CN114606554B - Preparation method of MOF/MXene/PPy@CelF porous nanomaterial and product and application thereof - Google Patents

Preparation method of MOF/MXene/PPy@CelF porous nanomaterial and product and application thereof Download PDF

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CN114606554B
CN114606554B CN202210216923.5A CN202210216923A CN114606554B CN 114606554 B CN114606554 B CN 114606554B CN 202210216923 A CN202210216923 A CN 202210216923A CN 114606554 B CN114606554 B CN 114606554B
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CN114606554A (en
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钟振蕾
禹杰
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Suzhou Miaohai Nanotechnology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • 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
    • 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
    • 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
    • H01G11/84—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

Abstract

The invention discloses a preparation method of a MOF/MXene/PPy@CelF porous nanomaterial, which comprises the following steps: s1, preparing an MXene material, a MOF material and a PPy@CelF material; preparing an MXene solution by adopting an HF acid etching method; preparing a PCN-222 precursor solution by benzoic acid, porphyrin ligand, zirconium chloride and N, N-diethyl formamide; preparing a PPy@CelF solution by adopting an in-situ polymerization method; s2, preparing an MXene/PCN-222 composite material; preparing an MXene film by an electrophoretic deposition method; preparing a PCN-222 layer on the MXene film by a rapid electrophoretic deposition technology to obtain a MXene/PCN-222 double-layer composite film; s3, preparing the MOF/MXene/PPy@CelF porous nano material by a dip coating method. The invention also discloses a corresponding product and application. The MOF material, the MXene and the polymer are compounded in a layered manner, so that the MXene is not stacked, the ion transmission is ensured, and the nanocomposite has very high reactive sites and flexibility.

Description

Preparation method of MOF/MXene/PPy@CelF porous nanomaterial and product and application thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a MOF/MXene/PPy@CelF porous nano material, a product and application thereof.
Background
Miniaturized and wearable electronics require an energy storage system that combines flexibility and excellent electrochemical performance. It is very attractive to design conventional energy storage devices, such as supercapacitors, as flexible structures to power these wearable devices. Electrode materials are an important component of flexible supercapacitors, which must possess electrochemical activity, mechanical strength, and even stretch properties during use. Attention has been turned to intrinsically flexible elastomeric polymers from traditional materials such as metal oxides and carbon materials. The novel two-dimensional material MXene can be cooperated with a three-dimensional polymer network, so that the electrochemical activity and the mechanical flexibility are enhanced, and the novel two-dimensional material MXene is expected to become a candidate material for flexible energy storage.
Although MXene materials show great promise in the energy storage field, self-aggregation and stacking are prone to occur due to size effects. In the prior art, inorganic metal ions and organic molecules are generally inserted between two-dimensional nano material sheets by an in-situ method or an MXene material is compounded with polymer molecules, CNTs and the like, so that the self-aggregation of the nano material sheets is reduced, the number of active reaction centers is increased, the transmission rate of electrolyte ions in an electrode material is improved, but the transmission rate of the ions is exponentially reduced along with the increase of the thickness of the electrode material.
Disclosure of Invention
In view of one or more of the above-mentioned drawbacks or improvements of the prior art, the present invention provides a method for preparing a porous nano-material of MOF/MXene/ppy@celf, and products and applications thereof, wherein the MOF material, MXene and polymer are laminated and combined, so that MXene is not stacked, ion transport is ensured, and the nano-composite has very high reactive sites and flexibility.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a method for preparing a MOF/MXene/ppy@celf porous nanomaterial, comprising the steps of:
s1, preparing an MXene material, a MOF material and a PPy@CelF material;
preparing an MXene solution by adopting an HF acid etching method; preparing a PCN-222 precursor solution by benzoic acid, porphyrin ligand, zirconium chloride and N, N-diethyl formamide; preparing a PPy@CelF solution by adopting an in-situ polymerization method;
s2, preparing an MXene/PCN-222 composite material;
s21, preparing an MXene film by an electrophoretic deposition method; taking a proper amount of the MXene nano-sheet solution prepared in the step S1, immersing one of a copper plate, a platinum plate or a nickel plate into the solution to serve as an anode, directly applying voltage to one of a carbon plate, a stainless steel plate or ITO conductive glass serving as a cathode for 30-60 seconds, taking out the anode, and vacuum drying at room temperature to obtain an MXene film;
s22, preparing a PCN-222 layer on the MXene film by a rapid electrophoretic deposition technology to obtain a MXene/PCN-222 double-layer composite film;
s3, preparing the MOF/MXene/PPy@CelF porous nano material by a dip coating method;
immersing the MXene/PCN-222 double-layer composite membrane into the PPy@CelF solution, removing the solution after 20-30 minutes, pouring ammonium persulfate solution on the PPy@CelF coated membrane, keeping oscillating, and washing for a plurality of times by deionized water to obtain the MOF/MXene/PPy@CelF porous nano material.
