CN113998693A - Preparation method of graphene nano-roll - Google Patents
Preparation method of graphene nano-roll Download PDFInfo
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- CN113998693A CN113998693A CN202111232142.7A CN202111232142A CN113998693A CN 113998693 A CN113998693 A CN 113998693A CN 202111232142 A CN202111232142 A CN 202111232142A CN 113998693 A CN113998693 A CN 113998693A
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Abstract
The invention relates to the technical field of graphene preparation, and particularly relates to a preparation method of a graphene nano roll. The preparation method of the graphene nano-roll comprises the following steps: dispersing mixed powder of MXene material and graphene in water to form dispersion liquid, and heating, wherein the concentration of the dispersion liquid is 0.1-1 mg/mL; and freezing the heated dispersion liquid completely by liquid nitrogen, and then freezing and drying. According to the invention, the MXene material and the graphene are dispersed in water to generate electrostatic repulsion, so that the hydrophilicity of the graphene is improved on the basis of no introduction of an auxiliary agent and no need of complex reaction with an organic polymer, the complete lamellar structure of the graphene is retained, and the conductivity is ensured. Through liquid nitrogen cooling lapping, on the basis of keeping graphite alkene complete structure, reduced the contact point between the lamella for the specific surface area of lamella is higher, has solved the problem that the lamella piled up.
Description
Technical Field
The invention relates to the technical field of graphene preparation, and particularly relates to a preparation method of a graphene nano roll.
Background
The graphene is sp2The hybridized and connected carbon atoms are tightly stacked into a new material with a single-layer two-dimensional honeycomb lattice structure, and the new material has excellent mechanical property, thermodynamic property, good conductivity, electrochemical property and large specific surface area, and has great application value in the fields of medicine, photoelectricity, sensors, catalysts, energy storage and the like. Because the process conditions for preparing a large amount of single-layer graphene are harsh and difficult to achieve, the graphene prepared by the prior art is generally multilayer, has the characteristics of excellent performance and high specific surface area in the nanoscale, and has the defects of obviously reduced or even completely ineffective lamellar stacking and poor dispersibility in water, so that the development of the graphene is restricted. From the application point of view, solving the problems of poor dispersibility and reduced specific surface area caused by the stacking of graphene sheets is an important prerequisite for achieving excellent performance and large-scale application. Therefore, many scholars have performed functional modification on graphene and have conducted extensive research.
At present, the means for modifying graphene mainly comprises covalent bond functional modification and non-covalent bond functional modification. The covalent bond functional modification is mainly realized by introducing organic micromolecules or macromolecules to perform chemical reaction with active double bonds or other oxygen-containing groups on the surface of graphene or graphene oxide to generate covalent bonds. Various organic compounds are inevitably introduced into the modification method, long organic reactions are carried out, the preparation process is polluted and complicated, and the dispersibility of the graphene in a specific organic solvent can only be generally aimed at. Furthermore, covalent bond functionalization generally tends to achieve modification by complexing various oxygen-containing functional groups on graphene derivatives (such as graphene oxide GO and reduced graphene oxide rGO, etc.) with other polymer systems. The introduced polymer group can destroy the large conjugated structure of the graphene sheet layer, so that the electrical properties of the graphene sheet layer are affected, and therefore, in order to keep the excellent characteristics of the original structure of graphene, a reducing agent needs to be introduced to restore the large-range conjugated structure of graphene. However, with the reduction, the repulsive force stabilizing effect generated between the oxygen-containing functional groups between the layers disappears, and then coagulation occurs, and even though a small molecular surfactant still exists, the dispersibility of the modified material is still poor. The non-covalent bond functional modification mainly comprises the following steps: pi-pi bond interactions, hydrogen bonding, ionic bonding, and electrostatic interactions. The modification method usually introduces an auxiliary agent such as a reducing agent, a modifying agent or a surfactant, and the modified graphene solves the dispersion problem of graphene, but does not have great effect on improving the specific surface area of a graphene lamellar layer.
Disclosure of Invention
Based on the method, the graphene nano coil is large in specific surface area and can be stably dispersed in water without an auxiliary agent.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of a graphene nano roll, which comprises the following steps:
dispersing mixed powder of MXene material and graphene in water to form dispersion liquid, and heating the dispersion liquid, wherein the concentration of the dispersion liquid is 0.1-1 mg/mL; and
and (3) completely freezing the heated dispersion liquid by liquid nitrogen, and then freeze-drying.
