CN111453732A - Three-dimensional porous MXene/rGO composite material and preparation method thereof - Google Patents
Three-dimensional porous MXene/rGO composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of functional materials, and provides a preparation method of a three-dimensional porous MXene/rGO composite material, which is prepared by mixing MXene, graphene oxide GO and SeO2Mixing with water, performing solid-liquid separation, and heating to obtain three-dimensional polymerPorous MXene/rGO composites. The present invention utilizes SeO2And carrying out an oxidation reduction reaction with GO under a heating condition to generate a shrivelled rGO sheet layer which is inserted between MXene layers, and simultaneously forming Se particles scattered between the MXene layers, wherein carbon dioxide gas generated by the reaction can also enable the composite material to generate a porous structure. The finally obtained three-dimensional porous MXene/rGO composite material not only solves the problem of stacking of two-dimensional MXene materials, but also has a certain supporting effect on the folded rGO sheet layer and Se particles between MXene layers so as to prevent the collapse of an MXene pore structure.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a three-dimensional porous MXene/rGO composite material and a preparation method thereof.
MXene is a novel layered transition metal carbide/nitride, is a novel two-dimensional material discovered for the first time in 2011, has the characteristics of high conductivity of graphene and hydrophilicity of graphene oxide, has the advantages of flexible and adjustable components, rich surface functional groups and the like, and has great potential in application of electrode materials of secondary batteries and super capacitors.
The problems faced by the current two-dimensional MXene material are serious agglomeration, easy stacking, difficult formation of a uniformly dispersed structure and poor preparation effect, thereby influencing the electrical property of the material. The method for manufacturing the two-dimensional MXene into the three-dimensional structure is an effective means for solving the stacking problem of the two-dimensional MXene materials.
In recent years, some three-dimensional MXene preparation methods are reported, and mainly comprise methods such as a template method, a gel method and self-assembly, wherein templates in the template method mainly comprise ice templates, foams and organic polymers; the gel method adopts GO or other flocculating agents (such as metal cations, PVA and the like) to induce MXene solution to flocculate; the self-assembly method mainly induces MXene particles to agglomerate by using charged particles. However, the three-dimensional MXene pore structure obtained by the preparation method is not stable enough and is easy to collapse.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a three-dimensional porous MXene/rGO composite material, which is simple to operate and directly utilizes SeO2The characteristic of redox reaction with GO under the heating condition solves the problem that the three-dimensional MXene pore structure is not stable enough and is easy to collapse.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a three-dimensional porous MXene/rGO composite material, which comprises the following steps:
(1) mixing MXene, graphene oxide GO and SeO2Mixing with water to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1)Carrying out solid-liquid separation to obtain MXene/GO/SeO2A composite material;
(3) MXene/GO/SeO obtained in the step (2)2And heating the composite material to obtain the three-dimensional porous MXene/rGO composite material.
Preferably, the MXene comprises Ti3C2Tx、Ti2CTx、V2CTx、Mo2CTx、Nb2CTx、Nb4C3Tx、Mo2TiC2TxAnd Mo2Ti2C3TxAt least one of (1).
Preferably, the mixed solution contains MXene 50-90 wt%, GO and SeO2The total mass content of (A) is 10-50%.
Preferably, the heating temperature is 300-600 ℃, and the heating time is 2-10 h.
Preferably, the heating rate is 2-10 ℃/min.
Preferably, the heated atmosphere is an inert atmosphere or a vacuum atmosphere.
Preferably, the inert atmosphere comprises at least one of nitrogen, argon and helium.
Preferably, the three-dimensional porous MXene/rGO composite material comprises MXene layers, and wrinkled rGO sheets and Se particles distributed among the MXene layers, wherein the MXene surfaces have a propped-open pore structure.
Preferably, the interlayer spacing of the MXene layer is 1.2-1.5 nm, and the pore size of the pore structure is 0.1-3.5 microns.
Preferably, the three-dimensional porous MXene/rGO composite material is applied to a super capacitor as an electrode material.
