CN112125334A - Metal oxide/carbon intercalated layer two-dimensional composite material and preparation method and application thereof - Google Patents
Metal oxide/carbon intercalated layer two-dimensional composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal oxide/carbon intercalated layer two-dimensional composite material and a preparation method and application thereof. The metal oxide/carbon intercalated layer two-dimensional composite material comprises metal oxide layers and carbon layers positioned between the metal oxide layers, wherein the carbon layers and the metal oxide layers are mutually interpenetrated; the layers of the metal oxide/carbon inter-inserted layer two-dimensional composite material are basically arranged in an overlapping way, or the layers are arranged in a staggered way; the thickness of the metal oxide/carbon inter-insertion layer two-dimensional composite material unit is 0.5-5 nm. The material can greatly improve the electron transmission in the metal oxide, also improves the contact area and the specific surface area of two-dimensional materials, is beneficial to catalysis, adsorption and surface energy storage, and is a potential new energy material.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a metal oxide/carbon intercalated layer two-dimensional composite material as well as a preparation method and application thereof.
Background
When the metal oxide material is used as a lithium ion battery, a supercapacitor, or a catalyst carrier for electrochemistry, the surface of the metal oxide material is often required to be subjected to conductive treatment because of poor conductivity. Generally, a conductive carbon material is coated on the surface by a method such as hydrothermal carbonization or high-temperature sintering carbonization. The carbon material can effectively improve the conductivity of metal organic matters, and has no obvious effect on improving the internal conductivity of metal oxides, particularly large-particle materials. Meanwhile, the carbon shell prepared by adopting the surface coating method can cause cracking and degradation of the carbon layer due to volume expansion in the chemical reaction, electrochemical reaction or physical adsorption process of internal metal oxidation.
Disclosure of Invention
The invention provides a preparation method of a metal oxide/carbon intercalated layer two-dimensional composite material, which comprises the following steps:
(1) carrying out intercalation reaction or surface modification reaction on the metal oxide two-dimensional material and an organic matter containing amino, and introducing an organic molecular layer between layers of the metal oxide two-dimensional material or the surface of the metal oxide two-dimensional material to obtain an organic molecular layer/metal oxide two-dimensional composite material;
(2) carbonizing the organic molecular layer/metal oxide two-dimensional composite material obtained in the step (1) to obtain the metal oxide/carbon intercalated layer two-dimensional composite material; alternatively, the first and second electrodes may be,
(3) carrying out polymerization reaction on the organic molecular layer/metal oxide two-dimensional composite material obtained in the step (1) to obtain a high molecular layer/metal oxide two-dimensional composite material; and carbonizing the polymer layer/metal oxide two-dimensional composite material to obtain the metal oxide/carbon intercalated layer two-dimensional composite material.
According to an embodiment of the present invention, in the step (1), the metal oxideThe two-dimensional material may be selected from at least one of an unprotonated, metal ion exchanged, protonated metal oxide layered material, and porous and/or non-porous metal oxide nanoplates; 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, 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 metal oxide two-dimensional material may be selected from protonated layered TiO2Material, nickel ion exchanged layered TiO2Material, non-porous TiO2Nanosheet, porous TiO2Nanosheets.
Wherein the size of the sheet layer of the metal oxide layered material is 100 nanometers to 50 micrometers, and the thickness of the sheet layer is 20 nanometers to 50 micrometers. Wherein the size of the sheet layer of the metal oxide nano sheet is 50 nanometers to 50 micrometers, and the thickness of the metal oxide nano sheet is 0.5 nanometers to 20 nanometers.
The metal oxide two-dimensional material can be prepared by a method known in the art, such as a solid-thermal sintering method, a hydrothermal method, a solvothermal method, a liquid-phase stripping method, a mechanical stripping method, an ion exchange method, and the like.
