CN110718398A - High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof - Google Patents

High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof Download PDF

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CN110718398A
CN110718398A CN201810770649.XA CN201810770649A CN110718398A CN 110718398 A CN110718398 A CN 110718398A CN 201810770649 A CN201810770649 A CN 201810770649A CN 110718398 A CN110718398 A CN 110718398A
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侯峰
宋丹
张愉昕
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Tianjin University
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    • H—ELECTRICITY
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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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    • 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
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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
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Abstract

The invention discloses a high-capacity carbon nano tube-cobaltosic sulfide nickel powder and a preparation method and application thereof, and the preparation method comprises the following steps of (1) weighing carbon nano tube powder and a surfactant, placing the carbon nano tube powder and the surfactant in an ethanol-water mixed solution, strongly stirring after uniform dispersion, simultaneously adding tetraethoxysilane, centrifuging, freeze-drying and grinding to obtain CNT @ SiO2. (2) Weighing the CNT @ SiO prepared in the step 12And carrying out heat treatment pretreatment on the powder under the argon protective atmosphere. (3) Weighing the CNT @ SiO after the heat treatment in the step 22Putting the powder into water solution, adding urea and Ni (NO) after ultrasonic dispersion3)2Solution and Co (NO)3)2Uniformly stirring the solution, carrying out hydrothermal reaction for 8-16h at the temperature of 80-160 ℃, carrying out suction filtration and drying to obtain CNT @ NiCoSilicate powder. (4) Weighing the powder prepared in the step 3, placing the powder in a water-ethanol mixed solution of sodium sulfide, carrying out hydrothermal reaction for 8-16h at the temperature of 100-2S4And (3) powder. The invention has the beneficial effects that: by pairing CNT @ SiO2The powder is subjected to heat treatment, so that the CNT @ NiCo is improved2S4Electrochemical capacity of the powder.

Description

High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of material chemistry, in particular to a high-capacity carbon nano tube-cobaltosic sulfide nickel powder and a preparation method and application thereof.
Background
The electrode material is used as an important component of the pseudo-capacitance capacitor, and the composition of the electrode material has an important influence on the capacity of the capacitor. Transition metal sulfides, which are typical materials having faradaic redox reaction characteristics, have higher capacity than transition metal oxides and electric double layer capacitors. Thus, transition metal sulfides are especially NiCo2S4As one of the representative compounds of binary transition metal sulfide, the nickel element and the cobalt element belong to variable valence metals, so that a rich oxidation-reduction energy storage mechanism can be provided in a pseudo-capacitance capacitor, the two elements have high content in earth crust, the manufacturing cost is not expensive, and the prepared product has excellent performance.
NiCo relative to the monotropic metal sulfide2S4Has better performance and NiCo2S4With NiCo2O4In contrast, NiCo2S4Is NiCo2O4100 times of the total weight of the powder. Thus, NiCo2S4The research of (2) has a profound influence on super capacitors, lithium ion batteries and the like. NiCo2S4As a sulfide material, it has low solubility in water and is difficult to synthesize by direct chemical synthesis, and NiCo is usually prepared by hydrothermal method, precursor conversion method, and template method2S4. However for NiCo prepared2S4The material, because of its not high theoretical capacity, is usually prepared as a composite material, which may be upgraded NiCo2S4Specific surface area and conductivity. The carbon nanotube is used as a nano carbon material with excellent conductivity and large specific surface area, and more reaction active sites are provided, so that the capacity of the material is improved.
Disclosure of Invention
The object of the present invention is to provide a solution to the prior art of NiCo2S4The defect of small capacity, and provides a high-capacity carbon nano tube-cobaltosic sulfide nickel powder;
another object of the present invention is to provide a method for preparing a high capacity carbon nanotube-nickel cobaltosic sulfide powder by applying a silicon oxide/carbon nanotube thin film (CNT @ SiO)2) And performing heat treatment, wherein the heat treatment can cause the volume of the amorphous silicon dioxide to expand, and can obviously improve the pipe diameter of the silicon oxide/carbon nano tube.