The invention provides a preparation method of a three-dimensional porous MXene/rGO composite material, which utilizes SeO2Carrying out oxidation reduction reaction with GO under the heating condition to obtain a product Se and carbon dioxide gas, wherein the reaction shrinks a rGO lamella inserted between MXene layers, Se particles in the product are scattered between the MXene layers, and the carbon dioxide gas generated by the reaction can also compoundThe material generates a porous structure, and the three-dimensional porous MXene/rGO composite material is finally obtained, so that the problem of stacking of two-dimensional MXene materials is solved, the folded rGO sheet layer and Se particles can play a certain supporting role between MXene layers, and the collapse of the pore structure of the MXene sheet layer is prevented. The SEM images of the three-dimensional porous MXene/rGO composite materials prepared in the examples show that the MXene material has a stretched pore structure on the surface, and the folded rGO sheets and Se particles formed among the MXene layers can play a certain supporting role to prevent the pore structure of the MXene sheets from collapsing.
Drawings
FIG. 1 is an SEM image of material 3DPM-80 prepared in example 1;
FIG. 2 is a graph of the rate capability of material 3DPM-80 prepared in example 1;
FIG. 3 shows the 50A g value of 3DPM-80 prepared in example 1-1A cycle curve at current density;
FIG. 4 is a CV curve for MXene;
FIG. 5 is a CV curve of 3DPM-80, a material prepared in example 1;
FIG. 6 is a CV curve of 3DPM-80 prepared in example 1 at low sweep speed;
FIG. 7 is a CV curve of the material prepared in example 1 at low sweep speed after 20000 cycles of 3DPM-80 cycles;
FIG. 8 is a rate curve for the 3DPM-90 composite material prepared in example 2;
FIG. 9 is a rate curve for the 3DPM-70 composite material prepared in example 3.
Detailed Description
The invention provides a preparation method of a three-dimensional porous MXene/rGO composite material, which comprises the following steps:
(1) mixing MXene, graphene oxide GO and SeO2Mixing with water to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution obtained in the step (1) to obtain MXene/GO/SeO2A composite material;
(3) MXene/GO/SeO obtained in the step (2)2And heating the composite material to obtain the three-dimensional porous MXene/rGO composite material.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
In the present invention, the operation is carried out at room temperature unless otherwise specified.
In the present invention, the water is deionized water.
MXene, graphene oxide GO and SeO2And mixing with water to obtain a mixed solution.
In the invention, the mass content of MXene in the mixed solution is preferably 50-90%, more preferably 55-85%, and most preferably 60-80%.
In the invention, the total mass content of GO and SeO2 in the mixed solution is preferably 10-50%, more preferably 15-45%, and most preferably 20-40%. In the present invention, said GO and SeO2The mass ratio of (A) to (B) is preferably GO and SeO2The material ratio of the reaction. In the embodiments of the present invention, the GO and SeO2Is preferably 1:1, in which case SeO2Can be completely reduced into Se simple substance.
The invention has no special regulation on the dosage of the water, and can realize MXene, graphene oxide GO and SeO2Dispersing in water.
The MXene, the graphene oxide GO and the SeO are treated by the method2The mixing with water is not particularly limited, and a mixing operation known to those skilled in the art may be employed.
In the present invention, the MXene preferably comprises Ti3C2Tx、Ti2CTx、V2CTx、Mo2CTx、Nb2CTx、Nb4C3Tx、Mo2TiC2TxAnd Mo2Ti2C3TxMore preferably comprises Ti3C2TxAnd/or Ti2CTx。
In the invention, MXene, graphene oxide GO and SeO are mixed2The mixing with water is preferably: MXene, graphene oxide GO and SeO2Respectively mixing with water to obtain aqueous solution; then mixing MXene aqueous solution, graphene oxide GO aqueous solution and SeO2The aqueous solutions are mixed.
The preparation method of the MXene aqueous solution is not particularly specified, and the preparation method of the MXene aqueous solution, which is well known to a person skilled in the art, can be adopted. In the embodiment of the invention, the MXene aqueous solution is preferably Ti3C2TxAqueous solution of the Ti3C2TxThe preparation method of the aqueous solution is preferably prepared according to the technical scheme disclosed in the application number CN 201910885633.8. The preparation method is the most mature and common method at present, and the obtained solute Ti3C2TxIs the most readily available MXene material compared to other MXene materials.
In the present invention, the preparation method of the graphene oxide GO aqueous solution preferably includes a modified Hummer's method, a Brodie method, or a staudenmai method. In the present examples, the modified Hummer's method is preferred. The preparation method has good timeliness and safer preparation process.
In the present invention, the SeO2The operation for preparing the aqueous solution is not particularly limited, and a salt solution preparation method well known to those skilled in the art may be employed.