According to an embodiment of the present invention, in the step (1), the organic substance containing an amino group may be selected from an organic small molecule containing at least one amino group, or one, two or more of hydrochloride, hydrobromide and nitrate thereof; for example, the organic small molecule may be selected from at least one of saturated alkylamine, aromatic amine, alcohol amine, amino acid and its corresponding hydrochloride, hydrobromide, nitrate, and the like; wherein the saturated alkylamine may be selected from C3-C16The aromatic amine may be selected from aniline, diphenylamine (e.g., o-diphenylamine, m-diphenylamine, p-diphenylamine), benzidine, 3' -diaminobenzidine, benzylamine, and derivatives of the above aromatic amines (e.g., ethylene)One, two or more kinds of phenylaniline, vinylbenzylamine, methylbenzylamine, phenylbenzylamine, etc.); the alcohol amine may be selected from one, two or more of ethanolamine, diethanolamine, isopropanolamine, etc.; the amino acid may be selected from one, two or more of p-aminobenzoic acid, p-aminomethyl benzoic acid, glycine, alanine, leucine, phenylalanine, tryptophan, serine, tyrosine, etc.; illustratively, the amino group-containing organic substance is selected from octylamine, benzylamine, biphenyldiamine, or p-aminobenzoic acid.
According to an embodiment of the present invention, in step (1), the number of the intercalation reaction or modification reaction is not limited, and may be one, two or more; namely, products after intercalation or modification reaction can be re-intercalated or re-modified by using other organic matters containing amino. Wherein the amino group-containing organic substance has the meaning as described above. Illustratively, first by octylamine with protonated layered TiO2Intercalation is realized, the obtained solid is subjected to a displacement reaction with an aniline solution to obtain a new intercalation product, and the intercalated small molecular layer in the product can be any mol ratio of octylamine to aniline, such as 1/1 or 1/4.
According to an embodiment of the present invention, in step (1), the intercalation reaction and the surface modification reaction may be performed in a solvent, and the solvent may be one, two or more selected from water, alcohols, aromatic hydrocarbons, esters, and saturated alkanes. Wherein, the alcohol can be selected from one, two or more of methanol, ethanol, isopropanol, butanol and the like, the aromatic hydrocarbon can be selected from one, two or more of toluene, xylene, benzene and the like, the ester can be selected from one, two or more of ethyl acetate, ethyl formate and the like, and the saturated alkane can be selected from one, two or more of cyclohexane, normal hexane and the like. Preferably, the organic solvent may be selected from one, two or more of methanol, ethanol, isopropanol; illustratively, the solvent is selected from a mixed solution of ethanol and water. The volume ratio of the mixed solution of ethanol and water is not particularly limited, and for example, the volume ratio of ethanol and water may be (1-20):1, preferably (1-10):1, and illustratively, the volume ratio of ethanol and water may be 1:1, 7:1, or 11: 1. Wherein, when the organic matter containing amino is in a liquid state or in a liquid state in a reaction temperature range, any other solvent can be not used, and the organic matter can be used as a reactant and can also be used as a solvent.
According to an embodiment of the present invention, in step (1), the intercalation reaction includes the following processes: and (2) mixing the metal oxide two-dimensional material and the organic matter containing amino, or mixing the metal oxide two-dimensional material, the organic matter containing amino and the solvent, and then reacting in a normal pressure heating mode, a hydrothermal mode, a solvothermal mode, a stirring mode, an ultrasonic mode or a microwave heating mode and the like. Preferably, the intercalation comprises the following processes: mixing the metal oxide two-dimensional material and the organic matter containing amino, or mixing the metal oxide two-dimensional material, the organic matter containing amino and the solvent, performing ultrasonic dispersion, and placing the mixture in a hydrothermal reaction kettle for heating reaction; wherein the heating temperature may be 50 to 180 deg.C, such as 80 to 140 deg.C, and as an example, the temperature may be 90 deg.C, 100 deg.C, 110 deg.C. Further, when the metal oxide two-dimensional material is selected from metal oxide layered materials, an organic molecular layer is introduced between layers of the metal oxide layered materials by using intercalation reaction.
According to an embodiment of the present invention, in the step (1), the surface modification reaction includes the following processes: mixing the metal oxide two-dimensional material and the organic matter containing amino, or mixing the metal oxide two-dimensional material, the organic matter containing amino and the solvent, and then reacting in the modes of normal pressure heating, hydrothermal reaction, stirring, ultrasonic heating or microwave heating and the like; preferably, stirring or sonication or the like is used. For example, the stirring time may be 1-48h, such as 2-24h, as an example, time may be 4h, 12h, 16 h; the reaction temperature may be room temperature to 180 deg.C, such as 50 to 140 deg.C, and as an example, the temperature may be room temperature, 60 deg.C, 100 deg.C, 120 deg.C.
