CN113930866A - Supercapacitor electrode material with capsule structure and preparation method and application thereof - Google Patents

Supercapacitor electrode material with capsule structure and preparation method and application thereof Download PDF

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CN113930866A
CN113930866A CN202111191437.4A CN202111191437A CN113930866A CN 113930866 A CN113930866 A CN 113930866A CN 202111191437 A CN202111191437 A CN 202111191437A CN 113930866 A CN113930866 A CN 113930866A
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electrode material
preparation
supercapacitor electrode
hollow mesoporous
ferric oxide
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路金林
黄莹莹
张怡
尹衍升
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Guangzhou Maritime University
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Abstract

A preparation method of a supercapacitor electrode material with a capsule structure comprises the following steps: s1: preparing a nano hollow mesoporous ferric oxide ball; s2: mixing the nano hollow mesoporous ferric oxide microspheres prepared in the step S1 with polyacrylonitrile and N, N-dimethylformamide and stirring to form a uniform electrostatic spinning precursor solution; s3: preparing polyacrylonitrile nano-fiber containing nano hollow mesoporous ferric oxide spheres through electrostatic spinning; s4: pre-oxidizing and carbonizing to obtain ferroferric oxide/carbon nanofiber composite material; s5: and (3) carrying out vulcanization treatment, and then carrying out vacuum low-temperature calcination on the obtained product in a tubular furnace to remove redundant sulfur so as to obtain the iron disulfide/carbon nanofiber composite electrode material. The iron disulfide/carbon nanofiber composite material prepared by the preparation method has a loose and porous structure, and simultaneously has the advantages of high specific surface area, high capacitance, low internal resistance and excellent cycle stability.

Description

Supercapacitor electrode material with capsule structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy materials, in particular to a supercapacitor electrode material with a capsule structure and a preparation method and application thereof.
Background
With the global exhaustion of fossil fuels and the increasing environmental pollution caused by greenhouse gas emission, people have urgent needs for renewable energy sources such as solar energy, wind energy and tidal energy. However, since the intermittency of these renewable energy sources makes them unsatisfactory for human needs, it is crucial to develop an energy storage device that is efficient, stable, and safe and reliable. Nowadays, secondary batteries play an important role in human life, and are very common in daily life, such as lead storage batteries in automobiles, nickel-hydrogen batteries in electric toys, and lithium batteries in mobile phones. These batteries have high energy density, but have low power density, slow charge and discharge rate, short service life and still have great limitations. Therefore, the super capacitor has the advantages of high power density, high charge and discharge rate, long service life and the like, and a novel energy storage device between the traditional capacitor and the secondary battery is concerned by people.
The energy storage of the capacitor mainly depends on the electrode material, so it is important to further develop the electrode material with high capacity and good performance. Carbon materials, conductive polymer materials, transition metal oxides and transition metal sulfides are several common supercapacitor materials. The carbon material is mainly applied to an electrode material of an electric double layer capacitor, and the conductive polymer, the transition metal oxide and the transition metal sulfide are mainly applied to an electrode material of a Faraday pseudo capacitor.
In recent years, transition metal sulfide has received more and more attention as a novel pseudocapacitance material applied to super capacitor energy storage. In general, since the electronegativity of the sulfur element is smaller relative to the oxide, a more flexible structure can be obtained after the sulfur atom replaces the oxygen atom. In addition, more redox reactions may occur during the electrochemical energy storage process. Meanwhile, transition metal sulfides have a variety of possible stoichiometric compositions, crystal structures, valence states, and nanocrystalline morphologies, resulting in higher electrochemical activity.
Transition metal sulfides generally have better electrical conductivity, mechanical stability, and thermal stability than transition metal oxides. Compared with carbon materials or common transition metal oxides, the abundant redox reaction of the transition metal sulfide enables the transition metal sulfide to have higher specific capacity or specific capacitance.
