CN110718398B - 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

Info

Publication number
CN110718398B
CN110718398B CN201810770649.XA CN201810770649A CN110718398B CN 110718398 B CN110718398 B CN 110718398B CN 201810770649 A CN201810770649 A CN 201810770649A CN 110718398 B CN110718398 B CN 110718398B
Authority
CN
China
Prior art keywords
cnt
composite material
powder
carbon nanotube
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810770649.XA
Other languages
Chinese (zh)
Other versions
CN110718398A (en
Inventor
侯峰
宋丹
张愉昕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201810770649.XA priority Critical patent/CN110718398B/en
Publication of CN110718398A publication Critical patent/CN110718398A/en
Application granted granted Critical
Publication of CN110718398B publication Critical patent/CN110718398B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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)2And uniformly stirring the solution, carrying out hydrothermal reaction for 8-16h at the temperature of 80-160 ℃, carrying out suction filtration and drying to obtain the 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 composite material 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 performanceAnd (4) 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 address the NiCo existing in the prior art2S4The defect of small capacity, and provides a high-capacity carbon nano tube-cobaltosic sulfide composite material;
another object of the present invention is to provide a method for preparing a high capacity carbon nanotube-cobaltosic sulfide composite 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 composite material to a supercapacitor, wherein the high-capacity carbon nanotube-cobaltosic sulfide composite material 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)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 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, in the step 3Ni (NO) of3)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 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)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 @ 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 ℃ 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 nanoRice pipe-cobaltosic sulfide composite (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 @ NiCo prepared by the method2S4The 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 powder has a structure 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 multiplying power performance is 5A/gThe capacity of 89.5 percent can be still maintained.
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 at the rotating speed of 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 min), centrifuging and washing the solution until the supernatant is neutral, and performing freeze drying at-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 ℃. WhileThen 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, 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-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, 0.16g CTAB is dissolved in a mixed solution of 30ml deionized water and 120ml ethanol, and then 1.5 g CTAB is addedFully shaking mL of ammonia water and 0.1g of CNTs in a beaker, performing ultrasonic dispersion for 40min, then performing magnetic stirring on the solution, stirring for 6h under the condition that the rotation speed is 70r/min, adding 1mL of 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), then performing centrifugal cleaning on the solution until the supernatant is neutral, and performing freeze drying at the temperature of minus 48 ℃ to obtain 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)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-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. Amorphous peak around 22 degree, amorphous SiO2The peaks at 26 ° and 44 ° in the figure are the peaks of the carbon nanotubes.
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 products of (a) have very distinct differences. 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. The amorphous peak at around 22 ℃ is inferred to be caused by the increase in temperature during the reaction, resulting in amorphous SiO2Tightly 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
CNT @ NiCo obtained for comparative example 1 and examples 1-32S4The 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 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, adding ethyl orthosilicate after uniform dispersion, centrifugally cleaning a product after reaction till 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, 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 the catalystTo carbon nanotube-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 method of claim 1, wherein the carbon nanotube-cobaltosic sulfide has a high capacityNickel composite material, characterized in that Ni (NO) in step 33)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 in a mixed solution of ethanol and water, adjusting the pH value of the mixed solution to 8-9, adding ethyl orthosilicate after uniform dispersion, centrifugally cleaning a product after reaction till 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, 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.
CN201810770649.XA 2018-07-13 2018-07-13 High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof Active CN110718398B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810770649.XA CN110718398B (en) 2018-07-13 2018-07-13 High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810770649.XA CN110718398B (en) 2018-07-13 2018-07-13 High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110718398A CN110718398A (en) 2020-01-21
CN110718398B true CN110718398B (en) 2021-12-07