As a further improvement of the present invention, in step S1, the MXene material is prepared as follows:
mixing and stirring MAX phase ceramic containing Al with HF acid to etch Ti 3 AlC 2 Al in (C); centrifugally washing etched Ti 3 AlC 2 Dispersing liquid until the pH value is more than or equal to 6; and (5) continuing centrifugal separation for 30-60 min, and collecting supernatant to obtain the two-dimensional lamellar MXene.
As a further improvement of the invention, the mass ratio of the MAX phase ceramic containing Al to the HF acid is 3: (10-20).
As a further improvement of the invention, the concentration of the HF acid is 8-50 wt%.
As a further improvement of the present invention, in step S1, the preparation of the MOF material specifically includes the following steps:
60 parts of benzoic acid, 1 part of porphyrin ligand and 1.25-1.5 parts of zirconium chloride are mixed with 10-20 parts of N, N-diethyl formamide, dissolved, heated in an oil bath at constant temperature, and the mixture is centrifuged for multiple times by adopting dimethylformamide and acetone to prepare the PCN-222 precursor solution.
As a further improvement of the invention, the constant-temperature oil bath heating temperature is 100-120 ℃ and the heating time is 12-24 hours.
As a further improvement of the present invention, in step S1, the preparation of the ppy@celf material specifically includes the following steps:
2-5 g of the dried CelF is taken and put into 150-300 mL of distilled water, and 1-1.5 ml of PPy is added after uniform mixing; 4-5 g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water and slowly addedAnd continuously stirring the mixture for 2-3 hours at the temperature of 0-5 ℃, and finally washing the mixture with distilled water to obtain the PPy@CelF solution.
As a further improvement of the invention, in the step S21, the electrophoretic deposition is finished step by step, the electrophoretic deposition process is finished twice, and the interval between each electrophoretic deposition is 10S and 15-30S;
as a further improvement of the present invention, in step S21, the applied voltage is preferably 20V/cm; the taking amount of the MXene nanosheet solution is preferably 30-40 mL.
As a further improvement of the invention, in the step S22, the PCN-222 layer is prepared on the MXene film by a rapid electrophoretic deposition technology, and specifically comprises the following steps:
immersing the copper plate covered with the MXene film into the PCN-222 precursor solution prepared in the step S1, applying an electric field with the strength of 20V/cm for 15-30 min, completing the deposition process in three times, performing electrophoretic deposition for 5-10 min each time, taking out the copper plate at intervals of 10min, and drying to obtain the MXene/PCN-222 composite double-layer film.
As a further improvement of the invention, in the step S3, the concentration of the ammonium persulfate solution is 0.03-0.05 g/ml.
According to a second aspect of the present invention there is provided a MOF/MXene/PPy@CelF porous nanomaterial prepared by the method described.
According to a third aspect of the invention, there is provided an application of the MOF/MXene/PPy@CelF porous nanomaterial in a supercapacitor, wherein the supercapacitor is assembled by the following steps:
cutting the MOF/MXene/PPy@CelF porous nano material into a rectangular film, and adhering the rectangular film to a non-conductive substrate to manufacture a film electrode; and sandwiching the solid electrolyte between two thin film electrodes to prepare the flexible supercapacitor.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
(1) The invention covers a PCN-222 film on an independent MXene two-dimensional material to produce a high-function flexible electrode with good deformability and editability. PCN-222 is inlaid on the MXene layers, forming a continuous conductive network structure between successive stacked MXene layers. In this configuration, the MXene layer may act as an adhesive and conductive additive to assemble the PCN-222 material, facilitating charge transfer. Meanwhile, the PCN-222 material can be used as a spacer, thereby expanding the interlayer distance, improving the ion transmission path, and maintaining the excellent elasticity of the composite film. In addition, the porous structure inserted into the MXene can provide a convenient transport path for ions. Finally, PCN-222/MXene was uniformly distributed throughout the three-dimensional polymer matrix PPy@CelF, thereby forming a mechanically reinforced system. With the benefit of the unique layered design, the three layers of components are assembled to form an interconnected multi-layer nano-structure, which can prevent serious coincidence of MXene nano-sheets, promote diffusion of electrolyte in a network and show special capacitance characteristics and mechanical behaviors.