In recent years, iron disulfide (FeS)2) The electrode material has the advantages of high theoretical specific capacitance, low preparation cost, wide resource distribution, no toxicity and the like, and is favored. However, FeS is present during the charge-discharge cycle, especially during charge-discharge at high current densities2The FeS is seriously restricted by the problems of high capacity attenuation caused by easy expansion of the volume of the electrode, poor cycle performance and the like2Application of electrode material. Currently, many researchers use FeS to improve this problem2FeS is prepared by compounding FeS with materials with high conductivity and high specific surface area2A composite electrode material. For example, chinese patent publication No. CN105336951A discloses a method for preparing a titanium dioxide-iron disulfide core-shell structure material, which comprises preparing FeS2Nanospheres, then on said FeS by means of surface modification2Preparing a titanium dioxide shell on the surface of the nanosphere. The methodThe titanium dioxide-iron disulfide core-shell structure material prepared by the method has high specific capacity and good cycling stability, and can be better applied to lithium ion batteries. Chinese patent publication No. CN107482185A discloses a FeS2The composite anode material is prepared through dispersing organic ferrous salt, thiourea, PVP and chelating agent in solvent, reaction polymerizing to form sol, further generating gel, heat treatment and grinding2Powder, then metal powder with the mass ratio of 0.1-2% is added for surface coating to obtain FeS2And (3) compounding the positive electrode material. Coating FeS with metal powder2The conductivity of the anode material can be enhanced, the rate performance can be improved, meanwhile, the corrosion of the electrolyte to the material can be relieved, the service life of the battery can be prolonged, and the discharge performance of the battery under large current can be effectively improved. Chinese patent publication No. CN108565442A discloses a preparation method of a core-shell composite sulfide material, which takes cobalt-containing solution as a raw material; then adding a sulfur source and FeS into the cobalt-containing solution2Powder; stirring; then placing the mixture into a high-pressure reaction kettle; reacting at 100 ℃ and 180 ℃ for at least 6 hours; cooling; solid-liquid separation; then mixing the obtained solid with elemental sulfur or directly heating to 410-500 ℃ in a sulfur-containing atmosphere, and preserving the heat for at least 10 hours; and cooling along with the furnace to obtain the core-shell composite sulfide material. The preparation method is simple in preparation process and low in cost, and the obtained product has excellent electrochemical performance and safety performance and is convenient for large-scale industrial application.
The invention has the characteristics of simple and efficient preparation method, no environmental pollution and the like, and the prepared FeS2The composite material has high capacity and good cycling stability. By carbon with FeS2The compound mode is expected to solve the FeS problem2The conductivity of the material can be greatly improved due to various problems. Therefore, it is very important to find a carbon-based material with simple preparation method, low cost, stable structure and large specific surface area.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of an iron disulfide/carbon nanofiber symmetrical all-solid-state supercapacitor electrode material with high specific capacity and excellent cycle performance.
The technical scheme adopted by the invention is as follows: a preparation method of a supercapacitor electrode material with a capsule structure comprises the following steps:
s1: preparing a nano hollow mesoporous ferric oxide ball: dissolving ferric trichloride hexahydrate in an ethylene glycol solution, stirring for 10-20 min to form a uniform mixed solution, adding a certain amount of ammonium acetate into the mixed solution, continuously stirring for 30-40 min to obtain a light yellow suspension, performing hydrothermal reaction on the light yellow suspension to obtain black powder, centrifugally washing and drying the obtained black powder, and calcining at 400-500 ℃ for 3-5 h to obtain a brownish red nano hollow mesoporous ferric oxide microsphere;
s2: mixing the nano hollow mesoporous ferric oxide microspheres prepared in the step S1 with polyacrylonitrile and N, N-dimethylformamide and stirring to form a uniform electrostatic spinning precursor solution;
s3: sucking the electrostatic spinning precursor solution prepared in the step S2 into a needle tube, and performing electrostatic spinning to prepare polyacrylonitrile nano-fiber containing nano hollow mesoporous ferric oxide spheres;
s4: placing the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres prepared in the step S3 into a tubular furnace for pre-oxidation treatment and carbonization treatment to obtain a ferroferric oxide/carbon nano-fiber composite material;
s5: and (4) putting the ferroferric oxide/carbon nanofiber composite material prepared in the step (S4) and excessive sulfur powder into a tubular furnace for vulcanization treatment, and then carrying out vacuum low-temperature calcination in the tubular furnace to remove excessive sulfur to obtain the iron disulfide/carbon nanofiber composite electrode material.
