CN112053861B - In-situ preparation method of three-dimensional conductive MOF @ MXene composite electrode - Google Patents
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- PUXBEKLSMBVFNW-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexamine hexahydrochloride Chemical compound Cl.Cl.Cl.Cl.Cl.Cl.NC1=CC=2C3=CC(=C(C=C3C3=CC(=C(C=C3C2C=C1N)N)N)N)N PUXBEKLSMBVFNW-UHFFFAOYSA-N 0.000 claims description 5
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
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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
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Abstract
The invention relates to the field of synthesis of composite materials, and provides an in-situ preparation method of a three-dimensional conductive MOF @ MXene composite electrode aiming at the problem of poor conductivity of MOF, which comprises the following steps: adding MAX phase powder into HF solution, etching for 5-24 h, centrifugally washing with deionized water until the pH of the upper layer solution is 6-7, and vacuum drying to obtain multilayer MXene powder; uniformly dispersing in deionized water, adding chloroacetic acid, stirring at room temperature, adding NaOH solution, stirring for reacting for 1-12 h, centrifuging, washing, and vacuum drying to obtain MXene-COOH powder; dispersing in deionized water, sequentially adding metal salt, ligand and ammonia water, blowing at 50-70 ℃, stirring for reaction, finally centrifuging, washing and drying to obtain the three-dimensional conductive MOF @ MXene composite powder. The method has the advantages of high efficiency, stability and simple process, and the prepared composite powder can be used as an electrode material of a super capacitor to realize stable and high-efficiency energy storage.
Description
Technical Field
The invention relates to the field of synthesis of composite materials, in particular to an in-situ preparation method of a three-dimensional conductive MOF @ MXene composite electrode.
Background
Electrochemical Double Layer Capacitors (EDLCs) have high power density and excellent cycle performance, have recently become a research hotspot, have great prospects in the application fields of smart grids, electric vehicles and the like, and even have a state of competing for the market of traditional batteries due to a great urge to try. The active electrode material of the capacitor is represented by active carbon, carbon nano tubes, porous graphene, metal oxide/hydroxide and the like, has the characteristics of large porosity, high specific surface area and the like, is favorable for increasing the contact between an active substance and a solution, and improves the energy storage efficiency. For example, an invention patent publication No. CN103828002A discloses an electrochemical double layer capacitor comprising a positive electrode and a negative electrode, wherein the carbon material incorporated into the positive electrode is a halogenated carbon material and the carbon material incorporated into the negative electrode is an unhalogenated carbon material. Further, the carbon materials respectively incorporated into the respective electrodes may have different pore size distributions. Of carbon materials incorporated in the positive electrodeThe pore volume ratio is greater than the pore volume ratio of the carbon material incorporated into the negative electrode. The pore volume ratio R is defined as R = V 1 V, wherein V 1 Is the total volume of pores with a pore diameter of less than 1nm, and V is the total volume of pores with a pore diameter of greater than 1 nm. One of the materials with high specific surface area is the Metal Organic Framework (MOF), which is synthesized by coordination interactions between metal sites or clusters and organic linkers. The ordered porosity is such that the specific MOF surface area is greater than 7000 m 2 And/g, electrolyte ions can be sufficiently adsorbed and active sites can be exposed, so that the capacitance performance of the material is improved. In addition, the metal nanoparticle catalyst has the advantages of adjustable pore size, ultrahigh specific surface area, various skeleton structures, surface modification introduction and the like, and is widely applied to the fields of adsorption and separation, catalysis, carriers and templates of metal nanoparticles, microreactors and the like. However, due to their poor conductivity, MOFs have been limited in their application in the electrochemical field.
Disclosure of Invention
The invention provides an in-situ preparation method of a three-dimensional conductive MOF @ MXene composite electrode, aiming at overcoming the problem of poor conductivity of MOF, the process is efficient and stable, the process flow is simple, energy is effectively saved, and the prepared three-dimensional conductive MOF @ MXene composite powder can be used as a super-capacitor electrode material to realize stable and efficient energy storage.
In order to achieve the purpose, the invention adopts the following technical scheme:
an in-situ preparation method of a three-dimensional conductive MOF @ MXene composite electrode comprises the following steps:
(1) adding MAX phase powder into HF solution, etching for 5-24 h, centrifugally washing with deionized water until the pH of the upper layer solution is 6-7, and vacuum drying to obtain multilayer MXene powder;
(2) uniformly dispersing the multi-layer MXene powder prepared in the step (1) in deionized water, adding chloroacetic acid, stirring at room temperature, adding NaOH solution, stirring for reacting for 1-12 h, centrifuging, washing, and vacuum drying to obtain MXene-COOH powder;
(3) dispersing MXene-COOH powder prepared in the step (2) in deionized water, sequentially adding metal salt, ligand and ammonia water, and performing air blowing at 50-70 ℃ and stirringThe drum gas is N 2 、O 2 And one or more mixed gases of Ar and air, and finally, centrifugally washing and drying to obtain the three-dimensional conductive MOF @ MXene composite powder.
