CN112366093A - Grid NiCo2O4/CNF material, preparation method thereof and application thereof in super capacitor - Google Patents
Grid NiCo2O4/CNF material, preparation method thereof and application thereof in super capacitor Download PDFInfo
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- CN112366093A CN112366093A CN202011017944.1A CN202011017944A CN112366093A CN 112366093 A CN112366093 A CN 112366093A CN 202011017944 A CN202011017944 A CN 202011017944A CN 112366093 A CN112366093 A CN 112366093A
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 229910005949 NiCo2O4 Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003990 capacitor Substances 0.000 title claims abstract description 22
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 104
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003266 NiCo Inorganic materials 0.000 claims description 38
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002121 nanofiber Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 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
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 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
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001075 voltammogram Methods 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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Abstract
The invention relates to a grid NiCo2O4the/CNF material, the preparation method and the application thereof in the super capacitor comprise the following steps: (1) placing cobalt salt, nickel salt and urea in water, stirring uniformly to obtain a mixed solution, adding carbon nanofiber, carrying out constant-temperature hydrothermal reaction for 5-24 h at 100-150 ℃, cooling to room temperature after the reaction is finished, taking out an intermediate product, washing and drying; (2) calcining the intermediate product prepared in the step (1) for 1 to 3 hours at the temperature of between 200 and 400 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material; the grid NiCo2O4Active of/CNF material as electrodeThe material is used in a super capacitor, the electrochemical performance of the super capacitor is improved, and the specific capacitance is 400-500F/g.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to grid NiCo2O4the/CNF material, the preparation method and the application thereof in the super capacitor.
Background
With the rapid development of the world economy and the continuous acceleration of the global progress of the economy, people have more and more requirements on energy, high-efficiency energy storage electric appliances are widely concerned, and an electrochemical super capacitor is one of the energy storage devices which are widely researched at present. The super capacitor has larger power density and can provide enough instantaneous power for braking of the vehicle. In addition, the super capacitor can also be applied to the aspects of military industry, material transportation, electronic storage devices and the like, and has wide application prospect.
Transition bimetallic oxide NiCo2O4As an electrode material of a super capacitor, the material has the characteristics of low price, low toxicity, specific crystal structure, high electrochemical activity and the like, and is increasingly paid high attention by researchers. The importance of (nano NiCo)2O4Structural characterization of electrode material and research on supercapacitor performance) by electrodeposition method to deposit green (Co, Ni) hydroxide precursor on foamed nickel, and annealing to prepare nano NiCo2O4The electrode material is 1mA/cm2The specific capacity of the charge-discharge current density reaches 1.4F/cm2。
Disclosure of Invention
To solve NiCo2O4The technical problem that the electrochemical performance of the material is not ideal due to the easy pulverization phenomenon existing as an electrode material is solved, and the grid NiC is providedo2O4the/CNF material, the preparation method and the application thereof in the super capacitor. The invention adopts electrostatic spinning method to prepare carbon nano-fiber, then carries out hydrothermal reaction on the carbon nano-fiber, nickel salt and cobalt salt, and then calcines the carbon nano-fiber to prepare NiCo2O4the/CNF material is applied to a supercapacitor electrode material, and the electrochemical performance of the material is improved.
In order to achieve the purpose, the invention is realized by the following technical scheme:
grid NiCo2O4The preparation method of the/CNF material comprises the following steps:
(1) placing cobalt salt, nickel salt and urea in water, stirring uniformly to obtain a mixed solution, adding carbon nanofiber, carrying out constant-temperature hydrothermal reaction for 5-24 h at 100-150 ℃, cooling to room temperature after the reaction is finished, taking out an intermediate product, washing and drying;
(2) calcining the intermediate product prepared in the step (1) for 1 to 3 hours at the temperature of between 200 and 400 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material;
the grid NiCo2O4the/CNF material is used in a super capacitor as an active material of an electrode.
Further, the preparation method of the carbon nanofiber in the step (1) comprises the following steps: dissolving polyacrylonitrile in N, N-dimethylformamide, stirring uniformly to obtain a polyacrylonitrile solution, placing the polyacrylonitrile solution in a needle cylinder for electrostatic spinning, and drying at room temperature after spinning to obtain polyacrylonitrile nano-fibers; and calcining the prepared polyacrylonitrile nano-fiber at 550-1500 ℃ in a nitrogen atmosphere to prepare the carbon nano-fiber.