Compared with the prior art, the preparation method has the characteristics of simplicity, high efficiency, low cost, environmental protection and the like. The invention adopts a hydrothermal method and an electrostatic spinning technology to prepare the iron disulfide/carbon nanofiber composite material, and FeS is prepared by using loose porous carbon nanofibers with large specific surface area2Packaging, thereby not only effectively improving the charging and discharging processesFeS2The phenomenon of structure collapse is caused by volume expansion, and meanwhile, the capsule structure can also prevent material pulverization, reduce the electrical contact between the material and a current collector, reduce side reaction between an electrode and electrolyte and improve the conductivity of the material to a certain extent. Therefore, the iron disulfide/carbon nanofiber composite material prepared by the preparation method has a loose and porous structure, and simultaneously has high specific surface area and high capacitance (1A g)-1The capacitance is 511F g-1) And the iron disulfide/carbon nanofiber composite material has low internal resistance and excellent cycle stability due to the capsule structure.
Preferably, in step S1, the concentration of ferric chloride hexahydrate in the mixed solution is 15-20 g/L, and the mass ratio of ferric chloride hexahydrate to ammonium acetate is (1.08-1.2): (0.9-1.1).
Preferably, in step S1, the reaction temperature of the hydrothermal reaction is 180 to 200 ℃, and the hydrothermal time is 28 to 32 hours.
Preferably, in step S1, the reagents used for centrifugal washing are deionized water and ethanol.
Preferably, in step S2, the mass ratio of the nano hollow mesoporous ferric oxide spheres to the polyacrylonitrile to the N, N-dimethylformamide is (3-3.5): (5-5.5): (45-55).
Preferably, in the step S2, the stirring temperature is 40-60 ℃, the stirring speed is 700-900 rpm, and the stirring time is 8-10 hours.
Preferably, in step S3, the electrospinning conditions are: the receiver is a stainless steel roller, and the rotating speed of the roller is 30-80 rpm; the voltage is 18-20 kV; the receiving distance is 18-22 cm; the spinning temperature is 20-40 ℃; the spinning humidity is 40-60% RH; the pushing speed is 40-80 mu L/min; the spinning time is 4-6 h.
Preferably, in the step S4, the pre-oxidation treatment is carried out at 230-280 ℃ for 2-3 h in an air atmosphere, and the temperature rise rate is 2-5 ℃/min; the carbonization treatment is carried out for 3-5 h at 450-500 ℃ in the nitrogen or argon atmosphere, and the temperature rise rate is 2-3 ℃/min.
Preferably, in the step S5, the vulcanization treatment is carried out at 400-450 ℃ for 8-10 h in a nitrogen or argon atmosphere, and the temperature rise rate is 2-3 ℃/min; and (3) carrying out vacuum low-temperature calcination at the calcination temperature of 200-220 ℃ for 10-12 h, wherein the heating rate is 2-5 ℃/min.
The invention also aims to provide a supercapacitor electrode material with a capsule structure, which is prepared by adopting the preparation method, and compared with the prior art, the supercapacitor electrode material has a loose and porous structure, high specific surface area and higher capacitance (1A g)-1The capacitance is 511F g-1) And the iron disulfide/carbon nanofiber composite material has low internal resistance, and the capsule structure enables the iron disulfide/carbon nanofiber composite material to have excellent cycling stability.
The invention also provides application of the supercapacitor electrode material with the capsule structure in preparation of a supercapacitor. Specifically, the electrode material can be used as a symmetrical all-solid-state supercapacitor electrode material, and the supercapacitor adopting the electrode material is prepared by the following steps:
1) preparing an electrode plate of the super capacitor: uniformly mixing the iron disulfide/carbon nanofiber composite material with acetylene black and polyvinylidene fluoride, dispersing the mixture in 1-methyl 2-pyrrolidone, and stirring for 3-5 hours to form a stable suspension; and coating the suspension on 1.6 multiplied by 1.6cm of foamed nickel, and drying for 8-12 hours in vacuum at the temperature of 70-80 ℃ to obtain the supercapacitor electrode. The mass ratio of the iron sulfide/three-dimensional porous carbon composite material to the acetylene black and the polyvinylidene fluoride is (7.2-8.6): (0.8-1.5): (0.8 to 1.5); the mass ratio of the 1-methyl 2-pyrrolidone to the iron disulfide/carbon nanofiber composite material is (8.8-9.5): (0.8 to 1.2); the mass of the mixed liquid coated on the foamed nickel is 4-8 mg.
2) Two electrodes prepared from the iron disulfide/carbon nanofiber composite material obtained in the step S1 and having the same mass are respectively used as the positive electrode and the negative electrode of the supercapacitor, and polyvinyl alcohol-potassium hydroxide gel with the size of 1.7 multiplied by 1.7cm is used as a working electrolyte to assemble the symmetrical all-solid-state supercapacitor.
