CN111463019B - Preparation method of core-shell structure electrode material - Google Patents
Preparation method of core-shell structure electrode material Download PDFInfo
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- CN111463019B CN111463019B CN202010290809.8A CN202010290809A CN111463019B CN 111463019 B CN111463019 B CN 111463019B CN 202010290809 A CN202010290809 A CN 202010290809A CN 111463019 B CN111463019 B CN 111463019B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000007772 electrode material Substances 0.000 title claims abstract description 39
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- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
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- 238000002156 mixing Methods 0.000 claims description 15
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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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
- H01G11/84—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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- 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
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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
本发明提供了一种核‑壳结构电极材料的制备方法，其包括如下步骤：一、SiO2纳米纤维的制备；二、微孔碳纳米管的制备；三、氮掺杂微孔碳纳米管的制备；四、氮掺杂微孔碳纳米管@聚苯胺核‑壳结构的制备；五、核‑壳结构电极材料的制备。微孔碳纳米管和聚苯胺提高了电极的比表面面积、导电性和比电容，大大提高电极的能量密度和循环使用次数。
The invention provides a preparation method of a core-shell structure electrode material, which comprises the following steps: 1. preparation of SiO2 nanofibers; 2. preparation of microporous carbon nanotubes; 3. nitrogen-doped microporous carbon nanotubes 4. Preparation of nitrogen-doped microporous carbon nanotubes@polyaniline core-shell structure; 5. Preparation of core-shell structure electrode material. Microporous carbon nanotubes and polyaniline improve the specific surface area, electrical conductivity and specific capacitance of the electrode, and greatly improve the energy density and cycle times of the electrode.
Description
Technical Field
The invention relates to a preparation method of a novel core-shell structure electrode material, belonging to the field of electrochemistry and inorganic materials.
Background
The structural performance of the electrode material plays a decisive role in various technical indexes of the super capacitor. Carbon materials have relatively low energy density as electrodes of electric double layer capacitors compared to other electrode materials, and cannot meet practical requirements. In order to increase the specific capacitance of the carbon material, the energy density and the power density of the carbon material are mainly increased by increasing the specific surface area of the carbon material, introducing heteroatoms, compounding with transition metal compounds or polymers and the like.
The increase in specific surface area is mainly to increase wettability between the electrolyte and the active material. Therefore, the specific surface area is large (500-3000 m)2High porosity carbon materials per gram) are typical representatives of such electrode materials. Compared with other carbon materials, the carbon nano-fiber and the carbon nano-tube are prepared by the following stepsThe composite material has large length-diameter ratio and large specific surface area, so that the composite material can be widely applied to the fields of photocatalysis, gas sensing, solar cells, hydrogen storage, capacitor electrodes and the like. The carbon nano tube with large specific surface area is an ideal electrode material of the super capacitor. For example, Chen et al uses a chemical vapor deposition method to prepare a vertical carbon nanotube array on an alumina template, and a layer of gold foil is sputtered on the bottom of the carbon nanotube array after the template is removed to serve as an electrode of a supercapacitor. The specific capacitance of the electrode was found to be 365F/g and to have good cycling stability (Chen Q L, Xue K H, Shen W, et al, Electrochimica Acta,2004,49, 4157). The carbon nano tube is chemically modified or compounded with other materials, so that the electrochemical performance of the carbon nano tube can be greatly improved, and a foundation is provided for further researching a super capacitor electrode material with high energy density. Pint et al use a vertical single-walled Carbon nanotube array grown on a single-crystal silicon substrate as a template, transfer the array to a Cu conductive substrate using a titanium/gold layer as a binder, and then uniformly cover a nanoscale alumina dielectric layer on the Carbon nanotube array, which has both high power and high energy density, and can be further applied to ultra-lightweight energy storage devices such as microchips and flexible devices (Pint cl, Nicholas nw, Xu S, et al, Carbon,2011,49: 4890). However, no relevant literature reports exist about the preparation of carbon nanotubes by using the thermally induced phase separation method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a core-shell structure electrode material.
