CN110970229B - NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof - Google Patents
NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110970229B CN110970229B CN201911381114.4A CN201911381114A CN110970229B CN 110970229 B CN110970229 B CN 110970229B CN 201911381114 A CN201911381114 A CN 201911381114A CN 110970229 B CN110970229 B CN 110970229B
- Authority
- CN
- China
- Prior art keywords
- composite material
- carbon
- nickel
- cobalt
- nico
- 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
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof. In the composite material, the mesocarbon microbeads account for 17.5-22.5% of the total mass of the composite material; the carbon nano tube accounts for 2.5-7.5% of the total mass of the composite material. The composite material is prepared by mixing NiCo2S4Is compounded with two carbon materials of mesocarbon microbeads and carbon nanotubes, thereby overcoming the defects of the prior pure-phase NiCo2S4The composite material has the advantages of unstable structure, low conductivity, short life cycle and fatal short plate with the actual specific capacity of the carbon material being less than 200F/g, and also obviously improves the specific capacity and the stability of cyclic charge and discharge when the composite material is used for a super capacitor.
Description
Technical Field
The invention relates to the field of composite material preparation, in particular to NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof.
Background
The traditional chemical energy storage device cannot meet the requirement of people on high energy storage devices due to the fatal defects of serious chemical pollution, short service life, high preparation cost and the like. The super capacitor has the advantages of environmental friendliness, excellent reversibility, high power density, long service life and the like, is widely applied to occasions with high requirements on instantaneous high electric energy, such as aerospace, microelectronic devices, electronic communication, wearable intelligent equipment and the like, and particularly has great attention in the field of novel energy automobiles.
The most critical factor determining the performance of a supercapacitor is its electrode material. Following the pseudocapacitance theory, noble metals possess large specific capacities, but their high cost and toxicity are prohibitive. And NiCo2S4The typical spinel structure material can also obtain a higher voltage window and specific capacity, has the characteristics of no toxicity and environmental friendliness, and is more suitable for replacing a noble metal material as a supercapacitor material. But pure NiCo2S4Its life cycle is limited due to the inherent disadvantages of transition metal sulfides, such as unstable structure, low conductivity, etc. While the stable structure and excellent conductivity of the carbon material are apparent, the actual specific capacity of less than 200F/g is fatal.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material prepared by mixing NiCo2S4Is compounded with two carbon materials of mesocarbon microbeads and carbon nanotubes, thereby overcoming the defects of the prior pure-phase NiCo2S4The composite material has the advantages of unstable structure, low conductivity, short life cycle and fatal short plate with the actual specific capacity of the carbon material being less than 200F/g, and also obviously improves the specific capacity and the stability of cyclic charge and discharge when the composite material is used for a super capacitor.
The second object of the present invention is to provide the above NiCo2S4The preparation method of the @ mesophase carbon microsphere/carbon nanotube composite material is simple and easy to implement, low in cost and environment-friendly.
The third object of the present invention is to provide the above NiCo2S4The application of the @ mesophase carbon microsphere/carbon nanotube composite material in the aspect of supercapacitor materials.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
NiCo2S4@ intermediate phase carbon microsphere/carbon nanotube composite material, wherein the intermediate phase carbon microsphere accounts for 17.5-22.5% of the total mass of the composite material; the carbon nano tube accounts for 2.5-7.5% of the total mass of the composite material.
Optionally, the mesophase carbon microspheres and the carbon nanotubes are the NiCo2S4The substrate material of (1).
Optionally, the NiCo2S4The nano needle structure is formed and loaded on the surface of the mesocarbon microbeads; the carbon nanotube is wound around the NiCo2S4A surface.
Alternatively, in the present invention, NiCo2S4The nano needles grow on the surface of the mesocarbon microbeads to form sea urchin-shaped spheres, so that the composite material is used as a porous material and has a larger specific surface area.