After mixed liquid is obtained, the mixed liquid is subjected to solid-liquid separation to obtain MXene/GO/SeO2A composite material.
In the present invention, the solid-liquid separation preferably comprises suction filtration and drying in this order.
The suction filtration mode is not specially specified in the invention, and the suction filtration mode known to those skilled in the art can be adopted. In the present invention, the drying preferably includes vacuum drying or freeze drying, more preferably freeze drying. In the present invention, the temperature of the freeze-drying is preferably-80 to-60 ℃. In the invention, the freeze drying time is preferably 36-48 h. The invention adopts freeze drying, and MXene can form a more uniform three-dimensional porous structure.
Obtaining MXene/GO/SeO2After compounding the material, the productThe MXene/GO/SeO2And heating the composite material to obtain the three-dimensional porous MXene/rGO composite material. GO and SeO2Carrying out redox reaction under heating condition to obtain shrivelled reduced graphene oxide sheet layer (rGO) and Se simple substance, and generating carbon dioxide gas. In the heating process, GO is reduced into rGO, and the reduced rGO is increased along with the temperature and SeO2Oxidation-reduction reaction (elemental C and SeO in rGO)2Reaction) to obtain a shrivelled reduced graphene oxide sheet layer (rGO) and a Se simple substance, and simultaneously generating carbon dioxide gas. In the present invention, since not all rGO is reacted, only SeO is reacted2That part of the contact has reacted, resulting in rGO being defective, wrinkling occurs, and the gases produced at the same time also cause rGO to wrinkle, so that the wrinkled rGO lamellae and Se particles simultaneously play a supporting role between the MXene layers, preventing the MXene pore structure from collapsing.
In the invention, the heating temperature is preferably 300-600 ℃, and more preferably 350-450 ℃; the heating time is preferably 2-10 h, and more preferably 4-6 h. In the invention, the heating rate is preferably 2-10 ℃/min, and more preferably 3-5 ℃/min.
In the present invention, the heating atmosphere is preferably an inert atmosphere or a vacuum atmosphere. In the present invention, the inert atmosphere preferably includes at least one of nitrogen, argon and helium.
The three-dimensional porous MXene/rGO composite material finally obtained by the preparation method provided by the invention not only solves the problem of stacking of two-dimensional MXene materials, but also has a certain supporting effect on the wrinkled rGO sheet layer and Se particles between the MXene layers, so that the collapse of the pore structure of the MXene sheet layer is prevented.
The invention also provides the three-dimensional porous MXene/rGO composite material prepared by the preparation method in the technical scheme, which comprises an MXene layer, a wrinkled rGO sheet layer distributed between the MXene layer and Se particles, wherein the MXene surface has a propped-up pore structure.
In the invention, the interlayer spacing of the MXene layer is 1.2-1.5 nm; the pore size of the pore structure is 0.1-3.5 μm.
The invention also provides application of the three-dimensional porous MXene/rGO composite material in the technical scheme as an electrode material in a super capacitor. In the invention, the application is preferably to prepare the three-dimensional porous MXene/rGO composite material into an electrode plate of a super capacitor. The preparation operation of the electrode plate is not particularly limited, and the technical scheme for preparing the electrode plate, which is well known by the technical personnel in the field, can be adopted.
The three-dimensional porous MXene/rGO composite material provided by the invention is made into an electrode plate, has excellent rate capability and cycle performance, and has specific capacity of 423F g at a sweep rate of 5mV/s as shown in an example-1The specific capacity is 202 Fg at a high sweep rate of 1000mV/s-1Has a high specific capacity of 50 A.g-1The capacity is not obviously attenuated after 20000 circles of circulation under high current, and the shape of the CV curve is hardly changed.
The following examples are provided to illustrate the preparation of the three-dimensional porous MXene/rGO composite material provided by the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Ti3C2TxPreparation of the aqueous solution
Adding 0.99g of L iF into a plastic bottle filled with 10m L hydrochloric acid (concentrated hydrochloric acid, the mass fraction is 36-38%), stirring for 5min to dissolve L iF, and then adding 1g of Ti3AlC2And stirring uniformly. And placing the obtained mixed solution into a constant-temperature water bath kettle at 35 ℃, and stirring and etching for 24 hours. Adding water into the product after the etching reaction, centrifuging for 4 times, repeatedly until the pH of the supernatant is approximately equal to 6, pouring out the supernatant, adding water again, performing ultrasonic treatment for 30min, centrifuging for 1h, and collecting the supernatant to obtain etched Ti3C2TxThe solution was weighed to 5m L Ti3C2TxFiltering the solution, drying and weighing to obtain Ti3C2TxThe concentration was 2.6mg/m L.