A preparation method of an electrode material with a core-shell structure comprises the following steps:
s1 preparation of SiO2A nanofiber;
s2 using the SiO2Preparing microporous carbon nano tubes by using nano fibers;
s3, preparing nitrogen-doped microporous carbon nanotubes by using the microporous carbon nanotubes;
s4, preparing a nitrogen-doped microporous carbon nanotube @ polyaniline core-shell material by using the nitrogen-doped microporous carbon nanotube;
s5, uniformly dispersing the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material, acetylene black and PTFE in absolute ethyl alcohol, coating the materials on foamed nickel, and performing vacuum drying and tabletting to obtain the core-shell structure electrode material;
the SiO2The preparation method of the nanofiber comprises the following steps:
dissolving polyvinyl butyral in a binary mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, dropwise adding tetraethyl orthosilicate, and uniformly mixing to obtain a quenching solution;
quenching the quenching solution at the temperature of between 40 ℃ below zero and 10 ℃ below zero, removing the N, N-dimethylformamide/dimethyl sulfoxide binary mixed solvent by using distilled water, washing and drying to obtain the polyvinyl butyral/SiO2Compounding nano fiber;
mixing the polyvinyl butyral/SiO2Calcining the composite nanofiber at 500-700 ℃ to obtain SiO2A nanofiber;
the preparation method of the microporous carbon nanotube comprises the following steps:
mixing SiO2Adding the nano-fibers and furfuryl alcohol into acetone, uniformly mixing, adding p-toluenesulfonic acid, magnetically stirring at normal temperature, and curing;
keeping the temperature of the cured product at 150 ℃, and calcining the cured product in a nitrogen atmosphere at 800-1500 ℃;
soaking the calcined product in sodium hydroxide ethanol solution for 12h, removing the silicon dioxide template, and finally drying to obtain the microporous carbon nanotube;
the preparation method of the nitrogen-doped microporous carbon nanotube comprises the following steps:
uniformly mixing the microporous carbon nanotube, aniline, hydrochloric acid and sodium dodecyl sulfate, dripping ammonium persulfate solution, and reacting at 0-5 ℃ to obtain a polyaniline/microporous carbon nanotube compound;
NH with the mass concentration of 0.5 percent is used for the polyaniline/microporous carbon nanotube compound4Activating, washing and drying the Cl solution to obtain an activated product;
under the protection of nitrogen, heating the activated product from 25 ℃ to 300 ℃, preserving heat for 2h, then heating from 300 ℃ to 1000 ℃, and preserving heat for 2h to obtain the nitrogen-doped microporous carbon nanotube;
the preparation method of the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell material comprises the following steps:
and uniformly mixing the nitrogen-doped microporous carbon nanotube, aniline, hydrochloric acid and sodium dodecyl sulfate, dripping ammonium persulfate solution, and reacting at the temperature of 2 ℃ to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell material.
Preferably, in the quenching solution, the mass concentration of the polyvinyl butyral is 4-6%, and the mass concentration of the tetraethyl orthosilicate is 0.4-0.8%.
Preferably, the SiO is2The mass ratio of the nano-fibers to the furfuryl alcohol is 1: (5-10).
As a preferred scheme, the mass ratio of the microporous carbon nanotube to the aniline is 1: (2-4).
As a preferred scheme, the mass ratio of the nitrogen-doped microporous carbon nanotube to the aniline is 1: (10-15).
As a preferred scheme, the mass ratio of the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material to the acetylene black to the PTFE is 8: 1: 1.
the basic principle of the invention is as follows:
1) PVB/SiO is obtained by taking polyvinyl butyral as a polymer template and tetraethoxysilane as a precursor through a thermally induced phase separation method2Compounding nanometer fiber, calcining to eliminate polymer template to obtain SiO2And (3) nano fibers.
2) With SiO2Polymerizing by taking nano-fiber as a template and furfuryl alcohol as a carbon source to obtain polyfurfuryl alcohol @ SiO2Carbonizing the nano-fiber under the protection of nitrogen to obtain microporous carbon @ SiO2Washing nano fiber to remove SiO template2Obtaining the microporous carbon nano tube.
3) The nitrogen-doped microporous carbon nanotube is obtained by using a microporous carbon nanotube as a matrix and aniline as a nitrogen source through polymerization, pre-oxidation and high-temperature carbonization in sequence.
4) And loading aniline on the surface of the carbon nano tube to obtain the nitrogen-doped microporous carbon nano tube @ polyaniline core-shell structure electrode material.
