CN111883745B - MOF/MXene/CF composite nano-sheet and synthesis method thereof - Google Patents

MOF/MXene/CF composite nano-sheet and synthesis method thereof Download PDF

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CN111883745B
CN111883745B CN202010542564.3A CN202010542564A CN111883745B CN 111883745 B CN111883745 B CN 111883745B CN 202010542564 A CN202010542564 A CN 202010542564A CN 111883745 B CN111883745 B CN 111883745B
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mxene
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CN111883745A (en
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郭玉香
张瑞楠
郭菁
姚焯
徐东辉
张德航
魏原驰
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University of Science and Technology Liaoning USTL
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a MOF/MXene/CF composite nano-sheet, which is obtained by electrostatic self-assembly of a MOF/MXene composite nano-material on the surface of carbon fiber cloth through a liquid phase deposition method. And processing metal atoms of the material by using the MAX material to obtain an MXene material, decomposing the MOF material to obtain metal atoms and organic ligands, enabling the metal atoms in the MOF to enter the MXene material, enabling the organic ligands to enter the MXene material along with the metal atoms, and forming the MOF/MXene/CF composite nano-sheet on the carbon fiber cloth by electrostatic self-assembly of the MOF/MXene/CF composite structure through a liquid phase deposition method. The composite nano-sheet is formed by inserting a secondarily generated MOF material into a MAX material after etching to obtain an MXene layered structure, and attaching the MXene layered structure to the surface of the layered structure; the MOF material generated in the second time is an organic ligand obtained after the original MOF is decomposed, and the organic ligand, the free metal atom A and the organic ligand, the free metal node and the organic ligand are self-assembled together through complexation.

Description

MOF/MXene/CF composite nano-sheet and synthesis method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a method for synthesizing a MOF/MXene/CF composite nano-sheet.
Background
Currently, the negative electrode materials in lithium ion batteries are mainly carbon materials, such as graphite, soft and hard carbon, or novel electrode materials, such as silicon carbon negative electrodes or transition metal oxides. With the exhaustion of petroleum energy and environmental pollution, the requirements of the market on battery capacity are gradually improved, and the lithium ion battery of the traditional negative electrode can not meet the current situation. In this case, the composite preparation of novel materials and application thereof to lithium ion batteries are becoming research hot spots.
MXene is used as a novel material and is a two-dimensional material with a structure similar to that of graphene, and the chemical formula is marked as M n+1 X n T x Wherein M represents a front transition metal, such as Ti, V, zr, mn, etc., X is a carbon element or a nitrogen element, and T is a surface functional group. The intermediate layer is etched from the MAX phase (a ternary layer compound, a being a group iii or iv element) of the precursor to obtain an MXene layered structure, but the sheets are prone to self-stacking, preventing electrolyte from wetting and rapid transfer of lithium ions between the layers in lithium battery applications. MOF materials are porous materials with regular pore structures, which are formed by combining metal ions and organic ligands through covalent bonds, coordination bonds, intermolecular forces and the like. The MOF material has a regular and controllable three-dimensional pore structure, and is beneficial to lithium ion storage and transmission. The CF (carbon fiber) material has high strength, small density, high durability and stable structure, and is suitable for use in high acid, alkali, salt and atmospheric corrosion environments.
At present, the application of the composite material in the field of super capacitors such as lithium batteries and the like is in a high-speed development period, and the electrode is always the important part of the capacitor for energy storage. MXene is a graphene-like two-dimensional material discovered in recent years, has ultrahigh volume specific capacity, metal-level conductivity, good hydrophilicity and rich surface chemistry, and is therefore used inThe flexible energy storage electrode material has wide application. In the patent (publication No. 109003836B) published by Hubei automotive industry college, a preparation method and application of a flexible fabric electrode based on MXene are disclosed. The MXene flexible fabric electrode is synthesized by an electroplating method: tiH is processed by 2 Sintering the powder A1 and the powder C according to a proportion, sieving to obtain MAX phase powder, chemically etching the MAX phase powder to obtain an MXene material, and carrying out low-temperature ultrasonic treatment and centrifugation to obtain Ti 3 C 2 And (3) an MXene colloid solution, and finally, placing the cleaned fabric into the diluted MXene solution for soaking, and drying in vacuum to obtain the fabric. The Ti can be effectively avoided in the process 3 C 2 Oxidation to TiO 2 The capacitor performance is obviously improved, the cost is low, and the capacitor is nontoxic and pollution-free and can be applied to the field of super capacitors. MXene is widely paid attention to because of high specific capacity, however, because the serious layer-by-layer stacking phenomenon is unfavorable for the rapid diffusion of ions in the vertical direction, the specific capacity of the MXene is influenced under the condition of high current density, and the poor oxidation resistance of the MXene seriously influences the conductivity and the circulation stability of the MXene, so that the layer stacking phenomenon of the MXene is improved by compounding the MXene with an active material with high specific capacity, and the oxidation resistance is improved to be particularly important.