According to an embodiment of the present invention, in the step (1), the mass-to-volume ratio (g/mL) of the metal oxide two-dimensional material, the amino group-containing organic substance, and the solvent may be 1 (0.05-200): (0-200); for example, the mass-to-volume ratio is 1 (0.15-5): 15-100) or 1 (0.2-2): 20-80, and for example, the mass-to-volume ratio may be 1:5:0 (in the case of no solvent), 1:0.4:75 or 1:1: 24.
According to the embodiment of the invention, in the step (2) and the step (3), the temperature of the carbonization treatment can be 300-. The time of the carbonization treatment can be 0.5-24h, such as 1.5-5h, and as an example, the time can be 2h, 4h, 8 h. Further, the carbonization treatment is performed in vacuum, inert atmosphere and/or reducing atmosphere, for example, the inert atmosphere may be at least one of nitrogen, helium, argon and the like, and the reducing atmosphere may be any mixture of hydrogen and ammonia with the inert atmosphere; illustratively, the carbonization treatment may be performed in a mixed atmosphere of nitrogen, and hydrogen.
According to an embodiment of the present invention, in the step (3), the polymerization reaction may be selected from photo polymerization, thermal polymerization, or oxidative polymerization. Wherein the light polymerization can be performed by light polymerization of visible light, ultraviolet light, X-ray and the like; the thermal polymerization or oxidative polymerization can be solid-gas thermal polymerization, solid-liquid thermal polymerization, solid-gas oxidative polymerization or solid-liquid oxidative polymerization. For example, the solid-gas oxidative polymerization is carried out in an oxygen-containing atmosphere (e.g., an oxygen atmosphere, an oxygen-containing oxygen-nitrogen mixed gas, an oxygen-argon mixed gas, etc.); for example, the oxidizing agent used for the solid-liquid oxidative polymerization may be one, two or more selected from oxygen, hydrogen peroxide, nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, sodium permanganate, and the like. Wherein the solid-gas thermal polymerization may incorporate an initiator into the metal oxide two-dimensional material by impregnation methods known in the art. Wherein, the solid-liquid thermal polymerization can directly introduce an initiator into a reaction solution; the initiator can be at least one of BPO, AIBN and the like; or other small molecules capable of reacting with amino, wherein the small molecules and the aminophenol ester on the intercalated organic molecular layer are subjected to polymerization through amidation reaction or aldehyde-amine condensation reaction. Wherein the small molecule may be selected from at least one of terephthalic acid, isophthalic acid, phthalic acid, biphenyldicarboxylic acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, terephthalaldehyde, isophthalaldehyde, phthalaldehyde, terephthalaldehyde, glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, and adipaldehyde, etc. Further, the temperature of the photo polymerization, thermal polymerization or oxidative polymerization may be room temperature to 400 ℃, such as 50 to 300 ℃, 100-; the time of the solid gas oxidative polymerization can be 0.5 to 12 hours, such as 1.5 to 5 hours, and as an example, the time can be 2 hours, 3 hours and 4 hours. Further, the temperature of the solid-liquid oxidation polymerization can be-40 to 200 ℃, for example-30 to 150 ℃; the time for the solid-liquid oxidative polymerization may be from 0.6 to 12 hours, for example from 1.5 to 5 hours. Wherein the amount of the oxidizing agent is an amount known in the art. Wherein the solvent in the polymerization reaction system has the meaning as described above.
