CN112850685A - Two-dimensional carbon material and preparation method and application thereof - Google Patents

Two-dimensional carbon material and preparation method and application thereof Download PDF

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CN112850685A
CN112850685A CN201911185620.6A CN201911185620A CN112850685A CN 112850685 A CN112850685 A CN 112850685A CN 201911185620 A CN201911185620 A CN 201911185620A CN 112850685 A CN112850685 A CN 112850685A
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carbon material
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CN112850685B (en
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申仲荣
胡艳杰
张明
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Xiamen Institute of Rare Earth Materials
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01M4/58—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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a two-dimensional carbon material and a preparation method and application thereof, and particularly provides a method for preparing the two-dimensional carbon material by taking small organic molecules as raw materials through a template method and the two-dimensional carbon material prepared by the method. The morphology structure of the two-dimensional carbon material is not particularly limited, for example, two-dimensional carbon materials with different morphology structures can be prepared according to different organic carbon source small molecule species, different preparation process temperatures and different post-treatment steps, and the two-dimensional carbon materials can be used in the fields of lithium ion battery materials, supercapacitor materials, adsorption materials, nano catalytic materials and the like. The two-dimensional carbon material has the following characteristics: 1) the specific surface area between the template layers is large, and the mass production preparation of the two-dimensional carbon material can be realized; 2) different elements, such as nitrogen, sulfur, phosphorus and the like, can be introduced into the intercalated carbon material to realize doping modification of the carbon material.

Description

Two-dimensional carbon material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of two-dimensional carbon materials, and particularly relates to a two-dimensional carbon material and a preparation method and application thereof.
Background
The two-dimensional carbon material has the characteristics of good thermal conductivity, electrical conductivity, mechanical strength, high specific surface area, film-forming property, low price and the like, is widely applied to the fields of thermoelectric materials, new energy electrode materials, catalytic materials, plastic or rubber additive materials and coatings, and has good application prospect.
According to the method for preparing the nanosheet or nanosheet superstructure from the graphite material, the graphene material prepared by physical grinding and other methods is basically a multi-layer graphene material, and meanwhile, the functionalization difficulty of the graphene is high due to the high stability of the carbon on the surface of the graphite. The graphene oxide prepared by the general Hammer chemical method has multiple defects and poor mechanical properties; in order to obtain a functionalized two-dimensional carbon material having thermal and electrical conductivity, etc., an additional reduction step is required, which complicates the preparation of a functionalized two-dimensional carbon material from graphite.
The existing method for preparing the two-dimensional carbon material by using small molecules as raw materials is to form a monomolecular self-assembly layer on solid-liquid, gas-liquid and solid-gas interfaces, and then to polymerize by illumination radiation, electron or ion radiation and to carry out thermal post-treatment. The method has complex preparation process, and is difficult to realize mass production because of limited interface area.
Chemical vapor deposition is also an effective method for preparing a large-area two-dimensional carbon material, however, it uses a nickel or copper substrate as a catalyst surface, and the carbon material needs to be peeled off from the surface by an etching treatment at a later stage, and the preparation is complicated and the mass production is low.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a two-dimensional carbon material, a preparation method and application thereof, and particularly provides a method for preparing the two-dimensional carbon material by taking small organic molecules as raw materials through a template method and the two-dimensional carbon material prepared by the method. The morphology structure of the two-dimensional carbon material is not particularly limited, and for example, two-dimensional carbon materials with different morphology structures can be prepared according to different organic carbon source small molecule species, different preparation process temperatures, and different post-treatment steps, and exemplarily, the two-dimensional carbon material includes a two-dimensional layer stacking carbon material, a two-dimensional nanosheet layer carbon material, or a two-dimensional layer column carbon material, and the two-dimensional carbon material can be used in the fields of lithium ion battery materials, supercapacitor materials, adsorption materials, nanocatalysis materials, and the like.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a two-dimensional carbon material is characterized in that a layered inorganic material is used as a template, and a single-functional group or multi-functional group organic molecular layer is introduced between layers of the layered inorganic material by carrying out ion exchange reaction and/or intercalation reaction and optional confinement reaction on the layered inorganic material, and then the two-dimensional carbon material is prepared by optional polymerization reaction, carbonization reaction and template removal reaction and optional physical stripping.
According to the invention, the two-dimensional carbon material morphology structure comprises two-dimensional layer stacked carbon material, two-dimensional nano-sheet layer carbon material and two-dimensional layer column carbon material.
In the invention, the thickness and the morphology structure of the two-dimensional carbon material can be adjusted according to the types of small molecules of the organic carbon source and the temperature of the carbonization reaction, and can also be adjusted according to the difference of post-treatment modes. For example, a thinner two-dimensional carbon material can be obtained with p-phenylenediamine and a thicker two-dimensional carbon material can be obtained with benzidine during intercalation; in the carbonization process, the two-dimensional layer stacking carbon material can be obtained by polymerization or carbonization sintering below the collapse temperature of the template; the two-dimensional layer stacked carbon material can be used for obtaining a two-dimensional nanosheet layer carbon material by a physical stripping method; and the template may be deformed, partially reduced, perforated by sintering and even collapsed by sintering due to the temperature and the atmosphere during the carbonization process, so that the two-dimensional pillared carbon material can be obtained.