In the invention, the mesophase carbon microsphere is a micron-sized carbon microsphere material derived from asphalt, the preparation cost is low, and the commercial value of the mesophase carbon microsphere in the field of electrochemical energy storage is proved. The carbon nanotube material has very good mechanical stability and large contact area in structure, can provide a large specific surface area for the composite material only by a small amount, has high conductivity, and has numerous tubular structures contributing to electronic channels and enhancing the conductivity of the composite material. This is also that we choose the mesocarbon microbeads/carbon nanotubes and NiCo2S4The reason for compounding is. In addition, the carbon sphere is negatively charged, and can electrostatically attract positive ions cobalt and nickel, thereby being beneficial to the growth of nickel cobaltate nanoneedles.
By looking up documents, the prior art is mostly the pure composition of nickel cobaltate and graphene, carbon tubes or carbon spheres. The cost of the graphene is too high, the dispersibility is poor, the graphene is easy to agglomerate, the size of a single carbon sphere is larger, the graphene is not a porous material, and the graphene is not suitable for being directly used as an ultra-electricity material. In the invention, the composite material is formed by growing NiCo on the surface2S4Sea urchin shape of nanoneedleThe morphology of the sphere belongs to a porous material, and the needle-shaped structure can also increase the specific surface area of the sphere. The mesocarbon microbeads and the carbon nanotubes respectively account for 17.5-22.5% and 7.5-2.5% of the total mass, wherein the capacitor material can be directly influenced by the carbon materials, and the capacity of the final product is reduced due to the low specific capacity of the mesocarbon microbeads and the carbon nanotubes when the proportion is large although the electrical conductivity is good; if the ratio is too low, the conductivity may be reduced and the stability may be deteriorated as shown by the reduced capacity retention for long cycles. Through a large number of experiments, the applicant selects the use amounts of the mesocarbon microbeads and the carbon nanotubes, so that excellent conductivity can be ensured, and the capacity of a final product can be ensured.
According to another object of the present invention, there is provided the above NiCo2S4A preparation method of a @ mesophase carbon microsphere/carbon nano tube composite material. The method comprises the following steps:
a) adding a cobalt source, a nickel source and a pH regulator into the aqueous dispersion of the mesocarbon microbeads and the carbon nanotubes, and uniformly mixing to obtain a precursor solution;
b) carrying out hydrothermal reaction on the precursor solution obtained in the step a) to obtain a precursor;
c) vulcanizing the precursor obtained in the step b) to obtain NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material.
Optionally, in step a), after the mesophase carbon microspheres and the carbon nanotubes are ultrasonically dispersed in water, an aqueous dispersion of the mesophase carbon microspheres and the carbon nanotubes is obtained.
Optionally, the power of the ultrasonic dispersion is 140W to 800W, preferably 600W; the time of ultrasonic dispersion is 10min to 60min, preferably 30 min.
Optionally, in step a), the cobalt source comprises a soluble cobalt salt.
Optionally, the soluble cobalt salt comprises at least one of cobalt nitrate, cobalt acetate, or cobalt chloride.
Optionally, the nickel source comprises a soluble nickel salt.
Optionally, the soluble nickel salt comprises at least one of nickel nitrate, nickel acetate, or nickel chloride.
Optionally, the molar ratio of the cobalt source to the nickel source is 0.8-1.2: 1.8-2.2.
Optionally, the cobalt source and the nickel source are in a molar ratio of 1: 2.
Optionally, the total concentration of cobalt ions in the cobalt source and nickel ions in the nickel source in the precursor solution is 0.1mol/L to 0.3 mol/L.
Optionally, the total concentration of cobalt ions in the cobalt source and nickel ions in the nickel source in the precursor solution is 0.225 mol/L.
Optionally, in step a), the pH adjusting agent is urea.
Optionally, in the step a), the molar ratio of the pH regulator to the total amount of metal ions of the cobalt source and the nickel source in the precursor solution is 3-5: 1.
Optionally, in step a), the molar ratio of the pH adjusting agent to the total amount of metal ions of the cobalt source and the nickel source in the precursor solution is 4: 1.
The shape of the composite material can be effectively adjusted by adjusting the use amount of the pH regulator (such as urea). The proper molar ratio of the pH regulator (such as urea) to the total metal ions of the cobalt source and the nickel source in the precursor liquid is selected, so that the precursor (cobalt nickel hydroxide) can be better formed in the hydrothermal reaction process.
Optionally, in the step b), the temperature of the hydrothermal reaction is 100-150 ℃ and the time is 5-10 h.