According to an embodiment of the present invention, in the step (3), the solid-liquid thermal polymerization and the solid-liquid oxidative polymerization are carried out in a solvent, and the solvent may be at least one selected from water and organic solvents; for example, the organic solvent may be selected from one, two or more of alcohols, aromatic hydrocarbons, esters, and saturated alkanes; wherein, the alcohol can be selected from one, two or more of methanol, ethanol, isopropanol and the like, the aromatic hydrocarbon can be selected from one, two or more of toluene, benzene and the like, the ester can be selected from one, two or more of ethyl acetate, ethyl formate and the like, and the saturated alkane can be selected from one, two or more of cyclohexane, normal hexane and the like. Preferably, the organic solvent may be selected from one, two or more of methanol, ethanol, isopropanol; illustratively, the solvent is selected from a mixed solution of ethanol and water. The volume ratio of the mixed solution of ethanol and water is not particularly limited, and for example, the volume ratio of ethanol and water may be (1-20):1, preferably (1-10):1, and illustratively, the volume ratio of ethanol and water may be 1:1, 7:1, or 11: 1.
And (3) carrying out polymerization reaction, wherein the purpose is to prevent evaporation loss of organic matters in the high-temperature carbonization process, and polymerizing surface-modified organic molecules or intercalated organic molecules to prepare a polymer layer.
According to an embodiment of the present invention, optionally, after the intercalation reaction or surface modification reaction of step (1) and the polymerization reaction of step (3) are completed, a solid powder may be obtained by separation and post-treatment methods such as centrifugation, filtration, drying, and the like. The drying may be any one of air drying, vacuum drying, oven drying, spray drying, and freeze drying.
According to an embodiment of the present invention, the preparation method further comprises step (4): and (4) carrying out acid cleaning on the metal oxide/carbon intercalated layer two-dimensional composite material obtained in the step (2) and the step (3). And (3) performing carbon thermal reaction on the metal oxide/carbon intercalated layer two-dimensional composite material obtained by the treatment in the steps (2) and (3) in a reducing atmosphere or an inert atmosphere, wherein metal particles may be separated out from a part of the doped metal oxide material. For example, nickel doped TiO2The layered structure will have nickel particles precipitated after heat treatment and the precipitated metal particles can be removed by pickling. The acid washing may be one, two or more of nitric acid, sulfuric acid, citric acid, hydrochloric acid, acetic acid and other common acids, such as hydrochloric acid or nitric acid. The acid used for the acid wash may be present in a concentration of 0.01M to 10M, preferably in a concentration of 0.1 to 5M, such as 0.5M, 1M or 2M. The acid wash temperature may be room temperature to 95 deg.C, preferably room temperature to 60 deg.C, illustratively room temperature or 50 deg.C. The pickling process can be carried out by standing, normal-pressure heating, hydrothermal reaction, stirring, ultrasonic or microwave heating and the like; preferably, stirring or sonication or the like is used. For example, the stirring time may be 1-48h, such as 2-24h, as an example, time may be 4h, 12h, 16 h; the solid matter after acid washing can be obtained by filtering, centrifuging, standing, removing the upper layer acid liquor after the solid matter is precipitated, and the like; the acid washing process may be repeated, for example, after acid washing, filtering and then acid washing again, and the process is repeated 1 to 5 times, preferably 2 to 4 times, and exemplarily 3 times. The pickled sample can be dried, real, by methods known in the artAir drying, spray drying, etc. to give a solid sample, illustratively, vacuum drying at 60 ℃ for 2 hours.
Wherein room temperature means 15-40 deg.C, such as 20-35 deg.C.
Further, the present invention provides a metal oxide/carbon intercalated layer two-dimensional composite material obtained by the above method. Preferably, the metal oxide/carbon intercalated layer two-dimensional composite material can be a metal oxide/graphite-like intercalated layer two-dimensional composite material; may illustratively be a layered TiO2Graphite-like two-dimensional composite material and TiO2A nano-sheet/graphite-like two-dimensional composite material.
According to the composite material, the metal oxide/carbon intercalated layer two-dimensional composite material comprises metal oxide layers and carbon layers positioned between the metal oxide layers, and the carbon layers and the metal oxide layers are mutually interpenetrated. Wherein the metal oxide has the meaning as described above.
According to the composite material of the present invention, the metal oxide/carbon intercalated two-dimensional composite material has a repeating unit thickness of 0.5 to 5nm, such as 0.4 to 3nm, and as an example, a repeating unit thickness of 1.1 nm. Wherein the repeating unit consists of a single layer of metal oxide and a single layer of carbon.