According to the invention, the method comprises the following steps:
1) taking a layered inorganic material as a template, carrying out at least one ion exchange reaction and/or intercalation reaction and optionally carrying out at least one confinement reaction on the layered inorganic material to prepare an organic/inorganic composite two-dimensional material with an organic molecular assembly layer introduced between layers;
2) optionally, carrying out polymerization reaction on the organic/inorganic composite two-dimensional material prepared in the step 1);
3) carrying out carbonization reaction on the organic/inorganic composite two-dimensional material obtained in the step 1) or the polymerized organic/inorganic composite two-dimensional material obtained in the step 2) to prepare a composite two-dimensional material containing a layered inorganic material;
4) performing template removing reaction on the composite two-dimensional material containing the layered inorganic material prepared in the step 3) to prepare the two-dimensional carbon material.
In the invention, the morphology structure of the two-dimensional carbon material prepared in the step 4) is a two-dimensional layer stacked carbon material or a two-dimensional layer column carbon material, and if the morphology structure is the two-dimensional layer stacked carbon material, the two-dimensional carbon material can be prepared into a single-layer or multi-layer two-dimensional nanosheet layer carbon material by a further physical stripping method.
According to the invention, the method further comprises the steps of:
5) and 4) obtaining the single-layer or multi-layer two-dimensional nano-sheet layer carbon material from the two-dimensional carbon material prepared in the step 4) by a physical stripping method.
According to the invention, in step 1), the layered inorganic material is selected from montmorillonite, layered metal oxide, layered metal hydroxide, and the like.
According to the present invention, in step 1), the montmorillonite is a conventional montmorillonite known in the art.
According to the invention, in step 1), the layered metal oxide is selected from the group consisting of amorphous metal oxidesProtonated layered metal oxides, metal ion-exchanged layered metal oxides, protonated layered metal oxides; preferably, the metal oxide may be selected from alkaline earth-transition metal oxides, for example, one, two or more of oxides of elements such as calcium, barium, titanium, niobium, ruthenium, vanadium, tungsten, tantalum, hafnium, zirconium, chromium, cobalt, molybdenum, manganese, lanthanum, cerium, praseodymium, neodymium, scandium, yttrium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc.; illustratively, the metal oxide may be selected from one, two or more of titanium oxide, niobium oxide, lanthanum oxide, tungsten oxide, and vanadium oxide. Preferably, the layered metal oxide may be selected from protonated layered TiO2Material, nickel ion exchanged layered TiO2Materials, and the like.
Wherein the lamellar size (diameter or side length) of the lamellar metal oxide is 20 nanometers to 50 micrometers, and the thickness is 20 nanometers to 50 micrometers.
Wherein the layered metal oxide, especially the non-protonated layered metal oxide, the metal ion-exchanged layered metal oxide and the protonated layered metal oxide can be prepared by methods known in the art, such as solid-thermal sintering, hydrothermal, solvothermal, liquid-phase exfoliation, mechanical exfoliation, ion-exchange, etc.
According to the invention, in step 1), the layered metal hydroxide is selected from the group consisting of hydrotalcite and hydrotalcite-like materials. Preferably, the metal hydroxide may be selected from metal hydroxides, for example, one, two or more of hydroxides of magnesium, aluminum, zinc, manganese, calcium, barium, titanium, niobium, ruthenium, vanadium, tungsten, tantalum, hafnium, zirconium, chromium, cobalt, molybdenum, and the like; illustratively, the layered metal hydroxide may be selected from magnesium aluminum carbonate type hydrotalcite, magnesium iron sulfate type hydrotalcite, nickel cadmium carbonate type hydrotalcite. Preferably, the magnesium aluminum dihydroxy root type hydrotalcite material.
According to the invention, in step 1), the ion exchange reaction comprises the following steps:
mixing the layered inorganic material with an ion exchanger, and reacting to prepare the organic/inorganic composite two-dimensional material with the organic molecular assembly layer introduced between the layers.
Wherein the ion exchanger is selected from at least one of hydrochloride of organic amine, nitrate of organic amine and alkali metal salt of organic acid (carboxylic acid, boric acid, sulfonic acid). The mass ratio of the layered inorganic material to the ion exchanger is 10:1-1: 100; the temperature of the ion exchange reaction is 0-200 ℃, and the time of the ion exchange reaction is 10 minutes-10 days; the type of ion exchange reaction may be one or more of hydrothermal, stirring, heating, microwave, ultrasound.
Wherein the hydrochloride of the organic amine is selected from the following hydrochlorides of organic amines: saturated alkylamines, aromatic-containing amines, saturated alkylamines containing other functional groups. Wherein the saturated alkylamine is, for example, CxH2x+1NH2Wherein x is an integer between 3 and 16; the aromatic hydrocarbon-containing amines are, for example, aniline, diphenylamine (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine), benzidine, benzylamine, and benzylamine derivatives (methylbenzylamine, phenylbenzylamine, etc.), 1,3, 5-triphenylamine, melamine, 3' -diaminobenzidine; the saturated alkylamine having another functional group is, for example, ethanolamine.