Optionally, in step b), the temperature of the hydrothermal reaction is 120 ℃ and the time is 8 h.
Optionally, in step b), washing and drying are further included after the hydrothermal reaction is finished.
Optionally, the washing is performed with water and/or ethanol; the drying is vacuum drying at 30-60 ℃.
Optionally, in step c), the vulcanizing agent used for vulcanizing is selected from at least one of sodium sulfide nonahydrate and thioacetamide.
Optionally, in step c), the vulcanizing agent used for vulcanizing is sodium sulfide nonahydrate.
Optionally, in the step c), the temperature of the vulcanization is 120-180 ℃ and the time is 8-24 h.
Optionally, in step c), the temperature of the vulcanization is 160 ℃ and the time is 12 h.
Optionally, in step c), the method further comprises washing, drying and grinding after the vulcanization is finished.
Optionally, the washing is performed with water and/or ethanol; the drying is vacuum drying at 30-60 ℃.
Optionally, the grinding time is 15min to 35min, preferably 30 min.
As an embodiment of the present invention, NiCo2S4The preparation method of the @ mesophase carbon microsphere/carbon nanotube composite material comprises the following steps:
1) after ultrasonically dispersing the mesocarbon microbeads and the carbon nanotubes in distilled water, adding nickel salt, cobalt salt and urea into the mesocarbon microbeads, wherein the mesocarbon microbeads are negatively charged and can adsorb positive nickel cobalt ions, the nickel salt and the cobalt salt provide the cobalt ions and the nickel ions, and uniformly stirring the mixture to enable more positive ions to be adsorbed on the carbon spheres to obtain a mixed solution;
2) carrying out hydrothermal reaction on the mixed solution obtained in the step 1) in a reaction kettle, crystallizing to form intermediate phase cobalt nickel hydroxide in the hydrothermal reaction process, wherein the cobalt nickel hydroxide is used as a precursor of a sulfide, and the structure of the cobalt nickel hydroxide is reserved after the subsequent vulcanization step; the urea is a pH regulator and has the function of regulating the appearance;
3) taking out the reactant obtained in the step 2), washing with water and ethanol, washing to remove cobalt and nickel ions which are not completely reacted, drying at low temperature in vacuum, vulcanizing by sodium sulfide nonahydrate, cooling to room temperature, washing with water and ethanol, and drying at low temperature in vacuum to obtain NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material.
According to another object of the present invention, there is also provided the above NiCo2S4The application of the @ mesophase carbon microsphere/carbon nanotube composite material in the aspect of supercapacitor materials.
Compared with the prior art, the invention has the beneficial effects that:
(1) the NiCo provided by the invention2S4@ mesophase carbon microsphere/carbon nanotube composite material prepared by mixing NiCo2S4Is compounded with two carbon materials of mesocarbon microbeads and carbon nanotubes, thereby overcoming the defects of the prior pure-phase NiCo2S4The composite material has the advantages of unstable structure, low conductivity, short life cycle and fatal short plate with the actual specific capacity of the carbon material being less than 200F/g, obviously improves the specific capacity and the stability of cyclic charge and discharge when being used for the super capacitor, and has good cost performance, high conductivity and difficult agglomeration.
(2) The NiCo provided by the invention2S4The preparation method of the @ mesophase carbon microsphere/carbon nanotube composite material is simple and easy to implement, low in cost and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic representation of NiCo prepared in example 1 of the invention2S4@ SEM picture of mesophase carbon microsphere/carbon nanotube composite material;
FIG. 2 is a schematic representation of NiCo prepared in example 1 of the present invention2S4The XRD curve diagram of the intermediate phase carbon microsphere/carbon nano tube composite material is @;
FIG. 3 is a schematic representation of NiCo prepared in example 1 of the present invention2S4@ mid-phase carbon microsphere/carbon nanotube composite material cyclic voltammetry curve;
FIG. 4 is a NiCo preparation from example 12S4@ intermediate phase carbon microsphere/carbon nanotube composite material constant current discharge curve diagram;
FIG. 5 is a NiCo preparation from example 12S4@ mesophase carbon microsphere/carbon nanotube composite material circulation stabilityEnergy diagram.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Ultrasonically dispersing 121.92mg of carbon spheres and 30.48mg of carbon nanotubes in distilled water for 30min, and then performing ultrasonic dispersion according to Ni2+/Co2+To this was added 1.5mmol Ni (NO) in a 1:2:12 molar ratio/urea3)2·6H2O、3mmol Co(NO3)2·6H2O and 18mmol of urea are stirred to obtain a uniform mixed solution;
(2) transferring the mixed solution into a hydrothermal reaction kettle, and reacting for 8 hours at 120 ℃;
(3) taking out the reactant, washing with deionized water and ethanol, vacuum drying at 60 deg.C for 24 hr, dissolving with 1.755g sodium sulfide nonahydrate in distilled water, and stirring for 20 min;
(4) transferring the mixed solution into a hydrothermal reaction kettle for vulcanization, and reacting for 12 hours at 160 ℃;
(5) and taking out the reactant, washing the reactant by deionized water and ethanol, and drying the reactant for 24 hours in vacuum at the temperature of 60 ℃ to obtain the final product.