The invention also aims to provide application of the high-capacity carbon nanotube-cobaltosic sulfide nickel powder in a super capacitor, wherein the high-capacity carbon nanotube-cobaltosic sulfide nickel powder has a specific capacity of 1200-2000F/g at a current density of 1A/g.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a high-capacity carbon nanotube-cobaltosic sulfide composite material is prepared by the following steps:
step 1, preparing a carbon nanotube-silicon oxide composite material:
weighing hydroxyl carbon nano tubes and a surfactant, placing the hydroxyl carbon nano tubes and the surfactant in a mixed solution of ethanol and water, adjusting the pH value of the mixed solution to 8-9, uniformly dispersing, adding tetraethoxysilane, centrifugally cleaning a product after the reaction is finished until the solution is neutral, and then freeze-drying and grinding the product at the temperature of-30 ℃ to-50 ℃ to obtain the carbon nano tube-silicon oxide composite material (CNT @ SiO)2)；
Step 2, the CNT @ SiO prepared in the step 1 is used2Placing the mixture in a tube furnace, and carrying out heat treatment at the temperature of 300-1200 ℃ under the argon protective atmosphere to obtain a heat treatment product;
step 3, putting the heat treatment product obtained in the step 2 into water to obtain an aqueous solution, after uniform dispersion, adjusting the pH value of the aqueous solution to 8-9, and then adding Ni (NO)3)2And Co (NO)3)2Obtaining a reaction system, stirring uniformly, carrying out hydrothermal reaction on the reaction system at the temperature of 80-160 ℃ for 8-16h, naturally cooling to the room temperature of 20-30 ℃, carrying out suction filtration and washing on the product, and drying the product at the temperature of 50-100 ℃ for 4-12h to obtain the carbon nano tube-cobalt nickel silicate composite material (CNT @ NiCoSili)cate)。
Step 4, placing the CNT @ NiCo organic prepared in the step 3 in a mixed solution of water and ethanol of sodium sulfide, performing hydrothermal reaction for 8-16h at the temperature of 100 ℃ and 200 ℃, naturally cooling to the room temperature of 20-30 ℃, washing a product, and performing freeze drying at the temperature of-30 ℃ to-50 ℃ to obtain the carbon nanotube-cobaltosic sulfide composite material (CNT @ NiCo)2S4)。
In the technical scheme, in the step 1, the ratio of the mass part of the hydroxyl carbon nano tube to the volume part of the tetraethoxysilane is 0.1 (1-1.5), wherein the unit of the mass part is g, the unit of the volume part is ml, and the dropping speed of the tetraethoxysilane is 50 microliters every 15-20 minutes.
In the technical scheme, in the step 1, the ratio of the mass part of the hydroxyl carbon nano tube to the volume part of the tetraethoxysilane is 0.1:1, wherein the unit of the mass part is g, the unit of the volume part is ml, the dropping speed of the tetraethoxysilane is 50 microliters every 18 minutes, and during dropping, the reaction system is stirred by magnetic force, the stirring speed is 70r/min, and the stirring time is 6-7 hours. The microscopic pipe diameter of the carbon nano tube-silicon oxide composite material can be improved by matching the parameters, the obtained carbon nano tube-silicon oxide composite material is of a coaxial coating structure, a layer of amorphous silicon dioxide is uniformly coated outside the carbon nano tube, and the pipe diameter is about 55-65 nm.
In the above technical solution, the heat treatment temperature in the step 2 is 700-.
In the above technical scheme, the heat treatment in step 2 is carried out by using buckling sintering, and the CNT @ SiO prepared in step 1 is subjected to annealing2Placing the ceramic square boat in a tube furnace for heat treatment.
Specifically, a small alumina ceramic wafer is placed in a large ceramic square boat, a sample to be thermally treated is placed on the ceramic wafer, a small ceramic wafer is placed and buckled on the ceramic wafer, then activated carbon is placed around the small ceramic square boat to avoid the oxidation of the sample, and the large ceramic square boat is covered on the small ceramic square boat after the whole process is completed.
In the above technical solution, in the step 1, the volume ratio of water to ethanol in the mixed solution of ethanol and water is 1: (3-5).
In the above technical scheme, the surfactant in step 1 is cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride.
In the above technical scheme, the mass ratio of the carbon nanotube powder to the surfactant in step 1 is 1: (12-20).
In the above technical solution, the pH value of the mixed solution is adjusted to 8-9 by using ammonia water or urea in step 1, and the pH value of the aqueous solution is adjusted to 8-9 by using ammonia water or urea in step 3.
In the above technical solution, Ni (NO) in the step 33)2And Co (NO)3)2In Ni2+And Co2+The molar ratio of (1) to (3).
In the technical scheme, the concentration of the sodium sulfide in the mixed solution of the water and the ethanol of the sodium sulfide in the step 4 is 1-2 g/L.
In the technical scheme, in the water and ethanol solution of the sodium sulfide in the step 4, the volume ratio of ethanol to water is 1 (2-4).