Wherein the nitrate of the organic amine is selected from the following nitrates of organic amines: saturated alkylamines, aromatic-containing amines, saturated alkylamines containing other functional groups. Wherein the saturated alkylamine is, for example, CxH2x+1NH2Wherein x is an integer between 3 and 16; the aromatic hydrocarbon-containing amines are, for example, aniline, diphenylamine (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine), benzidine, benzylamine, and benzylamine derivatives (methylbenzylamine, phenylbenzylamine, etc.), 1,3, 5-triphenylamine, melamine, 3' -diaminobenzidine; the saturated alkylamine having another functional group is, for example, ethanolamine.
Wherein the alkali metal salt of an organic acid is selected from an alkali metal salt of a carboxylic acid, an alkali metal salt of a boronic acid or an alkali metal salt of a sulfonic acid; illustratively, the alkali metal salt of the carboxylic acid is selected from the sodium, potassium, and cesium salts of the following carboxylic acids: benzoic acid, acetic acid,Phthalic acid (phthalic acid, isophthalic acid, terephthalic acid), biphenyl-4, 4' -dicarboxylic acid, 1,3, 5-benzenetricarboxylic acid. The alkali metal salts of boric acid are selected from the following sodium, potassium, and cesium salts of boric acid: phenylboronic acids, alkylphenylboronic acids (p-alkylphenylboronic acid, o-alkylphenylboronic acid, m-alkylphenylboronic acid, e.g. CxH2x+1C6H4B(OH)2Where x is an integer between 1 and 16), phenyl diboronic acid (o-phenyl diboronic acid, m-phenyl diboronic acid, p-phenyl diboronic acid), 4' -biphenyl diboronic acid. The alkali metal salt of the sulfonic acid is selected from the sodium, potassium, and cesium salts of the following sulfonic acids: benzene-sulfonic acids, alkyl-benzene-sulfonic acids (p-alkyl-, o-, m-alkyl-benzene-sulfonic acids, e.g. C)xH2x+1C6H4SO3H, wherein x ═ an integer between 1 and 16), benzenedisulfonic acid (o-, m-, p-benzenedisulfonic acid), 4' -biphenyldisulfonic acid.
According to the invention, in step 1), the intercalation reaction comprises the following steps:
mixing the layered inorganic material with the intercalation agent, and reacting to obtain the organic/inorganic composite two-dimensional material with the organic molecular assembly layer introduced between the layers.
Wherein the intercalation agent is selected from organic small molecules containing amine groups, organic small molecules containing organic acids (carboxylic acid, boric acid and sulfonic acid) and organic small molecules containing sulfhydryl groups; the mass ratio of the layered inorganic material to the intercalation agent is 10:1-1: 100; the temperature of the intercalation reaction is 0-200 ℃, and the time of the intercalation reaction is 10 minutes to 10 days; the intercalation reaction may be one or more of hydrothermal, stirring, heating, microwave, ultrasonic.
Preferably, the intercalating agent is selected from small organic molecules containing amine groups, including, for example, saturated alkylamines, aromatic-containing amines, saturated alkylamines containing other functional groups. Wherein the saturated alkylamine is, for example, CxH2x+1NH2Wherein x is an integer between 3 and 16; the aromatic hydrocarbon-containing amines are, for example, aniline, diphenylamine (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine), benzidine, benzylamine, and a derivative of benzylamine (A)Benzylamine, phenylbenzylamine, and the like), 1,3, 5-triphenylamine, melamine, 3' -diaminobenzidine; the saturated alkylamine having another functional group is, for example, ethanolamine.
Preferably, the intercalating agent is selected from small organic molecules containing carboxylic acids, including, for example, saturated alkyl carboxylic acids, aromatic hydrocarbon-containing carboxylic acids; the saturated alkyl carboxylic acid is, for example, CxH2x+1COOH, wherein x is an integer between 3 and 16; examples of the aromatic hydrocarbon-containing carboxylic acid include benzoic acid, acetic acid, phthalic acid (phthalic acid, isophthalic acid, terephthalic acid), biphenyl-4, 4' -dicarboxylic acid, and 1,3, 5-benzenetricarboxylic acid.
Preferably, the intercalating agent is selected from sulfonic acid containing small organic molecules, including, for example, saturated alkyl sulfonic acids, aromatic hydrocarbon containing sulfonic acids; the saturated alkylsulfonic acid is, for example, CxH2x+1SO3H, wherein x is an integer between 1 and 16; the aromatic hydrocarbon-containing sulfonic acid is, for example, benzenesulfonic acid, alkylbenzenesulfonic acid (p-alkylbenzenesulfonic acid, o-alkylbenzenesulfonic acid, m-alkylbenzenesulfonic acid, e.g. C)xH2x+1C6H4SO3H, wherein x ═ an integer between 1 and 16), benzenedisulfonic acid (o-, m-, p-benzenedisulfonic acid), 4' -biphenyldisulfonic acid.
Preferably, the intercalating agent is selected from small organic molecules containing boric acid, including, for example, saturated alkyl boric acids, aromatic hydrocarbon-containing boric acids; the saturated alkylboronic acid is, for example, CxH2x+1B(OH)2Wherein x is an integer between 1 and 16; the aromatic hydrocarbon-containing boric acid is, for example, phenylboronic acid, alkylphenylboronic acid (p-alkylphenylboronic acid, o-alkylphenylboronic acid, m-alkylphenylboronic acid, e.g. CxH2x+1C6H4B(OH)2Where x is an integer between 1 and 16), phenyl diboronic acid (o-phenyl diboronic acid, m-phenyl diboronic acid, p-phenyl diboronic acid), 4' -biphenyl diboronic acid.