Metal Organic Frameworks (MOFs) are crystalline framework materials with intramolecular pores formed by self-assembly of metal ions or clusters with organic ligands through coordination bonds under certain conditions. The material has large specific surface area, adjustable pore size and shape, easy modification, and the proton conductive and electron conductive MOF material has potential application value in the fields of fuel cells, electrocatalysis, lithium ion batteries, supercapacitors and the like. And other components are introduced into the MOF structure, so that the structure of the MOF can be finely adjusted, the adsorption performance, the catalytic activity, the electric conduction performance and the like are improved, and even the MOF has the performance which is not possessed originally. In the patent published by Nanjing university of post and telecommunications (publication number: 106611653A), a "one-step method" for preparing a novel MOF composite material is disclosed: etching the MAX material to obtain an MXene material and free A ions, and adding organic ligand molecules at the same time of etching, wherein the organic ligand molecules react with the A ions to form MOF on the surface of the MXene materialAnd (3) crystals, so that the MOF/MXene composite material with the MOF and MXene materials in a layered structure can be formed. In the published patent (publication number: 105047435B) of Shanghai engineering university, a method for synthesizing a manganese metal organic framework electrode material by a hydrothermal method and application thereof are disclosed: will contain Mn 2+ Adding the soluble salt, the organic acid and the bidentate nitrogen-containing ligand into deionized water, stirring and mixing uniformly, reacting for 48-96 hours in a reaction kettle at 120-200 ℃, cooling, filtering, washing, drying and the like after the reaction is finished, and obtaining the manganese metal organic framework electrode material, wherein the specific capacitance can reach 242F/g, and the manganese metal organic framework electrode material can be applied to high-power density power supply occasions.
The MOF has been widely focused on the characteristics of unique pore channel structures and transition metal elements, and electrodes taking the MOF as an active material or an active material carrier and electrodes taking the MOF as a precursor to form the active material or the active material carrier are successfully prepared, but the MOF as an electrode has slightly poorer conductivity than other electrode materials, and the maximum storage performance of a capacitor taking the MOF as the electrode cannot be exerted to the greatest extent. Secondly, the MOF has complex preparation process, influences the shape controllability of the MOF, ensures that the stability between preparation layers is poor, and limits the wide application of the MOF in electrode materials. Therefore, the preparation of the composite material with stable structure, large specific surface area, wider application range and greatly improved charge-discharge coulomb efficiency and circularity is very important.
Disclosure of Invention
The invention aims to provide a synthesis method of a MOF/MXene/CF composite nano-sheet, which overcomes the defects of the traditional MXene composite material in the aspects of small interlayer spacing, easy interlayer stacking and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the MOF/MXene/CF composite nano-sheet is obtained by electrostatic self-assembly of the MOF/MXene composite nano-material on the surface of the carbon fiber cloth by a liquid phase deposition method.
A method for synthesizing MOF/MXene/CF composite nano-sheets comprises the following specific steps:
step one, etching MAX materials: ball milling is carried out on MAX phase materials in organic solvent or water, vacuum drying is carried out, ball milling and sieving are carried out, and submicron-sized powder is obtained; immersing the powder in hydrofluoric acid, magnetically stirring at room temperature for 10-40 h, washing with deionized water to remove redundant acid solution, and drying at room temperature overnight to obtain MXene powder;
step two, decomposing MOF materials: the MOF material is decomposed for 2-5 hours at room temperature in an argon-filled environment by using a mixed solution of carbonate and bicarbonate, and is fully washed by deionized water to remove redundant salt solution, and is dried at room temperature overnight to obtain decomposed MOF powder;
step three, synthesizing the MOF/MXene nano material: adding the MXene powder obtained in the first step, the decomposed MOF powder obtained in the second step and an alcohol solution into a reaction kettle for synthesis reaction, wherein the molar ratio of the MXene powder to the decomposed MOF powder is (0.8-1.55): 1, a step of; hydrothermal treatment is carried out for 5 to 7 hours at the temperature of between 150 and 165 ℃ to obtain MOF/MXene suspension with charges;
step four, purifying the MOF/MXene suspension to remove unreacted ions and organic matters to obtain MOF/MXene precipitate;
and fifthly, adding an alcohol solution into the MOF/MXene precipitate, and performing electrostatic self-assembly on the surface of the carbon fiber cloth subjected to impurity removal by utilizing a liquid phase deposition method to obtain the MOF/MXene/CF composite nano-sheet.