MXene is a novel two-dimensional layered material, and is widely used as an electrode material of a supercapacitor due to the advantages of good metal conductivity, redox reaction active surface and the like. In particular, even though the MXene surface is full of abundant functional groups, it can still realize high conductivity and hydrophilicity, which makes it suitable for assembling various heterojunction composite materials. Therefore, the invention provides the method for combining MXene with excellent conductivity and conductive MOF by utilizing the characteristics of MXene to form a conductive network with high electronic and ionic conductivity so as to realize high-efficiency and stable energy storage, and the preparation method is simple and is beneficial to large-scale production.
The invention realizes the growth of the small-particle conductive MOF on the MXene by utilizing simple electrostatic adsorption between the MXene and metal ions. The preparation method of the composite electrode is universal, effective and mild, the sources of used reagent instruments are wide, and batch or industrial production can be realized; the solvent used in the invention can be obtained in laboratories or industrial production, the price is low, the source is wide, the used experimental equipment is convenient to operate, high-power equipment is not needed, and the production process is energy-saving and environment-friendly. The prepared three-dimensional conductive MOF @ MXene composite electrode material shows excellent electrochemical activity and stability in the super-capacitance under the conventional conditions.
Preferably, MXene in the step (1) is Ti 2 CT x 、Ti 3 C 2 T x 、Nb 2 CT x 、Ti 3 CNT x 、V 2 CT x 、Mo 2 CT x 、Ti 4 N 3 T x One kind of (1). Further preferably, MXene in the step (1) is Ti 3 C 2 T x 。
Preferably, the HF solution in step (1) has a mass fraction of 40%, and the feeding ratio of the MAX phase powder to the HF solution is 1 g of MAX phase powder (5-20 mL). Further preferably, the feeding ratio of MAX phase powder and HF solution in step (1) is 1 g MAX phase to 10 mL HF solution.
Preferably, the feeding mass ratio of MXene to chloroacetic acid in the step (2) is (0.2-2): (2-50). Further preferably, the feeding mass ratio of MXene to chloroacetic acid in the step (2) is 1: 10.
Preferably, the concentration of the NaOH solution in the step (2) is 1-10 mol/L. Further preferably, the concentration of the NaOH solution in the step (2) is 6 mol/L.
Preferably, in the step (3), the metal salt is nickel chloride hexahydrate, and the ligand is HATP & 6H 2 O。
Preferably, the feeding mass ratio of MXene-COOH, metal salt and ligand in the step (3) is (0.2-4): (0.5-5): 1-6). As a further preference, the feeding mass ratio of MXene-COOH, metal salt and ligand in the step (3) is 50:65: 97.
Preferably, the gas blown in the step (3) is N in a volume ratio of (1-5) to (0.1-2) 2 /O 2 And (4) mixing the gases. More preferably, the gas blown in the step (3) is N in a volume ratio of 2:1 2 /O 2 And (4) mixing the gases.
Preferably, the conductive MOF in the step (3) is Cu 3 (HHTP) 2 、Co-HAB、Ni 3 (HITP) 2 、Fe 2 (BDP) 3 To (3) is provided. As a further preference, the conductive MOF of step (3) is Ni 3 (HITP) 2 。
Therefore, the invention has the following beneficial effects: (1) the preparation method has the advantages of simple operation, mild condition, adjustable morphology, controllable structure, uniform component distribution and small nanosheet size; (2) the mass production or the industrial production can be realized; (3) the preparation method keeps the original shapes of MXene and conductive MOF, and has the excellent performances of the MXene and the conductive MOF; (4) after the composition, the performance of the super capacitor is greatly improved.
Drawings
FIG. 1 is a scanning electron microscope image of the three-dimensional conductive MOF @ MXene composite prepared in example 1.