In another aspect of the present invention, a method for preparing a high capacity carbon nanotube-cobaltosic sulfide composite material is also provided, which comprises the following steps:
step 1, preparing a carbon nanotube-silicon oxide composite material:
weighing hydroxyl carbon nano tubes and a surfactant, placing the hydroxyl carbon nano tubes and the surfactant in a mixed solution of ethanol and water, adjusting the pH value of the mixed solution to 8-9, uniformly dispersing, adding tetraethoxysilane, centrifugally cleaning a product after the reaction is finished until the solution is neutral, and then freeze-drying and grinding the product at the temperature of-30 ℃ to-50 ℃ to obtain the carbon nano tube-silicon oxide composite material (CNT @ SiO)2)；
Step 2, the CNT @ SiO prepared in the step 1 is used2Is placed in a tube furnace inCarrying out heat treatment at the temperature of 300-1200 ℃ under the argon protective atmosphere to obtain a heat treatment product;
step 3, putting the heat treatment product obtained in the step 2 into water to obtain an aqueous solution, after uniform dispersion, adjusting the pH value of the aqueous solution to 8-9, and then adding Ni (NO)3)2And Co (NO)3)2And (2) obtaining a reaction system, stirring uniformly, carrying out hydrothermal reaction on the reaction system at the temperature of 80-160 ℃ for 8-16h, naturally cooling to the room temperature of 20-30 ℃, carrying out suction filtration and washing on the product, and drying the product at the temperature of 50-100 ℃ for 4-12h to obtain the carbon nano tube-cobalt nickel silicate composite material (CNT @ NiCoSilicate).
Step 4, placing the CNT @ NiCo organic prepared in the step 3 in a mixed solution of water and ethanol of sodium sulfide, performing hydrothermal reaction for 8-16h at the temperature of 100 ℃ and 200 ℃, naturally cooling to the room temperature of 20-30 ℃, washing a product, and performing freeze drying at the temperature of-30 ℃ to-50 ℃ to obtain the carbon nanotube-cobaltosic sulfide composite material (CNT @ NiCo)2S4)。
In another aspect of the invention, the application of the high-capacity carbon nanotube-cobaltosic sulfide composite material in a super capacitor is also included.
In the technical scheme, the CNT @ NiCo prepared in the step 4 is applied2S4Uniformly dispersing a conductive agent and a binder in ethanol, pressing the mixture on foamed nickel after film forming, wherein the conductive agent is carbon black or acetylene black, and the binder is PTFE or PVDF, wherein CNT @ NiCo2S4The mass ratio of the powder to the conductive agent to the binder is 8: 1: 1.
in the technical scheme, the specific capacity of the high-capacity carbon nanotube-cobaltosic sulfide composite material under the current density of 1A/g is 1200-2000F/g.
In the technical scheme, when the heat treatment temperature in the step 2 is 700-.
Compared with the prior art, the invention has the beneficial effects that:
1. CNT produced by the methodNiCo2S4The powder has good performance of the super capacitor, and the synthesis process is simple, the product is uniform and the price is low.
2、CNT@SiO2After heat treatment, the amorphous SiO2The bonding with the carbon tube is tighter, and simultaneously, amorphous SiO is enabled2The volume expansion of the powder is beneficial to realizing the Co-phase embedding of Ni ions and Co ions in the process of forming silicate, the large void ratio is formed, the specific surface area is improved, and the powder is converted into CNT @ NiCo through the step of vulcanization2S4The electrochemical capacity of the powder can be improved.
3. CNT @ NiCo prepared by the method2S4The structure of the powder is that the lamella are mutually overlapped to form a large frame, the carbon tubes are inserted in the lamella to form a conductive network, the specific surface area is increased, the conductivity of the material is improved, the multiplying power performance of the material during charge and discharge under high current density is improved, and the 89.5 percent of capacity can be still kept under 5A/g.
Drawings
FIG. 1 shows CNT @ SiO obtained in comparative example 1 and examples 1 to 32SEM image of the powder.
FIG. 2 shows CNT @ SiO solid obtained in comparative example 1 and example 22TEM images of the powder.
FIG. 3 shows CNT @ SiO obtained in comparative example 1 and examples 1 to 32-powder XRD pattern.
FIG. 4 is an SEM image of the CNT @ NiCoSilicate powders obtained in comparative example 1 and examples 1-3.
FIG. 5 is an XRD image of the CNT @ NiCoSilicate powders obtained in comparative example 1 and examples 1-3.
