulfuric acid to control the pH value to be 2-5, heating the mixed solution to 80-90 ℃, continuously stirring for 1-1.5 hours, and finally filtering, washing and drying to obtain the electrode material.
2. The preparation method of the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the mass ratio of the hollow mesoporous silica spheres and the 3-aminopropyltriethoxysilane in the step 1) is 2.2-3.8, the toluene solution concentration of the 3-aminopropyltriethoxysilane is 0.07-0.1mol/L, and the reflux temperature is 95-120 ℃.
3. The method for preparing the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the ultrasonic power in the step 1) is 750-900W.
4. The preparation method of the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the molar ratio of the aniline monomer to the ammonium persulfate in the step 2) is (0.8-1.2): (1-1.5); the modified hollow mesoporous silica spheres and the aniline monomer have a mass ratio of (0.8-1.6): (1.6-3.6); the concentration of the hydrochloric acid solution is 0.8-1.2 mol/L; the dropping speed of the ammonium persulfate is 0.03-0.08 mL/min.
5. The method for preparing the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the stirring speed in the step 2) is 800-1500 rpm.
6. The preparation method of the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the mass ratio of the potassium permanganate to the polyaniline/hollow mesoporous silica sphere composite material in the step 3) is (20-25): (0.8-1.5).
7. The method as claimed in claim 1, wherein the stirring speed in step 3) is 500-800 rpm.
8. The preparation method of the all-solid-state supercapacitor positive electrode material according to claim 1, wherein the manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material obtained in the step 3) is used as an asymmetric all-solid-state supercapacitor positive electrode material:
uniformly mixing a manganese dioxide/polyaniline/hollow mesoporous silica ball composite material with acetylene black and polyvinylidene fluoride, dispersing the mixture in 1-methyl-2-pyrrolidone, and stirring for 2-6 hours to form stable suspension; and coating the suspension on (1.4-1.8) cm x (1.4-1.8) cm of foamed nickel, and performing vacuum drying at 40-80 ℃ for 8-12 hours to obtain the positive electrode plate of the supercapacitor.
9. The preparation method of the all-solid-state supercapacitor positive electrode material according to claim 8, wherein the mass ratio of the manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material to acetylene black and polyvinylidene fluoride is (7.5-8.5): (0.8-1.2): (0.8-1.2); the mass ratio of the 1-methyl-2-pyrrolidone to the manganese dioxide/polyaniline/hollow mesoporous silica sphere composite material is (7.5-8.5): (0.8-1.2); the thickness of the mixture coated on the nickel foam was 300-600 μm.
10. The preparation method of the all-solid-state supercapacitor positive electrode material according to claim 8, characterized in that commercial activated carbon is coated on (1.4-1.8) cm x (1.4-1.8) cm of nickel foam, vacuum drying is carried out for 8-12 hours at 40-80 ℃ to obtain a supercapacitor negative electrode plate, a supercapacitor positive electrode prepared by taking manganese dioxide/polyaniline/hollow mesoporous silica ball composite material as a raw material is assembled into an asymmetric all-solid-state supercapacitor by taking polyvinyl alcohol-potassium hydroxide gel as a working electrolyte, and electrochemical energy storage application is carried out.
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