The MAX material in the first step is selected from Mn 4 AlC 3 、V 4 AlC 3 One of the following; the organic solvent is ethanol solution with the concentration of 50 percent; the magnetic stirring rotating speed is 1200rmp; the PH value is between 6.5 and 8.5 after the deionized water is washed.
The MOF material in step two is selected from (C 5 H 5 )Mn(CO) 3 、(C 5 H 5 )V(CO) 3 One of the following; the mixed solution of carbonate and bicarbonate is NaCO 3 And NaHCO 3 NaCO 3 And NaHCO 3 The molar ratio is (0.3-0.5): (0.8-1.1), and the concentration of the mixed solution is (0.8-1.2) mol/L.
In the third step, the alcohol solution is ethanol solution with the concentration of 10 percent, and the pressure in the reaction kettle is 8MPa in the synthesis process.
And step four, adopting a centrifugal machine to remove impurities, wherein the centrifugal speed is 3000rmp.
And step five, removing impurities from the carbon fiber cloth by a method of: the impurity removal is carried out by nitric acid with the concentration of 60 percent, the ultrasonic power is 1000W, and the ultrasonic treatment is carried out for 45 minutes.
In the fifth step, the concentration of the alcohol solution is 10 percent of the alcohol solution,
operation of the liquid deposition method in the fifth step: immersing the carbon fiber cloth subjected to impurity removal in an alcohol solution of the MOF/MXene precipitate for more than 35 minutes, pouring the carbon fiber cloth into a 2-methylimidazole solution along with the solution, standing for 2-3 hours, washing with deionized water, and drying to obtain the MOF/MXene composite nano-sheet.
The MOF/MXene/CF composite nano-sheet is used for a lithium battery anode material.
In the first step, metal atoms of the material are removed to obtain an MXene material, in the second step, the MOF material is decomposed to obtain metal atoms and organic ligands, the metal atoms in the MOF material enter the MXene material, and the organic ligands enter the MXene material along with the metal atoms, so that the MOF/MXene composite structure is negatively charged, positive charges exist on the surface of the carbon fiber cloth after impurity removal, and electrostatic adsorption sites are provided for the positive charges of the carbon fiber cloth in the place where the negative charges exist in the MOF/MXene composite structure. After fully soaking the carbon fiber cloth and the alcohol solution of the MOF/MXene composite nano material, forming the MOF/MXene/CF composite nano sheet on the carbon fiber cloth by electrostatic self-assembly through a liquid phase deposition method.
Compared with the prior art, the invention has the beneficial effects that:
the composite nano-sheet is formed by inserting a secondarily generated MOF material into a MAX material after etching to obtain an MXene layered structure, and attaching the MXene layered structure to the surface of the layered structure; the MOF material generated in the second time is an organic ligand obtained after the original MOF is decomposed, and the organic ligand, the free metal atom A and the organic ligand, the free metal node and the organic ligand are self-assembled together through complexation.
The MXene material and the MOF material are combined to form a nano layered material with a sandwich structure, the MXene material and the MOF material are staggered and stacked, and on the basis of exerting excellent performance of high volume specific capacity of the MXene material, stability and microstructure controllability of the MOF material structure are utilized to be inserted between soft layers of the MXene material to play the same role as a supporting column, so that channels and spaces for diffusion and storage of ions can be provided to the greatest extent, a stable layered structure can be formed, and the application range is further enlarged, and charge-discharge coulomb efficiency and cycle performance of the material are improved.
Based on the MOF/MXene composite material, carbon fiber Cloth (CF) is introduced to enable the MOF/MXene composite material to be synthesized on the CF in situ, so that the MOF/MXene/CF composite nano-sheet with stable structure is formed. Secondly, the CF itself has conductivity and large specific surface area, and the storage capacity of the MOF/MXene/CF composite nano-sheet for ion pairs is further increased while the stability of the material is improved.
The method overcomes the defects of small interlayer spacing, easy stacking among layers and the like of the traditional MXene composite material, has great application prospect in the aspect of serving as an energy storage material in a super capacitor, can be directly used as a novel adhesive-free electrode, omits electrode plate preparation, reduces electrode volume and can be used as a flexible electrode. As a lithium battery cathode material, the stability, the energy storage and the utilization efficiency of the device are improved.
Detailed Description
The invention is further illustrated by the following examples:
the following examples illustrate the invention in detail. These examples are merely illustrative of the best embodiments of the invention and do not limit the scope of the invention.