Furthermore, the electrostatic spinning voltage is 10 KV-30 KV, the flow rate is 0.5 mL/h-5 mL/h, and the height is 10 cm-30 cm.
Still further, the concentration of the polyacrylonitrile in the N, N-dimethylformamide is 0.5 g/mL-2 g/mL.
Further, the cobalt salt is one of cobalt acetate, cobalt chloride and cobalt nitrate; the nickel salt is nickel sulfate or nickel nitrate.
Further, the molar ratio of the cobalt salt, the nickel salt and the urea is 1 (0.2-30) to 1-40; the dosage of the carbon nano fiber in the mixed solution is 0.01 g/mL-0.05 g/mL.
The invention provides a latticed NiCo prepared by the preparation method2O4a/CNF material.
In the last aspect of the invention, the latticed NiCo prepared by the preparation method is provided2O4Application of/CNF material in super capacitor and latticed NiCo2O4the/CNF material is used in a super capacitor as an active material of an electrode.
The beneficial technical effects are as follows:
the invention adopts an electrostatic spinning method to prepare carbon nano-fiber, and then the carbon nano-fiber, nickel salt and cobalt salt are subjected to hydrothermal reaction in an alkaline environment provided by urea and then calcined to prepare NiCo2O4/CNF material and application thereof in supercapacitor electrode material, carbon nanofiber and NiCo2O4The composite material can improve the stability of the main body of the composite material, and further improve the electrochemical performance of the super capacitor. In addition, the carbon nanofiber is obtained by adopting an electrostatic spinning method and calcination, the method is simple and effective, low in cost and free of pollution to the environment, and the prepared carbon nanofiber has good electric and heat conducting properties.
Drawings
FIG. 1 is a schematic representation of a grid-like NiCo prepared in example 12O4SEM topography of/CNF material.
FIG. 2 is a schematic representation of a grid-like NiCo prepared in example 12O4XRD pattern of CNF material.
Fig. 3 is an SEM topography (left) and an XRD pattern (right) of the carbon nanofiber prepared in example 4.
FIG. 4 shows NiCo obtained in comparative example 12O4SEM topography (left) and XRD pattern (right) of the material.
FIG. 5 is a schematic representation of a grid-like NiCo prepared in example 12O4CNF material, CNF from example 4 and NiCo from comparative example 12O4Application of material to measured cycles in supercapacitorsCyclic voltammograms.
FIG. 6 is a schematic representation of a grid-like NiCo prepared in example 12O4CNF Material, CNF from example 4 and NiCo from comparative example 12O4The material is applied to a constant current charge-discharge diagram measured in a super capacitor, wherein the a-grid NiCo2O4a/CNF material, b-CNF, c-NiCo2O4A material.
FIG. 7 is a schematic representation of a grid-like NiCo prepared in example 12O4CNF material, CNF from example 4 and NiCo from comparative example 12O4The material was applied to impedance plots measured in supercapacitors.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
Grid NiCo2O4The preparation method of the/CNF material comprises the following steps:
(1) mixing 0.8g of cobalt nitrate hexahydrate, 0.5g of nickel nitrate hexahydrate, 0.6g of urea and 50mL of deionized water (wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:0.63:3.7) to obtain a mixed solution, adding 1g of carbon nanofibers into the mixed solution, transferring the mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, carrying out constant-temperature hydrothermal reaction at the temperature of 110 ℃ for 10 hours, cooling the reaction kettle to room temperature, taking out an intermediate product, washing, and drying at normal temperature;
(2) calcining the intermediate product prepared in the step (1) for 1.5h at 400 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material.
Wherein the preparation method of the carbon nanofiber in the step (1) comprises the following steps: dissolving 1.2g of polyacrylonitrile in 12mL of N, N-dimethylformamide solvent, uniformly stirring to obtain a polyacrylonitrile solution, placing the polyacrylonitrile solution in a needle cylinder, carrying out electrostatic spinning under the conditions of 15KV voltage, flow rate of 1mL/h and height of 15cm, and drying at room temperature overnight after spinning is finished to obtain PAN nanofibers; and placing the prepared PAN nano-fiber in a porcelain boat, gradually heating from room temperature to 700 ℃ in a nitrogen atmosphere, and calcining for 6h to prepare the CNF carbon nano-fiber.
For NiCo prepared in this example2O4the/CNF material is observed by a scanning electron microscope and tested by X-ray diffraction, and an SEM image and an XRD image are respectively shown in figures 1 and 2. XRD spectrum shows that the material prepared in the example is NiCo2O4a/CNF material; from the SEM image, NiCo2O4The material is NiCo obtained by needle-like growth along the surface of the carbon nanofiber2O4the/CNF material is in a grid-shaped structure.