The invention has the beneficial effects that:
1) the core-shell structure is a microporous nano structure, so that the specific surface area is greatly improved, and the wettability between the electrolyte and the electrode material is improved;
2) the core-shell structure forms a three-dimensional interweaving net structure, which is beneficial to the rapid transmission of electrons and ions in the electrode material in the oxygen reduction process, and further improves the specific capacitance of the electrode material;
3) the doping of nitrogen element improves the active site of the carbon nano tube, so that the carbon nano tube can show better performance when oxygen is added;
4) in the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material, the microporous carbon nanotube provides a large specific surface area and good conductivity for an electrode, and the polyaniline provides a large specific capacitance for a composite fiber, so that the defect of a single carbon-based material is overcome. The specific capacitance and the recycling times of the electrode material are improved.
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 a preparation route of a core-shell structure electrode material prepared by the present invention.
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 preparation route of the preparation method of the core-shell structure electrode material provided by this embodiment is shown in fig. 1, and specifically includes the following steps:
SiO 22Preparation of nanofibers
1.8g of polyvinyl butyral was dissolved in a binary mixed solvent of 20g N, N-dimethylformamide and 15g of dimethyl sulfoxide, and 50 g of the solution was addedMagnetically stirring at the temperature of 5 hours for dissolution to form a solution A; dropwise adding 0.2g of tetraethyl orthosilicate into the solution A, and continuously stirring for 2 hours to obtain a precursor quenching solution B; quenching the precursor quenching solution B at-20 ℃ for 3h, soaking the precursor quenching solution B in distilled water after quenching, removing the mixed solvent, washing and drying to obtain the polyvinyl butyral/SiO2Compounding nano fiber; the nano-fiber is placed in a muffle furnace to be calcined for 2 hours at 500 ℃ to obtain SiO2And (3) nano fibers.
Preparation of microporous carbon nano-tube
0.04g of SiO2Adding nanofiber, 0.3g of furfuryl alcohol and 3g of acetone into a test tube, performing magnetic stirring to form a mixed solution, adding 0.01g of p-toluenesulfonic acid, and performing magnetic stirring at normal temperature to solidify the p-toluenesulfonic acid. After the curing is finished, the temperature is kept at 150 ℃ for 2 h. Calcining the product at 900 ℃ for 5h under the protection of nitrogen, then soaking the sample in a sodium hydroxide ethanol solution for 12h, removing the silicon dioxide template, and drying at 100 ℃ to obtain the microporous carbon nanotube.
Preparation of nitrogen-doped microporous carbon nano tube
Adding 0.05g of microporous carbon nanotube, 0.1g of aniline, 5mL of hydrochloric acid with the concentration of 0.3mol/L and 0.1g of sodium dodecyl sulfate into a three-neck flask, magnetically stirring to form a mixed solution, dropwise adding 2.0g of ammonium persulfate solution with the concentration of 0.4mol/L into the mixed solution, reacting for 5 hours at the temperature of 2 ℃, centrifuging, filtering and drying to obtain the polyaniline/microporous carbon nanotube composite. NH with mass concentration of 0.5 percent is used for polyaniline/microporous carbon nanotube compound4And (3) activating, washing, drying and heating the solution to 300 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, then heating to 1000 ℃ from 300 ℃, and preserving heat for 2h to obtain the nitrogen-doped microporous carbon nanotube.
Preparation of four, nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure
0.03g of nitrogen-doped microporous carbon nanotube, 0.3g of aniline, 6mL of hydrochloric acid with the concentration of 0.3mol/L and 0.15g of sodium dodecyl sulfate were added into a three-necked flask, and the mixture was magnetically stirred to form a mixed solution. Dropwise adding 3.0g of ammonium persulfate solution with the concentration of 0.4mol/L into a three-neck flask under the stirring condition, and after dropwise adding, continuing to react for 24 hours at the reaction temperature of 3 ℃. And filtering the precipitate after the reaction is finished, repeatedly washing the precipitate by using 1mol/L hydrochloric acid and acetone, and drying the precipitate in vacuum at the temperature of 50 ℃ for 24 hours to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure.
Preparation of electrode material with five-core-shell structure
Mixing a nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material, 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 under the pressure of 10MPa to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure electrode material.
The nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure electrode material prepared in the embodiment has a specific capacitance of 601F/g under the condition that the current density is 1A/g, and the capacitance is 88.1% of the initial value after 800 times of recycling.