Optionally, in the preparation method of the graphene nano-volume, the concentration of the dispersion is 0.1mg/mL to 0.5 mg/mL.
Optionally, in the preparation method of the graphene nanovolume, a mass ratio of the MXene material to the graphene is (0.1-1): 50.
optionally, in the preparation method of the graphene nanocoil, the graphene is at least one of graphene, graphene oxide, reduced graphene oxide, doped graphene oxide, and doped reduced graphene oxide.
Optionally, in the preparation method of the graphene nano roll, the oxygen content of the graphene is 0 to 40 at%.
Optionally, in the preparation method of the graphene nanovolume, the MXene material is Ti2C3Tx、Ti2CTxAnd Cr2CTxWherein T isxis-OH and/or-F.
Optionally, in the preparation method of the graphene nanocolloid, the freezing temperature is-30 ℃ to-80 ℃, and the time is 1h to 24 h; and/or
The temperature of the freeze drying is 0 ℃ to-50 ℃, and the time is 1h to 72 h.
Optionally, in the preparation method of the graphene nanocoil, the heating temperature of the dispersion liquid is 60 ℃ to 100 ℃.
Optionally, in the preparation method of the graphene nanocoil, a method for preparing the mixed powder of the MXene material and the graphene is ball milling.
Optionally, in the preparation method of the graphene nanocoil, the rotation speed of the ball mill is 200rpm to 700rpm, and the time is 0.5h to 72 h.
According to the invention, after the MXene material and the graphene are mixed and dispersed in water, electrostatic repulsion can be generated between the MXene material and the graphene, so that the hydrophilicity of the graphene is improved and the graphene is stably dispersed in water on the basis of not introducing additives such as a modifier, a surfactant, a reducing agent and the like and not needing complex reaction with organic polymers, and meanwhile, the complete lamellar structure of the graphene is kept, the conductivity is ensured, and a vital precondition is provided for preparing a graphene roll. Through liquid nitrogen cooling lapping, on the basis of keeping graphite alkene complete structure, reduced the contact point between the lamella to make the specific surface area of lamella higher, solved the problem that the lamella piled up. The number of coiled structures can be regulated by further regulating the concentration of the dispersion liquid, so that the optimal regulation of the specific surface area is realized. The preparation method provided by the invention has the advantages of no pollution in the whole process, high efficiency and high speed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an SEM image of a graphene nanocolloid prepared in example 1 of the present invention;
in fig. 2, (a) shows a dispersion state of a graphene roll without MXene material added in water, and (b) shows a dispersion state of a graphene roll prepared in example 1 of the present invention in water;
fig. 3 is an SEM image of a graphene nanocolloid prepared in example 2 of the present invention;
fig. 4 is an SEM image of the graphene nanocolloid prepared in comparative example 1 of the present invention.
Detailed Description
For purposes of promoting an understanding of the invention, reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular. "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the terms "about", "approximately", "substantially", and "substantially". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Terms and definitions:
SEM-scanning electron microscope
"graphene" is generally denoted by GF and is denoted by sp2The hybridized and connected carbon atoms are tightly packed into a material with a single-layer two-dimensional honeycomb lattice structure.
"graphene oxide" is generally indicated by GO and refers to an oxide of graphene, which has excellent dispersibility in water.
The term "reduced graphene oxide" is generally referred to as rGO, and means that a group having an oxidizing property is lost by reduction based on graphene oxide.
The "doped graphene" refers to graphene prepared by introducing doping atoms into a graphene lattice, and the doping atoms are usually N atoms, S atoms, F atoms, and the like.
"MXene materials" belong to two-dimensional inorganic compounds, generally consisting of a few atomic layer thicknesses of a carbide, nitride or carbonitride of a transition metal, of the general chemical formula Mn+1XnTxWherein M denotes a transition metal, X denotes carbon or nitrogen (n ═ 1, 2, 3), TxRefers to surface functional groups (e.g., -O, -H, -OH, and F, etc.).