Compared with the prior art, the super capacitor provided by the invention takes the iron disulfide/carbon nanofiber composite material as the positive material and the negative materialThe material, the polyvinyl alcohol-potassium hydroxide gel is used as the working electrolyte to assemble the symmetrical all-solid-state super capacitor, the voltage window is as high as 1.6V, and simultaneously, the capacitor has higher capacity retention rate, which indicates that the capsule structure effectively improves FeS2The FeS is subjected to volume expansion to collapse the structure in the cyclic charge-discharge process2The CNFs super capacitor has excellent cycle stability.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic view of an electrospinning apparatus in step S3 of example 1;
figure 2 is an SEM image of the iron disulfide/carbon nanofiber composite electrode material prepared in example 1;
FIG. 3 shows that the iron sulfide/carbon nanofiber composite material prepared in example 1 is in a range of 1-5A g-1A charge-discharge test curve under current density;
FIG. 4 shows that the iron sulfide/carbon nanocomposite prepared in example 1 is used as an electrode material to assemble a symmetrical all-solid-state supercapacitor with a current density of 4A g-1Capacity retention curve after 5000 cycles;
fig. 5 is a charge-discharge curve of a symmetrical all-solid-state supercapacitor assembled by the iron sulfide/carbon nanocomposite prepared in example 1 as an electrode material when the voltage window is 1.6V.
In FIG. 1, 1-plunger, 2-syringe, 3-needle, 4-receiver.
Detailed Description
Example 1
The preparation method of the supercapacitor electrode material with the capsule structure in the embodiment specifically comprises the following steps:
s1: preparing a nano hollow mesoporous ferric oxide ball: dissolving 2.16g of ferric trichloride hexahydrate in 120mL of glycol solution, stirring at the speed of 650rpm for 10min to form a uniform mixed solution, then adding 2g of ammonium acetate into the uniform mixed solution, continuously stirring for 30min to obtain a light yellow suspension, carrying out hydrothermal reaction on the light yellow suspension at the temperature of 180 ℃ for 30h, carrying out centrifugal washing with deionized water and glycol for several times to obtain microspheres, and finally calcining the microspheres at the temperature of 500 ℃ for 5h to obtain the nano hollow mesoporous ferric oxide spheres.
S2: 0.3g of the nano hollow mesoporous ferric oxide ball prepared in the step S1, 0.5g of polyacrylonitrile and 5g N, N-dimethylformamide are mixed and stirred at the temperature of 50 ℃ and the speed of 800rpm for 8 hours to form a uniform electrostatic spinning precursor solution.
S3: sucking the electrostatic spinning precursor solution prepared in the step S2 into a needle tube, and performing electrostatic spinning by using an electrostatic spinning apparatus shown in fig. 1, according to electrostatic spinning conditions: the receiver 4 is a stainless steel roller with the rotating speed of 60 rpm; the voltage is 18.46 kV; the receiving distance is 20 cm; the spinning temperature is 38 ℃; the spinning humidity is 60% RH; the pushing speed is 50 mu L/min; the spinning time is 4.5 h; and (3) obtaining the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres through electrostatic spinning.
S4: placing the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres prepared in the step S3 in a tubular furnace to carry out pre-oxidation treatment for 2 hours at 250 ℃ in air atmosphere, wherein the heating rate is 2 ℃/min; then carbonizing at 500 ℃ and a heating rate of 2 ℃/min for 3 hours under the nitrogen atmosphere to obtain the ferroferric oxide/carbon nanofiber composite material.
S5: putting the ferroferric oxide/carbon nanofiber composite material prepared in the step S4 and excessive sulfur powder into a tubular furnace, and vulcanizing at the temperature rise rate of 2 ℃/min for 8 hours, wherein the temperature of the ferroferric oxide/carbon nanofiber composite material and the excessive sulfur powder are 400 ℃ in the argon atmosphere; then the carbon nano-fiber composite electrode material is calcined in a tube furnace at the temperature of 200 ℃ and the heating rate of 2 ℃/min in vacuum at low temperature for 12h to remove the redundant sulfur, and the iron disulfide/carbon nano-fiber composite electrode material is obtained.
