CN113628893B - MXene/graphene/carbon nanotube gel with high multiplying power and long service life, and preparation method and application thereof - Google Patents
MXene/graphene/carbon nanotube gel with high multiplying power and long service life, and preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
Abstract
MXene/graphene/carbon nanotube gel with high multiplying power and long service life, and a preparation method and application thereof. The invention belongs to the field of super capacitor electrode materials and preparation thereof. The invention aims to solve the technical problems that MXene of the conventional super capacitor electrode material is easy to oxidize and stack and agglomerate. The MXene/graphene/carbon nano tube gel is formed by mutually crosslinking a two-dimensional MXene sheet layer, a graphene nanosheet and a carbon nano tube, and has a three-dimensional hierarchical porous structure. The three-dimensional porous open structure effectively inhibits serious stacking and agglomeration of two-dimensional MXene sheets, improves the surface utilization rate of the MXene material, increases the number of active sites, and increases the specific capacity of the material; meanwhile, the addition of the graphene and the vitamin C can inhibit the oxidation of MXene, so that the gel has better oxidation resistance; in addition, the porous structure can be used as a reservoir to shorten the diffusion path of electrolyte ions and improve the rate characteristic of the electrode.
Description
Technical Field
The invention belongs to the field of super capacitor electrode materials and preparation thereof, and particularly relates to MXene/graphene/carbon nanotube gel with high multiplying power and long service life, and a preparation method and application thereof.
Background
The super capacitor has important application in many fields due to its advantages of fast charge and discharge rate, high power density, long cycle life, wide working temperature range, etc. The electrode material is one of the key components of the super capacitor and plays a crucial role in the performance of the super capacitor. MXene, as a class of two-dimensional materials emerging in recent years, comprises transition metal carbide, nitride or carbonitride, has the advantages of rich surface functional groups, high Young modulus, large interlayer spacing, metallic conductivity, large specific surface area and the like, and is proved to be a supercapacitor electrode material with a great application prospect.
MXene is extremely easy to oxidize in air or at high temperature to cause the rapid reduction of the conductivity of MXene, and is similar to other two-dimensional materials, the MXene is easy to stack and agglomerate, the excellent characteristics of MXene are greatly restricted, and the application of MXene in the field of energy storage is further severely limited.
Disclosure of Invention
The invention provides MXene/graphene/carbon nanotube gel with high multiplying power and long service life, and a preparation method and application thereof, aiming at solving the technical problems that MXene as an electrode material of the conventional super capacitor is easy to oxidize and stack and agglomerate.
The MXene/graphene/carbon nanotube gel with high multiplying power and long service life is formed by mutually crosslinking a two-dimensional MXene sheet layer, a graphene nanosheet and a carbon nanotube, and has a three-dimensional hierarchical porous structure with the aperture of 2-10 microns.
The preparation method of MXene/graphene/carbon nanotube gel with high multiplying power and long service life comprises the following steps:
step 1: by using hydrochloric acid and lithium fluoride to react with Ti 3 AlC 2 Etching, ultrasonic-assisted stripping, centrifuging, and performing suction filtration to a constant volume to obtain MXene dispersion liquid with the concentration of 0.5-20 mg/mL -1 ；
Step 2: preparing graphite oxide dispersion liquid by a modified Hummer's method;
and step 3: carrying out acid treatment on the carbon nano tube to obtain a carbon nano tube dispersion liquid;
and 4, step 4: mixing the MXene dispersion liquid, the graphite oxide dispersion liquid and the carbon nano tube dispersion liquid, magnetically stirring until the mixture is uniformly mixed, then adding L-cysteine and vitamin C, continuously stirring until the mixture is uniformly mixed, and then reacting for 1-12 h at 50-85 ℃ to obtain the MXene/graphene/carbon nano tube gel with high multiplying power and long service life.