Example 2
The preparation method of the core-shell structure electrode material provided by the embodiment specifically comprises the following steps:
SiO 22Preparation of nanofibers
Dissolving 2.0g of polyvinyl butyral in a binary mixed solvent of 20g N, N-dimethylformamide and 15g of dimethyl sulfoxide, and magnetically stirring for 5 hours at 50 ℃ to dissolve to form a solution A; dropwise adding 0.25g of tetraethyl orthosilicate into the solution A, and continuously stirring for 2 hours to obtain a precursor quenching solution B; quenching the precursor quenching solution B at-30 ℃ for 3h, soaking the precursor quenching solution B in distilled water after quenching, removing the mixed solvent, washing and drying to obtain the polyvinyl butyral/SiO2Compounding nano fiber; the nano-fiber is put in a muffle furnace to be calcined for 2 hours at 700 ℃ to obtain SiO2And (3) nano fibers.
Preparation of microporous carbon nano-tube
0.04g of SiO2Adding nanofiber, 0.4g of furfuryl alcohol and 3g of acetone into a test tube, performing magnetic stirring to form a mixed solution, adding 0.01g of p-toluenesulfonic acid, and performing magnetic stirring at normal temperature to solidify the p-toluenesulfonic acid. After the curing is finished, the temperature is kept at 150 ℃ for 2 h. Calcining the product at 800 ℃ for 5h under the protection of nitrogen, soaking the sample in sodium hydroxide ethanol solution for 12h, and removingRemoving the silicon dioxide template, and drying at 100 ℃ to obtain the microporous carbon nano tube.
Preparation of nitrogen-doped microporous carbon nano tube
Adding 0.05g of microporous carbon nanotube, 0.15g of aniline, 5mL of hydrochloric acid with the concentration of 0.3mol/L and 0.1g of sodium dodecyl sulfate into a three-neck flask, magnetically stirring to form a mixed solution, dropwise adding 2.0g of ammonium persulfate solution with the concentration of 0.4mol/L into the mixed solution, reacting for 5 hours at 4 ℃, centrifuging, filtering and drying to obtain the polyaniline/microporous carbon nanotube composite. NH with mass concentration of 0.5 percent is used for polyaniline/microporous carbon nanotube compound4And (3) activating, washing, drying and heating the solution to 300 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, then heating to 1000 ℃ from 300 ℃, and preserving heat for 2h to obtain the nitrogen-doped microporous carbon nanotube.
Preparation of four, nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure
0.03g of nitrogen-doped microporous carbon nanotube, 0.35g of aniline, 6mL of hydrochloric acid with the concentration of 0.3mol/L and 0.15g of sodium dodecyl sulfate were added into a three-necked flask, and the mixture was magnetically stirred to form a mixed solution. Dropwise adding 3.0g of ammonium persulfate solution with the concentration of 0.4mol/L into a three-neck flask under the stirring condition, and after dropwise adding, continuing to react for 24 hours at the reaction temperature of 3 ℃. And filtering the precipitate after the reaction is finished, repeatedly washing the precipitate by using 1mol/L hydrochloric acid and acetone, and drying the precipitate in vacuum at the temperature of 50 ℃ for 24 hours to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure.
Preparation of electrode material with five-core-shell structure
Mixing a nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material, 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 under the pressure of 10MPa to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure electrode material.
The nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure electrode material prepared in the embodiment has a specific capacitance of 550F/g under the condition that the current density is 1A/g, and the capacitance is 90.1% of the initial value after 800 times of recycling.
Example 3
The preparation method of the core-shell structure electrode material provided by the embodiment specifically comprises the following steps:
SiO 22Preparation of nanofibers
Dissolving 2.2g of polyvinyl butyral in a binary mixed solvent of 20g N, N-dimethylformamide and 15g of dimethyl sulfoxide, and magnetically stirring for 5 hours at 50 ℃ to dissolve to form a solution A; dropwise adding 0.3g of tetraethyl orthosilicate into the solution A, and continuously stirring for 2 hours to obtain a precursor quenching solution B; quenching the precursor quenching solution B at-40 ℃ for 3h, soaking the precursor quenching solution B in distilled water after quenching, removing the mixed solvent, washing and drying to obtain the polyvinyl butyral/SiO2Compounding nano fiber; the nano-fiber is put in a muffle furnace to be calcined for 2 hours at the temperature of 600 ℃ to obtain SiO2And (3) nano fibers.
