CN114709086A - Nickel-based metal organic framework layered nanosheet array material and preparation and application thereof - Google Patents
Nickel-based metal organic framework layered nanosheet array material and preparation and application thereof Download PDFInfo
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 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
- H01G11/48—Conductive polymers
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- 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
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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- 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
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a nickel-based metal organic frame layered nano-sheet array material, a preparation method and an application thereof, wherein the chemical formula is [ Ni ]3(OH)2(C8H4O4)2(H2O)4]·2H2The material is prepared by taking basic nickel nitrate as a solid precursor, taking terephthalic acid as a ligand and adopting a solvothermal method under the action of a surfactant, wherein the molecular formula of the basic nickel nitrate is Ni3(NO3)2(OH)4(ii) a The preparation method has the advantages that the nucleation sites are dispersed by creatively utilizing the solid precursors, so that the prepared nickel-based MOF has unique morphology, the stacked structure of the sheets has rich pore channels, the permeation of electrolyte is facilitated, and the material has good performance when being used as an electrode material of a super capacitorGood electrochemical performance; in addition, the preparation method is simple in preparation process, low in cost and short in preparation period, can be used as the positive electrode material of the super capacitor at any time, and promotes the application of the MOF-based material in the field of electrochemical energy storage.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a nickel-based metal organic framework layered nanosheet array material and preparation and application thereof.
Background
With the rapid development of modern economy, the reserves of non-renewable energy sources such as coal, petroleum, diesel oil and the like on the earth are less and less. Meanwhile, the utilization of a large amount of traditional energy sources directly causes environmental problems such as PM 2.5, haze, greenhouse effect and the like. To solve or alleviate these existing problems, the development of renewable clean energy is imperative. Solar energy, tidal energy, wind energy and the like are clean energy which are researched more, but the limitations of high cost, region limitation and the like exist generally, so that the energy cannot be continuously provided, and the large-scale application to the actual life is difficult. Therefore, the research of electrochemical energy conversion and storage systems is very important. In recent years, electrochemical energy storage systems such as fuel cells, supercapacitors and second generation lithium batteries have been studied and developed. In various electrochemical energy storage devices, supercapacitors have the advantages of excellent power density, fast charge and discharge rate, long cycle life and the like, and have potential application prospects in the aspects of portable electronic products, standby power storage, electric automobiles and the like, and have attracted extensive attention in academia and industry in the past decades.
The performance of the electrode material almost determines the performance of the supercapacitor, but most of the traditional electrode materials such as carbon-based materials, metal oxide materials, conductive polymers and the like have the problems of low voltage window, small specific capacitance, poor cycling stability and the like. With the continuous and intensive research, researchers in the field find that a nickel-based Metal-organic framework (MOF) is a novel material with the advantages of ultrahigh porosity, adjustable pore size distribution, convenient synthesis, designable structure and the like, and has a wide application prospect in the field of electrochemical energy storage.
However, most of the existing nickel-based MOFs are still synthesized by a traditional solvothermal method, for example, a preparation method of carbon-supported nano nickel disclosed in chinese patent CN103464784B is to dissolve nickel salt in an organic solvent, and then add an organic ligand to obtain a mixed solution; transferring the mixed solution into a high-pressure kettle for high-temperature reaction to obtain a nickel-containing organic framework compound and carrying out post-treatment; and finally, placing the sample in a tubular furnace, and calcining at high temperature in inert gas to obtain the finished product of the carbon-supported nano nickel. Although this method is less difficult to operate, during the preparation of MOFs using soluble metal salts, foreign anionic impurities may be introduced, thus generating unnecessary waste; and the release process of the metal cations is relatively uncontrolled, it is not conducive to designing MOF materials that synthesize the desired morphological structure.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a nickel-based metal organic framework layered nanosheet array material and preparation and application thereof.