Testing and characterization
Please refer to fig. 2, which is an SEM image of the iron disulfide/carbon nanofiber composite electrode material prepared in this embodiment; from the figure, FeS can be observed2The particles are coated in the carbon nanofiber filament, and the carbon nanofiber filament has a rough surface.
Please refer to fig. 3, which shows the iron sulfide/carbon nanofiber composite prepared in this embodimentThe material is 1 to 5A g-1Charge and discharge test curve at current density. Some deviation of the charge-discharge curve from the triangle can be observed, and this result indicates that FeS2The CNFs composite electrode mainly depends on the electric double layer effect and the Faraday pseudocapacitance effect to store energy. Calculated, FeS2CNFs composite electrode at a current density of 1A g-1，2A g-1，3A g-1，4A g-1And 5A g-1Specific capacitances of 511F g, respectively-1，491.4F g-1，467.6F g-1，420.8F g-1And 390.6F g-1. Therefore, the iron sulfide and the carbon nanofiber are compounded, so that the conductivity of the electrode material is effectively improved, and the capsule structure obviously improves the rate of the electrode material.
The iron disulfide/carbon nanofiber composite electrode material prepared by the embodiment is used as a positive electrode material and a negative electrode material, polyvinyl alcohol-potassium hydroxide gel is used as a working electrolyte, and a symmetrical all-solid-state supercapacitor can be assembled by the method, which is specifically prepared by the following steps:
1) preparing an electrode plate of the super capacitor: uniformly mixing the iron disulfide/carbon nanofiber composite material with acetylene black and polyvinylidene fluoride, dispersing the mixture in 1-methyl 2-pyrrolidone, and stirring for 3-5 hours to form stable suspension; and coating the suspension on 1.6 multiplied by 1.6cm of foamed nickel, and drying for 8-12 hours in vacuum at 70-80 ℃ to obtain the supercapacitor electrode. The mass ratio of the iron sulfide/three-dimensional porous carbon composite material to the acetylene black and the polyvinylidene fluoride is (7.2-8.6): (0.8-1.5): (0.8 to 1.5); the mass ratio of the 1-methyl 2-pyrrolidone to the iron disulfide/carbon nanofiber composite material is (8.8-9.5): (0.8 to 1.2); the mass of the mixed liquid coated on the foamed nickel is 4-8 mg.
2) Two electrodes prepared from the iron disulfide/carbon nanofiber composite material obtained in the step S1 and having the same mass are respectively used as the positive electrode and the negative electrode of the supercapacitor, and polyvinyl alcohol-potassium hydroxide gel with the size of 1.7 multiplied by 1.7cm is used as a working electrolyte to assemble the symmetrical all-solid-state supercapacitor.
Please refer to fig. 4, which illustrates the iron sulfide/carbon nanofiber composite material prepared in this embodimentThe electrode material is assembled into a symmetrical all-solid-state supercapacitor with the current density of 4A g-1Capacity retention curve after 5000 cycles. From the figure, FeS can be seen2The capacity retention of CNFs supercapacitors was 87.5%. Thus, it can be seen that FeS2The CNFs super capacitor has higher capacitance retention rate, which indicates that the capsule structure effectively improves FeS2The FeS is subjected to volume expansion to collapse the structure in the cyclic charge-discharge process2The CNFs super capacitor has excellent cycle stability. As shown in fig. 5, the voltage window of the supercapacitor is up to 1.6V.
Example 2
The preparation method of the supercapacitor electrode material with the capsule structure in the embodiment specifically comprises the following steps:
s1: preparing a nano hollow mesoporous ferric oxide ball: dissolving 4.4g of ferric trichloride hexahydrate in 240mL of glycol solution, stirring at 650rpm for 15min to form a uniform mixed solution, adding 4g of ammonium acetate into the uniform mixed solution, continuously stirring for 35min to obtain a light yellow suspension, carrying out hydrothermal reaction on the light yellow suspension at the temperature of 180 ℃ for 30h, carrying out centrifugal washing with deionized water and glycol for several times to obtain microspheres, and finally calcining the microspheres at 500 ℃ for 3h to obtain the nano hollow mesoporous ferric oxide spheres.
S2: 0.7g of the nano hollow mesoporous ferric oxide spheres prepared in the step S1, 1.1g of polyacrylonitrile and 11g N, N-dimethylformamide are mixed and stirred at 50 ℃ and 800rpm for 10 hours to form a uniform electrostatic spinning precursor solution.