The invention provides a preparation method of a graphene nano roll, which comprises the following steps:
dispersing mixed powder of MXene material and graphene in water to form dispersion liquid, and heating, wherein the concentration of the dispersion liquid is 0.1-1 mg/mL; and
after the heated dispersion was completely frozen by liquid nitrogen, it was freeze-dried.
According to the invention, MXene materials and graphene can generate electrostatic repulsion when dispersed in water, so that the hydrophilicity of the graphene is improved and the graphene is stably dispersed in water on the basis of not introducing additives such as a modifier, a surfactant and a reducing agent and not needing complex reaction with organic polymers, and meanwhile, the complete lamellar structure of the graphene is retained, the conductivity is ensured, and the vital precondition is provided for preparing the graphene roll. Through liquid nitrogen cooling lapping, on the basis of keeping graphite alkene complete structure, reduced the contact point between the lamella to make the specific surface area of lamella higher, solved the problem that the lamella piled up. The number of coiled structures can be regulated by further regulating the concentration of the dispersion liquid, so that the optimal regulation of the specific surface area is realized. The preparation method provided by the invention has the advantages of no pollution in the whole process, high efficiency and high speed.
In some embodiments, the concentration of the dispersion may also be 0.2mg/mL, 0.3mg/mL, 0.4mg/mL, 0.5mg/mL, 0.6mg/mL, 0.8mg/mL, 0.9mg/mL, etc., preferably 0.1mg/mL to 0.5 mg/mL. The finally prepared graphene is better in coiling and larger in specific surface area by regulating and controlling the concentration of the dispersion liquid, and the occurrence of graphene stacking behavior is further avoided.
In some embodiments, the mass ratio of the MXene material to the graphene can be (0.1-1): 50, and can also be 0.2:50, 0.4:50, 0.5:50, 0.8:50 and the like.
In some embodiments, the graphene may be at least one of Graphene (GF), Graphene Oxide (GO), reduced graphene oxide (rGO), doped graphene oxide, and doped reduced graphene oxide. Preferably, the graphene used in the present invention is Graphene (GF).
In some embodiments, the doping atoms in the doped graphene, the doped graphene oxide and the doped reduced graphene oxide may be doping atoms commonly used in the art, including but not limited to metal atoms, such as Fe atoms, Cu atoms, Co atoms, Ni atoms, Zn atoms, etc., non-metal atoms, such as N atoms, P atoms, S atoms, B atoms, F atoms, etc. Preferably, the doping atoms are non-metal atoms, and more preferably, the doping atoms are one or more of N atoms, S atoms, and F atoms.
In some embodiments, the graphene may be one or more of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene. The number of layers of the few-layer graphene can be 3-10, and the number of layers of the multi-layer graphene can be 10-100. Preferably, the graphene is single-layer graphene, double-layer graphene or 3-10 layers of few-layer graphene.
In some embodiments, the graphene may have an oxygen content of 0 to 40 at%, and may further have an oxygen content of 2 at%, 5 at%, 8 at%, 10 at%, 15 at%, 20 at%, 25 at%, 30 at%, 32 at%, 38 at%, or the like.
In some embodiments, the MXene material can be any MXene material with a hydrophilic surface functional group, such as Ti2C3Tx、Ti2CTxAnd Cr2CTxWherein T isxis-OH and/or-F.
In some embodiments, the method of completely freezing the heated dispersion by liquid nitrogen may be any method known in the art, for example, liquid nitrogen may be poured into the dispersion, the dispersion may be poured into liquid nitrogen, or a container containing the dispersion may be placed in liquid nitrogen.
In some embodiments, the temperature and time of freezing can be determined according to the freezing condition of the dispersion, and can be, for example, -30 ℃ to-80 ℃, or-35 ℃, 40 ℃, 50 ℃, 68 ℃, 75 ℃ or the like, and the time can be 1h to 24h, or 5h, 7h, 10h, 12h, 15h, 18h, 20h or the like, based on the freezing condition of the dispersion.
In some embodiments, the temperature of freeze drying may be 0 ℃ to-50 ℃, may be-40 ℃, -35 ℃, -20 ℃, -10 ℃, -5 ℃ and the like, and the time may be 1h to 72h, and may be 5h, 8h, 10h, 15h, 20h, 30h, 40h, 50h, 60h and the like.