Preparation of graphene oxide aqueous solution
Adding 1.75g of graphite powder into 65m L concentrated sulfuric acid, stirring for 30min at 0-4 ℃, and thenSlowly adding 7.5g of potassium permanganate, stirring at 0-4 ℃ for 60min, placing the obtained mixed solution into a 35 ℃ constant-temperature water bath kettle, stirring and reacting for 4-6 h, adding 60m L deionized water into the reaction system, controlling the temperature of the system to be lower than 85 ℃, heating the system to 98 ℃, keeping the temperature for 5min, cooling the reaction system to room temperature, centrifuging to remove supernatant, adding hydrochloric acid (3 mol/L), centrifuging until supernatant and 1 mol/L BaCl are obtained2Adding water, centrifuging repeatedly until the pH of the supernatant is more than 6, performing ultrasonic treatment for 60min, centrifuging for 1h, collecting the supernatant to obtain graphene oxide aqueous solution, weighing 5m L graphene oxide solution, filtering, drying, and weighing to obtain graphene oxide with the concentration of 1mg/m L.
SeO2Preparation of the aqueous solution
0.03g of SeO was weighed2The powder is dissolved in deionized water of 30m L and stirred for 20min to prepare SeO of 1mg/m L2And (3) solution.
Preparation of three-dimensional porous MXene/rGO composite material
Mixing MXene aqueous solution, GO aqueous solution, and SeO2Mixing the aqueous solution according to the mass ratio of solute to solute of 8: 1, performing ultrasonic dispersion for 20min to uniformly disperse the aqueous solution, performing suction filtration to form a film, performing freeze drying for 48h at-60 ℃, and performing thermal reduction on the dried material for 2h at 450 ℃ under the protection of argon atmosphere to obtain a three-dimensional porous MXene/rGO composite material, which is recorded as 3 DPM-80.
Example 2
The other operations are the same as those of example 1 except for the MXene aqueous solution, GO aqueous solution, SeO2The solute mass ratio of the aqueous solution is 9: 0.5, and the three-dimensional porous MXene/rGO composite material is obtained and is marked as 3 DPM-90.
Example 3
The other operations are the same as those of example 1 except for the MXene aqueous solution, GO aqueous solution, SeO2The solute mass ratio of the aqueous solution is 7: 1.5, and the three-dimensional porous MXene/rGO composite material is obtained and is marked as 3 DPM-70.
Material characterization and supercapacitor performance testing
The characterization test was performed on the material 3DPM-80 prepared in example 1, and the test results are shown in FIG. 1: SEM shows that the MXene material surface has a stretched pore structure.
The material prepared in the embodiment 1-3 is cut into an electrode slice, a polypropylene porous membrane is a diaphragm, an electrolyte is a sulfuric acid solution of 3 mol/L, the material prepared in the embodiment 1-3 is cut into an electrode slice serving as a working electrode, YP (activated carbon) serves as a counter electrode, a silver chloride electrode serves as a reference electrode, and a three-electrode super capacitor is assembled at a voltage range of-0.5-0.2V.
FIG. 2 is a graph of the rate capability of 3DPM-80 prepared in example 1, from which it can be seen that the specific capacity is 423 Fg at a sweep rate of 5mV/s-1The specific capacity is 202 Fg at a high sweep rate of 1000mV/s-1The high specific capacity and the rate capability of the compound are all superior to those of the MXene material Ti prepared in the simple example 13C2Tx；
FIG. 3 shows the 50A g value of 3DPM-80 prepared in example 1-1The current density at 50A g is shown in FIG. 3-1The capacity is not obviously attenuated after circulating for 20000 circles under high current;
FIG. 4 is a CV curve of MXene (specifically MXene material Ti)3C2Tx) (ii) a FIG. 5 is a CV curve of 3DPM-80, a material prepared in example 1; FIG. 6 is a CV curve of 3DPM-80 prepared in example 1 at low sweep speed; FIG. 7 is a CV curve of the material prepared in example 1 at low sweep speed after 20000 cycles of 3DPM-80 cycles; it can be seen from fig. 4-7 that the CV curve shape of the material 3DPM-80 prepared in example 1 is almost unchanged, showing excellent rate capability and cycle capability of the material, and both rate capability and cycle capability are superior to MXene.