S3: sucking the electrostatic spinning precursor solution prepared in the step S2 into a needle tube, and according to electrostatic spinning conditions: the receiver is a stainless steel roller with the rotating speed of 45 rpm; the voltage is 19.5 kV; the receiving distance is 22 cm; the spinning temperature is 30 ℃; the spinning humidity is 60% RH; the pushing speed is 60 mu L/min; spinning for 5h to obtain the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres.
S4: placing the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres prepared in the step S3 in a tubular furnace to perform pre-oxidation treatment for 2.5 hours at 260 ℃ in air atmosphere, wherein the heating rate is 3 ℃/min; then carbonizing at 500 ℃ and a heating rate of 2 ℃/min for 3 hours under the nitrogen atmosphere to obtain the ferroferric oxide/carbon nanofiber composite material.
S5: and (4) putting the ferroferric oxide/carbon nanofiber composite material prepared in the step (S4) and excessive sulfur powder into a tubular furnace under the argon atmosphere at 400 ℃, carrying out vulcanization treatment for 8h at the heating rate of 2 ℃/min, then carrying out vacuum low-temperature calcination for 12h at the heating rate of 2 ℃/min in the tubular furnace at 200 ℃ to remove redundant sulfur, and thus obtaining the iron disulfide/carbon nanofiber composite electrode material.
Through tests, the iron disulfide/carbon nanofiber composite material prepared by the embodiment has a loose and porous structure, and meanwhile, has the advantages of high specific surface area, high capacitance, low internal resistance and excellent cycle stability.
Example 3
The preparation method of the supercapacitor electrode material with the capsule structure in the embodiment specifically comprises the following steps:
s1: preparing a nano hollow mesoporous ferric oxide ball: dissolving 3.3g of ferric trichloride hexahydrate in 200mL of glycol solution, stirring at 650rpm for 15min to form a uniform mixed solution, adding 3g of ammonium acetate into the uniform mixed solution, continuously stirring for 35min to obtain a light yellow suspension, carrying out hydrothermal reaction on the light yellow suspension at the temperature of 180 ℃ for 30h, carrying out centrifugal washing with deionized water and glycol for several times to obtain microspheres, and finally calcining the microspheres at 500 ℃ for 3h to obtain the nano hollow mesoporous ferric oxide spheres.
S2: 0.64g of the nano hollow mesoporous ferric oxide spheres prepared in the step S1, 1.04g of polyacrylonitrile and 9.6g N, N-dimethylformamide are mixed and stirred at 50 ℃ at the speed of 800rpm for 10 hours to form a uniform electrostatic spinning precursor solution.
S3: sucking the electrostatic spinning precursor solution prepared in the step S2 into a needle tube, and according to electrostatic spinning conditions: the receiver is a stainless steel roller with the rotating speed of 50 rpm; the voltage is 18.9 kV; the receiving distance is 21 cm; the spinning temperature is 30 ℃; the spinning humidity is 60% RH; the pushing speed is 40 mu L/min; spinning for 6h to obtain the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres.
S4: placing the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres prepared in the step S3 in a tubular furnace to perform pre-oxidation treatment for 2 hours at 280 ℃ in air atmosphere, wherein the heating rate is 2 ℃/min; then carbonizing at 500 ℃ and a heating rate of 2 ℃/min for 3 hours under the nitrogen atmosphere to obtain the ferroferric oxide/carbon nanofiber composite material.
S5: and (4) putting the ferroferric oxide/carbon nanofiber composite material prepared in the step (S4) and excessive sulfur powder into a tubular furnace under the argon atmosphere at 450 ℃, carrying out vulcanization treatment at the heating rate of 2 ℃/min for 9h, then carrying out vacuum low-temperature calcination at 220 ℃ and the heating rate of 2 ℃/min for 10h in the tubular furnace to remove excessive sulfur, and thus obtaining the iron disulfide/carbon nanofiber composite electrode material.
Through tests, the iron disulfide/carbon nanofiber composite material prepared by the embodiment has a loose and porous structure, and meanwhile, has the advantages of high specific surface area, high capacitance, low internal resistance and excellent cycle stability.
The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention. For example, the experimental parameters and the raw material amounts in the above examples are not limited to the parameter values in the above examples, as long as the object of the present invention can be achieved within the parameter values disclosed in the claims.