Example 2
Grid NiCo2O4The preparation method of the/CNF material comprises the following steps:
(1) mixing 0.7g of cobalt nitrate hexahydrate, 0.6g of nickel nitrate hexahydrate, 0.45g of urea and 50mL of deionized water (wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:0.8:3.1) to obtain a mixed solution, adding 1.5g of carbon nanofibers into the mixed solution, transferring the mixed solution into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining, carrying out constant-temperature hydrothermal reaction at the temperature of 100 ℃ for 12 hours, cooling the reaction kettle to room temperature, taking out an intermediate product, washing, and drying at room temperature;
(2) calcining the intermediate product prepared in the step (1) for 1.5h at 300 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material.
Wherein the preparation method of the carbon nanofiber in the step (1) comprises the following steps: dissolving 1.5g of polyacrylonitrile in 12mL of N, N-dimethylformamide solvent, uniformly stirring to obtain a polyacrylonitrile solution, placing the polyacrylonitrile solution in a needle cylinder, carrying out electrostatic spinning under the conditions of 20KV voltage, flow rate of 0.8mL/h and height of 16cm, and drying at room temperature overnight after spinning is finished to obtain PAN nanofibers; and placing the prepared PAN nano-fiber in a porcelain boat, gradually heating the PAN nano-fiber from room temperature to 700 ℃ in a nitrogen atmosphere, and calcining the PAN nano-fiber for 10.2 hours to obtain the CNF carbon nano-fiber.
Example 3
Grid NiCo2O4The preparation method of the/CNF material comprises the following steps:
(1) mixing 0.8g of cobalt nitrate hexahydrate, 0.6g of nickel nitrate hexahydrate, 0.7g of urea and 50mL of deionized water (wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:0.77:4.3) to obtain a mixed solution, adding 1.5g of carbon nanofibers into the mixed solution, transferring the mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, carrying out constant-temperature hydrothermal reaction at the temperature of 120 ℃ for 13 hours, cooling the reaction kettle to room temperature, taking out an intermediate product, washing, and drying at room temperature;
(2) calcining the intermediate product prepared in the step (1) for 1.5h at 300 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material.
Wherein the preparation method of the carbon nanofiber in the step (1) comprises the following steps: dissolving 2g of polyacrylonitrile in 12mL of N, N-dimethylformamide solvent, uniformly stirring to obtain a polyacrylonitrile solution, placing the polyacrylonitrile solution in a needle cylinder, carrying out electrostatic spinning under the conditions of 18KV voltage, flow rate of 0.8mL/h and height of 15cm, and drying at room temperature overnight after spinning is finished to obtain PAN nanofibers; and placing the prepared PAN nano-fiber in a porcelain boat, gradually heating the PAN nano-fiber from room temperature to 900 ℃ in a nitrogen atmosphere, and calcining the PAN nano-fiber for 10 hours to obtain the CNF carbon nano-fiber.
Example 4
Grid NiCo2O4The preparation method of the/CNF material comprises the following steps:
(1) mixing 0.9g of cobalt nitrate hexahydrate, 1.1g of nickel nitrate hexahydrate, 0.8g of urea and 50mL of deionized water (wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:0.74:4.3) to obtain a mixed solution, adding 1.2g of carbon nanofibers into the mixed solution, transferring the mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, carrying out constant-temperature hydrothermal reaction at the temperature of 120 ℃ for 12 hours, cooling the reaction kettle to room temperature, taking out an intermediate product, washing, and drying at room temperature;
(2) calcining the intermediate product prepared in the step (1) for 1.5h at 300 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material.
Wherein the preparation method of the carbon nanofiber in the step (1) comprises the following steps: dissolving 1.1g of polyacrylonitrile in 12mL of N, N-dimethylformamide solvent, uniformly stirring to obtain a polyacrylonitrile solution, placing the polyacrylonitrile solution in a needle cylinder, carrying out electrostatic spinning under the conditions of 19KV voltage, flow rate of 0.9mL/h and height of 18cm, and drying at room temperature overnight after spinning is finished to obtain PAN nanofibers; and placing the prepared PAN nano-fiber in a porcelain boat, gradually heating from room temperature to 800 ℃ in a nitrogen atmosphere, and calcining for 9 hours to obtain the CNF carbon nano-fiber.