According to the composite material of the invention, the layers of the metal oxide/carbon intercalated layer two-dimensional composite material can be basically arranged in an overlapping mode or staggered mode.
According to the composite material of the present invention, the thickness of the metal oxide/carbon intercalated layer two-dimensional composite material may be 20 nm to 50 μm, for example, 100 nm to 30 μm, 500 nm to 15 μm.
According to the composite material of the invention, the specific surface area of the metal oxide/carbon intercalated layer two-dimensional composite material is 10-480m2G, e.g. 100-470m2/g、300-450m2/g。
According to the composite material, the metal oxide/carbon intercalated layer two-dimensional composite material is a metal oxide/graphite-like intercalated layer two-dimensional composite material.
Further, the invention also provides application of the metal oxide/carbon intercalated layer two-dimensional composite material in the fields of energy storage devices (such as lithium ion batteries, supercapacitors and the like), adsorption, catalysis and the like.
The invention has the beneficial effects that:
the graphite-like carbon material is embedded between the metal oxide layers, so that the invention has the following advantages:
1) the electron transmission in the metal oxide can be greatly improved;
2) the structural collapse caused by volume expansion in the processes of adsorption, electrochemical reaction and chemical reaction is avoided, and the stability of the material is greatly improved;
3) the mutual insertion layer structure of the two-dimensional materials greatly improves the contact area or the specific surface area, is beneficial to catalysis, adsorption and surface energy storage, and is a potential new energy material.
Drawings
FIG. 1 is example 1 protonated TiO2Scanning electron microscope photo of layered material intercalated benzylamine.
FIG. 2 is a layered TiO after protonation2Layered TiO after intercalation of (lower) benzylamine2(middle) and layered TiO prepared after 500 ℃ carbonization2XRD pattern of/type graphite two-dimensional composite material.
FIG. 3 is the layered TiO of example 22Raman spectrum of/graphite-like two-dimensional composite material.
FIG. 4 shows example 3TiO2Scanning electron microscope photos of the composite material with the nano-sheet/benzidine surface modified.
FIG. 5 shows example 5TiO2And (3) a transmission electron microscope photo of the nano sheet/graphite-like composite material.
FIG. 6 shows example 5TiO2STEM of the nano-sheet/graphite-like composite material and mapping maps of C, Ti and O.
Fig. 7 is a graph of rate performance of the battery under different discharge currents in test example 1.
FIG. 8 shows the results of test example 1 containing TiO2And (3) a circulation stability diagram of the button cell made of the graphite composite two-dimensional material.
FIG. 9 is a flow chart of the preparation of a metal oxide/carbon intercalated two-dimensional composite material according to the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. 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.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Protonated layered TiO2By reacting anhydrous potassium carbonate with anatase TiO2Grinding and mixing according to the molar ratio of 1.3/4, performing solid phase sintering at 950 ℃, and protonating in 1M hydrochloric acid to prepare the catalyst. 2.0g of protonated layered TiO2The material, 2.5mL benzylamine and 60mL ethanol/water (1/1 vol/vol) mixed solution are placed in a 100mL hydrothermal kettle, after ultrasonic dispersion, heated to 100 ℃ for reaction for 12 hours, cooled to room temperature, filtered, washed by a large amount of water, and dried to obtain a sample, namely protonated TiO22.1g of layered material intercalated benzylamine. The scanning electron micrograph of the obtained sample is shown in FIG. 1: the morphology thereof maintains a layered structure; the repeat units of the layered structure (monolayer TiO) are characterized by XRD in FIG. 22Layer + monolayer benzylamine) thickness from 0.88nm (protonated layered TiO) before reaction2) Broadening to 2.2nm after intercalation (layered TiO after benzylamine intercalation)2)。
Example 2
Protonated TiO obtained in example 12The layered material intercalation benzylamine solid is treated for 3 hours at 500 ℃ in a tubular furnace in nitrogen atmosphere to obtain layered TiO2Graphite-like two-dimensional composite material.
FIG. 2 is a protonized layered TiO2XRD data after (lower) intercalation (middle), and after (upper) charring. It shows that the interlamellar spacing after benzylamine intercalation is significantly increased, and after carbonization, the interlamellar spacing is slightly decreased, andthe difference in protonated layer thickness was about 0.4nm, corresponding to the thickness of single layer graphene.