Preparation of microporous carbon nano-tube
0.04g of SiO2Adding nanofiber, 0.25g of furfuryl alcohol and 3g of acetone into a test tube, performing magnetic stirring to form a mixed solution, adding 0.01g of p-toluenesulfonic acid, and performing magnetic stirring at normal temperature to solidify the p-toluenesulfonic acid. After the curing is finished, the temperature is kept at 150 ℃ for 2 h. Calcining the product at 1000 ℃ for 5h under the protection of nitrogen, soaking the sample in a sodium hydroxide ethanol solution for 12h, removing the silicon dioxide template, and drying at 100 ℃ to obtain the microporous carbon nanotube.
Preparation of nitrogen-doped microporous carbon nano tube
Adding 0.05g of microporous carbon nanotube, 0.18g of aniline, 5mL of hydrochloric acid with the concentration of 0.3mol/L and 0.1g of sodium dodecyl sulfate into a three-neck flask, magnetically stirring to form a mixed solution, dropwise adding 2.0g of ammonium persulfate solution with the concentration of 0.4mol/L into the mixed solution, reacting for 5 hours at the temperature of 3 ℃, centrifuging, filtering and drying to obtain the polyaniline/microporous carbon nanotube composite. NH with mass concentration of 0.5 percent is used for polyaniline/microporous carbon nanotube compound4And (3) activating, washing, drying and heating the solution to 300 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, then heating to 1000 ℃ from 300 ℃, and preserving heat for 2h to obtain the nitrogen-doped microporous carbon nanotube.
Preparation of four, nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure
0.03g of nitrogen-doped microporous carbon nanotube, 0.4g of aniline, 6mL of hydrochloric acid with the concentration of 0.3mol/L and 0.15g of sodium dodecyl sulfate were added into a three-necked flask, and the mixture was magnetically stirred to form a mixed solution. Dropwise adding 3.0g of ammonium persulfate solution with the concentration of 0.4mol/L into a three-neck flask under the stirring condition, and after dropwise adding, continuing to react for 24 hours at the reaction temperature of 3 ℃. And filtering the precipitate after the reaction is finished, repeatedly washing the precipitate by using 1mol/L hydrochloric acid and acetone, and drying the precipitate in vacuum at the temperature of 50 ℃ for 24 hours to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure.
Preparation of electrode material with five-core-shell structure
Mixing a nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material, 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 under the pressure of 10MPa to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure electrode material.
The nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure electrode material prepared in the embodiment has a specific capacitance of 590F/g under the condition that the current density is 1A/g, and the capacitance is 89.4% of the initial value after 800 times of recycling.
Comparative example 1
The difference from the example 1 is that the microporous carbon nanotube obtained in the second step is directly used for preparing an electrode. Under the condition that the current density is 1A/g, the specific capacitance is 330F/g, and after 800 times of cyclic use, the capacitance is 87.1 percent of the initial value.
Comparative example 2
The difference from the embodiment 1 is that the nitrogen-doped microporous carbon nanotube obtained in the third step is directly used for preparing an electrode. Under the condition that the current density is 1A/g, the specific capacitance is 390F/g, and after 800 times of cyclic use, the capacitance is 91.2 percent of the initial value.
Comparative example 3
The difference from the embodiment 1 lies in that the third step is omitted, that is, the microporous carbon nanotube prepared in the second step is directly used in the fourth step to obtain the microporous carbon nanotube @ polyaniline electrode. Under the condition that the current density is 1A/g, the specific capacitance is 513F/g, and after the capacitor is recycled for 800 times, the capacitance is 90.4 percent of the initial value.
Comparative example 4
The difference from the embodiment 1 is that the step one is omitted, namely the carbon fiber is directly obtained through the step two, and the subsequent steps are unchanged, so that the carbon fiber @ polyaniline core-shell structure electrode material is finally obtained. Under the condition that the current density is 1A/g, the specific capacitance is 440F/g, and after 800 times of cyclic use, the capacitance is 89.2 percent of the initial value.