The technical scheme disclosed by the invention is as follows: a nickel-base metal-organic frame laminated nano-sheet array material has a chemical formula of [ Ni ]3(OH)2(C8H4O4)2(H2O)4]·2H2The material is prepared by taking basic nickel nitrate as a solid precursor, taking terephthalic acid as a ligand and adopting a solvothermal method under the action of a surfactant, wherein the molecular formula of the basic nickel nitrate is Ni3(NO3)2(OH)4。
Furthermore, the solid precursor is of a spherical structure, the diameter of the sphere is 1-5 mu m, the surface is not smooth, the solid precursor is formed by stacking sheet structures, and the thickness of each sheet is 50-100 nm.
Furthermore, the nickel-based metal organic framework layered nanosheet array material is in an orderly stacked lamellar structure, the thickness of the nanosheets is 20-30nm, and the overall shape is regular.
Further, the surfactant is polyvinylpyrrolidone (PVP) or Sodium Dodecyl Sulfate (SDS).
The preparation method of the nickel-based metal organic framework layered nanosheet array material comprises the following steps:
s1, mixing Ni (NO)3)2·6H2Dissolving O in acetone, performing ultrasonic dispersion, placing in a reaction kettle, adding ethanol, stirring, placing in an oven for reaction, taking out the reaction kettle after reaction, and cooling at room temperature;
s2, carrying out post-treatment on the substance obtained in the step S1 to obtain a basic nickel nitrate precursor;
s3, weighing a certain amount of basic nickel nitrate precursor and terephthalic acid in a reaction kettle, adding DMF, adding KOH into the mixed solution, adding a surfactant, stirring, putting into an oven for hydrothermal reaction, taking out the reaction kettle after the reaction is finished, and cooling at room temperature;
and S4, carrying out post-treatment on the substance obtained in the step S3 to obtain the nickel-based metal organic framework structure material.
Further, in step S1, the reaction temperature in the oven is 130-170 ℃, and the reaction time is 3-5 h.
Further, in step S3, the mass ratio of the basic nickel nitrate to the terephthalic acid is 0.8-1.2: 1.
Further, in step S3, the concentration of KOH is 0.2M, and the volume ratio of the solvent DMF to KOH is 8-12: 1; the concentration of the surfactant is 0-2 mg/mL-1。
Further, in step S3, the temperature of the hydrothermal reaction is 80-120 ℃, and the reaction time is 6-10 h.
The nickel-based metal organic framework layered nanosheet array material can be applied to a supercapacitor, and specifically, the obtained nickel-based MOF is used as an electrode material, and the current density is 1Ag-1The specific capacitance can reach 1574Fg-1。
The invention has the beneficial effects that:
1. the MOF material is prepared by adopting a solid precursor method, the nucleation sites for the growth of the organic metal framework are dispersed, and the method has no external anion interference and can reduce the generation of waste products; along with the continuous progress of the reaction, as the ligand is excessive, Ni ions are continuously consumed, the spherical particle size is continuously reduced until the spherical particle size completely disappears, metal ions are gradually combined with the ligand, the nucleation and growth processes of the MOF can be effectively controlled, the sheet structure gradually occupies the main body appearance, is generated around the spherical structure and is gradually self-assembled into a layer-by-layer stacking structure, the conversion from a solid precursor to the MOF is realized, the obtained material is rich in a porous structure, can be used as an electrode material and an electrocatalysis material of clean energy, and has a wide market prospect;
2. compared with the traditional method for preparing the nickel-based MOF by using the soluble metal salt, the method for preparing the MOF by using the solid precursor has the advantages that the metal ions in the solid-phase material are more effectively constrained, so that the metal ions are released in a more controllable mode from the space-time perspective, the morphological structure of the product can be designed, the reaction can be controlled to be continuous and stable, the yield of the product can be improved, the prepared product has a good laminated morphology through precise detailed design, the regular morphology is more beneficial to the permeation of electrolyte and the transfer of electrons in an electrochemical test, and the electrochemical performance of the material can be improved;