(2) According to the invention, polypyrrole (PPy) is coated on CelF in situ to be used as a matrix of MOF/MXene, so that the MOF/MXene/PPy@CelF composite layered material is prepared, and meanwhile, the composite material deposited with polypyrrole and MOF still has conductivity. The introduction of PCN-222 reduces the charge transfer resistance, adds active reaction sites, and PPy@CelF is used as a flexible conductive matrix, and the introduction of the PCN-222 improves the overall conductivity, stability and flexibility.
(3) Compared with the MXene/PPy@CelF, the MOF/MXene/PPy@CelF material prepared by the invention has higher electric double layer capacitance and larger working voltage window, and the interlayer space between MXene nano sheets can be widened by introducing the MOF, so that the ion exchange interface area is effectively increased.
Drawings
FIG. 1 is a schematic diagram of a layered structure of a MOF/MXene/PPy@CelF porous nanomaterial prepared by an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a preparation method of a MOF/MXene/@ PPy@CelF nano material, which comprises the following steps:
(1) Preparing an MXene material, a MOF material and a PPy@CelF material;
(1-1) preparing MXene by adopting an HF acid etching method, which comprises the following steps:
mixing and stirring the MAX phase ceramic containing Al with HF acid uniformly, and carrying out etching reaction at 25-85 ℃ to etch Al in the MAX phase ceramic;
centrifugally washing the etched dispersion until the pH value is more than or equal to 6 to ensure that HF acid is washed and MAX phase is prevented from being excessively corroded;
and (5) continuing centrifugal separation for 30-60 min, and collecting supernatant to obtain the two-dimensional lamellar MXene solution.
(1-2) preparation of MOF materials specifically comprises the following steps:
60 parts by weight of benzoic acid (BEN), 1 part by weight of porphyrin ligand (TCPP) and 1.25-1.5 parts by weight of zirconium chloride (ZrCl 4) are mixed with 10-20 parts by volume of N, N-diethyl formamide (DEF) and dissolved, the mixture is heated in an oil bath at constant temperature, and the mixture is centrifuged for multiple times by adopting Dimethylformamide (DMF) and acetone, so that PCN-222 precursor solution is prepared.
The preparation of the PPy@CelF material (1-3) specifically comprises the following steps:
preparing a PPy@CelF material by adopting an in-situ polymerization method; adding 2-5 g of the dried CelF into 150-300 mL of distilled water, uniformly mixing, and adding 1-1.5 ml of PPy; 4-5 g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water, slowly added into the mixture, continuously stirred for 2-3 h at the temperature of 0-5 ℃, and finally washed by distilled water to obtain PPy@CelF solution.
Further, in the step (1-1), the Al-containing MAX phase ceramic comprises Ti 3 AlC 2 Or V 2 AlC; when the MXene material is prepared, the mass ratio of the MAX phase ceramic containing Al to the HF acid is 3: (10-20), wherein the concentration of the HF acid is 8-50 wt%, the temperature during stirring is 45-50 ℃ and the time is 2-24 hours; preferably, use is made ofCentrifuging the deionized water, wherein the rotating speed of the centrifuging is 3000-3600 r/min; in addition, because HF is extremely toxic and highly corrosive, a HF acid synthesis route can be adopted, liF/HCl or NH can be used 4 F/H 2 SO 4 And (5) solution etching.
Further, when the MOF material is prepared in the step (1-2), the constant-temperature oil bath heating temperature is 100-120 ℃ and the heating time is 12-24 hours.
Further, in the step (1-3), the cellulose fiber CelF is selected from bleached softwood pulp, and is obtained after mechanical treatment by using a beater, and the present invention is not particularly limited and may be carried out by a conventional method of the prior art.
(2) Preparation of MXene/PCN-222 composite Material
(2-1) preparation of MXene film by electrophoretic deposition
And (3) taking a proper amount (preferably 30-40 mL) of the MXene nanosheet solution prepared in the step (1-1), immersing a copper plate into the solution to serve as an anode, directly applying voltage (preferably 20V/cm) to serve as a cathode, continuously for 30-60 s, taking out the copper plate, and drying in vacuum at room temperature to obtain the MXene film. In the preferred embodiment, in order to further improve the surface morphology of the MXene film and increase the compactness of the MXene film, the deposition is carried out by adopting a step-by-step completion method, and the electrophoretic deposition process is completed in two times, wherein each electrophoretic deposition time is 15-20 s, and the interval is 10s.