The CNF carbon nanofibers produced in this example were subjected to observation by a scanning electron microscope and X-ray diffraction test, and the SEM image and the XRD image are shown in fig. 3.
Comparative example 1
NiCo2O4The preparation method comprises the following steps:
(1) mixing 0.8g of cobalt nitrate hexahydrate, 0.5g of nickel nitrate hexahydrate, 0.6g of urea and 50mL of deionized water (wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:0.63:3.7) to obtain a mixed solution, then transferring the mixed solution into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining, carrying out constant-temperature hydrothermal reaction for 10 hours at the temperature of 110 ℃, cooling the reaction kettle to room temperature, taking out an intermediate product, washing, and drying at room temperature;
(2) calcining the intermediate product prepared in the step (1) for 1.5h at 400 ℃ in an oxygen atmosphere, and cooling to prepare NiCo2O4A material.
For NiCo prepared in this comparative example2O4The material was observed by a scanning electron microscope and subjected to an X-ray diffraction test, and an SEM chart and an XRD chart are shown in FIG. 4.
Grid NiCo from example 12O4CNF material, CNF from example 4 and NiCo from comparative example 12O4The material was applied as an active material in a supercapacitor and then subjected to electrochemical testing. Electrochemical testing the above materials were subjected to electrochemical analysis using an electrochemical workstation (CHI 660). The electrode body is a three-electrode system, the working electrode is foamed nickel, the counter electrode is a platinum mesh electrode, and the reference electrode is a saturated calomel electrode.
The active material, PVDF and acetylene black of the above example were mixed in a mass ratio of 8:1:1, isopropanol was added as a dispersant, and after uniform stirring, the coating was applied to a nickel foam working electrode in the application range of 1.0 cm × 1.0 cm, and dried in a vacuum oven at 60 ℃ for 12 hours. Then, electrochemical performance tests were performed.
Grid NiCo from example 12O4CNF material, CNF from example 4 and NiCo from comparative example 12O4The cyclic voltammogram of the material applied to a supercapacitor at a scan rate of 5mV/s is shown in FIG. 5. As can be seen from fig. 5, the CV curve shows a quasi-reversible electron transfer process, indicating that the measured capacitance is mainly based on redox, unlike the electrical double layer capacitor CV curve which approaches the ideal rectangle. Albeit NiCo2O4CNF, CNF and NiCo2O4All oxidation-reduction reactions occur, but the NiCo of the present invention2O4the/CNF composite shows a stronger redox peak current and a larger integrated area, which indicates that the NiCo of the invention2O4the/CNF composite material has larger capacitance.
The specific capacitance is calculated as follows:
where Cs is the specific capacitance (F/g), I is the current (A), m is the electrode material mass (g), V is the scanning speed (V/s), and Δ V is the voltage range (V). At 5mV/s, the grid-like NiCo of inventive example 12O4The specific capacitance of the/CNF material electrode is 443F/g; NiCo of the examples 2 to 4 of the present invention was measured at 5mV/s2O4The specific capacitance of the/CNF material electrode is 400F/g-500F/g.
Grid NiCo from example 12O4CNF Material, CNF from example 4 and NiCo from comparative example 12O4The constant current charge-discharge diagram of the material applied to the super capacitor measured in 6M KOH under different current densities of 2A/g, 3A/g, 4A/g and 6A/g is shown in FIG. 6. As can be seen from FIG. 6, the current density increased from 2A/g to 6A/g, and the voltage was non-linear with time, but NiCo of the present invention2O4The charge-discharge time of the electrode material of the/CNF material is longer, which shows that NiCo2O4Internal resistance ratio NiCo of/CNF material2O4And the side surface reflects that the conductivity of the material is better, and the material shows better capacitance characteristics.