Further limiting, the step 1 is carried out by reacting hydrochloric acid and lithium fluoride on Ti 3 AlC 2 The specific steps of etching are as follows: adding lithium fluoride into hydrochloric acid solution, stirring until the lithium fluoride is dissolved, and then adding Ti 3 AlC 2 Stirring the powder, transferring the powder into an oil bath after the powder is uniformly stirred, heating and stirring the powder, and after the reaction is finishedCooling to room temperature, centrifuging and washing until the pH value is more than 6 and the solution is in an ink state to obtain the multi-layer MXene.
Further limited, the concentration of the hydrochloric acid solution is 6-12 mol.L -1 Said Ti 3 AlC 2 The ratio of the mass of (a) to the volume of the hydrochloric acid solution is 0.5g: (5 to 20) mL of the above-mentioned Ti 3 AlC 2 The mass ratio of the lithium fluoride to the lithium fluoride is 1: (0.5-2).
Further limiting, the time for adding the lithium fluoride into the hydrochloric acid solution and stirring is 5-60 min, and the Ti is added 3 AlC 2 The stirring time after the powder is 5-60 min.
Further limited, the reaction temperature of the oil bath is 30-60 ℃, the heating and stirring time is 12-48 h, the centrifugal rotation speed is 3000-5000 rpm, and the centrifugal washing time is 1-10 min.
Further limiting, the frequency of the ultrasonic auxiliary stripping in the step 1 is 30-50 kHz, the time of the ultrasonic auxiliary stripping is 10-120 min, the rotating speed of the centrifugal after stripping is 3000-5000 rpm, and the time of the centrifugal after stripping is 10-120 min
Further limiting, the specific steps of preparing the graphite oxide dispersion liquid by the modified Hummer's method in the step 2 are as follows: taking concentrated sulfuric acid, cooling to below 3 ℃ in an ice bath, and cooling at a temperature of 1 g/min -1 Adding natural graphite at the speed of (1), stirring for 30min, and then stirring at the speed of 5 g.min -1 Adding potassium permanganate at the speed of (1), keeping the reaction temperature below 10 ℃ in the adding process, continuing stirring after the adding is finished, enabling the solution to release heat in the stirring process to enter a medium-temperature reaction stage, manually stirring at the medium-temperature reaction stage until the solution is viscous, adding distilled water, continuing stirring, finally adding hydrogen peroxide, and centrifugally washing until the pH value is more than 6.
Further, the concentrated sulfuric acid has a concentration of 18mol · L -1 The volume ratio of the concentrated sulfuric acid to the natural graphite is (200-250) mL:10g, wherein the volume ratio of the concentrated sulfuric acid to the potassium permanganate is (200-250) mL:60g, wherein the volume ratio of concentrated sulfuric acid to distilled water is (200-250): 3000, the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is (200-250): 200.
further limiting, the stirring time is 10-90 min after the natural graphite is added, the stirring time is 0.5-3 h after the potassium permanganate is added, the stirring time is 10-60 min after the distilled water is added, the centrifugal speed is 2000-8000 rpm, and the centrifugal time is 3-20 min.
Further, the concentration of the graphite oxide dispersion in the step 2 is limited to 0.5 to 20 mg/mL -1 。
Further limited, the specific steps of the acid treatment in step 3 are as follows: adding the carbon nano tube into mixed acid consisting of concentrated nitric acid and concentrated sulfuric acid, carrying out oil bath reflux reaction, cooling to room temperature after the reaction is finished, washing a solid product to be neutral, and adding water to a constant volume to obtain a carbon nano tube dispersion liquid.
Further defined, the ratio of the mass of the carbon nanotubes to the volume of the mixed acid is 5g: (50-250) mL, wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid in the mixed acid is 1: (0.2-5).
Further limiting, the temperature of the oil bath reflux reaction is 80-120 ℃, and the time for reaction is started for 0.5-4 h when the reflux occurs.