Preferably, the intercalating agent is selected from small organic molecules containing mercapto groups, including, for example, saturated alkyl mercaptans, aromatic-containing mercaptans or thiophenols; the saturated alkyl mercaptan is, for example, CxH2x+1SH, where x is between 1 and 16An integer number; the aromatic hydrocarbon-containing mercaptan or thiophenol is, for example, thiophenol, alkylthiophenol (p-alkylthiophenol, o-alkylthiophenol, m-alkylthiophenol, e.g. CxH2x+1C6H4SH, where x ═ an integer between 1 and 16) benzene-1, 4-dithiol, benzene-1, 3-dithiol, benzene-1, 2-dithiol, biphenyl-4, 4' -dithiol.
According to the invention, in step 1), the limiting reaction specifically comprises the following steps:
mixing an organic/inorganic composite two-dimensional material which is prepared by ion exchange reaction and/or intercalation reaction and is introduced with an organic molecular assembly layer between layers with a single-functional group or multi-functional group micromolecule substance which can react with one of amino, sulfonic group, carboxylic group or boric acid group, and reacting to prepare the organic/inorganic composite two-dimensional material which is introduced with an organic functional molecular assembly layer between layers.
In the present invention, the purpose of the confinement reaction is to adjust the carbon thickness in the layer, dope the element, prepare a covalent bond organic framework (COF) and a Metal Organic Framework (MOF), and partially polymerize to prevent small molecules from escaping during the subsequent heat treatment.
According to the present invention, the single-functional group or multi-functional group small molecule substance capable of reacting with an amino group may form at least one of a macromolecule, a covalent bond organic framework (COF), and a Metal Organic Framework (MOF) through an amidation reaction, a Schiff base (Schiff base) reaction, an ion coordination reaction, and the like.
Preferably, the mono-or multi-functional small molecule substance capable of reacting with an amino group is selected from carboxylic acids, aldehydes, metal ions coordinated to an amino group; for example, selected from formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, (ortho, meta, para) dibenzoic acid, 1,3, 5-tribenzoic acid, citric acid, boric acid, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, (ortho, meta, para) dibenzoaldehyde, 1,3, 5-tribenzoaldehyde, and derivatives of the above; the metal ions include iron, cobalt, nickel, chromium, copper, ruthenium, rhodium, palladium, silver, cadmium, platinum, hydrochlorides with different valence states, nitrates, sulfates, acetates, phosphates, perchlorates, hypochlorites and the like.
Wherein, carboxylic acid substances can generate amidation reaction, aldehyde substances can generate Schiff base reaction, and metal ion substances coordinated with amino groups can generate ion coordination reaction.
According to the present invention, the mono-functional group or multi-functional group small molecule substance capable of reacting with a sulfonic acid group, a carboxylic acid group, a boronic acid group may form at least one of a macromolecule, a covalent bond organic framework (COF) by an acid-base neutralization reaction or the like.
Preferably, the single-functional group or multi-functional group small molecule substance capable of reacting with a sulfonic acid group, a carboxylic acid group and a boric acid group is selected from organic substances containing amino groups; examples include saturated alkylamines, aromatic-containing amines, saturated alkylamines containing other functional groups. Wherein the saturated alkylamine is, for example, CxH2x+1NH2Wherein x is an integer between 3 and 16; the aromatic hydrocarbon-containing amines are, for example, aniline, diphenylamine (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine), benzidine, benzylamine, and benzylamine derivatives (methylbenzylamine, phenylbenzylamine, etc.), 1,3, 5-triphenylamine, melamine, 3' -diaminobenzidine; the saturated alkylamine having another functional group is, for example, ethanolamine.
According to the invention, in step 1), the ion exchange reaction, the intercalation reaction and the confinement reaction can be carried out in an environment in which a solvent exists, wherein the solvent comprises one or more mixed solutions of water, alcohols (methanol, ethanol, isopropanol and the like), aromatic hydrocarbon solutions (toluene, benzene and the like), esters (ethyl acetate and the like), ketones (acetone and the like), and saturated alkane (cyclohexane, normal hexane and the like) solutions; when the intercalation material is liquid in the reaction temperature range, the intercalation material may be used as the solvent without using a solvent.
According to the present invention, in the step 2), the polymerization reaction includes at least one of oxidative polymerization, photo polymerization, thermal polymerization, and the like.
Illustratively, the oxidative polymerization specifically includes the steps of:
contacting the organic/inorganic composite two-dimensional material prepared in the step 1) with an oxidant for reaction.
The oxidant may be an oxygen atmosphere, or an atmosphere containing oxygen, such as an oxygen-nitrogen mixture, an oxygen-argon mixture; the reaction temperature is 20-400 ℃;
the oxidant can be one or more of hydrogen peroxide, nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, sodium permanganate and the like; the reaction temperature is 40-200 ℃;
illustratively, the photopolymerisation specifically comprises the steps of:
placing the organic/inorganic composite two-dimensional material prepared in the step 1) under the illumination condition for reaction.
The illumination condition is, for example, one or more of visible light, ultraviolet light, X-ray, and the like.