Example 2
(1) 137.16mg of carbon spheres and 15.24mg of carbon nanotubes were ultrasonically dispersed in distilled water for 30min, followed by Ni2+/Co2+To this was added 1.5mmol Ni (NO) in a 1:2:12 molar ratio/urea3)2·6H2O、3mmol Co(NO3)2·6H2O and 18mmol of urea are stirred to obtain a uniform mixed solution;
(2) transferring the mixed solution into a hydrothermal reaction kettle, and reacting for 8 hours at 120 ℃;
(3) taking out the reactant, washing with deionized water and ethanol, vacuum drying at 30 deg.C for 24 hr, dissolving with 1.755g sodium sulfide nonahydrate in distilled water, and stirring for 20 min;
(4) transferring the mixed solution into a hydrothermal reaction kettle for vulcanization, and reacting for 12 hours at 160 ℃;
(5) and taking out the reactant, washing the reactant by deionized water and ethanol, and performing vacuum drying at the temperature of 30 ℃ for 24 hours to obtain a final product.
Example 3
(1) 106.68mg of carbon spheres and 45.72mg of carbon nanotubes were ultrasonically dispersed in distilled water for 30min, followed by Ni2+/Co2+To this was added 1.5mmol Ni (NO) in a 1:2:12 molar ratio/urea3)2·6H2O、3mmol Co(NO3)2·6H2O and 18mmol of urea are stirred to obtain a uniform mixed solution;
(2) transferring the mixed solution into a hydrothermal reaction kettle, and reacting for 8 hours at 120 ℃;
(3) taking out the reactant, washing with deionized water and ethanol, vacuum drying at 60 deg.C for 24 hr, dissolving with 1.755g sodium sulfide nonahydrate in distilled water, and stirring for 20 min;
(4) transferring the mixed solution into a hydrothermal reaction kettle for vulcanization, and reacting for 12 hours at 160 ℃;
(5) and taking out the reactant, washing the reactant by deionized water and ethanol, and drying the reactant for 24 hours in vacuum at the temperature of 60 ℃ to obtain the final product.
Experimental example 1
NiCo prepared as described in example 12S4The @ intermediate phase carbon microsphere/carbon nanotube composite material is typical, and is subjected to SEM scanning electron microscope, XRD test, cyclic voltammetry curve graph measurement, constant current discharge test and cyclic stability performance test.
As can be seen from the SEM photograph of FIG. 1, NiCo prepared according to the present invention2S4The composite material of the carbon microsphere and the carbon nano tube with the intermediate phase forms carbon sphere loaded NiCo2S4The structure of the nanometer needle, and the carbon nanometer tube is wound on the surface.
In FIG. 2, PDF #20-0782 is a standard card, NCS @ MCMB/CNT, MCMB, CNT and NCS represent a composite product and pure mesophase carbon microspheres respectivelyCarbon nanotubes and pure NiCo2S4(ii) a As can be seen from FIG. 2, the resulting NiCo was prepared2S4@ mesophase carbon microsphere/carbon nanotube composite material containing NiCo2S4A phase.