A synthetic method of MOF/MXene/CF composite nano-sheets comprises the steps of carrying out electrostatic self-assembly on the surface of carbon fiber cloth by a liquid phase deposition method on MOF/MXene/CF composite nano-materials to obtain MOF/MXene/CF composite nano-sheets with self-supporting structures; the method comprises the following specific steps:
step one, etching MAX materials: grinding the MAX material into MAX material with submicron size by using a ball mill, and etching the MAX material with submicron size to obtain free metal atom A and MXene lamellar structure; ball milling is carried out on MAX phase materials in organic solvent or water, vacuum drying is carried out, ball milling and sieving are carried out, and submicron-sized powder is obtained; immersing the powder in hydrofluoric acid, magnetically stirring at room temperature for 10-40 h, washing with deionized water to remove redundant acid solution, and drying at room temperature overnight to obtain MXene powder;
step two, decomposing MOF materials: decomposing the MOF material into metal nodes and organic ligands using an aqueous carbonate and bicarbonate solution; the MOF material is decomposed for 2-5 hours at room temperature in an argon-filled environment by using a mixed solution of carbonate and bicarbonate, and is fully washed by deionized water to remove redundant salt solution, and is dried at room temperature overnight to obtain decomposed MOF powder;
step three, synthesizing the MOF/MXene composite nano material: adding the MXene powder obtained in the first step, the decomposed MOF powder obtained in the second step and an alcohol solution into a reaction kettle for synthesis reaction, wherein the molar ratio of the MXene powder to the decomposed MOF powder is (0.8-1.55): 1, a step of; hydrothermal treatment is carried out for 5 to 7 hours at the temperature of between 150 and 165 ℃ to obtain MOF/MXene suspension with charges;
step four, purifying the MOF/MXene suspension to remove unreacted ions and organic matters to obtain MOF/MXene precipitate;
and fifthly, adding an alcohol solution into the MOF/MXene precipitate, and performing electrostatic self-assembly on the surface of the carbon fiber cloth subjected to impurity removal by utilizing a liquid phase deposition method to obtain the MOF/MXene/CF composite nano-sheet.
Example 1
Synthesis method of MOF/MXene/CF composite nano-sheet, mn is selected 4 AlC 3 And (C) 5 H 5 )Mn(CO) 3 As MAX materials and MOF materials, MXene materials Mn having a layered structure are included 4 C 3 The free metal node V is inserted in the MOF crystal which takes Al as a node and cyclopentadiene as an organic ligand on the surface of the layered structure and the material, and the carbon cloth is used as a carrier.
The method comprises the following specific steps:
step one, etching MAX materials: 20mL of 50% ethanol solution was used as a dispersant, and 1.2g Mn was obtained 4 AlC 3 Ball milling in ethanol for 30h, vacuumDrying, ball milling and sieving to obtain submicron Mn 4 AlC 3 And (3) powder. Submicron Mn 4 AlC 3 Immersing the powder in 300mL of 49% hydrofluoric acid, magnetically stirring at 1200rmp room temperature for 20h, washing the solution with deionized water to remove excessive acid solution, keeping pH between 6.5-8.5, and drying at room temperature overnight to obtain Mn 4 C 3 And (3) powder.
Step two, decomposing MOF materials: 1.5g (C) 5 H 5 )Mn(CO) 3 In a glove box filled with argon gas, the reaction mixture was subjected to (C 5 H 5 )Mn(CO) 3 Is dissolved in 200mLNaCO at room temperature 3 And NaHCO 3 NaCO in the mixed solution of (a) 3 And NaHCO 3 The molar ratio of the mixed solution of (2) is 0.3:0.8, the concentration of the mixed solution is 1.2mol/L, the reaction time is 2.5 hours, and the reaction time is equal to (C 5 H 5 )Mn(CO) 3 Fully decomposing, fully washing with deionized water to remove redundant salt solution, and drying at room temperature overnight to obtain Mn-MOFs powder in a decomposed state.
Step three, synthesizing the MOF/MXene composite nano material: adding the dried powder in the first step and the second step into a stainless steel reaction kettle with polytetrafluoroethylene as a lining, taking 0.8g of MXene powder in the first step, 1g of decomposed powder in the second step, adding 30mL of 10% ethanol solution, and carrying out hydrothermal treatment for 5 hours in the reaction kettle under the pressure of 8Mpa and the temperature of 155 ℃ to obtain the MOF/MXene composite nano-sheet suspension.
And step four, purifying and removing unreacted ions and organic matters, centrifuging the MOF/MXene composite nano-sheet suspension for 5 minutes at 3000rmp, washing with deionized water for 3 times, and vacuum drying the solid precipitate at 65 ℃ overnight.