FIG. 6 shows the CNT @ NiCo obtained in comparative example 1 and examples 1 to 32S4SEM image of the powder.
FIG. 7 shows the CNT @ NiCo obtained in comparative example 1 and examples 1 to 32S4TEM images of the powder.
FIG. 8 shows the CNT @ NiCo obtained in comparative example 1 and examples 1 to 32S4XRD pattern of powder.
FIG. 9 is the CNT @ NiCo obtained in comparative example 12S4-0 cyclic voltammetry test curves at different scan rates.
FIG. 10 shows the CNT @ NiCo obtained in comparative example 12S4-0 galvanostatic charge-discharge curve at different charge-discharge rates.
FIG. 11 shows the CNT @ NiCo obtained in example 12S4-1 cyclic voltammetry test curves at different scan rates.
FIG. 12 shows the CNT @ NiCo obtained in example 12S4-1 galvanostatic charge-discharge curves at different charge-discharge rates.
FIG. 13 shows the CNT @ NiCo obtained in example 22S4-2 cyclic voltammetry test curves at different scan rates.
FIG. 14 shows the CNT @ NiCo obtained in example 22S4-2 galvanostatic charge-discharge curves at different charge-discharge rates.
FIG. 15 shows the CNT @ NiCo obtained in example 32S4-3 cyclic voltammetry test curves at different scan rates.
FIG. 16 shows the CNT @ NiCo obtained in example 32S4-3 galvanostatic charge-discharge curves at different charge-discharge rates.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Comparative example 1 (No. CNT @ SiO)2For heat treatment)
Step 1, dissolving 0.16g of Cetyl Trimethyl Ammonium Bromide (CTAB) in a mixed solution of 30mL of deionized water and 120mL of ethanol, adding 1.5mL of ammonia water and 0.1g of hydroxyl Carbon Nanotubes (CNTs), fully shaking uniformly in a beaker, performing ultrasonic dispersion for 40min, then performing magnetic stirring on the solution, stirring for 6h under the condition that the rotating speed is 70r/min, adding 1mL of Tetraethoxysilane (TEOS) into the solution for multiple times in the stirring process (adding 1mL of tetraethoxysilane for 20 times, namely adding 50 microliters of tetraethoxysilane every 18 minutes), and then performing centrifugal washing on the solutionThe supernatant is purified to be neutral, and is frozen and dried at the temperature of minus 48 ℃ to obtain CNT @ SiO2Powder, denoted CNT @ SiO2-0。
Step 2, taking 30mg of the prepared CNT @ SiO2Adding the powder into a glass bottle with a blue cover, adding 40ml of deionized water, performing ultrasonic dispersion for 40min, adding 1g of urea, dissolving, and adding 1ml of 0.1mol/L Ni (NO)3)2And 2ml of 0.1mol/L Co (NO)3)2Magnetically stirring the solution for 5min, sealing the bottle mouth, carrying out hydrothermal reaction at 105 ℃ for 12h, then naturally cooling to room temperature, carrying out suction filtration and cleaning to neutrality, and drying at 60 ℃ for 12h to obtain a powder carbon nano tube-cobalt nickel silicate composite material which is marked as CNT @ NiCoSilicate-0.
Step 3, taking 10mg of CNT @ NiCoSilicate-0 prepared in the step 2, adding 10ml of ethanol and 30ml of deionized water, and adding 0.1477g of Na2S·9H2And O, transferring the mixture into a 50ml hydrothermal kettle after ultrasonic treatment for 40min, and carrying out hydrothermal reaction for 12h at 160 ℃. Then, the obtained product is centrifuged and cleaned, and freeze-dried to obtain the carbon nano tube-cobaltosic sulfide composite material (CNT @ NiCo)2S4) Denoted CNT @ NiCo2S4-0。
Example 1(CNT @ SiO)2Heat treatment at 600 deg.C
Step 1, dissolving 0.16g CTAB in a mixed solution of 30mL deionized water and 120mL ethanol, then adding 1.5mL ammonia water and 0.1g CNTs, fully shaking up in a beaker, performing ultrasonic dispersion for 40min, then performing magnetic stirring on the solution, stirring for 6h under the condition that the rotating speed is 70r/min, adding 1mL TEOS into the solution for multiple times in the stirring process (adding 1mL tetraethoxysilane for 20 times, namely adding 50 microliters of tetraethoxysilane every 18 min), then performing centrifugal washing on the solution until the supernatant is neutral, and performing freeze drying at-48 ℃ to obtain the @ CNT SiO2And (3) powder.