The anode may be a platinum plate, a nickel plate, or the like, and the anode may be a stainless steel plate, ITO conductive glass, or the like.
(2-2) preparing a PCN-222 layer on MXene by a rapid electrophoretic deposition technique;
immersing the copper plate covered with the MXene layer into the solution, applying an electric field with the strength of 20V/cm for 15-30 min, and completing the deposition step by step in a preferred embodiment, wherein the deposition is completed 3 times, each time of electrophoresis deposition is carried out for 5-15 min, and the interval is 10min. And then taking out and drying to obtain the MXene/PCN-222 composite double-layer membrane.
(3) Preparing the MOF/MXene/PPy@CelF porous nano material by a dip coating method;
immersing the prepared MXene/PCN-222 double-layer composite membrane into the obtained PPy@CelF solution, removing the solution after 20-30 minutes, directly pouring ammonium persulfate solution (with the concentration of 0.03-0.05 g/ml) on the PPy@CelF coated membrane without cleaning the membrane, keeping oscillating, and then washing with deionized water for a plurality of times to obtain the MOF/MXene/PPy@CelF porous nano material (three-layer composite membrane material).
The invention provides a process for synthesizing an MXene/PCN-222 double-layer composite film in a short time, which comprises the steps of firstly, obtaining a 600-800 nanometer thick two-dimensional flaky MXene layer within 30-60 s through electrophoretic deposition (EPD); the thickness of the MXene layer is about 600-800 nanometers, the MXene nano sheets are well stacked, if the thickness is too small, the mechanical strength of the MXene layer is poor, the EPD time prepared by the MXene layer is set to be about 30-60 seconds, and the sufficient mechanical strength and proper conductivity can be maintained. Next, using the MXene layer as a conductive substrate, a 300-500 nm thick PCN-222 layer was grown rapidly on top of the MXene layer by FCDS within 20 minutes. The final MXene/PCN-222 bilayer composite film can be easily peeled from the substrate due to the weak static electricity between the MXene layer and the substrate and the close-packed structure of the two-dimensional nanoplatelets.
The stacking of sheets in MXene films can lead to slow ion transport, impeding its conductivity rate. Other materials can be intercalated in the layer spacing with larger MXene, so that the density of the material is further increased, the material has higher volume specific capacity, and the optimization of electrochemical performance can be realized by utilizing the high conductivity of the MXene and the high specific capacity of the pseudocapacitance material, so that the MOF material and the MXene are assembled together, and the MXene electrode material with high active sites and a porous structure can be obtained. The polymer material has good processability and good film forming property, and the preparation of the matrix film is an important method for preparing electrode material devices. Cellulose fiber (CelF) is a biodegradable and renewable material with excellent properties, pulp cellulose fiber, and has a series of advantages of flexibility, light weight, etc. Polypyrrole (PPy) is used as a common conductive polymer, has the advantages of good stability, high conductivity, easy synthesis, environmental friendliness and the like, and particularly has the advantages of low cost, strong metal ion adsorption capacity and the like, and the PPy nanocomposite synthesized by combining other nano materials can remarkably enhance the ion diffusivity and increase the contact area so as to enhance the capacitance.
The MOF/MXene/PPy@CelF porous nanomaterial can be applied to a supercapacitor, and the corresponding supercapacitor assembling method comprises the following steps: the MOF/MXene/ppy@celf composite film was cut into rectangular films, and then electrodes were fabricated by bonding the rectangular films to a non-conductive substrate, and a flexible supercapacitor was obtained by sandwiching a solid electrolyte between two thin film electrodes.
The solid electrolyte may be selected from H 2 SO 4 /PVA、H 3 PO 4 /PVA、H 3 PO 4 Polybenzimidazole (PBI) wherein H 2 SO 4 The preparation method of the PVA comprises the following steps: 3g of polyvinyl alcohol is added into 30ml of deionized water, and after stirring at 90 ℃ until the mixture is transparent, 3g of H is added dropwise 2 SO 4 To obtain H 2 SO 4 PVA electrolyte. Alternatively, the substrate may be selected from polyethylene terephthalate, polytetrafluoroethylene (PTFE) or polypropylene materials.