And fifthly, respectively carrying out ultrasonic treatment on the carbon fiber cloth with the side length of 5mm in 20mL of absolute ethyl alcohol and 100mL of deionized water, carrying out ultrasonic treatment with the power of 1000w for 45min so as to remove impurities on the surface of the carbon fiber cloth, and arranging the cleaned carbon fiber in 10mL of nitric acid with the concentration of 60%, and treating for 10h, and cleaning and drying for later use. And (3) dissolving the solid precipitate obtained in the step (IV) in deionized water, immersing the carbon fiber cloth subjected to impurity removal treatment in the solution for more than 30 minutes, rapidly pouring the carbon fiber cloth into a 2-methylimidazole solution along with the solution, and standing for 2 hours. Finally, the mixture is rinsed with deionized water and dried in a drying oven at 65 ℃. Obtaining the MOF/MXene/CF composite nano-sheet.
Mn 4 AlC 3 And (C) 5 H 5 )Mn(CO) 3 As MAX materials and MOF materials, mn 4 AlC 3 Etching to separate Al ions to obtain MXene material Mn 4 C 3 And free Al, decomposed at the same time as etching (C 5 H 5 )Mn(CO) 3 Obtaining free metal nodes Mn, cyclopentadiene and carboxyl, wherein Mn is the content of cyclopentadiene and Al in Mn 4 C 3 Forming MOF crystal with Al as node and cyclopentadiene as ligand by interlayer self-assembly, metal node Mn entering Mn 4 C 3 Surface voids of Mn 4 C 3 And (3) reforming MOF crystals taking Mn as a node and cyclopentadiene and free carboxyl as ligands on the surface, finally obtaining the MOF/MXene composite material, soaking the MOF/MXene composite material in ethanol solution, and soaking and standing the MOF/MXene composite material and the treated CF together, thus obtaining the MOF/MXene/CF composite nano-sheet.
The sweep speed of the composite nano sheet in cyclic voltammetry is 2mVs -1 Its specific capacity is up to 252F g -1 At high specific capacitance, e.g. 5A g -1 The current density circulates 3000 times at a large sweeping speed, and the capacitance retention rate reaches 99%.
Example 2
Synthesis method of MOF/MXene/CF composite nano-sheet, mn is selected 4 AlC 3 And (C) 5 H 5 )Mn(CO) 3 As MAX materials and MOF materials, MXene materials Mn having a layered structure are included 4 C 3 The free metal node V is inserted in the MOF crystal which takes Al as a node and cyclopentadiene as an organic ligand on the surface of the layered structure and the material, and the carbon cloth is used as a carrier.
The method comprises the following specific steps:
step one, MAX material treatment: 20mL of 50% ethanol solution is selected as a dispersing agent, 1.2. 1.2gMn is taken 4 AlC 3 Ball milling in ethanol for 30h, vacuum drying, ball milling and sieving to obtain submicron Mn 4 AlC 3 And (3) powder. Submicron Mn 4 AlC 3 The powder is immersed in 300mL of hydrofluoric acid with the concentration of 49%, and after being magnetically stirred for 25 hours at the room temperature of 1200rmp, the solution is fully washed by deionized water to remove redundant acid solution, the PH after washing is ensured to be between 6.5 and 8.5, and the solution is dried overnight at room temperature. Obtaining Mn 4 C 3 And (3) powder.
Step two, decomposing MOF materials: 1.5g (C) 5 H 5 )Mn(CO) 3 In a glove box filled with argon gas, the reaction mixture was subjected to (C 5 H 5 )Mn(CO) 3 Is dissolved in 200mLNaCO at room temperature 3 And NaHCO 3 In the mixed solution (C), the reaction time was 3.5 hours 5 H 5 )Mn(CO) 3 Fully decomposing, fully washing with deionized water to remove redundant salt solution, and drying at room temperature overnight to obtain Mn-MOFs powder.
And thirdly, synthesizing the MOF/MXene composite nano material, adding the powder obtained after drying in the first step and the second step into a stainless steel reaction kettle taking polytetrafluoroethylene as a lining, wherein 0.8g of the MXene powder in the first step and 1g of the powder obtained after decomposition in the second step are taken, adding 30mL of ethanol solution with the concentration of 10%, and carrying out hydrothermal treatment for 6 hours in the reaction kettle under the pressure of 8Mpa and 160 ℃ to obtain the MOF/MXene composite nano suspension.
And step four, purifying and removing unreacted ions and organic matters, centrifuging the MOF/MXene composite nano-sheet suspension for 5 minutes at 3000rmp, washing with deionized water for 3 times, and vacuum drying the solid precipitate at 65 ℃ overnight.