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 (6)
1. A preparation method of an electrode material with a core-shell structure is characterized by comprising the following steps:
s1 preparation of SiO2A nanofiber;
s2 using the SiO2Preparing microporous carbon nano tubes by using nano fibers;
s3, preparing nitrogen-doped microporous carbon nanotubes by using the microporous carbon nanotubes;
s4, preparing a nitrogen-doped microporous carbon nanotube @ polyaniline core-shell material by using the nitrogen-doped microporous carbon nanotube;
s5, uniformly dispersing the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material, acetylene black and PTFE in absolute ethyl alcohol, coating the materials on foamed nickel, and performing vacuum drying and tabletting to obtain the core-shell structure electrode material;
the SiO2The preparation method of the nanofiber comprises the following steps:
dissolving polyvinyl butyral in a binary mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, dropwise adding tetraethyl orthosilicate, and uniformly mixing to obtain a quenching solution;
quenching the quenching solution at the temperature of between 40 ℃ below zero and 10 ℃ below zero, removing the N, N-dimethylformamide/dimethyl sulfoxide binary mixed solvent by using distilled water, washing and drying to obtain the polyvinyl butyral/SiO2Composite nanofiberMaintaining;
mixing the polyvinyl butyral/SiO2Calcining the composite nanofiber at 500-700 ℃ to obtain SiO2A nanofiber;
the preparation method of the microporous carbon nanotube comprises the following steps:
mixing SiO2Adding the nano-fibers and furfuryl alcohol into acetone, uniformly mixing, adding p-toluenesulfonic acid, magnetically stirring at normal temperature, and curing;
keeping the temperature of the cured product at 150 ℃, and calcining the cured product in a nitrogen atmosphere at 800-1500 ℃;
soaking the calcined product in sodium hydroxide ethanol solution for 12h, removing the silicon dioxide template, and finally drying to obtain the microporous carbon nanotube;
the preparation method of the nitrogen-doped microporous carbon nanotube comprises the following steps:
uniformly mixing the microporous carbon nanotube, aniline, hydrochloric acid and sodium dodecyl sulfate, dripping ammonium persulfate solution, and reacting at 0-5 ℃ to obtain a polyaniline/microporous carbon nanotube compound;
NH with the mass concentration of 0.5 percent is used for the polyaniline/microporous carbon nanotube compound4Activating, washing and drying the Cl solution to obtain an activated product;
under the protection of nitrogen, heating the activated product from 25 ℃ to 300 ℃, preserving heat for 2h, then heating from 300 ℃ to 1000 ℃, and preserving heat for 2h to obtain the nitrogen-doped microporous carbon nanotube;
the preparation method of the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell material comprises the following steps:
and uniformly mixing the nitrogen-doped microporous carbon nanotube, aniline, hydrochloric acid and sodium dodecyl sulfate, dripping ammonium persulfate solution, and reacting at the temperature of 2 ℃ to obtain the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell material.
2. The method for preparing the core-shell structure electrode material according to claim 1, wherein the quenching solution contains polyvinyl butyral in a mass concentration of 4-6% and tetraethyl orthosilicate in a mass concentration of 0.4-0.8%.
3. The method for producing a core-shell structured electrode material according to claim 1, wherein the SiO is2The mass ratio of the nano-fibers to the furfuryl alcohol is 1: (5-10).
4. The method for preparing the core-shell structure electrode material according to claim 1, wherein the mass ratio of the microporous carbon nanotubes to the aniline is 1: (2-4).
5. The method for preparing the core-shell structure electrode material according to claim 1, wherein the mass ratio of the nitrogen-doped microporous carbon nanotube to the aniline is 1: (10-15).
6. The method for preparing the core-shell structure electrode material according to claim 1, wherein the mass ratio of the nitrogen-doped microporous carbon nanotube @ polyaniline core-shell structure material to the acetylene black to the PTFE is 8: 1: 1.
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| WO2019070814A1 (en) * | 2017-10-03 | 2019-04-11 | University Of South Florida | High specific capacitance solid state supercapacitor and method of manufacture |
| CN110718399A (en) * | 2019-10-21 | 2020-01-21 | 中南林业科技大学 | Polyaniline-carbon nanotube electrode material based on core-shell structure, preparation method and supercapacitor |
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| WO2019070814A1 (en) * | 2017-10-03 | 2019-04-11 | University Of South Florida | High specific capacitance solid state supercapacitor and method of manufacture |
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