3. according to the method, the nickel-based MOF is prepared by using the solid precursor, and based on the rapid kinetics principle, the use of organic solvents such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF) and the like commonly used in the conventional MOF synthesis can be avoided or reduced to the greatest extent, so that the environment-friendly conversion from solid to MOF is realized;
4. the nickel-based MOF designed by the application is used as an electrode material to prepare a working electrode, and the current density is 1Ag-1The specific capacitance of the time can reach 1574Fg-1The electrochemical performance is good; the material can be applied to the field of super capacitors, is used as an electrode material of the super capacitor, can also be applied to buckle-type asymmetric super capacitors, has high practical application value, and provides an idea for simple preparation of clean energy materials;
5. the nickel-based metal organic framework layered nanosheet array material is prepared in a short time through a simple solid precursor synthesis method, the preparation process is simpler, the preparation time is saved, the cost is low, and the large-scale commercial popularization is facilitated.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a solid precursor basic nickel nitrate prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image of the nickel-based metal organic framework layered nanosheet array material prepared in example 1;
fig. 3 is a Scanning Electron Microscope (SEM) image of the nickel-based metal organic framework layered nanosheet array material prepared in example 2;
fig. 4 is an X-ray diffraction pattern (XRD) of the nickel-based metal-organic framework layered nanosheet array material prepared in example 2;
fig. 5 is a Scanning Electron Microscope (SEM) image of the nickel-based metal organic framework layered nanosheet array material prepared in example 3;
FIG. 6 is a Cyclic Voltammogram (CV) of the nickel-based metal-organic framework layered nanosheet array material prepared in example 3; the voltage is set to 0-0.6V, and the scanning rate is 5, 10, 20, 30, 40, 50, 70, 100mVs-1；
FIG. 7 is a constant current charge-discharge diagram (GCD) of the nickel-based metal organic framework layered nanosheet array material prepared in example 3, with the voltage set to 0-0.5V and the current density set to 1, 2, 3, 4, 5, 7, 10Ag-1。
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1: preparation of nickel-based metal organic framework layered nanosheet array material
S1, mixing 2.5g of Ni (NO)3)2·6H2Dissolving O in 2.5mL of acetone, ultrasonically dissolving for 30min, standing for 8h to obtain a uniform dispersion liquid, adding the uniform dispersion liquid into a reaction kettle, adding 20mL of ethanol, stirring for 1h, putting the mixture into an oven, reacting at 150 ℃ for 3.5h, taking out the reaction kettle, and cooling at room temperature;
s2, repeatedly carrying out centrifugal separation on the reaction product for multiple times by using deionized water and ethanol at room temperature, removing surface impurities of the reaction product after ultrasonic washing, and then placing the washed reaction product in an oven for drying at 60 ℃ to obtain a basic nickel nitrate precursor;
s3, weighing 0.1487g of basic nickel nitrate and 0.166g of terephthalic acid in a reaction kettle, adding 20mL of DMF, adding 2mL of KOH with the concentration of 0.2M into the mixed solution, not adding PVP solution, stirring for about 1min, putting the mixed solution into an oven for hydrothermal reaction, reacting at 100 ℃ for 8h, taking out the reaction kettle, and cooling at room temperature;
s4, repeatedly carrying out centrifugal separation on the reaction product by using ethanol and deionized water at room temperature for multiple times, removing surface impurities of the reaction product after ultrasonic washing, and then placing the washed reaction product in an oven for drying at 60 ℃ to finally obtain the nickel-based metal organic framework layered nanosheet array material;
s5, when preparing an electrode material, compounding the prepared nickel-based metal organic framework layered nanosheet array material with conductive agent superconducting carbon black and binder polyvinylidene fluoride according to the mass ratio of 80:15:5, grinding, and coating the mixture on a foamed nickel current collector to serve as a working electrode.