And fifthly, respectively carrying out ultrasonic treatment on the carbon cloth with the side length of 5mm in 20mL of absolute ethyl alcohol and 100mL of deionized water, carrying out ultrasonic treatment for 45min at the power of 1000w so as to remove impurities on the surface of the carbon cloth, and arranging the cleaned carbon in 10mL of nitric acid with the concentration of 60%, and then carrying out cleaning and drying for later use. And dissolving the MOF/MXene composite nano solid precipitate in deionized water, immersing the pretreated carbon cloth in the solution for more than 30 minutes, rapidly pouring the carbon cloth into a 2-methylimidazole solution along with the solution, and standing for 2 hours. And finally, washing with deionized water, and drying in a drying oven at 65 ℃ to obtain a finished product.
MXene material Mn with layered structure 4 C 3 Free metal nodes V interpenetrated in the layered structure and materialMOF crystals with Al as nodes and cyclopentadiene as organic ligands on the material surface and carbon cloth as a carrier.
The sweep speed of the composite nano sheet in cyclic voltammetry is 2mVs -1 Its specific capacity is up to 246F g -1 At high specific capacitance, e.g. 5A g -1 The current density circulates 3000 times at a large sweeping speed, and the capacitance retention rate reaches 97%.
Example 3
A synthetic method of MOF/MXene/CF composite nano-sheet selects V 4 AlC 3 And (C) 5 H 5 )V(CO) 3 As MAX materials and MOF materials, MXene materials V having a layered structure are included 4 C 3 Free metal nodes Mn are inserted in MOF crystals which take Al as nodes and cyclopentadiene as organic ligands on the surfaces of the layered structure and the material, and carbon cloth is used as a carrier. The method comprises the following specific steps:
step one, MAX material treatment: 20mL of 50% ethanol solution is selected as a dispersing agent, 1.2. 1.2g V is taken 4 AlC 3 Ball milling in ethanol for 20 hr, vacuum drying, ball milling and sieving to obtain submicron V 4 AlC 3 And (3) powder. V of submicron order 4 AlC 3 Immersing the powder in 300mL of 49% hydrofluoric acid, magnetically stirring at 1200rmp for 20h at room temperature, washing the solution with deionized water to remove excessive acid solution, keeping pH between 6.5-8.5, and drying at room temperature overnight to obtain V 4 C 3 And (3) powder.
Step two, decomposing MOF materials: 1.5g (C) 5 H 5 )V(CO) 3 In a glove box filled with argon gas, the reaction mixture was subjected to (C 5 H 5 )V(CO) 3 Is dissolved in 200mLNaCO at room temperature 3 And NaHCO 3 In the mixed solution (C), the reaction time was 2.5 hours 5 H 5 )V(CO) 3 Fully decomposing, fully washing with deionized water to remove redundant salt solution, and drying at room temperature overnight to obtain the V-MOFs powder.
Step three, synthesizing the MOF/MXene composite nano material: and (3) adding the dried powder in the first step and the second step into a stainless steel reaction kettle with polytetrafluoroethylene as a lining, wherein 0.8g of MXene powder in the first step and 1g of decomposed powder in the second step are taken, 30mL of ethanol solution with the excessive concentration of 10% is added, and the mixture is subjected to hydrothermal treatment at the pressure of 8Mpa and the temperature of 155 ℃ for 5 hours to obtain the MOF/MXene composite nano suspension.
And step four, purifying and removing unreacted ions and organic matters, centrifuging the MOF/MXene composite nano-sheet suspension for 5 minutes at 3000rmp, washing with deionized water for 3 times, and vacuum drying the solid precipitate at 65 ℃ overnight.
And fifthly, respectively carrying out ultrasonic treatment on the carbon cloth with the side length of 5mm in 20mL of absolute ethyl alcohol and 100mL of deionized water, carrying out ultrasonic treatment for 45min at the power of 1000w so as to remove impurities on the surface of the carbon cloth, and arranging the cleaned carbon in 10mL of nitric acid with the concentration of 60%, and then carrying out cleaning and drying for later use. And dissolving the MOF/MXene composite nano-sheet solid precipitate in deionized water, immersing the pretreated carbon cloth in the solution for more than 30 minutes, rapidly pouring the carbon cloth into a 2-methylimidazole solution along with the solution, and standing for 2 hours. And finally, washing with deionized water, and drying in a drying oven at 65 ℃ to obtain a finished product.
The sweep speed of the composite nano sheet in cyclic voltammetry is 2mVs -1 Its specific capacity is up to 242F g -1 At high specific capacitance, e.g. 5A g -1 The current density circulates 3000 times at a large sweeping speed, and the capacitance retention rate reaches 99%.