FIG. 3 is a layered TiO2And the Raman spectrum of the/graphite-like two-dimensional composite material shows a D peak and a G peak of the graphene-like.
Example 3
Protonated TiO of example 12Preparation of TiO by liquid phase exfoliation of layered Structure with 5 wt% aqueous tetrabutylammonium hydroxide2A nanosheet solution. Stripped TiO21.0g of nanosheet spray-dried sample is added dropwise to a solution of biphenyldiamine (0.4g/25mL of ethanol) in a mixed solution of 50mL of ethanol/water (7/1 volume ratio). After stirring for 4 hours, filtration was carried out to obtain TiO21.1g of the composite material after the surface modification of the nano-sheets/the biphenyldiamine. The scanning electron microscope of the composite material is shown in FIG. 4: the material shows a distinct layer-stacking morphology on a microscopic scale.
Example 4
The solid obtained in example 3 was subjected to oxidative polymerization in a tube furnace at 200 ℃ under an oxygen atmosphere for 2 hours to obtain polybiphenyldiamine/TiO21.1g of nanosheet composite.
Example 5
The solid from example 4 was brought to 10% H at 550 deg.C2/90％N2Sintering the mixture in a tube furnace for 2 hours in mixed gas to obtain TiO2The high-power transmission electron microscope of the nano sheet/graphite-like composite material is shown in figure 5, and the nano sheet/graphite-like composite material shows an obvious layered structure and repeating units (single-layer TiO)2Nanosheet + monolayer-like graphite) had a thickness of 1.1 nm. Mapping data of the elemental composition shows that the element composition is TiO2Composite with carbon (fig. 6).
Test example 1
The TiO of example 52The/graphite-like two-dimensional composite material is used as a positive electrode, the lithium metal is used as a negative electrode, and the 1MLiPF6the/EC-DMC is assembled into the lithium ion 2032 coin cell by electrolyte.
Comparative example: with layered TiO of non-intercalated carbon2The positive electrode was assembled under the same conditions as the other positive electrodes.
Ratio performance pair under different discharge currentsTwo cells were compared. As shown in FIG. 7, the example 5TiO compound was included2The battery made of the graphite-like two-dimensional composite material has more excellent specific capacity and rate capability. FIG. 8 shows the reaction with TiO2The battery constructed by taking the graphite-like two-dimensional composite material as the anode material has excellent cycle stability, and the coulomb efficiency is still kept close to 100 percent after 200-circle test.
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. The metal oxide/carbon intercalated layer two-dimensional composite material is characterized by comprising metal oxide layers and carbon layers positioned between the metal oxide layers, wherein the carbon layers and the metal oxide layers are mutually interpenetrated.
2. The metal oxide/carbon intercalated two-dimensional composite material as recited in claim 1 wherein said metal oxide/carbon intercalated two-dimensional composite material is substantially overlapped from layer to layer or staggered from layer to layer;
preferably, the thickness of the repeating unit of the metal oxide/carbon intercalated layer two-dimensional composite material is 0.5-5nm, and the repeating unit consists of a single layer of metal oxide and a single layer of carbon;
preferably, the metal oxide is selected from at least one of an aprotic, ion-exchange, protonated metal oxide layered material, and porous and/or non-porous metal oxide nanoplates; preferably an alkaline earth-transition metal oxide;
preferably, the metal oxide/carbon intercalated layer two-dimensional composite material is a metal oxide/graphite-like intercalated layer two-dimensional composite material.