FIG. 8 is a graph of the rate of change of the 3DPM-90 composite material prepared in example 2, and it can be seen from FIG. 8 that the specific capacity at a sweep rate of 5mV/s is 391F g-1And a specific capacity of 180 Fg at a high sweep rate of 1000mV/s-1。
FIG. 9 is a plot of the rate of change of the 3DPM-70 composite material prepared in example 3, and from FIG. 9 it can be seen that the specific capacity at a sweep rate of 5mV/s is 404F g-1The specific capacity at a high sweep rate of 1000mV/s is 165 Fg-1。
From the above embodiments, it can be seen that the three-dimensional porous MXene/rGO composite material finally obtained by the method provided by the invention not only solves the problem of stacking of two-dimensional MXene materials, but also has a certain supporting effect on the wrinkled rGO sheet layer and Se particles between MXene layers to prevent the collapse of the pore structure of the MXene sheet layer, and also has good electrical properties.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a three-dimensional porous MXene/rGO composite material comprises the following steps:
(1) mixing MXene, graphene oxide GO and SeO2Mixing with water to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution obtained in the step (1) to obtain MXene/GO/SeO2A composite material;
(3) MXene/GO/SeO obtained in the step (2)2And heating the composite material to obtain the three-dimensional porous MXene/rGO composite material.
2. The method according to claim 1, wherein MXene in the step (1) comprises Ti3C2Tx、Ti2CTx、V2CTx、Mo2CTx、Nb2CTx、Nb4C3Tx、Mo2TiC2TxAnd Mo2Ti2C3TxAt least one of (1).
3. The preparation method according to claim 1, wherein the mixed solution obtained in the step (1) contains MXene 50-90 wt%, and GO and SeO2The total mass content of (A) is 10-50%.
4. The method according to claim 1, wherein the heating in step (3) is carried out at a temperature of 300 to 600 ℃ for 2 to 10 hours.
5. The production method according to claim 1 or 4, wherein the heating in the step (3) is performed at a temperature increase rate of 2 to 10 ℃/min.
6. The production method according to claim 1, wherein the heated atmosphere in the step (3) is an inert atmosphere or a vacuum atmosphere.
7. The method of claim 6, wherein the inert atmosphere comprises at least one of nitrogen, argon, and helium.
8. The three-dimensional porous MXene/rGO composite material prepared by the preparation method of any one of claims 1 to 7 comprises an MXene layer, and wrinkled rGO sheets and Se particles distributed among the MXene layer, wherein the MXene surface has a propped-up pore structure.
9. The three-dimensional porous MXene/rGO composite material of claim 8, wherein the MXene layer has a layer spacing of 1.2-1.5 nm and the pore size of the pore structure is 0.1-3.5 μm.
10. Use of the three-dimensional porous MXene/rGO composite material of claim 8 or 9 as an electrode material in a supercapacitor.
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| CN112687867A (en) * | 2020-12-25 | 2021-04-20 | 惠州亿纬锂能股份有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN113503992A (en) * | 2021-07-19 | 2021-10-15 | 东南大学 | Flexible pressure sensor based on multilayer composite film and preparation method thereof |
| CN114105130A (en) * | 2021-11-25 | 2022-03-01 | 哈尔滨工业大学 | Preparation method of graphene oxide/MXene composite material with sea urchin-like structure |
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| CN113503992A (en) * | 2021-07-19 | 2021-10-15 | 东南大学 | Flexible pressure sensor based on multilayer composite film and preparation method thereof |
| CN113503992B (en) * | 2021-07-19 | 2022-11-29 | 东南大学 | Flexible pressure sensor based on multilayer composite film and preparation method thereof |
| CN114105130A (en) * | 2021-11-25 | 2022-03-01 | 哈尔滨工业大学 | Preparation method of graphene oxide/MXene composite material with sea urchin-like structure |
| CN114105130B (en) * | 2021-11-25 | 2023-02-07 | 哈尔滨工业大学 | Preparation method of graphene oxide/MXene composite material with sea urchin-like structure |
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