Illustratively, the heating polymerization specifically includes the steps of:
putting the organic/inorganic composite two-dimensional material prepared in the step 1) into a tubular furnace, heating under pure oxygen atmosphere, and reacting.
The heating temperature is 100-350 ℃, and the heating time is 30 minutes-10 hours.
The purpose of the polymerization reaction is to prevent the evaporation loss of organic matters introduced between the layers of the layered inorganic material in the high-temperature carbonization process, and to prepare a polymer macromolecule layer by polymerizing surface-modified organic molecules or intercalated organic molecules.
According to the invention, in the step 3), the temperature of the carbonization reaction is 200-1200 ℃, and the preparation of the two-dimensional layer stacked carbon material and the preparation of the two-dimensional layer column carbon material are respectively corresponding to the preparation of the two-dimensional layer stacked carbon material and the preparation of the two-dimensional layer column carbon material by controlling whether the inorganic template is sintered, perforated or collapsed or not through the temperature. For the preparation of the two-dimensional layer stacking carbon material, the temperature is preferably 200-800 ℃; the time of the carbonization reaction is 0.5 to 24 hours, such as the reaction temperature is 400 ℃ and 600 ℃, and the reaction time is 1 to 12 hours; for the preparation of the two-dimensional layered column carbon material, 500-1200 ℃ is preferred; the time of the carbonization reaction is 0.5 to 24 hours, such as the reaction temperature is 700 ℃ and 1000 ℃, and the reaction time is 1 to 3 hours; the atmosphere of the carbonization reaction is inert (nitrogen, argon, helium and the like) or reducing atmosphere (any combination of hydrogen and inert atmosphere (nitrogen, argon, helium and the like)).
Illustratively, the morphology of the two-dimensional carbon material produced is controlled by adjusting the temperature of the carbonization reaction process, e.g., TiO2Base laminate template (e.g. titanic acid H)2Ti4O9) After inserting para-phenylenediamine molecular layer by intercalation reaction, polymerizing para-phenylenediamine into TiO at 200 deg.C in pure oxygen atmosphere2An interpenetration layer structure of poly-p-phenylenediamine. Sintering the structure for 6 hours at 500 ℃ in an inert atmosphere to obtain TiO2A carbon material is stacked in layers. Or mixing TiO with2Sintering of interpenetrated layer structure of poly-p-phenylenediamine at 800 ℃ to produce TiO2The template collapses to anatase or rutile during sintering, and part of the contact portion of the carbon layer sinters to form TiO2A pillared layered carbon material. Both materials can be treated with hydrofluoric acid to remove TiO2And respectively obtaining a two-dimensional layer stacking carbon material and a two-dimensional layer column carbon material by using the template. In particular, the two-dimensional layer stacking carbon material can be further physically stripped by grinding ultrasound and the like to prepare a single-layer or multi-layer two-dimensional nano-sheet layer carbon material.
The layered inorganic material may be the same as the original composition structure during carbonization, and may have any possibility of deformation, partial reduction, perforation by sintering, or even collapse by sintering due to temperature and atmosphere during carbonization.
According to the invention, in step 4), the de-templating reaction comprises the use of an acid treatment, a base treatment, or a special etching treatment. The acid treatment is carried out in a solution containing one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid and hydrofluoric acid; the alkali treatment is carried out in a solution containing one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; the special etching treatment is carried out in a solution containing amine fluoride. The solution also comprises one or a mixture of water, methanol, ethanol and the like in any proportion.
According to the invention, in the step 5), the physical stripping method comprises one or more of grinding, ultrasound, stirring, centrifugation and standing; the physical stripping can be carried out directly by using a solid phase or by adding a solvent or a solution containing a surfactant, wherein the solvent comprises one or more mixed solutions of water, alcohols (such as methanol, ethanol, isopropanol, ethylene glycol, glycerol, etc.), aromatic hydrocarbon solutions (such as toluene, benzene, etc.), esters (such as ethyl acetate, etc.), saturated alkanes (such as cyclohexane, N-hexane, etc.), ethers (such as diethyl ether), tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide, etc.; surfactants (such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, and other common mixed alkyl ammonium hydroxides, such as trimethylhexadecylammonium hydroxide, and one or more of C4-C18 alkylbenzene cyclic acids, C4-C18 alkylsulfuric acids, C4-C18 alkylcarboxylic acids, and alkali metal salts thereof).
The invention also provides a two-dimensional carbon material prepared by the method.
The invention also provides application of the two-dimensional carbon material in the fields of energy storage, adsorption and catalysis.
Preferably, the material is used in the fields of lithium ion battery materials, supercapacitor materials, adsorption materials and nano-catalytic materials.
The invention has the beneficial effects that:
the invention relates to a two-dimensional carbon material prepared by an inorganic layered template, which has the following characteristics:
1) the specific surface area between the template layers is large, and the mass production preparation of the two-dimensional carbon material can be realized;
2) different elements such as nitrogen, sulfur, phosphorus and the like can be introduced into the intercalation carbon material to realize doping modification of the carbon material;
3) different from graphene functionalization, functional groups are easily introduced to the surface of the carbon material prepared by small molecules, and diversified two-dimensional carbon materials can be prepared according to needs while the physical properties of graphene are kept.
4) Different chemical compositions and structures in the layered template can be utilized, and the method has wide application prospect for realizing catalysis, introducing inorganic doping or coordination metal and the like in the carbonization process.