Step 2, the prepared CNT @ SiO2Placing the powder in a ceramic square boat, placing the powder in a tube furnace in a buckling mode, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature at a certain cooling rate to obtain the heat-treated CNT @ SiO2Powder, denoted CNT @ SiO2-1。
Step 3, taking 30mg of the prepared CNT @ SiO2Adding the powder into a glass bottle with a blue cover, adding 40ml of deionized water, performing ultrasonic dispersion for 40min, adding 1g of urea, dissolving, and adding 1ml of 0.1mol/L Ni (NO)3)2And 2ml of 0.1mol/L Co (NO)3)2And magnetically stirring the solution for 5min, sealing the bottle mouth, carrying out hydrothermal reaction at 105 ℃ for 12h, then naturally cooling to room temperature, carrying out suction filtration and washing to neutrality, and drying at 60 ℃ for 12h to obtain powder CNT @ NiCoSilicate-1.
Step 4, taking 10mg of CNT @ NiCoSilicate-1 prepared in the previous step, adding 10ml of ethanol and 30ml of deionized water, and adding 0.1477g of Na2S·9H2And O, transferring the mixture into a 50ml hydrothermal kettle after ultrasonic treatment for 40min, and carrying out hydrothermal reaction for 12h at 160 ℃. Then, the obtained product is centrifuged and cleaned, and freeze-dried to obtain CNT @ NiCo2S4Powder product, noted CNT @ NiCo2S4-1。
Example 2(CNT @ SiO)2Heat treatment at 800 deg.C
Step 1, dissolving 0.16g CTAB in a mixed solution of 30mL deionized water and 120mL ethanol, then adding 1.5mL ammonia water and 0.1g CNTs, fully shaking up in a beaker, performing ultrasonic dispersion for 40min, then performing magnetic stirring on the solution, stirring for 6h under the condition that the rotating speed is 70r/min, adding 1mL TEOS into the solution for multiple times in the stirring process (adding 1mL tetraethoxysilane for 20 times, namely adding 50 microliters of tetraethoxysilane every 18 min), then performing centrifugal washing on the solution until the supernatant is neutral, and performing freeze drying at-48 ℃ to obtain the @ CNT SiO2And (3) powder.
Step 2, the prepared CNT @ SiO2Placing the powder in a ceramic square boat, placing the powder in a tube furnace in a buckling burning mode, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature at a certain cooling rate to obtain the heat-treated CNT @ SiO2Powder, denoted CNT @ SiO2-2。
Step 3, taking 30mg of the prepared CNT @ SiO2Adding the powder into a glass bottle with a blue cover, adding 40ml of deionized water, performing ultrasonic dispersion for 40min, adding 1g of urea, and dissolving1ml of 0.1mol/L Ni (NO) was added3)2And 2ml of 0.1mol/L Co (NO)3)2And magnetically stirring the solution for 5min, sealing the bottle mouth, carrying out hydrothermal reaction at 105 ℃ for 12h, then naturally cooling to room temperature, carrying out suction filtration and washing to neutrality, and drying at 60 ℃ for 12h to obtain powder CNT @ NiCoSilicate-2.
Step 4, taking 10mg of the CNT @ NiCoSilicate-2 prepared in the previous step, adding 10ml of ethanol and 30ml of deionized water, and adding 0.1477g of Na2S·9H2And O, transferring the mixture into a 50ml hydrothermal kettle after ultrasonic treatment for 40min, and carrying out hydrothermal reaction for 12h at 160 ℃. Then, the obtained product is centrifuged and cleaned, and freeze-dried to obtain CNT @ NiCo2S4Powder product, noted CNT @ NiCo2S4-2。
Step 3(CNT @ SiO)2Heat treatment at 1000 deg.C
Step 1, dissolving 0.16g CTAB in a mixed solution of 30mL deionized water and 120mL ethanol, then adding 1.5mL ammonia water and 0.1g CNTs, fully shaking up in a beaker, performing ultrasonic dispersion for 40min, then performing magnetic stirring on the solution, stirring for 6h under the condition that the rotating speed is 70r/min, adding 1mL TEOS into the solution for multiple times in the stirring process (adding 1mL tetraethoxysilane for 20 times, namely adding 50 microliters of tetraethoxysilane every 18 min), then performing centrifugal washing on the solution until the supernatant is neutral, and performing freeze drying at-48 ℃ to obtain the @ CNT SiO2And (3) powder.