Further, the concentration of the carbon nanotube dispersion in the step 3 is 0.5 to 10 mg/mL -1 。
Further limiting, the volume ratio of the MXene dispersion liquid to the graphite oxide dispersion liquid in the step 4 is 70: (20 to 40).
Further limiting, the volume ratio of the MXene dispersion liquid to the carbon nanotube dispersion liquid in the step 4 is 70: (0.5-2).
Further limiting, the mass ratio of the L-cysteine to the MXene dispersion in the step 4 is (20-40): 70.
further limiting, the mass ratio of the vitamin C to the MXene dispersion liquid in the step 4 is (20-40): 70.
the MXene/graphene/carbon nano tube gel with high multiplying power and long service life is applied to a super capacitor cathode material.
Further limiting, the specific steps of preparing the supercapacitor negative electrode material by using MXene/graphene/carbon nanotube gel are as follows: and soaking MXene/graphene/carbon nano tube gel in ultrapure water, cleaning and slicing to obtain the supercapacitor negative electrode material.
Compared with the prior art, the invention has the following advantages:
1) The invention adds graphite oxide and vitamin C in the process of preparing gel. The graphene oxide is reduced into graphene in the formation process of gel, and the graphene is coated on the surface of the MXene sheet layer, so that the oxidation of MXene can be inhibited, and the problem that MXene is easy to oxidize is solved; the vitamin C reacts with functional groups on the surface of MXene to reduce the MXene, so that the oxidation of MXene/graphene/carbon nano tube gel is further inhibited, and the MXene/graphene/carbon nano tube gel has good oxidation resistance.
2) The added graphene oxide has the effect of promoting MXene to form gel, and the MXene/carbon nano tube without the added graphene oxide can form a three-dimensional porous structure but cannot form gel. The gel material can be directly used as an electrode without adding any conductive matrix and adhesive, so that the electrochemical performance (specific capacity and rate characteristic) of the electrode material is prevented from being reduced due to resistance generated by the adhesion of the electrode material and the conductive matrix.
3) The MXene/graphene/carbon nano tube gel has a three-dimensional porous open structure, and inhibits serious stacking and agglomeration of two-dimensional MXene sheets, so that an interface of the MXene/graphene/carbon nano tube gel is effectively utilized, the number of active sites is increased, and the specific capacity of a material is increased; in addition, the porous structure can be used as a reservoir to shorten the diffusion path of electrolyte ions, improve the rate characteristic of the electrode, and can realize high-rate rapid charge and discharge when used as a super capacitor electrode material.
4) The method of the invention has the advantages of easily obtained reagents, no toxicity, no harm, simple process, easy mass production and realization of industrialization.
Drawings
Fig. 1 is a scanning electron micrograph of MXene/graphene/carbon nanotube gel of example 1;
fig. 2 is a transmission electron micrograph of MXene/graphene/carbon nanotube gel of example 1;
fig. 3 is a specific capacity change curve diagram of MXene/graphene/carbon nanotube gel as a supercapacitor electrode at different scanning speeds;
fig. 4 is a graph of cycle performance of MXene/graphene/carbon nanotube gel as supercapacitor electrode.
Detailed Description
Example 1: the MXene/graphene/carbon nanotube gel with high magnification and long service life is formed by mutually crosslinking a two-dimensional MXene sheet layer, a graphene nanosheet and a carbon nanotube, and has a three-dimensional hierarchical porous structure and a pore size distribution of 2-10 μm.