Example 4
A synthetic method of MOF/MXene/CF composite nano-sheet selects V 4 AlC 3 And (C) 5 H 5 )V(CO) 3 As MAX materials and MOF materials, MXene materials V having a layered structure are included 4 C 3 Free metal nodes Mn are inserted in MOF crystals which take Al as nodes and cyclopentadiene as organic ligands on the surfaces of the layered structure and the material, and carbon cloth is used as a carrier. The method comprises the following specific steps:
step one, MAX material treatment: 20mL of 50% ethanol solution is selected as a dispersing agent, 1.2. 1.2g V is taken 4 AlC 3 Ball milling in ethanol for 30h, vacuum drying, ball milling and sieving to obtain submicron V 4 AlC 3 And (3) powder. V of submicron order 4 AlC 3 The powder was immersed in 300mL of water at a concentration of 4In 9% hydrofluoric acid, after magnetic stirring for 25 hours at room temperature with the rotation speed of 1200rmp, fully washing the solution with deionized water to remove redundant acid solution, ensuring the PH after washing to be between 6.5 and 8.5, and drying overnight at room temperature to obtain V 4 C 3 And (3) powder.
Step two, decomposing MOF materials: 1.5g (C) 5 H 5 )V(CO) 3 In a glove box filled with argon gas, the reaction mixture was subjected to (C 5 H 5 )V(CO) 3 Is dissolved in 200mLNaCO at room temperature 3 And NaHCO 3 In the mixed solution (C), the reaction time was 2.5 hours 5 H 5 )V(CO) 3 Fully decomposing, fully washing with deionized water to remove redundant salt solution, and drying at room temperature overnight to obtain the V-MOFs powder.
Step three, synthesizing the MOF/MXene composite nano material: and (3) adding the dried powder in the first step and the second step into a stainless steel reaction kettle with polytetrafluoroethylene as a lining, wherein 0.8g of MXene powder in the first step and 1g of decomposed powder in the second step are taken, 30mL of ethanol solution with the excessive concentration of 10% is added, and the mixture is subjected to hydrothermal treatment at the pressure of 8Mpa and the temperature of 160 ℃ for 6 hours to obtain the MOF/MXene composite nano suspension.
And step four, purifying and removing unreacted ions and organic matters, centrifuging the MOF/MXene composite nano-sheet suspension for 5 minutes at 3000rmp, washing with deionized water for 3 times, and vacuum drying the solid precipitate at 65 ℃ overnight.
Step five, synthesizing on CF: respectively carrying out ultrasonic treatment on carbon cloth with the side length of 5mm in 20mL of absolute ethyl alcohol and 100mL of deionized water, carrying out ultrasonic treatment with the power of 1000w for 45min to remove impurities on the surface of the carbon cloth, arranging the cleaned carbon in 10mL of nitric acid with the concentration of 60%, and carrying out treatment for 10h, cleaning and drying for later use. And dissolving the MOF/MXene composite nano-sheet solid precipitate in deionized water, immersing the pretreated carbon cloth in the solution for more than 30 minutes, rapidly pouring the carbon cloth into a 2-methylimidazole solution along with the solution, and standing for 2 hours. And finally, washing with deionized water, and drying in a drying oven at 65 ℃ to obtain a finished product.
The sweep speed of the composite nano sheet in cyclic voltammetry is 2mVs -1 Its specific capacity is up to 242F g -1 At high specific capacitance, e.g. 5A g -1 The current density circulates 3000 times at a large sweeping speed, and the capacitance retention rate reaches 97%.
According to the invention, the MAX material is etched, the MAX material is decomposed to obtain the MXene layered material and free metal ions A, the MOF material is separated while etching, free metal nodes and organic ligands which are the same as the metal ions in the layered structure are obtained, and the ions are subjected to complexation with the organic ligands on the surface and between layers of the MXene material to form MOF crystals for the second time, so that the MOF/MXene composite nano material with the MOF and MXene material in a layered mutually overlapped structure can be formed.
Due to the structural characteristics of the MAX material, the obtained MXene layered structure has the characteristic of uniform layer spacing distribution, has high structural controllability, and provides conditions for the penetration and attachment of MOFs. MOF crystals based on MXene layered structure are more uniform and controllable in structure than traditional MOF materials, MOF/MXene composite nano materials with different interlayer distances can be obtained according to different microscopic radiuses of metal nodes, and the application of the MOF/MXene composite nano materials in the energy storage fields of lithium batteries and the like is expanded. Through selecting MAX materials, the structural characteristics of layer thickness, layer spacing and the like of the MXene layered structure can be adjusted, so that the structural diversity and controllability of the MOF/MXene composite nano material are realized; by selecting CF materials, the MOF/MXene/CF composite nano-sheet with a self-supporting structure can be formed, so that the stability of the materials is improved, and meanwhile, the CF has stronger electron accepting and transferring performance, so that the performance of storing and transmitting lithium ions of the composite nano-sheet can be improved, and the composite nano-sheet can be directly used as a novel non-adhesive electrode.