Step 2, the prepared CNT @ SiO2Placing the powder in a ceramic square boat, placing the powder in a tube furnace in a buckling burning mode, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature at a certain cooling rate to obtain the heat-treated CNT @ SiO2Powder, denoted CNT @ SiO2-3。
Step 3, taking 30mg of the prepared CNT @ SiO2Adding the powder into a glass bottle with a blue cover, adding 40ml of deionized water, performing ultrasonic dispersion for 40min, adding 1g of urea, dissolving, and adding 1ml of 0.1mol/L Ni (NO)3)2And 2ml of 0.1mol/L Co (NO)3)2Magnetically stirring the solution for 5min, sealing the bottle mouth, carrying out hydrothermal reaction at 105 ℃ for 12h, naturally cooling to room temperature, and carrying out suction filtration and washingAnd cleaning to be neutral, and drying at 60 ℃ for 12h to obtain powder CNT @ NiCoSilicate-3.
Step 4, taking 10mg of the CNT @ NiCoSilicate-3 prepared in the previous step, adding 10ml of ethanol and 30ml of deionized water, and adding 0.1477g of Na2S·9H2And O, transferring the mixture into a 50ml hydrothermal kettle after ultrasonic treatment for 40min, and carrying out hydrothermal reaction for 12h at 160 ℃. Then, the obtained product is centrifuged and cleaned, and freeze-dried to obtain CNT @ NiCo2S4Powder product, noted CNT @ NiCo2S4-3。
CNT @ SiO obtained for comparative example 1 and examples 1-32SEM test of the powder to obtain the image shown in FIG. 1, and CNT @ SiO obtained in comparative example 1 and example 22TEM test of the powder gave the image shown in FIG. 2, and the CNT @ SiO prepared from FIGS. 1 and 22The powder is of a coaxial coating structure, a layer of amorphous silicon dioxide is uniformly coated outside the carbon tube, and the CNT @ SiO is subjected to heat treatment2The heat treatment causes the amorphous silica to expand in volume for increasing tube diameter, and the amorphous SiO on the CNT surface2CNT @ SiO that will bond more tightly to CNT without heat treatment2The pipe diameter of-0 is about 60nm, and after heat treatment at 800 ℃, CNT @ SiO2The pipe diameter of-2 reaches about 80 nm.
CNT @ SiO obtained in comparative example 1 and examples 1 to 32XRD testing is carried out on the powder to obtain the image shown in figure 3, and CNTs @ SiO is obtained after heat treatment at different temperatures2The peak shapes were not significantly different. Is located at 22oAmorphous peaks at the left and right, amorphous SiO2At 26 in the figureoAnd 44oThe peak at (a) is the peak of the carbon nanotube.
SEM test of the CNT @ NiCoSilicate powders obtained in comparative example 1 and examples 1-3 gave images as shown in FIG. 4, and after hydrothermal reaction by adding nickel ions and cobalt ions, silica reacted with them to form silicates forming a very distinct lamellar structure which forms a very distinct lamellar structure with protoCNTs @ SiO2There are significant differences in the structure of (a). Wherein the CNT @ NiCoSilicate-2 can be seen as a very uniform lamella under a scanning electron microscope, and CNTs @ SiO at other temperatures2The silicate product of (A) has very significant differencesOtherwise. The CNT @ NiCoSilicate-0 has poor growth, uneven distribution and thicker lamella; the growth of the CNT @ NiCoSilicate-1 lamella is obviously improved, but the lamella distribution is scattered; the CNT @ NiCoSilicate-2 lamella has excellent growth, very uniform distribution and thinner lamella; the CNT @ NiCoSilicate-3 lamellar growth causes agglomeration, so that the porosity is reduced, and the specific surface area is reduced. It can be seen that CNT @ NiCoSilicate-2 has a uniform and most porous microstructure.
XRD testing was performed on the CNT @ NiCoSilicate powders obtained in comparative example 1 and examples 1-3 to obtain an image shown in FIG. 5, and CNTs @ SiO processed at four temperatures2The peak shapes of the synthesized CNTs @ NiCosilite almost remained the same, corresponding to nickel silicate 49-1859 and cobalt silicate 21-0872 of PDF card, respectively. Is located at 22oThe nearby amorphous peak is inferred to be amorphous SiO during the reaction due to the temperature rise2Tightly combined with CNTs, and residual SiO not completely reacted in the reaction2。
CNT @ NiCo obtained for comparative example 1 and examples 1-32S4SEM and TEM tests are carried out on the powder to obtain images shown in figures 6 and 7, after vulcanization, the original lamellar structure is not damaged, the appearance of the powder is consistent with that of CNTs @ NiCosilite, and the CNT @ NiCo is more obvious from the TEM image shown in figure 72 S 40 poorly lamellar and easily forming agglomerated particles, CNT @ NiCo2S42 sheets grew well.