Fig. 1 is an SEM image of a precursor basic nickel nitrate prepared in this example, and it can be seen from the SEM image that the obtained basic nickel nitrate is a spherical structure with a non-smooth surface, the particle size of the sphere is 1-5 μm, the surface of the microsphere is assembled by nano-sheets, and the thickness of the single sheet is 50-100 nm.
Fig. 2 is an SEM image of the nickel-based metal organic framework layered nanosheet array material prepared in this embodiment, the obtained material is an ordered sheet structure stacked layer by layer, the nanosheets are thin, the thickness is about 20-30nm, and the overall morphology is regular.
The prepared sample has good electrochemical performance and is used as an electrode material of a super capacitor, and the current density of the sample is 1Ag-1Specific capacitance of 1400Fg-1。
Example 2: preparation of nickel-based metal organic framework layered nanosheet array material
Example 2 differs from example 1 only in that a PVP solution was used in step S3, and the remaining steps are the same, and the specific procedure of step S3 is as follows:
s3, weighing 0.1487g of basic nickel nitrate and 0.166g of terephthalic acid in a reaction kettle, adding 20mL of DMF, adding 2mL of KOH with the concentration of 0.2M into the mixed solution, and adding 2mL of KOH with the concentration of 1 mg/mL-1Stirring the PVP solution for 1min, putting the PVP solution into an oven for hydrothermal reaction, taking out the reaction kettle after reacting for 8h at 100 ℃, and cooling at room temperature;
fig. 3 is an SEM image of the nickel-based metal organic framework layered nanosheet array material prepared in this embodiment, the obtained material is an ordered sheet-like structure stacked layer by layer, the nanosheets are sheet-like, have a thickness of about 20-30nm, are regular in overall morphology, and have a small amount of spherical precursors.
Fig. 4 is an XRD pattern of the nickel-based metal organic framework layered nanosheet array material prepared in this example, the prepared material is denoted as NiBDC, and is consistent with single crystal simulation data (No.638866), and no other miscellaneous peak exists, which proves that the nickel-based metal organic framework material is successfully synthesized.
The sample prepared by the embodiment has good electrochemical performance, and can be used as an electrode material of a super capacitor with the current density of 1Ag-1Specific capacitance of 1360Fg-1。
Example 3: preparation of nickel-based metal organic framework layered nanosheet array material
Example 3 differs from example 2 only in that different concentrations of PVP solutions were used in step S3, the remaining steps are the same, and the specific procedure of step S3 is as follows:
s3, weighing 0.1487g of basic nickel nitrate and 0.166g of terephthalic acid in a reaction kettle, adding 20mL of DMF, adding 2mL of KOH with the concentration of 0.2M into the mixed solution, and adding 2mL of KOH with the concentration of 2 mg/mL-1Stirring the PVP solution for 1min, putting the PVP solution into an oven for hydrothermal reaction, taking out the reaction kettle after reacting for 8h at 100 ℃, and cooling at room temperature;
fig. 5 is an SEM image of the nickel-based metal organic framework layered nanosheet array material prepared in this embodiment, the obtained material has an ordered sheet structure stacked layer by layer, the nanosheets are in a sheet shape, the thickness of the nanosheets is about 20-30nm, the overall morphology is regular, and the overall size is reduced to some extent.
FIG. 6 is a cyclic voltammogram (scan rates of 5, 10, 20, 30, 40, 50, 70, 100mV · s, respectively) of the nickel-based metal-organic framework layered nanosheet array material prepared in this example-1) Obvious redox peaks can be observed, and the area of the closed graph is increased along with the increase of the sweep rate as the sweep rate is gradually moved towards two sides, and the redox peaks mainly come from OH in the electrochemical reaction-Pseudocapacitance resulting from faradaic redox reactions of intercalation and delamination.