The method for preparing the high-rate, long-life MXene/graphene/carbon nanotube gel of example 1 was carried out according to the following steps:
step 1: by using hydrochloric acid and lithium fluoride to react with Ti 3 AlC 2 Etching, ultrasonically stripping at 40kHz for 20min, centrifuging at 4000rpm for 30min, and vacuum-filtering to desired volume to obtain MXene dispersion with concentration of 10 mg/mL -1 (ii) a The reaction is carried out by hydrochloric acid and lithium fluoride to Ti 3 AlC 2 The specific steps of etching are as follows: 0.8g of lithium fluoride was weighed into 10mL of 9M hydrochloric acid solution and stirred for 10min, followed by addition of 0.5g of Ti 3 AlC 2 Stirring the powder while adding, transferring the powder into an oil bath at 40 ℃ after stirring for 30min, heating and stirring for 36h, cooling to room temperature after the reaction is finished, and centrifugally washing at 3500rpm until the pH value is more than 6 and the solution is in an ink state to obtain multilayer MXene;
step 2: preparing graphite oxide dispersion liquid by an improved Hummer's method; the method comprises the following specific steps: 230mL of 18 mol/L -1 Cooling concentrated sulfuric acid in ice bath to below 3 deg.C, and cooling at a temperature of 1 g/min -1 Adding 10g of natural graphite at the speed of (1), stirring for 30min, and then stirring at the speed of 5 g/min -1 Adding 60g of potassium permanganate at the speed of (1), keeping the reaction temperature below 10 ℃ in the adding process, continuing to stir for 2h after the adding is finished, enabling the solution to release heat in the stirring process to enter a medium-temperature reaction stage, keeping the solution at about 40 ℃ in the stage, manually stirring until the solution is viscous, adding 800mL of distilled water, continuing to stir until the temperature rises to 91 ℃, continuing to add 800mL of distilled water, stirring for 5min, pouring 1.2L of distilled water, then uniformly stirring, and then stirring at 20 mL/min -1 Adding 200mL of hydrogen peroxide until the solution turns golden yellow, and finally adding the obtained acidityCentrifuging and washing the solution at 5000rpm for 5min until the pH value is more than 6, wherein the concentration of the graphite oxide dispersion liquid is 10 mg/mL -1 ；
And 3, step 3: 5g of carbon nanotubes were added to a mixed acid of 151mL of concentrated nitric acid and concentrated sulfuric acid (38 mL of concentrated nitric acid in the mixed acid, 14 mol. L concentration) -1 113mL of concentrated sulfuric acid, 18 mol. L of concentrated sulfuric acid -1 ) Performing oil bath reflux reaction at 110 ℃, starting timing reaction for 2 hours when reflux occurs, cooling to room temperature after the reaction is finished, washing a solid product to be neutral, adding water to a constant volume to obtain the product with the concentration of 5.9 mg/mL -1 The carbon nanotube dispersion liquid of (1);
and 4, step 4: mixing 2.1mL of MXene dispersion liquid, 0.87mL of graphite oxide dispersion liquid and 0.05mL of carbon nano tube dispersion liquid, magnetically stirring until the mixture is uniformly mixed, then adding 9mg of L-cysteine and 9mg of vitamin C, continuously stirring until the mixture is uniformly mixed, and then reacting for 4 hours at 70 ℃ to obtain the MXene/graphene/carbon nano tube gel with high magnification and long service life.
Fig. 1 is a scanning electron micrograph of the MXene/graphene/carbon nanotube gel of example 1, and fig. 2 is a transmission electron micrograph of the MXene/graphene/carbon nanotube gel of example 1.
As can be seen from the figure, the three-dimensional MXene/graphene/carbon nanotube composite material has a clear and interconnected three-dimensional porous network structure. The size of three-dimensional pores of MXene/graphene/carbon nano tube gel is 2-10 μm, the pore walls are formed by crosslinking of graphene nanosheets and MXene nanosheets, the carbon nano tubes are successfully adsorbed on the surfaces of the MXene and the graphene nanosheets, and the MXene, the graphene and the carbon nano tube gel coexist in a large visual field range.
Example 2: the specific steps of preparing the supercapacitor negative electrode material by using the MXene/graphene/carbon nanotube gel with high magnification and long service life in the embodiment 1 are as follows: soaking MXene/graphene/carbon nano tube gel in ultrapure water, cleaning, directly testing the slices as electrodes, cleaning after testing, drying in a vacuum oven for more than 12 hours, and weighing the mass.