FIG. 2 is a graph of the properties of the three-dimensional conductive MOF @ MXene composite prepared in example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipments used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
Three-dimensional Ni 3 (HITP) 2 The in-situ preparation method and the super-capacitor application of the @ MXene composite electrode comprise the following steps: (1) multilayer Ti 3 C 2 T x Preparation of powder: adding 1 g of Ti into a round-bottom centrifuge tube 3 AlC 2 Solid and 10 mL HF (40 wt%), stirring and reacting for 24 h at 35 ℃, washing for 6 times by deionized water after the reaction is finished until the pH is reduced to 6, and vacuum drying the obtained product for 24 h at 60 ℃ to obtain multilayer Ti 3 C 2 T x A powder;
（2）Ti 3 C 2 T x preparation of-COOH: 300 mg of multi-layered Ti was added to a 100 mL glass bottle 3 C 2 T x Stirring the powder, 5 g chloroacetic acid and 300 mL of 0 ℃ aqueous solution for 1 h at room temperature, adding 32 mL of 6M NaOH aqueous solution, stirring in a 60 ℃ water bath kettle at constant temperature for reaction for 3 h, after the reaction is finished, centrifugally washing for 6 times, and drying in vacuum to obtain Ti 3 C 2 T x -COOH powder;
(3) three-dimensional Ni 3 (HITP) 2 Preparation of @ MXene composite powder: 50mg of Ti prepared in step (2) 3 C 2 T x the-COOH powder was added to 3 mL of an aqueous solution of nickel chloride hexahydrate (64.8 mg), and after stirring the mixture uniformly, 28 mL of HATP 6H was added thereto 2 O (97.4 mg) aqueous solution and 0.9 mL of concentrated aqueous ammonia (25 wt%), 60 ℃ Drum N 2 /O 2 Stirring with gas for reaction for 3 h, centrifuging and washing for 6 times after the reaction is finished, and drying in vacuum to obtain three-dimensional Ni 3 (HITP) 2 @ MXene composite powder.
Performance testing
The sample of example 1 was selected for characterization and analysis, and the test results are shown in the figure.FIG. 1 is three-dimensional Ni obtained in example 1 3 (HITP) 2 SEM image of the @ MXene composite powder, it can be seen that three-dimensional Ni was obtained 3 (HITP) 2 The transverse dimension of the @ MXene composite material is about 10 microns, and small particles of Ni are fully distributed on the transverse dimension 3 (HITP) 2 . FIG. 2 is three-dimensional Ni 3 (HITP) 2 And @ MXene composite material supercapacitive performance diagram.
Example 2
Three-dimensional Ni 3 (HITP) 2 @Ti 2 CT x The in-situ preparation method of the composite electrode and the application of the super capacitor comprise the following steps: (1) multilayer Ti 2 CT x Preparation of powder: adding 1 g of Ti into a round-bottom centrifuge tube 2 AlC solid and 5 mL HF (40% wt), stirring and reacting for 5 h at 35 ℃, washing for 6 times by deionized water after the reaction is finished until the pH value is reduced to 7, and carrying out vacuum drying on the obtained product for 24 h at 60 ℃ to obtain multilayer Ti 2 CT x Powder;
（2）Ti 2 CT x preparation of-COOH: a100 mL glass bottle was charged with 12 mg of multi-layered Ti 2 CT x Stirring the powder, 3 g chloroacetic acid and 300 mL of 0 ℃ aqueous solution for 1 h at room temperature, adding 32 mL of 1M NaOH aqueous solution, stirring and reacting in a 60 ℃ water bath kettle for 1 h at constant temperature, after the reaction is finished, centrifugally washing for 6 times, and drying in vacuum to obtain Ti 3 C 2 T x -COOH powder;
(3) three-dimensional Ni 3 (HITP) 2 @Ti 2 CT x Preparation of composite powder: 2 mg of Ti prepared in the step (2) 3 C 2 T x the-COOH powder was added to 3 mL of an aqueous solution of nickel chloride hexahydrate (50 mg), and after stirring the mixture uniformly, 28 mL of HATP.6H was added in this order 2 O (60 mg) aqueous solution and 0.9 mL of strong ammonia water (25 wt%), stirring and reacting for 3 h at 50 ℃ with Ar gas, after the reaction is finished, centrifugally washing for 6 times, and drying in vacuum to obtain three-dimensional Ni 3 (HITP) 2 @Ti 2 CT x And (3) compounding the powder.
Example 3
Three-dimensional Ni 3 (HITP) 2 @ V 2 CT x In situ preparation of composite electrodesThe method and the super capacitor application comprise the following steps: (1) multilayer V 2 CT x Preparation of powder: adding 1 g V into a round-bottom centrifuge tube 2 Stirring AlC solid and 20 mL HF (40% wt) at 35 ℃ for reaction for 10 h, washing with deionized water for 6 times after the reaction is finished until the pH value is reduced to 7, and carrying out vacuum drying on the obtained product at 60 ℃ for 24 h to obtain a multilayer V 2 CT x Powder;
（2）V 2 CT x preparation of-COOH: 300 mg of multilayers of V were added to a 100 mL glass bottle 2 CT x Stirring the powder, 300 mg chloroacetic acid and 300 mL of 0 ℃ aqueous solution for 1 h at room temperature, adding 32 mL of 10M NaOH aqueous solution, stirring in a 60 ℃ water bath kettle at constant temperature for reaction for 12 h, after the reaction is finished, centrifugally washing for 6 times, and drying in vacuum to obtain V 2 CT x -COOH powder;
(3) three-dimensional Ni 3 (HITP) 2 @ V 2 CT x Preparation of composite powder: 4mg of V obtained in step (2) 2 CT x the-COOH powder was added to 3 mL of an aqueous solution of nickel chloride hexahydrate (0.5 mg), and after stirring the mixture uniformly, 28 mL of HATP 6H was added thereto 2 O (1 mg) aqueous solution and 0.9 mL of concentrated ammonia water (25 wt%), stirring with air at 70 ℃ for reaction for 3 h, centrifugally washing for 6 times after the reaction is finished, and drying in vacuum to obtain three-dimensional Ni 3 (HITP) 2 @ V 2 CT x And (3) compounding the powder.