In some embodiments, the method for preparing the mixed powder of the MXene material and the graphene may be any solid-solid mixing method, such as grinding, ball milling, and the like. Preferably, the mixing method to form the mixed powder is ball milling.
In some embodiments, the rotation speed and time of the ball milling are not limited, for example, the rotation speed of the ball milling may be 200rpm to 700rpm, or may be 300rpm, 450rpm, 500rpm, 600rpm, 650rpm, etc., and the time of the ball milling may be 0.5h to 72h, or may be 1h, 2.5h, 5h, 8h, 10h, 15h, 20h, 30h, 40h, 50h, 60h, 70h, etc., based on that the MXene material and the graphene are ball-milled to be uniform without large agglomerates.
In some embodiments, any operation process such as stirring, ultrasonic vibration, etc. that can promote the dispersion effect can be used in the dispersion process. Preferably, the dispersion is promoted by mechanical stirring for 1 to 24 hours, and may be 3, 5, 8, 10, 12, 15, 20, and the like.
In some embodiments, the dispersion is heated at a temperature of 60 ℃ to 100 ℃, and may be 70 ℃, 80 ℃, 85 ℃, 90 ℃, or the like. The graphene is coiled by heating the dispersion liquid to a certain temperature and then generating a temperature difference by combining with subsequent liquid nitrogen freezing.
In some embodiments, the water may be one or more of deionized water, ultrapure water.
The method for preparing the graphene nanovolume according to the present invention will be described in further detail with reference to specific examples and comparative examples. The following examples are provided by way of illustration of drugs and instruments which are commercially available unless otherwise specified.
Example 1 preparation of graphene nanocoils
1) Mixing Ti2C3Tx(Txis-OH and-F) and graphene are mixed according to the mass ratio of 0.5:50, and are dispersed in deionized water after ball milling for 4 hours at 400rpm to obtain dispersion liquid with the concentration of 0.1 mg/mL;
2) stirring and heating the dispersion liquid to 60 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the graphene nano-roll. The SEM test results of the graphene nanocoils are shown in fig. 1. As can be seen from fig. 1, the graphene nano-grade prepared by the present embodiment is rolled into a large number of rolls, the rolling performance is good, the contact point between the rolled sheet layer and the sheet layer is small, and the stacking of the sheet layer is reduced, so that the specific surface area of the graphene nano-grade is large. The graphene modified by the MXene material has good hydrophilicity, so that the dispersion liquid can stably exist, and a vital precondition is provided for preparing the graphene roll.
And (3) testing the dispersibility:
preparing a graphene roll without the MXene material into 0.5mg/mL aqueous dispersion, preparing a graphene roll modified by the MXene material into 0.5mg/mL aqueous dispersion, uniformly stirring, and standing for 6 h. As can be seen from (a) in fig. 2, the graphene roll without modification shows obvious delamination and sedimentation in water, while as can be seen from (b) in fig. 2, the graphene roll after modification of the MXene material stably exists in water.
Example 2 preparation of graphene nanocoils
This example 2 was prepared substantially identically to example 1, except that: ti2C3TxThe mass ratio to graphene was 0.8: 50. The specific steps are described as follows:
1) mixing Ti2C3Tx(Txis-OH and-F) and graphene are mixed according to the mass ratio of 0.8:50, and are dispersed in deionized water after ball milling for 4 hours at 400rpm to obtain a dispersion liquid with the concentration of 0.1 mg/mL;
2) stirring and heating the dispersion liquid to 60 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the graphene nano-roll. The SEM test results of the graphene nanocoils are shown in fig. 3. As can be seen from fig. 3, the graphene nano-grade prepared by the present embodiment is rolled into a large number of rolls, the rolling performance is good, the contact point between the rolled sheet layer and the sheet layer is small, and the stacking of the sheet layer is reduced, so that the specific surface area of the graphene nano-grade is large.
Example 3 preparation of graphene nanocoils
This example 3 was prepared substantially identically to example 1,the difference lies in that: MXene material is Cr2CTxThe concentration of the dispersion liquid is 1mg/mL, and the ball milling rotating speed and the ball milling time are different. The specific steps are described as follows:
1) mixing Cr2CTx(Txis-OH and-F) and graphene are mixed according to the mass ratio of 0.5:50, and are dispersed in deionized water after ball milling for 5 hours at 600rpm to obtain dispersion liquid with the concentration of 1 mg/mL;
2) stirring and heating the dispersion liquid to 60 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the graphene nano-roll.