As can be seen from the cyclic voltammogram of FIG. 3, NiCo prepared according to the present invention2S4The @ mesophase carbon microsphere/carbon nanotube composite material shows good cyclic voltammetry characteristics and Co3+/Co2+And Ni3+/Ni2+The oxidation reduction peak is generated, and the core principle of the super capacitor is pseudocapacitance, which indicates that the super capacitor is the pseudocapacitance.
As can be seen from the constant current discharge curve of FIG. 4, NiCo prepared by the present invention2S4@ mesophase carbon microsphere/carbon nanotube composite material with current density of 1, 1.5, 2, 5 and 10A g-1The specific capacitance values of the lower pairs are 1680, 1647, 1572, 1252, 836, respectively, indicating the energy storage capability at different current densities.
As can be seen from the cycle stability plot of FIG. 5, NiCo prepared according to the present invention2S4@ mesophase carbon microsphere/carbon nanotube composite material is 10A g-1The specific capacitance value of 76.9% is still kept after 1000 cycles under the current density, which shows that the stability is good and the capacity is not attenuated.
The results of the above morphology and performance tests show that the NiCo prepared by the invention2S4The @ mesophase carbon microsphere/carbon nanotube composite material meets the expected requirements of experiments, can meet the requirements of supercapacitor materials, and has excellent performance indexes and good stability.
The samples prepared in the embodiments 2 and 3 are tested by the same characterization means, and the appearance and various performance indexes of the samples are similar to those of the sample prepared in the embodiment 1, which is not described herein again.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (22)
1.NiCo2S4The @ mesophase carbon microsphere/carbon nanotube composite material is characterized in that in the composite material, the mesophase carbon microsphere accounts for 17.5-22.5% of the total mass of the composite material; the carbon nano tube accounts for 2.5-7.5% of the total mass of the composite material;
the NiCo2S4The nano needle structure is formed and loaded on the surface of the mesocarbon microbeads;
the carbon nanotube is wound around the NiCo2S4A surface.
2. The NiCo of claim 12S4The preparation method of the @ mesophase carbon microsphere/carbon nanotube composite material is characterized by comprising the following steps:
a) adding a cobalt source, a nickel source and a pH regulator into the aqueous dispersion of the mesocarbon microbeads and the carbon nanotubes, and uniformly mixing to obtain a precursor solution;
b) carrying out hydrothermal reaction on the precursor solution obtained in the step a) to obtain a precursor;
c) vulcanizing the precursor obtained in the step b) to obtain NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material.
3. The method according to claim 2, wherein in step a) the cobalt source comprises a soluble cobalt salt.
4. The method of claim 3, wherein the soluble cobalt salt comprises at least one of cobalt nitrate, cobalt acetate, or cobalt chloride.
5. The method of claim 2, wherein in step a), the nickel source comprises a soluble nickel salt.
6. The method of claim 5, wherein the soluble nickel salt comprises at least one of nickel nitrate, nickel acetate, or nickel chloride.
7. The method according to claim 2, wherein the molar ratio of the cobalt source to the nickel source in step a) is 0.8-1.2: 1.8-2.2.
8. The method of claim 7, wherein the cobalt source and the nickel source are present in a molar ratio of 1: 2.
9. The method according to claim 2, wherein in step a), the total concentration of cobalt ions in the cobalt source and nickel ions in the nickel source in the precursor solution is 0.1mol/L to 0.3 mol/L.
10. The method according to claim 2, wherein in step a) the pH adjusting agent is urea.
11. The method according to claim 2, wherein the molar ratio of the total amount of metal ions of the cobalt source and the nickel source in the pH regulator and the precursor solution in step a) is 3-5: 1.
12. The method according to claim 11, wherein the molar ratio of the total amount of metal ions of the cobalt source and the nickel source in the pH adjuster and the precursor solution is 4: 1.
13. The method according to claim 2, wherein the temperature of the hydrothermal reaction in step b) is 100 ℃ to 150 ℃ and the time is 5h to 10 h.
14. The method according to claim 13, wherein in step b), the temperature of the hydrothermal reaction is 120 ℃ and the time is 8 h.
15. The method according to claim 2, wherein the hydrothermal reaction in step b) further comprises washing and drying after the hydrothermal reaction is finished.
16. The method according to claim 15, wherein the washing is performed with water and/or ethanol; the drying is vacuum drying at 30-60 ℃.