Fig. 3 is a specific capacity change curve of MXene/graphene/carbon nanotube gel as a supercapacitor electrode at different scanning speeds, and fig. 4 is a cycle performance curve of MXene/graphene/carbon nanotube gel as a supercapacitor electrode.
As can be seen from the figure, MXene/graphene/carbon nano tube is subjected to electrochemical performance test under the condition of three electrodes, and when the scanning speed is 2mV · s -1 The specific capacitance can reach 312 F.g -1 When the scanning rate is increased to 3 V.s -1 The capacity retention was 52%. After 100000 cycles, the capacity retention rate can reach 97.1 percent, and the ultra-long cycle life is realized.
Claims (9)
1. A preparation method of MXene/graphene/carbon nanotube gel with high multiplying power and long service life is characterized in that the gel is formed by mutually crosslinking a two-dimensional MXene sheet layer, a graphene nanosheet and a carbon nanotube, the MXene/graphene/carbon nanotube gel has a three-dimensional hierarchical porous structure, and the pore diameter is 2-10 mu m;
the preparation method comprises the following steps:
step 1: by using hydrochloric acid and lithium fluoride to react with Ti 3 AlC 2 Etching, ultrasonically stripping, centrifuging, and performing suction filtration to a constant volume to obtain MXene dispersion liquid with the concentration of 0.5-20 mg/mL ‒1 ；
Step 2: preparing graphite oxide dispersion liquid by an improved Hummer's method;
and step 3: carrying out acid treatment on the carbon nano tube to obtain a carbon nano tube dispersion liquid;
and 4, step 4: mixing the MXene dispersion liquid, the graphite oxide dispersion liquid and the carbon nano tube dispersion liquid, magnetically stirring until the mixture is uniformly mixed, adding L-cysteine and vitamin C, continuously stirring until the mixture is uniformly mixed, and then reacting for 1 to 12 hours at 50 to 85 ℃ to obtain the MXene/graphene/carbon nano tube gel with high magnification and long service life.
2. The method for preparing MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 1, wherein the step 1 comprises reacting Ti with hydrochloric acid and lithium fluoride 3 AlC 2 The specific steps of etching are as follows: adding lithium fluoride into hydrochloric acid solution, stirring until the lithium fluoride is dissolved,followed by addition of Ti 3 AlC 2 Stirring the powder, transferring the powder into an oil bath after uniformly stirring, heating and stirring, cooling to room temperature after reaction, centrifugally washing until the pH value is more than 6 and the solution is in an ink shape to obtain a multilayer MXene, wherein in the step 1, the ultrasonic auxiliary stripping frequency is 30 to 50kHz, the ultrasonic auxiliary stripping time is 10 to 120min, the centrifugal rotation speed after stripping is 3000 to 5000rpm, and the centrifugal time after stripping is 10 to 120 min.
