CN110970229A - 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
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- CN110970229A CN110970229A CN201911381114.4A CN201911381114A CN110970229A CN 110970229 A CN110970229 A CN 110970229A CN 201911381114 A CN201911381114 A CN 201911381114A CN 110970229 A CN110970229 A CN 110970229A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 239000004005 microsphere Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002931 mesocarbon microbead Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910003266 NiCo Inorganic materials 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 8
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 7
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 transition metal sulfides Chemical class 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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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
- H01G11/22—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
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- 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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- 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
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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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 NiCo2S4With mesocarbon microbeads andthe carbon nano tube is compounded with two carbon materials, thereby overcoming the defect of the existing 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. Carbon nanotube material having a very good mechanical stability and a large contact area in its construction, which provides a large ratio for the composite material with only a small amountThe surface area is large, and the conductivity is high, and countless tubular structures contribute to electron channels, so that the conductivity of the composite material is enhanced. 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 surface2S4The sea urchin-shaped sphere of the nanoneedle belongs to a porous material, and the specific surface area of the nanoneedle can be increased due to the needle-shaped structure. 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 12S4The circulation stability performance diagram of the @ mesophase carbon microsphere/carbon nanotube composite material.
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, pure mesophase carbon microspheres, carbon nanotubes and pure NiCo, respectively2S4(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 aboveThe shape and performance test results 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 (10)
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.
2. The composite material of claim 1, wherein said NiCo2S4The nano needle structure is formed and loaded on the surface of the mesocarbon microbeads;
the carbon nanotube is wound around the NiCo2S4A surface.
3. The NiCo of claim 1 or 22S4The 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.
4. The method according to claim 3, wherein in step a), the cobalt source comprises a soluble cobalt salt;
preferably, the soluble cobalt salt comprises at least one of cobalt nitrate, cobalt acetate or cobalt chloride;
preferably, the nickel source comprises a soluble nickel salt; more preferably, the soluble nickel salt comprises at least one of nickel nitrate, nickel acetate, or nickel chloride;
preferably, the molar ratio of the cobalt source to the nickel source is 0.8-1.2: 1.8-2.2, preferably 1: 2;
preferably, the total concentration of cobalt ions in the cobalt source and nickel ions in the nickel source in the precursor solution is 0.1 mol/L-0.3 mol/L.
5. The method according to claim 3 or 4, wherein in step a) the pH adjusting agent is urea;
preferably, in the 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 3-5: 1, and preferably 4: 1.
6. The method according to claim 3, wherein in the step b), the temperature of the hydrothermal reaction is 100-150 ℃ and the time is 5-10 h;
preferably, in step b), the temperature of the hydrothermal reaction is 120 ℃ and the time is 8 h.
7. The method according to claim 3 or 6, wherein in step b), the hydrothermal reaction further comprises washing and drying after the hydrothermal reaction is finished;
preferably, the washing is carried out with water and/or ethanol; the drying is vacuum drying at 30-60 ℃.
8. The method according to claim 3, wherein in step c), the vulcanizing agent used for vulcanizing is selected from at least one of sodium sulfide nonahydrate and thioacetamide, preferably sodium sulfide nonahydrate;
preferably, in the step c), the vulcanization temperature is 120-180 ℃ and the time is 8-24 h;
further preferably, in step c), the temperature of the vulcanization is 160 ℃ and the time is 12 h.
9. The method according to claim 3 or 8, wherein in step c), the vulcanizing further comprises washing, drying and grinding after the vulcanizing is finished;
preferably, the washing is carried out with water and/or ethanol; the drying is vacuum drying at 30-60 ℃.
10. The NiCo of claim 1 or 22S4The application of the @ mesophase carbon microsphere/carbon nanotube composite material in the aspect of supercapacitor materials.
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| 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 |
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