17. The method according to claim 2, wherein in step c), the vulcanizing agent used for vulcanizing is selected from at least one of sodium sulfide nonahydrate and thioacetamide.
18. The method according to claim 17, wherein the vulcanizing agent used for the vulcanization is sodium sulfide nonahydrate.
19. The process according to claim 2, wherein in step c), the temperature of the vulcanization is 120 ℃ to 180 ℃ for 8h to 24 h.
20. The process according to claim 19, wherein in step c) the vulcanization is carried out at a temperature of 160 ℃ for a period of 12 h.
21. The method according to claim 2, wherein the step c) further comprises washing, drying and grinding after the end of the sulfurization.
22. The method according to claim 21, wherein the washing is performed with water and/or ethanol; the drying is vacuum drying at 30-60 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911381114.4A CN110970229B (en) | 2019-12-27 | 2019-12-27 | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
| PCT/CN2020/139270 WO2021129787A1 (en) | 2019-12-27 | 2020-12-25 | Nico2s4@mesocarbon microbead/carbon nanotube composite material, preparation method for same, and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911381114.4A CN110970229B (en) | 2019-12-27 | 2019-12-27 | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110970229A CN110970229A (en) | 2020-04-07 |
| CN110970229B true CN110970229B (en) | 2020-11-06 |
Family
ID=70036943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911381114.4A Active CN110970229B (en) | 2019-12-27 | 2019-12-27 | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110970229B (en) |
| WO (1) | WO2021129787A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970229B (en) * | 2019-12-27 | 2020-11-06 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
| CN111916288A (en) * | 2020-07-28 | 2020-11-10 | 陕西科技大学 | Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof |
| CN112011249B (en) * | 2020-08-17 | 2021-11-30 | 湖南开磷雁峰塔涂料有限公司 | High-strength flame-retardant water-based epoxy resin coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014048098A1 (en) * | 2012-09-26 | 2014-04-03 | 华为技术有限公司 | Composite negative electrode material for lithium ion battery, preparation method thereof and lithium ion battery |
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Water-system asymmetric super-capacitor based on NiCo2S4 and NiCo2S4 composite material |
| CN105129871A (en) * | 2015-07-31 | 2015-12-09 | 徐靖才 | Preparation method of NiCo2S4/carbon nanotube composite material |
| CN107924768A (en) * | 2015-08-26 | 2018-04-17 | 纳米技术仪器公司 | Porous particle and production method as the interconnection 3D graphenes of electrode of super capacitor active material |
| CN109309203A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application |
| CN109621997A (en) * | 2019-01-10 | 2019-04-16 | 兰州大学 | NiCo2S4/ C microsphere nano composite material, preparation method and its application |
| CN110233058A (en) * | 2019-07-15 | 2019-09-13 | 浙江工业大学 | A kind of self assembly hollow form NiCo2S4 material, preparation method and its application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104088016B (en) * | 2014-07-03 | 2016-06-08 | 浙江理工大学 | The one dimension NiCo on activated carbon fiber surface2S4Crystal array and its preparation method |
| KR101933937B1 (en) * | 2016-05-25 | 2018-12-31 | 재단법인대구경북과학기술원 | Hierarchical NiCo2S4 Nanowire Arrays Supported on Ni Foam: An Efficient and Durable Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions |
| CN110970229B (en) * | 2019-12-27 | 2020-11-06 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
-
2019
- 2019-12-27 CN CN201911381114.4A patent/CN110970229B/en active Active
-
2020
- 2020-12-25 WO PCT/CN2020/139270 patent/WO2021129787A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014048098A1 (en) * | 2012-09-26 | 2014-04-03 | 华为技术有限公司 | Composite negative electrode material for lithium ion battery, preparation method thereof and lithium ion battery |
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Water-system asymmetric super-capacitor based on NiCo2S4 and NiCo2S4 composite material |
| CN105129871A (en) * | 2015-07-31 | 2015-12-09 | 徐靖才 | Preparation method of NiCo2S4/carbon nanotube composite material |