3. The metal oxide/carbon intercalated two-dimensional composite material as claimed in claim 1 or 2, wherein the thickness of said two-dimensional composite material is comprised between 20 nm and 50 μm;
preferably, the specific surface area of the metal oxide/carbon intercalated layer two-dimensional composite material is 10-480m2/g。
4. A method for preparing a metal oxide/carbon intercalated two dimensional composite material as claimed in any one of claims 1 to 3 comprising the steps of:
(1) carrying out intercalation reaction or surface modification reaction on the metal oxide two-dimensional material and an organic matter containing amino, and introducing an organic molecular layer between layers of the metal oxide two-dimensional material or the surface of the metal oxide two-dimensional material to obtain an organic molecular layer/metal oxide two-dimensional composite material;
(2) carbonizing the organic molecular layer/metal oxide two-dimensional composite material obtained in the step (1) to obtain the metal oxide/carbon intercalated layer two-dimensional composite material; alternatively, the first and second electrodes may be,
(3) carrying out polymerization reaction on the organic molecular layer/metal oxide two-dimensional composite material obtained in the step (1) to obtain a high molecular layer/metal oxide two-dimensional composite material; carbonizing the polymer layer/metal oxide two-dimensional composite material to obtain the metal oxide/carbon intercalated layer two-dimensional composite material;
optionally, further comprising step (4): and (3) carrying out acid washing on the metal oxide/carbon intercalated layer two-dimensional composite material obtained in the step (2) and/or the step (3) to remove metal particles possibly formed in the carbonization process.
5. The process for the preparation of a metal oxide/carbon intercalated two-dimensional composite material according to claim 4 wherein in step (1) the metal oxide has the meaning as defined in claim 2;
preferably, the metal oxide two-dimensional material is selected from protonated layered TiO2Material, non-porous TiO2Nanosheet, porous TiO2Nanosheets;
preferably, the sheet size of the metal oxide layered material is 100 nanometers to 50 micrometers, and the thickness is 20 nanometers to 50 micrometers;
preferably, the metal oxide nanosheets have a lamella size of 50 nanometers to 50 micrometers and a thickness of 0.5 nanometers to 20 nanometers.
6. The method for preparing a metal oxide/carbon intercalated layer two-dimensional composite material according to claim 4 or 5, wherein in the step (1), the amino group-containing organic matter is selected from small organic molecules containing at least one amino group, or one, two or more of hydrochloride, hydrobromide and nitrate thereof;
preferably, the number of intercalation or modification reactions is one, two or more;
optionally, the intercalation reaction and surface modification reaction further comprise a solvent selected from one, two or more of water, alcohols, aromatic hydrocarbons, esters and saturated alkanes.
7. The process for the preparation of a metal oxide/carbon intercalated two-dimensional composite material according to any one of claims 4 to 6 wherein in step (1) the intercalation or surface modification reaction comprises the following steps: mixing the metal oxide two-dimensional material with the organic matter containing the amino, or mixing the metal oxide two-dimensional material, the organic matter containing the amino and the solvent, and then reacting in a normal-pressure heating mode, a hydrothermal mode, a stirring mode, an ultrasonic mode or a microwave heating mode;
wherein the mass-volume ratio (g/mL/mL) of the metal oxide two-dimensional material, the amino-containing organic substance and the solvent is 1 (0.05-200) to (0-200).
8. The method for preparing a two-dimensional composite material with metal oxide/carbon intercalated layers as defined in any one of claims 4 to 7, wherein in the steps (2) and (3), the temperature of the carbonization treatment is 300 ℃ and 1200 ℃, and the time of the carbonization treatment is 0.5 to 24 hours;
wherein the carbonization treatment is carried out in vacuum, inert atmosphere and/or reducing atmosphere;
preferably, in the step (3), the polymerization reaction is selected from photopolymerization, thermal polymerization or oxidative polymerization;
wherein the photopolymerisation is performed by visible light, ultraviolet light and X-ray photopolymerisation; the thermal polymerization or oxidative polymerization is solid-gas thermal polymerization, solid-liquid thermal polymerization, solid-gas oxidative polymerization or solid-liquid oxidative polymerization; preferably, the solid-liquid thermal polymerization and solid-liquid oxidative polymerization are carried out in a solvent selected from at least one of water and an organic solvent;
optionally, the intercalation reaction or the surface modification reaction in the step (1), and/or the polymerization reaction in the step (3) is completed, and then the solid powder is obtained through separation and post-treatment methods.
9. A metal oxide/carbon intercalated two-dimensional composite material prepared according to any one of claims 4 to 8.
10. Use of the metal oxide/carbon intercalated two-dimensional composite material according to any one of claims 1 to 3 in the fields of energy storage devices, adsorption or catalysis.
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