5) The interlayer spacing of the layer column material can be controlled through the selection of the template, and the adjustment effect can be played in the fields of energy storage, adsorption and catalysis.
Drawings
FIG. 1 is the protonated nickel-doped-TiO of example 12Scanning electron microscope photo of layered inorganic material intercalated benzidine.
FIG. 2 is the protonated nickel-doped-TiO of example 12Scanning electron microscope photo of oxidation polymerization after intercalation of layered inorganic material with benzidine.
FIG. 3 is the benzidine/Nickel-doped layered TiO of example 12Color change contrast photographs of the composite before (left) and after (right) oxidative polymerization.
FIG. 4 shows two-dimensional carbon/TiO 2 treated by carbonization in a hydrogen/nitrogen mixed gas at 500 ℃ for 3 hours in example 12Scanning electron microscope photograph of the layered template.
FIG. 5 is the two-dimensional carbon/TiO formed after 1mol/L hydrochloric acid treatment of example 12Scanning electron microscope of the laminated composite material.
FIG. 6 is TiO removal with 10% hydrofluoric acid for example 12Scanning electron microscope of two-dimensional carbon particles behind the template.
FIG. 7 is a scanning electron microscope of the two-dimensional carbon/rutile and nickel particles in the form of a columnar layer formed after high temperature sintering at 900 ℃ in example 2.
FIG. 8 is a scanning electron microscope of two-dimensional carbon/rutile in the form of a columnar layer formed by sintering at a high temperature of 900 ℃ and then removing nickel by hydrochloric acid treatment in example 2.
FIG. 9 shows the removal of nickel by hydrochloric acid treatment and the removal of rutile by hydrofluoric acid (TiO) after high-temperature sintering at 900 ℃ in example 22) Scanning electron microscope of the formed layer column two-dimensional carbon.
Fig. 10 is a transmission electron microscope and carbon (C) nitrogen (N) element scanning photograph of the two-dimensional carbon nanomembrane after being peeled by grinding of example 1, which is shown as a nitrogen-doped carbon nanomembrane.
FIG. 11 is a flow chart of a manufacturing process of the present invention.
Fig. 12 is a graph of specific capacities of layered carbons in test example 1 at different charge and discharge rates.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Optionally indicating the presence or absence of the stated feature, and also indicating that the stated feature must be present, although the particular choice may be arbitrary.
Example 1
(1) Preparation of protonated layered nickel-doped TiO2
Anhydrous potassium carbonate, nickel oxide and anatase phase TiO2Grinding, mixing and tabletting according to a molar ratio of 1.3:0.2:4, solid-phase sintering at 1150 ℃ for 6 hours, and protonating by 1M hydrochloric acid.
(2) Intercalation reaction
1.0g of the protonated, layered nickel-doped TiO prepared above was taken2The materials, 1.0g of benzidine and 60mL of mixed solution of ethanol/water (5:1 volume ratio) are put in a 100mL hydrothermal kettle, ultrasonically dispersed, heated to 100 ℃ for reaction for 12 hours, cooled to room temperature, filtered, washed by a large amount of ethanol and dried to obtain the benzidine/nickel doped layered TiO21.1g of composite two-dimensional material. The scanning electron micrograph of the obtained sample is shown in FIG. 1.
(3) Polymerisation reaction
1.1g of benzidine/nickel-doped layered TiO prepared as described above2Treating the composite two-dimensional material in a tubular furnace at the temperature of 200 ℃ for 2 hours in the oxygen atmosphere of 100cc/min to obtain the layered TiO doped with the polybenzidine/nickel2FIG. 2 shows a SEM image of 1.0g of the two-dimensional composite material. After oxidative polymerization, the original earthy yellow color of the appearance color is changed into black,as shown in fig. 3.
(4) Carbonization reaction
0.5g of the polybenzidine/nickel-doped layered TiO prepared above was taken2The composite two-dimensional material is placed in a corundum crucible and then placed in a tube furnace, and is sintered for 3 hours at 500 ℃ in mixed gas of hydrogen (10% v/v)/nitrogen (90% v/v) to obtain 0.45g of black solid. The scanning electron micrograph is shown in fig. 4, in which the small surface particles are nickel particles reduced by doping nickel in a reducing atmosphere, because the doped nickel forms metallic nickel nanoparticles in the reducing atmosphere, and the scanning electron micrograph shows that particulate matter is evident on the surface of the grains.
(5) Stripping platemaking reaction
Soaking the solid material prepared after the carbonization reaction in a mixed solution of 20mL of 1mol/L hydrochloric acid and 5mL of ethanol for 1 day, filtering and drying in vacuum to obtain the carbon/TiO20.4g of composite two-dimensional material, as shown in FIG. 5 by scanning electron microscopy, nickel metal particles on the surface before reaction had been removed. The mixture was further treated with 10mL of 10% v/v hydrofluoric acid solution at 100 ℃ for 5 hours, cooled to room temperature, filtered and washed with water to obtain 0.12g of a black solid after drying. The scanning electron micrograph (fig. 6) shows a layered carbon deposit.