It should be noted that the material of the present invention, which is not limited by the present invention, may be obtained directly in the prior art or by a preparation method of the prior art; the preparation process according to the invention, which is not described in detail, is indicated by the conventional processes which can be carried out by the person skilled in the art.
In order to better illustrate the preparation method, the product and the application of the invention, the following specific examples are provided:
example 1
8wt% HF acid was dissolved in 20ml deionized water with 100mg Ti 3 AlC 2 Mixing. Stirring at 45deg.C for 12 hr, centrifuging with deionized water at 3000r/min, and washing etched Ti 3 AlC 2 Dispersing liquid until the pH value is more than or equal to 6; continuing centrifugal separation for 30min, and collecting supernatant to obtain two-dimensional lamellar MXene;
3g of benzoic acid, 50mg of porphyrin ligand and 75mg of zirconium chloride were mixed with 10ml of N, N-diethylformamide and sonicated for 30 minutes. Sealing under magnetic stirring, and heating in oil bath at 100deg.C for 24 hr. Centrifuging the mixture for 5 times by using dimethylformamide and acetone, and removing redundant benzoic acid and porphyrin ligand to obtain PCN-222 precursor solution;
adding 2g of dried CelF (bleached cork pulp cellulose fiber) into 150 distilled water, uniformly mixing, and adding 1ml of PPy; 4g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water, slowly added into the mixture, continuously stirred for 3 hours at the temperature of 0-5 ℃, and washed by distilled water to obtain PPy@CelF solution.
Pouring 30mL of the prepared MXene nanosheet solution into a 50mL beaker, immersing a copper plate into the solution to serve as an anode, taking a carbon plate as a cathode, directly applying voltage of 20V/cm for 30s, depositing for 15s each time at intervals of 10s, taking out the copper plate, and vacuum drying at room temperature to obtain an MXene film;
immersing the copper plate covered with the MXene layer into the solution, applying an electric field with the strength of 20V/cm for 15min, completing the deposition process in 3 times, performing electrophoretic deposition for 5min each time at intervals of 10min, taking out and drying to obtain the MXene/PCN-222 composite double-layer film;
immersing the MXene/PCN-222 double-layer composite membrane into a PPy@CelF solution, removing the solution after 20 minutes, pouring an ammonium persulfate solution on the PPy@CelF coated membrane, keeping oscillating, and then flushing with deionized water for a plurality of times to obtain the MOF/MXene/PPy@CelF porous nano material.
The MOF/MXene/PPy@CelF porous nanocomposite prepared in the embodiment is applied to a supercapacitor (H is adopted as electrolyte) 2 SO 4 and/PVA, polyethylene terephthalate is selected as a substrate), the electrochemical performance of the super capacitor is tested, the energy density can reach 35Wh/kg under the power density of 750W/kg, the composite electrode has high specific capacitance of 507F/g under the scanning rate of 50mV/s, the high capacity of 254F/g is also kept under the scanning rate of 100mV/s, after 1000 times of circulation, the curve is stable, the specific capacitance can still be kept at 93% of the initial value after 4500 times of circulation, and the electrochemical performance is not obviously changed during bending and twisting.
Example 2
8wt% HF acid was dissolved in 20ml deionized water with 100mg Ti 3 AlC 2 Mixing. Stirring at 45deg.C for 24 hr, centrifuging with deionized water at 3000r/min, and washing etched Ti 3 AlC 2 The dispersion liquid is prepared into a liquid preparation,until the pH value is more than or equal to 6; continuing centrifugal separation for 60min, and collecting supernatant to obtain two-dimensional lamellar MXene;
3g of benzoic acid, 50mg of porphyrin ligand and 75mg of zirconium chloride were mixed with 10ml of N, N-diethylformamide and sonicated for 30 minutes. Sealing under magnetic stirring, and heating in 120 deg.C constant temperature oil bath for 24 hr. Centrifuging the mixture for 5 times by using dimethylformamide and acetone, and removing redundant benzoic acid and porphyrin ligand to obtain PCN-222 precursor solution;
adding 5g of dried CelF (bleached cork pulp cellulose fiber) into 300mL of distilled water, uniformly mixing, and adding 1.5mL of PPy; 5g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water, slowly added into the mixture, continuously stirred for 3 hours at the temperature of 0-5 ℃, and washed by distilled water to obtain PPy@CelF solution.