Grid NiCo from example 12O4CNF material, CNF from example 4 and NiCo from comparative example 12O4The impedance profile measured for the material applied to the supercapacitor is shown in figure 7. In theory, an almost vertical impedance line is an ideal capacitor. However, as can be seen from FIG. 7, in the low frequency region, the grid-like NiCo2O4The radius of the impedance arc of the CNF material is the largest, which illustrates the grid-like NiCo of the invention2O4the/CNF material has good capacitance characteristics and good diffusion performance. Comparing the impedances of the three materials, CNF and NiCo2O4The compounding of the material can improve the conductivity of the whole material, the NiCo of the invention2O4the/CNF material has a higher electrical conductivity,the transfer of electrons can be accelerated. Carbon nanofibers and NiCo2O4The combination of (2) improves the stability of the main body of the composite material, and further improves the electrochemical performance of the super capacitor.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. Grid NiCo2O4The preparation method of the/CNF material is characterized by comprising the following steps:
(1) placing cobalt salt, nickel salt and urea in water, stirring uniformly to obtain a mixed solution, adding carbon nanofiber, carrying out constant-temperature hydrothermal reaction for 5-24 h at 100-150 ℃, cooling to room temperature after the reaction is finished, taking out an intermediate product, washing and drying;
(2) calcining the intermediate product prepared in the step (1) for 1 to 3 hours at the temperature of between 200 and 400 ℃ in an oxygen atmosphere, and cooling to prepare the latticed NiCo2O4a/CNF material;
the grid NiCo2O4the/CNF material is used in a super capacitor as an active material of an electrode.
2. The reticulated NiCo of claim 12O4The preparation method of the/CNF material is characterized in that the preparation method of the carbon nanofiber in the step (1) comprises the following steps: dissolving polyacrylonitrile in N, N-dimethylformamide, stirring uniformly to obtain a polyacrylonitrile solution, placing the polyacrylonitrile solution in a needle cylinder for electrostatic spinning, and drying at room temperature after spinning to obtain polyacrylonitrile nano-fibers; and calcining the prepared polyacrylonitrile nano-fiber at 550-1500 ℃ in a nitrogen atmosphere to prepare the carbon nano-fiber.
3. The reticulated NiCo of claim 22O4The preparation method of the/CNF material is characterized in that the electrostatic spinning voltage is 10 KV-30 KV, the flow rate is 0.5 mL/h-5 mL/h, and the height is 10 cm-30 cm.
4. The reticulated NiCo of claim 22O4The preparation method of the/CNF material is characterized in that the concentration of the polyacrylonitrile in the N, N-dimethylformamide is 0.5 g/mL-2 g/mL.
5. The reticulated NiCo of any of claims 1 to 42O4The preparation method of the/CNF material is characterized in that the cobalt salt is one of cobalt acetate, cobalt chloride and cobalt nitrate; the nickel salt is nickel sulfate or nickel nitrate.
6. The reticulated NiCo of claim 52O4The preparation method of the/CNF material is characterized in that the molar ratio of the cobalt salt, the nickel salt and the urea is 1 (0.2-30) to 1-40; the dosage of the carbon nano fiber in the mixed solution is 0.01 g/mL-0.05 g/mL.
7. The grid-shaped NiCo prepared by the preparation method of any one of claims 1 to 62O4a/CNF material.
8. The grid-shaped NiCo prepared by the preparation method of any one of claims 1 to 62O4Use of/CNF materials in supercapacitors, characterized in that the grid-like NiCo2O4the/CNF material is used in a super capacitor as an active material of an electrode.
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| CN107424847A (en) * | 2017-07-21 | 2017-12-01 | 张娟 | A kind of preparation method of nitrogen-doped carbon nano-fiber Supported Co acid nickel combination electrode material |
| CN107993849A (en) * | 2017-11-27 | 2018-05-04 | 陕西科技大学 | A kind of flexible electrode material of carbon fiber loaded cobalt acid nickel nano-array and preparation method thereof |
| CN109273278A (en) * | 2018-10-23 | 2019-01-25 | 陕西科技大学 | A kind of preparation method of cobalt acid nickel nano wire cladding carbon fiber flexible electrode material |
| CN109449011A (en) * | 2018-10-23 | 2019-03-08 | 陕西科技大学 | A kind of preparation method growing needle-shaped network structure cobalt acid nickel flexible electrode using carbon fiber as supporter |
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| CN106847523A (en) * | 2016-12-29 | 2017-06-13 | 吴中区穹窿山德毅新材料技术研究所 | A kind of flexible super capacitor electrode material and its application |
| CN107424847A (en) * | 2017-07-21 | 2017-12-01 | 张娟 | A kind of preparation method of nitrogen-doped carbon nano-fiber Supported Co acid nickel combination electrode material |
| CN107993849A (en) * | 2017-11-27 | 2018-05-04 | 陕西科技大学 | A kind of flexible electrode material of carbon fiber loaded cobalt acid nickel nano-array and preparation method thereof |
| CN109273278A (en) * | 2018-10-23 | 2019-01-25 | 陕西科技大学 | A kind of preparation method of cobalt acid nickel nano wire cladding carbon fiber flexible electrode material |
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Application publication date: 20210212 |