(6) Physical stripping
0.1g of the solid prepared by template removal is added with 2 mL of azomethidone by using a mortar for grinding, then diluted into 20mL of azomethidone, subjected to ultrasonic treatment for 10 minutes, centrifuged at 3000 rpm, and taken as upper layer dispersion liquid, so as to obtain a dispersion solution of carbon nanosheets, wherein transmission electron microscopy and element morphology diagrams of the dispersion solution are shown in fig. 10, and the dispersion solution is nitrogen-doped carbon nanosheets.
Example 2
The other operation steps are the same as example 1, except that the carbonization reaction of step (4) in example 1 is replaced by the following steps:
(4) carbonization reaction
0.5g of the polybenzidine/nickel-doped layered TiO prepared above was taken2Placing the composite two-dimensional material in a corundum crucible, placing the corundum crucible into a tubular furnace, and sintering the corundum crucible in pure nitrogen at 900 ℃ for 3 hours to obtain the composite two-dimensional materialTo a black solid of 0.41 g. The scanning electron micrograph thereof is shown in FIG. 7. Doped nickel and layered TiO in high temperature reducing atmosphere2The nano-sheets can be sintered into granular nickel metal particles and rutile phase TiO2。
(5) Stripping platemaking reaction
Soaking the solid material prepared after the carbonization reaction in a mixed solution of 20mL of 1mol/L acid and 5mL of ethanol for 1 day, filtering and drying in vacuum to obtain the carbon/TiO20.35g of composite two-dimensional material, as shown in FIG. 8 by scanning electron microscopy, nickel metal particles on the surface before reaction had been removed. The mixture was further treated with 10mL of 10% v/v hydrofluoric acid solution at 100 ℃ for 5 hours, cooled to room temperature, filtered and washed with water to obtain 0.12g of a black solid after drying. Scanning electron micrographs thereof (fig. 9) show the sheet-to-sheet undulating stack of layer-columnar carbon structures.
Example 3
The other procedure was the same as in example 1 except that the polymerization reaction of step (3) in example 1 was replaced with the following procedure:
(3) confinement reaction
1.1g of benzidine/nickel-doped layered TiO obtained by the preparation2Dispersing the composite two-dimensional material in 60mL ethanol solution of 0.1mol/L benzene dicarbaldehyde, refluxing and stirring at 78 ℃ overnight, filtering, washing with a large amount of ethanol, and drying to obtain the nickel-doped TiO intercalated with the Schiff base polymer formed by benzidine and terephthalaldehyde21.1g of composite two-dimensional material.
Test example 1
The layered carbon stack prepared in the step (5) of example 1 is applied to the energy storage performance of a lithium ion battery.
The layered carbon deposit prepared in step (5) of example 1 was mixed with PVDF and activated carbon at a mass ratio of 8: 1:1 mixing and mixing the slurry in NMP, coating an electrode sheet on a copper foil, and evaluating the specific capacity by using a half cell using lithium as a counter electrode.
At different charge and discharge rates we found that the specific capacity exceeds 500mAh/g (FIG. 12), which is much larger than the theoretical capacity of the graphite used in industry. And simultaneously, the battery still shows a capacity of 145mAh/g at a high charge-discharge rate of 12.8A/g, is much higher than graphite, and has a quick charge-discharge performance compared with the existing commercial battery.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a two-dimensional carbon material is characterized in that a layered inorganic material is used as a template, a single-functional group or multi-functional group organic molecular layer is introduced between layers of the layered inorganic material through ion exchange reaction and/or intercalation reaction and optional confinement reaction, and then the two-dimensional carbon material is prepared through optional polymerization reaction, carbonization reaction and template removal reaction and optional physical stripping.
2. The method of claim 1, wherein the topographical structure of the two-dimensional carbon material comprises two-dimensional layer packed carbon material, two-dimensional nanosheet carbon material, two-dimensional layer pillar carbon material.
3. The method according to claim 1 or 2, wherein the method comprises the steps of:
1) taking a layered inorganic material as a template, carrying out at least one ion exchange reaction and/or intercalation reaction and optionally carrying out at least one confinement reaction on the layered inorganic material to prepare an organic/inorganic composite two-dimensional material with an organic molecular assembly layer introduced between layers;
2) optionally, carrying out polymerization reaction on the organic/inorganic composite two-dimensional material prepared in the step 1);
3) carrying out carbonization reaction on the organic/inorganic composite two-dimensional material obtained in the step 1) or the polymerized organic/inorganic composite two-dimensional material obtained in the step 2) to prepare a composite two-dimensional material containing a layered inorganic material;
4) performing template removing reaction on the composite two-dimensional material containing the layered inorganic material prepared in the step 3) to prepare the two-dimensional carbon material.
4. A method according to any of claims 1-3, wherein the method further comprises the step of:
5) and 4) obtaining the single-layer or multi-layer two-dimensional nano-sheet layer carbon material from the two-dimensional carbon material prepared in the step 4) by a physical stripping method.
5. The process according to any one of claims 1 to 4, wherein in step 1) the layered inorganic material is selected from montmorillonite, layered metal oxide, layered metal hydroxide, and the like.
Preferably, in step 1), the layered metal oxide is selected from the group consisting of an unprotonated layered metal oxide, a metal ion-exchanged layered metal oxide, a protonated layered metal oxide; the layered metal hydroxide is selected from the group consisting of hydrotalcite and hydrotalcite-like materials.