Example 4 preparation of graphene nanocoils
This example 4 was prepared substantially identically to example 3, except that: the dispersion was heated at different temperatures. The specific steps are described as follows:
1) mixing Cr2CTx(Txis-OH and-F) and graphene are mixed according to the mass ratio of 0.5:50, and are dispersed in deionized water after ball milling for 5 hours at 600rpm to obtain dispersion liquid with the concentration of 1 mg/mL;
2) stirring and heating the dispersion liquid to 80 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the graphene nano-roll.
Example 5 preparation of graphene nanocoils
This example 5 was prepared substantially identically to example 1, except that: MXene material is Ti2CTxThe graphene is graphene oxide, and the concentration and the heating temperature of the dispersion liquid are different. The specific steps are described as follows:
1) mixing Ti2CTx(Txis-OH and-F) and graphene oxide are mixed according to the mass ratio of 0.5:50, and are dispersed in deionized water after ball milling for 5 hours at 600rpm to obtain dispersion liquid with the concentration of 0.5 mg/mL;
2) stirring and heating the dispersion liquid to 80 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the graphene oxide nano-roll.
Example 6 preparation of graphene nanocoils
This example 6 was prepared substantially identically to example 5, except that: the graphene is reduced graphene oxide, Ti2CTxThe mass ratio of the dispersion liquid to the graphene oxide is different from that of the dispersion liquid. The specific steps are described as follows:
1) mixing Ti2CTx(Txis-OH and-F) and reduced graphene oxide are mixed according to the mass ratio of 1:50, and are dispersed in deionized water after ball milling for 5 hours at 600rpm to obtain dispersion liquid with the concentration of 0.2 mg/mL;
2) stirring and heating the dispersion liquid to 80 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the reduced graphene oxide nano-roll.
Experiments prove that the SEM test results of examples 3 to 6 are similar to those of example 1, and more and better graphene rolls can be formed, which is not described herein again.
Comparative example 1 preparation of graphene nanocoils
Comparative example 1 was prepared substantially the same as example 1, except that: the concentration of the dispersion was 2 mg/mL. The specific steps are described as follows:
1) mixing Ti2C3Tx(Txis-OH and-F) and graphene are mixed according to the mass ratio of 0.8:50, and are dispersed in deionized water after ball milling for 4 hours at 400rpm to obtain dispersion liquid with the concentration of 2 mg/mL;
2) stirring and heating the dispersion liquid to 60 ℃, then quickly pouring liquid nitrogen into the dispersion liquid, precooling for 6h at-30 ℃, and then freeze-drying for 24h at-50 ℃ to obtain the graphene nano-roll. The SEM test results of the graphene nanocoils are shown in fig. 4. As can be seen from fig. 4, the graphene nano-roll prepared by the comparative example has a small number of rolls and a poor roll forming property, and the sheets are stacked together and have a small specific surface area.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a graphene nano roll is characterized by comprising the following steps:
dispersing mixed powder of MXene material and graphene in water to form dispersion liquid, and heating the dispersion liquid, wherein the concentration of the dispersion liquid is 0.1-1 mg/mL; and
and (3) completely freezing the heated dispersion liquid by liquid nitrogen, and then freeze-drying.
2. The method according to claim 1, wherein the concentration of the dispersion is 0.1mg/mL to 0.5 mg/mL.
3. The method for preparing the graphene nanovolume according to claim 1, wherein the mass ratio of the MXene material to the graphene is (0.1-1): 50.
4. the method of claim 1, wherein the graphene is at least one of graphene, graphene oxide, reduced graphene oxide, doped graphene oxide, and doped reduced graphene oxide.
5. The method for preparing graphene nanocoils according to claim 4, wherein the graphene has an oxygen content of 0 to 40 at%.
6. The method for preparing the graphene nanovolume according to claim 1, wherein the MXene material is Ti2C3Tx、Ti2CTxAnd Cr2CTxWherein T isxis-OH and/or-F.