3. The method for preparing MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 2, wherein the specific steps of preparing graphite oxide dispersion liquid by modified Hummer's method in step 2 are as follows: cooling concentrated sulfuric acid in ice bath to below 3 deg.C at a temperature of 1 g/min ‒1 Adding natural graphite at the speed of (1), stirring for 30min, and stirring at the speed of (5 g.min) ‒1 Adding potassium permanganate at the speed of (1), keeping the reaction temperature below 10 ℃ in the adding process, continuing stirring after the adding is finished, enabling the solution to release heat in the stirring process to enter a medium-temperature reaction stage, manually stirring until the solution is viscous at the stage, adding distilled water, continuing stirring, finally adding hydrogen peroxide, centrifugally washing until the pH value is more than 6, and enabling the concentration of the graphite oxide dispersion liquid in the step 2 to be 0.5-20 mg/mL ‒1 。
4. The method for preparing the MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 3, wherein the concentration of the hydrochloric acid solution is 6 to 12 mol. L ‒1 Said Ti 3 AlC 2 The ratio of the mass of (a) to the volume of the hydrochloric acid solution is 0.5g: (5 to 20) mL of the titanium compound, the titanium compound 3 AlC 2 The mass ratio of the lithium fluoride to the lithium fluoride is 1: (0.5 to 2), adding the lithium fluoride into the hydrochloric acid solution, stirring for 5 to 60min, and adding Ti 3 AlC 2 Stirring for 5 to 60min after the powder is formed, wherein the oil bath reaction temperature is 30 to 60 ℃, the heating stirring time is 12 to 48h, the centrifugal rotation speed is 3000 to 5000rpm, and the centrifugal washing time is 1 to 10 min; the concentration of the concentrated sulfuric acid is 18 mol.L ‒1 Volume of said concentrated sulfuric acid and natural graphiteThe mass ratio of (2) to (2) is (200 to 250) mL:10g, the ratio of the volume of the concentrated sulfuric acid to the mass of the potassium permanganate is (200 to 250) mL:60g, the volume ratio of the concentrated sulfuric acid to the distilled water is (200 to 250): 3000, wherein the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is (200 to 250): 200, adding natural graphite, stirring for 10 to 90min, adding potassium permanganate, stirring for 0.5 to 3h, adding distilled water, stirring for 10 to 60min, centrifuging at a rotating speed of 2000 to 8000rpm, and centrifuging for 3 to 20min.
5. The method for preparing the MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 1, wherein the acid treatment in the step 3 comprises the following specific steps: adding carbon nanotubes into mixed acid consisting of concentrated nitric acid and concentrated sulfuric acid, carrying out oil bath reflux reaction, cooling to room temperature after the reaction is finished, washing a solid product to be neutral, adding water to a constant volume to obtain a carbon nanotube dispersion liquid, wherein the ratio of the mass of the carbon nanotubes to the volume of the mixed acid is 5g: (50 to 250) mL, wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid in the mixed acid is 1: (0.2 to 5), the temperature of the oil bath reflux reaction is 80 to 120 ℃, the reaction is started for 0.5 to 4 hours when the reflux occurs, and the concentration of the carbon nano tube dispersion liquid in the step 3 is 0.5 to 10 mg/mL ‒1 。
6. The method for preparing the MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 1, wherein the volume ratio of the MXene dispersion liquid to the graphite oxide dispersion liquid in the step 4 is 70: (20 to 40), wherein the volume ratio of the MXene dispersion liquid to the carbon nanotube dispersion liquid in the step 4 is 70: (0.5 to 2).
7. The method for preparing the MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 1, wherein the mass ratio of the L-cysteine to the MXene dispersion in the step 4 is (20 to 40): 70, the mass ratio of the vitamin C to the MXene dispersion liquid in the step 4 is (20 to 40): 70.
8. the application of the MXene/graphene/carbon nanotube gel with high rate and long service life of claim 1, wherein the MXene/graphene/carbon nanotube gel is used for preparing a supercapacitor negative electrode material.
9. The application of the MXene/graphene/carbon nanotube gel with high magnification and long service life as claimed in claim 8, wherein the specific steps for preparing the cathode material of the supercapacitor by using the MXene/graphene/carbon nanotube gel are as follows: and soaking MXene/graphene/carbon nano tube gel in ultrapure water, cleaning and slicing to obtain the supercapacitor negative electrode material.
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| CN115246640B (en) * | 2022-03-04 | 2023-08-29 | 成都大学 | Three-dimensional HCNTs@Ti 3 C 2 T x MXene hybrid aerogel microsphere as well as preparation method and application thereof |
| CN114854237B (en) * | 2022-04-13 | 2023-09-19 | 中国科学院海洋研究所 | Method for inhibiting oxidation of MXene nano material and application of MXene nano material in anticorrosive paint |
| CN114864297B (en) * | 2022-05-25 | 2023-03-24 | 河南工业大学 | Preparation method of MXene/zinc oxide/graphene composite material |
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