Pouring 40mL of the prepared MXene nanosheet solution into a 50mL beaker, immersing a copper plate into the solution to serve as an anode, directly applying 20V/cm voltage to serve as a cathode, continuously depositing for 60 seconds each time for 30 seconds at intervals of 10 seconds, taking out the copper plate, and vacuum drying at room temperature to obtain an MXene film;
immersing the copper plate covered with the MXene layer into the solution, applying an electric field with the strength of 20V/cm for 30min, completing the deposition process in 3 times, performing electrophoretic deposition for 10min each time at intervals of 10min, taking out and drying to obtain the MXene/PCN-222 composite double-layer film;
immersing the MXene/PCN-222 double-layer composite membrane into a PPy@CelF solution, removing the solution after 30 minutes, pouring an ammonium persulfate solution on the PPy@CelF coated membrane, keeping oscillating, and then flushing with deionized water for a plurality of times to obtain the MOF/MXene/PPy@CelF porous nano material.
The MOF/MXene/PPy@CelF porous nanocomposite prepared in the embodiment is applied to a supercapacitor (H is adopted as electrolyte) 2 SO 4 Polyethylene terephthalate as substrate), the super capacitor is subjected to electrochemical performance test, the energy density can reach 37Wh/kg under the power density of 750W/kg, the composite electrode has high specific capacitance of 524F/g under the scanning rate of 50mV/s, the high capacity of 262F/g is also maintained under the scanning rate of 100mV/s,after 1000 times of circulation, the curve is stable, and after 4500 times of circulation, the specific capacitance can still be kept at 95% of the initial value, and the electrochemical performance is not changed obviously during bending and twisting.
Example 3
8wt% HF acid was dissolved in 20ml deionized water with 100mg Ti 3 AlC 2 Mixing. Stirring at 45deg.C for 2 hr, centrifuging with deionized water at 3000r/min, and washing etched Ti 3 AlC 2 Dispersing liquid until the pH value is more than or equal to 6; continuing centrifugal separation for 50min, and collecting supernatant to obtain two-dimensional lamellar MXene;
3g of benzoic acid, 50mg of porphyrin ligand and 62.5mg of zirconium chloride were mixed with 12ml of N, N-diethylformamide and sonicated for 30 minutes. Sealing under magnetic stirring, and heating in 120 deg.C constant temperature oil bath for 24 hr. Centrifuging the mixture for 5 times by using dimethylformamide and acetone, and removing redundant benzoic acid and porphyrin ligand to obtain PCN-222 precursor solution;
3g of dried CelF (bleached cork pulp cellulose fiber) is added into 200mL of distilled water, and 1mL of PPy is added after uniform mixing; 4g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water, slowly added into the mixture, continuously stirred for 3 hours at the temperature of 0-5 ℃, and washed by distilled water to obtain PPy@CelF solution.
Pouring 35mL of the prepared MXene nanosheet solution into a 50mL beaker, immersing a copper plate into the solution to serve as an anode, taking a carbon plate as a cathode, directly applying voltage of 20V/cm for 40s, depositing for 20s each time at intervals of 10s, taking out the copper plate, and vacuum drying at room temperature to obtain an MXene film;
immersing the copper plate covered with the MXene layer into the solution, applying an electric field with the strength of 20V/cm for 21min, completing the deposition process in 3 times, performing electrophoretic deposition for 7min each time at intervals of 10min, taking out and drying to obtain the MXene/PCN-222 composite double-layer film;
immersing the MXene/PCN-222 double-layer composite membrane into a PPy@CelF solution, removing the solution after 25 minutes, pouring an ammonium persulfate solution on the PPy@CelF coated membrane, keeping oscillating, and then flushing with deionized water for a plurality of times to obtain the MOF/MXene/PPy@CelF porous nano material.
The MOF/MXene/PPy@CelF porous nanocomposite prepared in the embodiment is applied to a supercapacitor (H is adopted as electrolyte) 2 SO 4 The PVA and the substrate are selected from polyethylene terephthalate), the electrochemical performance of the super capacitor is tested, the energy density can reach 33Wh/kg under the power density of 750W/kg, the composite electrode has high specific capacitance of 500F/g under the scanning rate of 50mV/s, the high capacitance of 246F/g is also kept under the scanning rate of 100mV/s, after 1000 times of circulation, the curve is stable, after 4500 times of circulation, the specific capacitance can still be kept at 92% of the initial value, and the electrochemical performance is not obviously changed during bending and twisting.