7. The method for preparing the graphene nano-coil according to any one of claims 1 to 6, wherein the freezing temperature is-30 ℃ to-80 ℃ and the time is 1h to 24 h; and/or
The temperature of the freeze drying is 0 ℃ to-50 ℃, and the time is 1h to 72 h.
8. The method for preparing the graphene nanocoil according to any one of claims 1 to 6, wherein the dispersion liquid is heated at a temperature of 60 ℃ to 100 ℃.
9. The method for preparing the graphene nanovolume according to any one of claims 1 to 6, wherein a method for preparing the mixed powder of the MXene material and the graphene is ball milling.
10. The method for preparing the graphene nano-coil according to claim 9, wherein the rotation speed of the ball mill is 200rpm to 700rpm, and the time is 0.5h to 72 h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170106857A (en) * | 2016-03-14 | 2017-09-22 | 한국에너지기술연구원 | Preparing method of the 3D porous structured graphene/Mxene composite by ice-templating method and 3D porous structured graphene/Mxene composite by the same method |
| CN107265442A (en) * | 2017-06-30 | 2017-10-20 | 中国科学院宁波材料技术与工程研究所 | A kind of nitrogen-doped graphene nanometer roll three-dimensional macro material and preparation method thereof |
| CN107633954A (en) * | 2016-07-19 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of graphene/MXene combination electrode materials and its application |
| CN110550632A (en) * | 2019-09-29 | 2019-12-10 | 西南交通大学 | MXene/GO hybrid aerogel microsphere wave absorbing agent and preparation method thereof |
| CN111252760A (en) * | 2020-01-22 | 2020-06-09 | 哈尔滨工业大学 | Preparation method of graphene oxide nano roll and composite material thereof |
| CN111825091A (en) * | 2020-05-07 | 2020-10-27 | 武汉理工大学 | Three-dimensional graphene composite material loaded with single-layer flower-like MXene nanosheets and preparation method and application thereof |
| CN112103485A (en) * | 2020-08-29 | 2020-12-18 | 温州玖源锂电池科技发展有限公司 | Preparation method of 0D/2D quantum dot/graphene nanocolloid heterostructure electrode material |
| CN113329603A (en) * | 2021-05-17 | 2021-08-31 | 江南大学 | Light porous MXene-based composite film electromagnetic shielding material and preparation method thereof |
-
2021
- 2021-10-22 CN CN202111232142.7A patent/CN113998693A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170106857A (en) * | 2016-03-14 | 2017-09-22 | 한국에너지기술연구원 | Preparing method of the 3D porous structured graphene/Mxene composite by ice-templating method and 3D porous structured graphene/Mxene composite by the same method |
| CN107633954A (en) * | 2016-07-19 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of graphene/MXene combination electrode materials and its application |
| CN107265442A (en) * | 2017-06-30 | 2017-10-20 | 中国科学院宁波材料技术与工程研究所 | A kind of nitrogen-doped graphene nanometer roll three-dimensional macro material and preparation method thereof |
| CN110550632A (en) * | 2019-09-29 | 2019-12-10 | 西南交通大学 | MXene/GO hybrid aerogel microsphere wave absorbing agent and preparation method thereof |
| CN111252760A (en) * | 2020-01-22 | 2020-06-09 | 哈尔滨工业大学 | Preparation method of graphene oxide nano roll and composite material thereof |
| CN111825091A (en) * | 2020-05-07 | 2020-10-27 | 武汉理工大学 | Three-dimensional graphene composite material loaded with single-layer flower-like MXene nanosheets and preparation method and application thereof |
| CN112103485A (en) * | 2020-08-29 | 2020-12-18 | 温州玖源锂电池科技发展有限公司 | Preparation method of 0D/2D quantum dot/graphene nanocolloid heterostructure electrode material |
| CN113329603A (en) * | 2021-05-17 | 2021-08-31 | 江南大学 | Light porous MXene-based composite film electromagnetic shielding material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JINPING ZHAO 等: ""Facile Preparation of Large-scale Graphene Nanoscrolls from Graphene Oxide Sheets by Cold Quenching in Liquid Nitrogen"", 《CARBON》 * |
| 强亮生 等: "《新型功能材料制备技术与分析表征方法》", 30 September 2017, 哈尔滨工业大学出版社 * |
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