| CN107924768A (en) * | 2015-08-26 | 2018-04-17 | 纳米技术仪器公司 | Porous particle and production method as the interconnection 3D graphenes of electrode of super capacitor active material |
| CN109309203A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application |
| CN109621997A (en) * | 2019-01-10 | 2019-04-16 | 兰州大学 | NiCo2S4/ C microsphere nano composite material, preparation method and its application |
| CN110233058A (en) * | 2019-07-15 | 2019-09-13 | 浙江工业大学 | A kind of self assembly hollow form NiCo2S4 material, preparation method and its application |
Non-Patent Citations (1)
| Title |
|---|
| Bimetallic NiCo2S4 Nanoneedles Anchored on Mesocarbon Microbeads as Advanced Electrodes for Asymmetric supercapacitors;Yu Zhang et al;《Nano-Micro Lett》;20190423;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110970229A (en) | 2020-04-07 |
| WO2021129787A1 (en) | 2021-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wen et al. | Hierarchical MoS2 nanowires/NiCo2O4 nanosheets supported on Ni foam for high-performance asymmetric supercapacitors | |
| Lang et al. | Facile approach to prepare loose-packed NiO nano-flakes materials for supercapacitors | |
| Xiao et al. | Rapid microwave-assisted fabrication of 3D cauliflower-like NiCo 2 S 4 architectures for asymmetric supercapacitors | |
| Lang et al. | A facile approach to the preparation of loose-packed Ni (OH) 2 nanoflake materials for electrochemical capacitors | |
| Li et al. | In situ growth of nickel-cobalt oxyhydroxide/oxide on carbon nanotubes for high performance supercapacitors | |
| CN110970229B (en) | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof | |
| Huang et al. | Facilely synthesized porous ZnCo 2 O 4 rodlike nanostructure for high-rate supercapacitors | |
| Chakrabarty et al. | Controlling the electrochemical performance of β-Ni (OH) 2/carbon nanotube hybrid electrodes for supercapacitor applications by La doping: A systematic investigation | |
| Ali et al. | Hydrothermal synthesis of cerium‐doped Co3O4 nanoflakes as electrode for supercapacitor application | |
| Xie et al. | A coralliform-structured γ-MnO2/polyaniline nanocomposite for high-performance supercapacitors | |
| Zhou et al. | Multi-layer-stacked Co 9 S 8 micro/nanostructure directly anchoring on carbon cloth as a flexible electrode in supercapacitors | |
| Xiong et al. | Synthesis of porous Ni–Co–Mn oxide nanoneedles and the temperature dependence of their pseudocapacitive behavior | |
| Lian et al. | Facile synthesis of hierarchical MnO 2 sub-microspheres composed of nanosheets and their application for supercapacitors | |
| Yang et al. | The in-situ growth of zinc-aluminum layered double hydroxides on graphene and its application as anode active materials for Zn-Ni secondary battery | |
| Zhu et al. | In situ growth of MnO 2 nanosheets on activated carbon fibers: a low-cost electrode for high performance supercapacitors | |
| Luo et al. | Urchin-like NiCo 2 O 4 hollow microspheres with oxygen vacancies synthesized by self-template for supercapacitor | |
| Zhang et al. | Construction of MnO2 nanowires@ Ni1− xCoxOy nanoflake core-shell heterostructure for high performance supercapacitor | |
| Quan et al. | High-performance pseudo-capacitor energy storage device based on a hollow-structured copper sulfide nanoflower and carbon quantum dot nanocomposite | |
| Gao et al. | High dispersion and electrochemical capacitive performance of NiO on benzenesulfonic functionalized carbon nanotubes | |
| Hong et al. | Enhanced electrochemical performance of hollow Cu-Co selenide for hybrid supercapacitor applications | |
| Hu et al. | Synthesis and electrochemical capacitance of sheet-like cobalt hydroxide | |
| Zhang et al. | Microwave-assisted green synthesis of manganese molybdate nanorods for high-performance supercapacitor | |
| CN110282663B (en) | Method for preparing nano materials with different dimensions based on same metal iron ions | |
| Shi et al. | Carbonate doped NiCo-LDH modified with PANI for high performance asymmetric supercapacitors | |
| Chen et al. | Polycrystalline iron oxide nanoparticles prepared by C-dot-mediated aggregation and reduction for supercapacitor application |
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 |