Family

ID=69209267

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810770649.XA Active CN110718398B (en) 2018-07-13 2018-07-13 High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110718398B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463026B (en) * 2020-03-31 2022-05-10 深圳大学 Nickel-cobalt-sulfur/carbon nanotube composite material and preparation method and application thereof
CN111748140B (en) * 2020-07-13 2022-10-04 山东东宏管业股份有限公司 CNTs (carbon nanotubes) conduction technology-based combustible gas composite pipe and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129871A (en) * 2015-07-31 2015-12-09 徐靖才 Preparation method of NiCo2S4/carbon nanotube composite material
CN105244482A (en) * 2015-09-12 2016-01-13 复旦大学 Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010014650A2 (en) * 2008-07-29 2010-02-04 Honda Motor Co., Ltd. Preferential growth of single-walled carbon nanotubes with metallic conductivity
CN101857234B (en) * 2010-06-10 2012-05-23 天津大学 Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method
CN104229729A (en) * 2014-08-21 2014-12-24 南京航空航天大学 Method for transferring carbon nanotube vertical array to flexible polymer substrate
CN105252432A (en) * 2015-09-24 2016-01-20 安徽威铭耐磨材料有限公司 Carbon-contained nanotube reinforced nano ceramic binding agent diamond grinding wheel and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129871A (en) * 2015-07-31 2015-12-09 徐靖才 Preparation method of NiCo2S4/carbon nanotube composite material
CN105244482A (en) * 2015-09-12 2016-01-13 复旦大学 Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"表面修饰碳纳米管/环氧树脂复合材料的界面结构与性能";崔伟;《中国博士学位论文全文数据库 工程科技I辑》;20111015(第10期);正文第86-111页 *

Also Published As

Publication number Publication date
CN110718398A (en) 2020-01-21

Similar Documents

Publication Publication Date Title
Wang et al. Controllable synthesis of SnO 2@ C yolk–shell nanospheres as a high-performance anode material for lithium ion batteries
Sun et al. A hybrid ZnO/Si/porous-carbon anode for high performance lithium ion battery
Xia et al. Green and facile fabrication of hollow porous MnO/C microspheres from microalgaes for lithium-ion batteries
Hong et al. Hierarchical SnO2 nanoclusters wrapped functionalized carbonized cotton cloth for symmetrical supercapacitor
CN102906016B (en) The method preparing two-dimentional interlayer nano material based on Graphene
Nithya et al. Effect of pH on the sonochemical synthesis of BiPO4 nanostructures and its electrochemical properties for pseudocapacitors
Lu et al. In situ-formed hollow cobalt sulfide wrapped by reduced graphene oxide as an anode for high-performance lithium-ion batteries
Choi et al. Three-dimensional porous graphene-metal oxide composite microspheres: Preparation and application in Li-ion batteries
CN106904596A (en) The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application
CN110610816A (en) Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material
KR101975033B1 (en) Graphene having pores made by irregular and random, and Manufacturing method of the same
CN105679551B (en) Based on Ni (OH)2The graphene nano wall electrode of super capacitor preparation method of/NiO nano particles
CN105271170B (en) Preparation method of nano carbon and composite material of nano carbon
Yi et al. Tailored silicon hollow spheres with Micrococcus for Li ion battery electrodes
Kim et al. Synthesis of microsphere silicon carbide/nanoneedle manganese oxide composites and their electrochemical properties as supercapacitors
Yao et al. Design and synthesis of hierarchical NiCo 2 S 4@ NiMoO 4 core/shell nanospheres for high-performance supercapacitors
Dai et al. High-yield synthesis of carbon nanotube–porous nickel oxide nanosheet hybrid and its electrochemical capacitance performance
Sun et al. Porous Si/C anode materials by Al–Si dealloying method with PEA surfactant assisted cross-linked carbon coating for lithium-ion battery applications
CN110718398B (en) High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof
Feng et al. One-step for in-situ etching and reduction to construct oxygen vacancy modified MoO2/reduced graphene oxide nanotubes for high performance lithium-ion batteries
KR20170094123A (en) Method for producing metal compound particle group, metal compound particle group, and electrode for electricity storage device containing metal compound particle group
Jiao et al. Controlled scalable synthesis of yolk-shell structured large-size industrial silicon with interconnected carbon network for lithium storage
Li et al. Controllable synthesis of 3D hierarchical cactus-like ZnCo2O4 films on nickel foam for high-performance asymmetric supercapacitors
CN109755570A (en) Three-dimensional combination electrode material and preparation method thereof, electrode and energy storage device
Feng et al. Core–shell structured MnSiO 3 supported with CNTs as a high capacity anode for lithium-ion batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

Address after: 300452 Binhai Industrial Research Institute Campus of Tianjin University, No. 48 Jialingjiang Road, Binhai New Area, Tianjin

Patentee after: Tianjin University

Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92

Patentee before: Tianjin University