Example 4
8wt% HF acid was dissolved in 20ml deionized water with 100mg Ti 3 AlC 2 Mixing. After mixing, stirring for 24 hours at 50 ℃, centrifugally washing etched Ti with deionized water at the rotating speed of 3200r/min 3 AlC 2 Dispersing liquid until the pH value is more than or equal to 6; continuing centrifugal separation for 40min, and collecting supernatant to obtain two-dimensional lamellar MXene;
3g of benzoic acid, 50mg of porphyrin ligand and 70mg of zirconium chloride were mixed with 15ml of N, N-diethylformamide and sonicated for 40 minutes. Sealing under magnetic stirring, and heating in 120 deg.C constant temperature oil bath for 24 hr. Centrifuging the mixture for 5 times by using dimethylformamide and acetone, and removing redundant benzoic acid and porphyrin ligand to obtain PCN-222 precursor solution;
adding 4g of dried CelF (bleached cork pulp cellulose fiber) into 250mL of distilled water, uniformly mixing, and adding 1.5mL of PPy; 5g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water, slowly added into the mixture, continuously stirred for 3 hours at the temperature of 0-5 ℃, and washed by distilled water to obtain PPy@CelF solution.
Pouring 40mL of the prepared MXene nanosheet solution into a 50mL beaker, immersing a copper plate into the solution to serve as an anode, taking a carbon plate as a cathode, directly applying voltage of 20V/cm for 50s, depositing for 25s each time at intervals of 10s, taking out the copper plate, and vacuum drying at room temperature to obtain an MXene film;
immersing the copper plate covered with the MXene layer into the solution, applying an electric field with the strength of 20V/cm for 24min, completing the deposition process in 3 times, performing electrophoretic deposition for 8min each time at intervals of 10min, taking out and drying to obtain the MXene/PCN-222 composite double-layer film;
immersing the MXene/PCN-222 double-layer composite membrane into a PPy@CelF solution, removing the solution after 20 minutes, pouring an ammonium persulfate solution on the PPy@CelF coated membrane, keeping oscillating, and then flushing with deionized water for a plurality of times to obtain the MOF/MXene/PPy@CelF porous nano material.
The MOF/MXene/PPy@CelF porous nanocomposite prepared in the embodiment is applied to a supercapacitor (H is adopted as electrolyte) 2 SO 4 The PVA and the substrate are selected from polyethylene terephthalate), the super capacitor is subjected to electrochemical performance test, the energy density can reach 32Wh/kg under the power density of 750W/kg, the composite electrode has high specific capacitance of 512F/g under the scanning rate of 50mV/s, the high capacitance of 252F/g is also kept under the scanning rate of 100mV/s, after 1000 times of circulation, the curve is stable, the specific capacitance can still be kept at 94% of the initial value after 4500 times of circulation, and the ion storage performance is not obviously reduced during bending and torsion.
The electrochemical performance of the supercapacitors was tested using the electrochemical workstation for examples 1 to 4. The scanning speed of CV test is 0.050-0.300V/s, and the potential is-0.1-0.20V. Constant-current charge and discharge tests are carried out at a current of 0.6-12.0A/g; 4000 cycles are performed with a current of 1.0A/g, and the voltages are all 0-0.8V. The bending angles were set to 0 °, 60 °,90 °, 180 °, and 270 °, respectively. By combining the embodiments, the prepared MOF/MXene/PPy@CelF composite material has the energy density of more than 30Wh/kg under the power density of 750W/kg, has the specific capacitance of about 250F/g under the sweeping speed of 50mv/s, and has the advantages that the curve is stable after 1000 times of circulation, and the specific capacitance can still be kept at more than 90% of the initial value after 4500 times of circulation, thus having good circulation performance. Under different bending angles, the CV curve has no obvious change, which indicates that the flexibility is better. It can be seen that the resulting composite material can significantly improve the electrochemical capacitance performance and the cycling stability of the electrode material due to the large surface area of the MOF/MXene/ppy@celf nano conductive layer and the synergistic effect and electron conduction between ppy@celf and the MOF/MXene nano sheets.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. The preparation method of the MOF/MXene/PPy@CelF porous nanomaterial is characterized by comprising the following steps of:
s1, preparing an MXene material, a MOF material and a PPy@CelF material;
preparing an MXene solution by adopting an HF acid etching method; preparing a PCN-222 precursor solution by benzoic acid, porphyrin ligand, zirconium chloride and N, N-diethyl formamide; preparing a PPy@CelF solution by adopting an in-situ polymerization method;
s2, preparing an MXene/PCN-222 composite material;
s21, preparing an MXene film by an electrophoretic deposition method; taking a proper amount of the MXene nano-sheet solution prepared in the step S1, immersing one of a copper plate, a platinum plate or a nickel plate into the solution to serve as an anode, directly applying voltage to one of a carbon plate, a stainless steel plate or ITO conductive glass serving as a cathode for 30-60 seconds, taking out the anode, and vacuum drying at room temperature to obtain an MXene film;
s22, preparing a PCN-222 layer on the MXene film by a rapid electrophoretic deposition technology to obtain a MXene/PCN-222 double-layer composite film;
s3, preparing the MOF/MXene/PPy@CelF porous nano material by a dip coating method;
immersing the MXene/PCN-222 double-layer composite membrane into the PPy@CelF solution, removing the solution after 20-30 minutes, pouring ammonium persulfate solution on the PPy@CelF coated membrane, keeping oscillating, and washing for a plurality of times by deionized water to obtain the MOF/MXene/PPy@CelF porous nano material.