CNT @ NiCo obtained for comparative example 1 and examples 1-32S4The powder was subjected to XRD measurement to obtain an image shown in FIG. 8, and first, CNT @ NiCo was formed in each of comparative example 1 and examples 1 to 32S4Powder bodies all corresponding to NiCo2S4PDF cards, without heat treatment (comparative example 1), or at too high a heat treatment temperature (comparative example 3), produce Co9S8Co is inhibited at medium-high temperature9S8And amorphous SiO is caused by high temperature2The bonding with CNTs is tight, so that residual SiO still exists after vulcanization is finished2。
For comparative example 1 and example1-3 obtained CNT @ NiCo2S4The powder was subjected to cyclic voltammetry tests of different magnifications to obtain curves as shown in fig. 9, 11, 13 and 15, and it can be seen from the graphs that a pair of redox peaks appear in the images, which are in accordance with the characteristics of the cobaltosic sulfide nickel-nickel composite material.
CNT @ NiCo obtained in comparative example 1 and examples 1 to 32S4The powder is subjected to chronopotentiometric detection at different charge and discharge rates to obtain curves as shown in figures 10, 12, 14 and 16,
as can be seen, CNT @ NiCo was measured at a charge/discharge rate of 1A/g2S40 discharge time 603s, calculated to correspond to a capacitance value of 1507.5F/g, while a capacitance value of 851.3F/g at 5A/g remains 56.46%;
CNT @ NiCo at 1A/g charge/discharge rate2S4-1 sample discharge time 575s, calculated to correspond to a capacitance value of 1437.5F/g, whereas a capacitance value of 1258.75F/g at 5A/g, retained 87.56%;
CNT @ NiCo at 1A/g charge/discharge rate2S4Discharge time of 779s was calculated for-2, corresponding to a capacitance of 1927.5F/g, whereas the capacitance at 5A/g was 1685F/g, which retained 86.52%.
CNT @ NiCo at 1A/g charge/discharge rate2S4-3 sample discharge time 571s, calculated for a value of 1427.5F/g, and a value of 1278.75F/g at 5A/g, with a retention of 89.57%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A high-capacity carbon nanotube-cobaltosic sulfide composite material is characterized by being prepared by the following steps:
step 1, preparing a carbon nanotube-silicon oxide composite material:
weighing hydroxyl carbon nano-tube and surfactant, placing in ethanol and waterAdjusting the pH value of the mixed solution to 8-9, uniformly dispersing, adding ethyl orthosilicate, centrifugally washing a product after the reaction is finished until the solution is neutral, and then freeze-drying and grinding at-30 to-50 ℃ to obtain the carbon nano tube-silicon oxide composite material, namely CNT @ SiO2；
Step 2, the CNT @ SiO prepared in the step 1 is used2Placing the mixture in a tube furnace, and carrying out heat treatment at the temperature of 300-1200 ℃ under the argon protective atmosphere to obtain a heat treatment product;
step 3, putting the heat treatment product obtained in the step 2 into water to obtain an aqueous solution, after uniform dispersion, adjusting the pH value of the aqueous solution to 8-9, and then adding Ni (NO)3)2And Co (NO)3)2Obtaining a reaction system, stirring uniformly, carrying out hydrothermal reaction on the reaction system at the temperature of 80-160 ℃ for 8-16h, naturally cooling to the room temperature of 20-30 ℃, carrying out suction filtration and washing on a product, and drying the product at the temperature of 50-100 ℃ for 4-12h to obtain a carbon nano tube-cobalt nickel silicate composite material, namely CNT @ NiCoSilicate;
step 4, placing the CNT @ NiCoSilicate prepared in the step 3 in a water and ethanol mixed solution of sodium sulfide, performing hydrothermal reaction for 8-16h at the temperature of 100 ℃ and 200 ℃, naturally cooling to the room temperature of 20-30 ℃, washing a product, and performing freeze drying at the temperature of-30 ℃ to-50 ℃ to obtain the carbon nanotube-cobaltosic sulfide composite material, namely the CNT @ NiCo2S4。
2. The high-capacity carbon nanotube-cobaltosic sulfide composite material according to claim 1, wherein in the step 1, the ratio of the mass fraction of the hydroxyl carbon nanotubes to the volume fraction of the tetraethoxysilane is 0.1 (1-1.5), wherein the unit of the mass fraction is g, the unit of the volume fraction is ml, the dropping speed of the tetraethoxysilane is 50 microliters per 15-20 minutes, the carbon nanotube-silicon oxide composite material is of a coaxial coating structure, a layer of amorphous silicon dioxide is uniformly coated on the outer surface of a carbon tube, and the tube diameter is 55-65 nm.