Claims (10)

1. The preparation method of the supercapacitor electrode material with the capsule structure is characterized by comprising the following steps:
s1: preparing a nano hollow mesoporous ferric oxide ball: dissolving ferric trichloride hexahydrate in an ethylene glycol solution, stirring for 10-20 min to form a uniform mixed solution, adding a certain amount of ammonium acetate into the mixed solution, continuously stirring for 30-40 min to obtain a light yellow suspension, performing hydrothermal reaction on the light yellow suspension to obtain black powder, centrifugally washing and drying the obtained black powder, and calcining at 400-500 ℃ for 3-5 h to obtain a brownish red nano hollow mesoporous ferric oxide microsphere;
s2: mixing the nano hollow mesoporous ferric oxide microspheres prepared in the step S1 with polyacrylonitrile and N, N-dimethylformamide and stirring to form a uniform electrostatic spinning precursor solution;
s3: sucking the electrostatic spinning precursor solution prepared in the step S2 into a needle tube, and performing electrostatic spinning to prepare polyacrylonitrile nano-fiber containing nano hollow mesoporous ferric oxide spheres;
s4: placing the polyacrylonitrile nano-fiber containing the nano hollow mesoporous ferric oxide spheres prepared in the step S3 into a tubular furnace for pre-oxidation treatment and carbonization treatment to obtain a ferroferric oxide/carbon nano-fiber composite material;
s5: and (4) putting the ferroferric oxide/carbon nanofiber composite material prepared in the step (S4) and excessive sulfur powder into a tubular furnace for vulcanization treatment, and then carrying out vacuum low-temperature calcination in the tubular furnace to remove excessive sulfur to obtain the iron disulfide/carbon nanofiber composite electrode material.
2. The method for preparing the supercapacitor electrode material with the capsule structure according to claim 1, wherein in step S1, the concentration of ferric trichloride hexahydrate in the mixed solution is 15-20 g/L, and the mass ratio of ferric chloride hexahydrate to ammonium acetate is (1.08-1.2): 0.9-1.1.
3. The method for preparing the supercapacitor electrode material with the capsule structure according to claim 1, wherein in the step S1, the reaction temperature of the hydrothermal reaction is 180-200 ℃, and the hydrothermal time is 28-32 h.
4. The preparation method of the supercapacitor electrode material with the capsule structure according to claim 1, wherein in step S2, the mass ratio of the nano hollow mesoporous ferric oxide spheres to the polyacrylonitrile to the N, N-dimethylformamide is (3-3.5): (5-5.5): (45-55).
5. The preparation method of the supercapacitor electrode material with the capsule structure according to claim 1, wherein in the step S2, the stirring temperature is 40-60 ℃, the stirring speed is 700-900 rpm, and the stirring time is 8-10 hours.
6. The method for preparing the encapsulated supercapacitor electrode material according to claim 1, wherein in step S3, the electrospinning conditions are as follows: the receiver is a stainless steel roller, and the rotating speed of the roller is 30-80 rpm; the voltage is 18-20 kV; the receiving distance is 18-22 cm; the spinning temperature is 20-40 ℃; the spinning humidity is 40-60% RH; the pushing speed is 40-80 mu L/min; the spinning time is 4-6 h.
7. The method for preparing the supercapacitor electrode material with the capsule structure according to claim 1, wherein in step S4, the pre-oxidation treatment is carried out at 230-280 ℃ for 2-3 h in an air atmosphere, and the temperature rise rate is 2-5 ℃/min; the carbonization treatment is carried out for 3-5 h at 450-500 ℃ in the nitrogen or argon atmosphere, and the temperature rise rate is 2-3 ℃/min.
8. The preparation method of the supercapacitor electrode material with the capsule structure according to claim 1, wherein in the step S5, the vulcanization treatment is carried out at 400-450 ℃ for 8-10 h in a nitrogen or argon atmosphere, and the temperature rise rate is 2-3 ℃/min; and (3) carrying out vacuum low-temperature calcination at the calcination temperature of 200-220 ℃ for 10-12 h, wherein the heating rate is 2-5 ℃/min.
9. A supercapacitor electrode material with a capsule structure, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the encapsulated supercapacitor electrode material according to claim 9 in the preparation of a supercapacitor.
CN202111191437.4A 2021-10-13 2021-10-13 Supercapacitor electrode material with capsule structure and preparation method and application thereof Pending CN113930866A (en)

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