Comparing examples 1-3, example 1 adopted the best reaction parameters, so the three-dimensional Ni obtained 3 (HITP) 2 The @ MXene composite powder has the best supercapacitive performance.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (7)
1. An in-situ preparation method of a three-dimensional conductive MOF @ MXene composite electrode is characterized by comprising the following steps: (1) adding MAX phase powder into HF solution with mass fraction of 40% for etching for 5-24 h, centrifugally washing with deionized water until the pH of the upper layer solution is 6-7, and vacuum drying to obtain multilayer MXene powder; the MXene is Ti 2 CT x 、Ti 3 C 2 T x 、Nb 2 CT x 、Ti 3 CNT x 、V 2 CT x 、Mo 2 CT x 、Ti 4 N 3 T x One of (1);
(2) uniformly dispersing the multi-layer MXene powder prepared in the step (1) in deionized water, adding chloroacetic acid, stirring at room temperature, adding NaOH solution, stirring for reacting for 1-12 h, centrifuging, washing, and vacuum drying to obtain MXene-COOH powder;
(3) dispersing MXene-COOH powder prepared in the step (2) in deionized water, sequentially adding metal salt, ligand and ammonia water, and blowing at 50-70 ℃ for stirring reaction, wherein the blowing gas is N with the volume ratio of (1-5) to (0.1-2) 2 /O 2 And mixing the gases, and finally, centrifugally washing and drying to obtain the three-dimensional conductive MOF @ MXene composite powder.
2. The method of claim 1, wherein the ratio of the MAX phase powder to the HF solution in step (1) is 1 g of MAX phase powder (5-20 mL) of HF solution.
3. The in-situ preparation method of the three-dimensional conductive MOF @ MXene composite electrode according to claim 1, wherein the feeding mass ratio of MXene to chloroacetic acid in step (2) is (0.2-2) to (2-50).
4. The in-situ preparation method of the three-dimensional conductive MOF @ MXene composite electrode according to claim 1, wherein the concentration of the NaOH solution in the step (2) is 1-10 mol/L.
5. The in-situ preparation method of the three-dimensional conductive MOF @ MXene composite electrode according to claim 1 or 4, wherein the metal salt in step (3) is nickel chloride hexahydrate and the ligand is HATP 6H 2 O。
6. The in-situ preparation method of the three-dimensional conductive MOF @ MXene composite electrode according to claim 1, wherein the feeding mass ratio of MXene-COOH, metal salt and ligand in the step (3) is (0.2-4): (0.5-5): 1-6).
7. The in-situ preparation method of the three-dimensional conductive MOF @ MXene composite electrode according to claim 1 or 6, wherein the conductive MOF in step (3) is Cu 3 (HHTP) 2 、Co-HAB、Ni 3 (HITP) 2 、Fe 2 (BDP) 3 To (3) is provided.
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| CN113984859B (en) * | 2021-09-28 | 2023-10-20 | 西安建筑科大工程技术有限公司 | Preparation method of nitrogen-doped MXene/MOF derivative composite material and formaldehyde sensor |
| CN113912063B (en) * | 2021-11-03 | 2023-05-12 | 河海大学 | Ti (titanium) 3 C 2 T x Base electrode material, preparation method and application thereof |
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| CN114974916B (en) * | 2022-07-04 | 2024-01-30 | 桂林电子科技大学 | Fibrous MXene-loaded NiCoS composite material and preparation method and application thereof |
| CN115101736B (en) * | 2022-07-19 | 2023-08-04 | 江苏先丰纳米材料科技有限公司 | Three-dimensional NiPc-NiFe@Ti 3 C 2 T x Preparation method of MXene composite material, and product and application thereof |
| CN117228736A (en) * | 2023-05-22 | 2023-12-15 | 西安交通大学 | Ni3 (HITP) 2 Preparation method of Mxene heterostructure and ethanol sensor |
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