The MOF/MXene/CF composite nano-sheet combines three structures, the specific surface area and the porosity of the material are increased, the controllability of the structure improves the utilization rate of the material, and the structure is more stable and can be directly used as a novel non-adhesive electrode, so that the composite nano-sheet improves the energy storage and the utilization efficiency.
The method is simple and safe to operate, solves the problem of reaction of the acid solution and the MAX material which are introduced in advance, ensures high yield and purity, basically avoids the introduction of new impurities and byproducts, and simultaneously solves the problem of poor stability of the composite structure of the two materials.

Claims (5)

1. The MOF/MXene/CF composite nano-sheet is characterized in that MOF materials generated secondarily are inserted into MAX materials after etching to obtain an MXene layered structure, and the MOF/MXene/CF composite nano-sheet is attached to the surface of the layered structure; the MXene material is combined with the MOF material to form a nano layered material with a sandwich structure, wherein the MXene material and the MOF material are staggered and stacked, and the MOF material is inserted between soft layers of the MXene to play a role of a support column, so that a channel and a space for diffusion and storage of ions are provided;
the method comprises the steps of performing electrostatic self-assembly on the surface of carbon fiber cloth by a liquid phase deposition method on the MOF/MXene composite nano material to obtain a MOF/MXene/CF composite nano sheet with a self-supporting structure; based on the MOF/MXene composite material, introducing a carbon fiber cloth CF to enable the MOF/MXene composite material to be synthesized on the CF in situ, wherein the specific steps are as follows:
step one, etching MAX materials: ball milling MAX phase material in organic solvent or water, wherein MAX phase material is selected from Mn 4 AlC 3 、V 4 AlC 3 One of the following; vacuum drying, ball milling and sieving to obtain submicron-sized powder; immersing the powder in hydrofluoric acid, magnetically stirring for 10-40 h at room temperature, washing with deionized water to remove redundant acid solution, washing with deionized water, and drying at room temperature overnight to obtain MXene powder;
step two, decomposing MOF materials: dissolving MOF material in a mixed solution of carbonate and bicarbonate in an environment filled with argon, decomposing for 2-5 hours at room temperature, fully washing with deionized water to remove redundant salt solution, and drying at room temperature overnight to obtain decomposed MOF powder; the MOF material is selected from (C 5 H 5 ）Mn（CO） 3 、（C 5 H 5 ）V（CO） 3 One of the following; the mixed solution of carbonate and bicarbonate is NaCO 3 And NaHCO 3 NaCO 3 And NaHCO 3 The molar ratio is (0.3-0.5): (0.8-1.1), the concentration of the mixed solution is 0.8-1.2 mol/L;
step three, synthesizing the MOF/MXene nano material: adding the MXene powder obtained in the first step, the decomposed MOF powder obtained in the second step and an alcohol solution into a reaction kettle for synthesis reaction, wherein the molar ratio of the MXene powder to the decomposed MOF powder is (0.8-1.55): 1, a step of; hydrothermal treatment is carried out for 5 to 7 hours at the temperature of between 150 and 165 ℃ to obtain MOF/MXene suspension with charges;
step four, purifying the MOF/MXene suspension to remove unreacted ions and organic matters to obtain MOF/MXene precipitate;
adding an alcohol solution into the MOF/MXene precipitate, and performing electrostatic self-assembly on the surface of the carbon fiber cloth subjected to impurity removal by using a liquid phase deposition method to obtain the MOF/MXene/CF composite nano-sheet;
the impurity removing method for the carbon fiber cloth comprises the following steps: removing impurities by using nitric acid with the concentration of 60%, and performing ultrasonic treatment for 45 minutes at the ultrasonic power of 1000W;
operation of the liquid deposition method: immersing the carbon fiber cloth subjected to impurity removal in an alcohol solution of MOF/MXene precipitate for more than 35 minutes, wherein the alcohol solution is an alcohol solution with the concentration of 10%, pouring the carbon fiber cloth into a 2-methylimidazole solution along with the solution, standing for 2-3 hours, washing with deionized water, and drying to obtain the MOF/MXene composite nano-sheet.
2. The MOF/MXene/CF composite nano-sheet according to claim 1, wherein the organic solvent in the first step is 50% ethanol solution; the magnetic stirring speed is 1200rmp.
3. The MOF/MXene/CF composite nano-sheet according to claim 1, wherein the alcohol solution in the third step is 10% alcohol solution, and the pressure in the reaction kettle in the synthesis process is 8MPa.
4. The MOF/MXene/CF composite nanosheets of claim 1, wherein the fourth step is removing impurities using a centrifuge at a rate of 3000rmp.
5. The MOF/MXene/CF composite nano-sheet according to claim 1, which is used for a lithium battery anode material.
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