6. The method according to any one of claims 1-5, wherein in step 1), the ion exchange reaction comprises the steps of:
mixing the layered inorganic material with an ion exchanger, and reacting to prepare the organic/inorganic composite two-dimensional material with the organic molecular assembly layer introduced between the layers.
Preferably, the ion exchanger is selected from at least one of the hydrochloride of an organic amine, the nitrate of an organic amine and the alkali metal salt of an organic acid (carboxylic acid, boric acid, sulfonic acid). The mass ratio of the layered inorganic material to the ion exchanger is 10:1-1: 100; the temperature of the ion exchange reaction is 0-200 ℃, and the time of the ion exchange reaction is 10 minutes-10 days; the type of ion exchange reaction may be one or more of hydrothermal, stirring, heating, microwave, ultrasound.
Preferably, in step 1), the intercalation reaction includes the following steps:
mixing the layered inorganic material with the intercalation agent, and reacting to obtain the organic/inorganic composite two-dimensional material with the organic molecular assembly layer introduced between the layers.
Preferably, the intercalating agent is selected from the group consisting of small organic molecules containing amine groups, small organic molecules containing organic acids (carboxylic acids, boronic acids, sulfonic acids), and small organic molecules containing mercapto groups; the mass ratio of the layered inorganic material to the intercalation agent is 10:1-1: 100; the temperature of the intercalation reaction is 0-200 ℃, and the time of the intercalation reaction is 10 minutes to 10 days; the intercalation reaction may be one or more of hydrothermal, stirring, heating, microwave, ultrasonic.
Preferably, in step 1), the confinement reaction specifically comprises the following steps:
mixing an organic/inorganic composite two-dimensional material which is prepared by ion exchange reaction and/or intercalation reaction and is introduced with an organic molecular assembly layer between layers with a single-functional group or multi-functional group micromolecule substance which can react with one of amino, sulfonic group, carboxylic group or boric acid group, and reacting to prepare the organic/inorganic composite two-dimensional material which is introduced with an organic functional molecular assembly layer between layers.
7. The method according to any one of claims 1 to 6, wherein in step 2), the polymerization reaction comprises at least one of oxidative polymerization, photopolymerization, thermal polymerization, and the like.
Preferably, the oxidative polymerization specifically comprises the steps of:
contacting the organic/inorganic composite two-dimensional material prepared in the step 1) with an oxidant for reaction.
Preferably, the oxidizing agent may be an oxygen atmosphere, or an atmosphere containing oxygen, such as an oxygen-nitrogen mixture, an oxygen-argon mixture; the reaction temperature is 20-400 ℃;
preferably, the oxidant can be one or more of hydrogen peroxide, nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, sodium permanganate and the like; the reaction temperature is 40-200 ℃;
preferably, the photopolymerisation specifically comprises the following steps:
placing the organic/inorganic composite two-dimensional material prepared in the step 1) under the illumination condition for reaction.
Preferably, the illumination condition is one or more of visible light, ultraviolet light, X-ray, and the like, for example.
Preferably, the heating polymerization specifically comprises the following steps:
putting the organic/inorganic composite two-dimensional material prepared in the step 1) into a tubular furnace, heating under pure oxygen atmosphere, and reacting.
Preferably, the heating temperature is 100-350 ℃, and the heating time is 30 minutes-10 hours.
8. The method as claimed in any one of claims 1 to 7, wherein, in step 3), the temperature of the carbonization reaction in step 3) is 200-1200 ℃, and the preparation of the two-dimensional layer stacked carbon material and the preparation of the two-dimensional layer column carbon material correspond to the preparation of the two-dimensional layer stacked carbon material and the preparation of the two-dimensional layer column carbon material respectively by controlling whether the inorganic template is sintered for perforation or collapse through the temperature. For the preparation of the two-dimensional layer stacking carbon material, the temperature is preferably 200-800 ℃; the time of the carbonization reaction is 0.5 to 24 hours, such as the reaction temperature is 400 ℃ and 600 ℃, and the reaction time is 1 to 12 hours; for the preparation of the two-dimensional layered column carbon material, 500-1200 ℃ is preferred; the time of the carbonization reaction is 0.5 to 24 hours, such as the reaction temperature is 700 ℃ and 1000 ℃, and the reaction time is 1 to 3 hours; the atmosphere of the carbonization reaction is inert (nitrogen, argon, helium and the like) or reducing atmosphere (any combination of hydrogen and inert atmosphere (nitrogen, argon, helium and the like)).
Preferably, in step 4), the de-templating reaction includes using an acid treatment, a base treatment, or a special etching treatment. The acid treatment is carried out in a solution containing one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid and hydrofluoric acid; the alkali treatment is carried out in a solution containing one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; the special etching treatment is carried out in a solution containing amine fluoride. The solution also comprises one or a mixture of water, methanol, ethanol and the like in any proportion.
Preferably, in the step 5), the physical stripping method comprises one or more of grinding, ultrasound, stirring, centrifugation and standing; physical stripping can be carried out directly using a solid phase or in a solution with addition of a solvent or addition of a surfactant.
9. A two-dimensional carbon material produced by the method according to any one of claims 1 to 8.
10. Use of the two-dimensional carbon material of claim 9 in the fields of energy storage, adsorption, and catalysis.
Preferably, the material is used in the fields of lithium ion battery materials, supercapacitor materials, adsorption materials and nano-catalytic materials.
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