2. The method for preparing a porous nano material of MOF/MXene/ppy@celf according to claim 1, wherein in step S1, the steps for preparing the MXene material are as follows:
mixing and stirring MAX phase ceramic containing Al with HF acid to etch Ti 3 AlC 2 Al in (C); centrifugally washing etched Ti 3 AlC 2 Dispersing liquid until the pH value is more than or equal to 6; and (5) continuing centrifugal separation for 30-60 min, and collecting supernatant to obtain the two-dimensional lamellar MXene.
3. The method for preparing the MOF/MXene/PPy@CelF porous nanomaterial according to claim 1, wherein the mass ratio of the MAX phase ceramic containing Al to the HF acid is 3: (10-20).
4. The method for preparing the MOF/MXene/ppy@celf porous nanomaterial according to claim 1, wherein in step S1, the preparation of the MOF material specifically comprises the following steps:
60 parts of benzoic acid, 1 part of porphyrin ligand and 1.25-1.5 parts of zirconium chloride are mixed with 10-20 parts of N, N-diethyl formamide, dissolved, heated in an oil bath at constant temperature, and the mixture is centrifuged for multiple times by adopting dimethylformamide and acetone to prepare the PCN-222 precursor solution.
5. The method for preparing the MOF/MXene/PPy@CelF porous nanomaterial according to claim 4, wherein the constant-temperature oil bath heating temperature is 100-120 ℃ and the heating time is 12-24 hours.
6. The method for preparing the MOF/MXene/PPy@CelF porous nanomaterial according to claim 1, wherein in the step S1, the preparation of the PPy@CelF material specifically comprises the following steps:
adding 2-5 g of the dried CelF into 150-300 mL of distilled water, uniformly mixing, and adding 1-1.5 ml of PPy; 4-5 g FeCl 3 ·6H 2 O is dissolved in 50mL of distilled water, slowly added into the mixture, continuously stirred for 2-3 h at the temperature of 0-5 ℃, and finally washed by distilled water to obtain PPy@CelF solution.
7. The method for preparing the MOF/MXene/PPy@CelF porous nanomaterial according to claim 1, wherein in the step S21, the electrophoretic deposition process is completed in two times, and each time, the electrophoretic deposition is carried out for 15-30S, and the interval is 10S.
8. The method for preparing a porous nano material of MOF/MXene/ppy@celf according to claim 1, wherein in step S22, the PCN-222 layer is prepared on the MXene film by the rapid electrophoretic deposition technique, specifically comprising the following steps:
immersing the copper plate covered with the MXene film into the PCN-222 precursor solution prepared in the step S1, applying an electric field with the strength of 20V/cm for 15-30 min, completing the deposition process in three times, performing electrophoretic deposition for 5-10 min each time, taking out the copper plate at intervals of 10min, and drying to obtain the MXene/PCN-222 composite double-layer film.
9. A MOF/MXene/ppy@celf porous nanomaterial prepared by the method of any one of claims 1-8.
10. Use of the MOF/MXene/ppy@celf porous nanomaterial of claim 9 in a supercapacitor, characterized in that the supercapacitor assembly method is:
cutting the MOF/MXene/PPy@CelF porous nano material into a rectangular film, and adhering the rectangular film to a non-conductive substrate to manufacture a film electrode; and sandwiching the solid electrolyte between two thin film electrodes to prepare the flexible supercapacitor.
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