3. The high-capacity carbon nanotube-cobaltosic sulfide composite material as claimed in claim 1, wherein the heat treatment temperature in step 2 is 700-.
4. The high capacity carbon nanotube-nickel cobaltosic sulfide composite material of claim 1, wherein in the step 1, the volume ratio of water to ethanol in the mixed solution of ethanol and water is 1: (3-5), the surfactant is cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride, and the mass ratio of the carbon nano tube powder to the surfactant is 1: (12-20), and adjusting the pH value of the mixed solution to 8-9 by using ammonia water or urea.
5. The high capacity carbon nanotube-cobaltosic sulfide composite material of claim 1, wherein the Ni (NO) in step 3 is Ni (NO)3)2And Co (NO)3)2In Ni2+And Co2+The molar ratio of (1) to (3), and in the step 3, the pH value of the aqueous solution is adjusted to 8-9 by using ammonia water or urea.
6. The high-capacity carbon nanotube-cobaltosic sulfide composite material of claim 1, wherein the concentration of sodium sulfide in the mixed solution of water and ethanol of sodium sulfide in the step 4 is 1-2g/L, and the volume ratio of ethanol to water in the water and ethanol solution is 1 (2-4).
7. A preparation method of a high-capacity carbon nanotube-cobaltosic sulfide composite material comprises the following steps:
step 1, preparing a carbon nanotube-silicon oxide composite material:
weighing hydroxyl carbon nano tubes and a surfactant, placing the hydroxyl carbon nano tubes and the surfactant into a mixed solution of ethanol and water, adjusting the pH value of the mixed solution to 8-9, adding ethyl orthosilicate after uniform dispersion, centrifuging and cleaning a product after reaction is finished until the solution is neutralThen freeze-drying and grinding the mixture at the temperature of between 30 ℃ below zero and 50 ℃ below zero to obtain the carbon nano tube-silicon oxide composite material, namely CNT @ SiO2；
Step 2, the CNT @ SiO prepared in the step 1 is used2Placing the mixture in a tube furnace, and carrying out heat treatment at the temperature of 300-1200 ℃ under the argon protective atmosphere to obtain a heat treatment product;
step 3, putting the heat treatment product obtained in the step 2 into water to obtain an aqueous solution, after uniform dispersion, adjusting the pH value of the aqueous solution to 8-9, and then adding Ni (NO)3)2And Co (NO)3)2Obtaining a reaction system, stirring uniformly, carrying out hydrothermal reaction on the reaction system at the temperature of 80-160 ℃ for 8-16h, naturally cooling to the room temperature of 20-30 ℃, carrying out suction filtration and washing on a product, and drying the product at the temperature of 50-100 ℃ for 4-12h to obtain a carbon nano tube-cobalt nickel silicate composite material, namely CNT @ NiCoSilicate;
and 4, placing the CNT @ NiCoSilicate prepared in the step 3 in a mixed solution of water and ethanol of sodium sulfide, performing hydrothermal reaction for 8-16h at the temperature of 100-200 ℃, naturally cooling to the room temperature of 20-30 ℃, washing a product, and performing freeze drying at the temperature of-30 ℃ to-50 ℃ to obtain the carbon nanotube-cobaltosic sulfide composite material.
8. Use of the high capacity carbon nanotube-dicobalt tetrasulfide composite material of any one of claims 1-6 in a supercapacitor.
9. The use of claim 8, wherein said CNT @ NiCo produced in step 4 is applied2S4Uniformly dispersing a conductive agent and a binder in ethanol, pressing the mixture on foamed nickel after film forming, wherein the conductive agent is carbon black or acetylene black, and the binder is PTFE or PVDF, wherein CNT @ NiCo2S4The mass ratio of the powder to the conductive agent to the binder is 8: 1: 1.
10. the use of claim 8, wherein the high capacity carbon nanotube-cobaltosic sulfide composite has a specific capacity of 1200 to 2000F/g at a current density of 1A/g.
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