FIG. 7 is a constant current charge-discharge diagram of the nickel-based metal organic framework layered nanosheet array material prepared in this example, calculated to have current densities of 1, 2, 3, 4, 5, 7 and 10Ag-1The specific capacitance is 1574, 1484, 1428, 1352, 1320, 1204, 1070Fg-1. The material prepared by the embodiment also has excellent electrochemical performance.
Tests show that the nickel-based metal organic framework layered nanosheet array material prepared by the solid precursor method has a regular laminated morphology, and is simple in preparation process and short in time consumption. Can be applied to the field of electrochemical energy storage, and has good electrochemical performance after being prepared into an electrode material.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, and the technical features of the present invention are not limited thereto, and other embodiments that can be made by those skilled in the art without departing from the technical scope of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The nickel-based metal organic framework layered nanosheet array material is characterized in that the material has a chemical formula of [ Ni3(OH)2(C8H4O4)2(H2O)4]·2H2The material is prepared by taking basic nickel nitrate as a solid precursor, taking terephthalic acid as a ligand and adopting a solvothermal method under the action of a surfactant, wherein the molecular formula of the basic nickel nitrate is Ni3(NO3)2(OH)4。
2. The nickel-based metal organic framework layered nanosheet array material of claim 1, wherein the solid precursor is of a spherical structure, the spherical diameter is 1-5 μm, the surface is not smooth, the nanosheets are stacked in a sheet-like structure, and the thickness of each single sheet is 50-100 nm.
3. The nickel-based metal organic framework layered nanosheet array material of claim 1, wherein the nickel-based metal organic framework layered nanosheet array material is in an orderly stacked lamellar structure, the nanosheets are 20-30nm thick, and the overall morphology is regular.
4. The nickel-based metal-organic framework layered nanosheet array material of claim 1, wherein the surfactant is polyvinylpyrrolidone or sodium dodecyl sulfate.
5. A preparation method of a nickel-based metal organic framework layered nanosheet array material is used for preparing the nickel-based metal organic framework layered nanosheet array material as defined in any one of claims 1 to 4, and is characterized by comprising the following specific steps:
s1, mixing Ni (NO)3)2·6H2Dissolving O in acetone, performing ultrasonic dispersion, placing in a reaction kettle, adding ethanol, stirring, placing in an oven for reaction, taking out the reaction kettle after reaction, and cooling at room temperature;
s2, carrying out post-treatment on the substance obtained in the step S1 to obtain a basic nickel nitrate precursor;
s3, weighing a certain amount of basic nickel nitrate precursor and terephthalic acid in a reaction kettle, adding DMF, adding KOH into the mixed solution, adding a surfactant, stirring, putting into an oven for hydrothermal reaction, taking out the reaction kettle after the reaction is finished, and cooling at room temperature;
and S4, carrying out post-treatment on the substance obtained in the step S3 to obtain the nickel-based metal organic framework structure material.
6. The method for preparing the nickel-based metal organic framework layered nanosheet array material of claim 5, wherein in step S1, the temperature of the reaction in the oven is 130-170 ℃, and the reaction time is 3-5 h.
7. The method for preparing the nickel-based metal organic framework layered nanosheet array material of claim 5, wherein in step S3, the mass ratio of the basic nickel nitrate to the terephthalic acid is 0.8-1.2: 1.
8. The method for preparing the nickel-based metal organic framework layered nanosheet array material of claim 5, wherein in step S3, the concentration of KOH is 0.2M, and the volume ratio of the solvent DMF to the KOH is 8-12: 1; the concentration of the surfactant is 0-2 mg/mL-1。
9. The preparation method of the nickel-based metal organic framework layered nanosheet array material of claim 5, wherein in step S3, the hydrothermal reaction is carried out at a temperature of 80-120 ℃ for a reaction time of 6-10 h.
10. Application of the nickel-based metal organic framework layered nanosheet array in the field of supercapacitors as defined in any one of claims 1 to 4, wherein the nickel-based MOF is used as an electrode material and has a current density of 1Ag-1The specific capacitance of the time can reach 1574Fg-1。
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