CN113628893A - MXene/graphene/carbon nanotube gel with high multiplying power and long service life as well as preparation method and application thereof - Google Patents
MXene/graphene/carbon nanotube gel with high multiplying power and long service life as well as preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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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 nano sheet 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 two-dimensional material 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 has proved to be a supercapacitor electrode material with 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 mu m.
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 Ti3AlC2Etching, ultrasonically assisting 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 1-12 hours 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 Ti3AlC2The specific steps of etching are as follows: adding lithium fluoride into hydrochloric acid solution, stirring until the lithium fluoride is dissolved, and then adding Ti3AlC2Stirring the powder, transferring the powder into an oil bath after uniformly stirring, heating and stirring, cooling to room temperature after the reaction is finished, and centrifugally washing until the pH value is more than 6 and the solution is in an ink state to obtain the multilayer MXene.
Further limiting, the concentration of the hydrochloric acid solution is 6-12 mol.L-1Said Ti3AlC2The ratio of the mass of (a) to the volume of the hydrochloric acid solution is 0.5 g: (5-20) mL of the above-mentioned Ti3AlC2The 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 added3AlC2The stirring time after the powder is 5-60 min.
Further limiting, the oil bath reaction temperature 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, in the step 1, the frequency of ultrasonic auxiliary stripping is 30-50 kHz, the time of ultrasonic auxiliary stripping is 10-120 min, the rotating speed of centrifugation after stripping is 3000-5000 rpm, and the time of centrifugation 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: cooling concentrated sulfuric acid in ice bath to below 3 deg.C at a temperature of 1 g/min-1Adding natural graphite at a speed of 30 deg.C and stirringmin, then at 5 g.min-1Adding 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-1The volume of the concentrated sulfuric acid and the mass of the natural graphite are in a ratio of (200-250) mL: 10g, wherein the volume of the concentrated sulfuric acid to the mass of the potassium permanganate is (200-250) mL: 60g, 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.
and 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 rotating speed is 2000-8000 rpm, and the centrifugal time is 3-20 min.
Further limiting, the concentration of the graphite oxide dispersion liquid in the step 2 is 0.5-20 mg/mL-1。
Further limiting, the specific steps of the acid treatment in the 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 the carbon nano tube dispersion liquid.
Further defined, the ratio of the mass of the carbon nanotubes to the volume of the mixed acid is 5 g: (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 reaction is started for 0.5-4 h when the reflux occurs.
Further limiting, the concentration of the carbon nanotube dispersion liquid in the step 3 is 0.5-10 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: (20-40).
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 liquid 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 nanotube gel with high multiplying power and long service life is applied to the cathode material of the super capacitor.
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 graphene oxide added in the invention has the effect of promoting MXene to form gel, and MXene/carbon nano tube without graphene oxide can not form gel although a three-dimensional porous structure can be formed. 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, inhibits serious stacking and agglomeration of two-dimensional MXene sheets, effectively utilizes an interface of the MXene/graphene/carbon nano tube gel, increases the number of active sites and increases the specific capacity of a material; 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 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 pore size distribution of 2-10 microns.
The method for preparing the high-rate and long-life MXene/graphene/carbon nanotube gel of example 1 comprises the following steps:
step 1: by using hydrochloric acid and lithium fluoride to react with Ti3AlC2Etching, 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 Ti3AlC2The specific steps of etching are as follows: 0.8g of lithium fluoride was weighed into 10mL of a 9M hydrochloric acid solution and stirred for 10min, followed by 0.5g of Ti3AlC2Stirring the powder while adding the powder, transferring the powder into an oil bath at 40 ℃ after stirring for 30min, heating and stirring the powder for 36h, cooling the powder to room temperature after the reaction is finished, and centrifugally washing the powder at 3500rpm until the pH value is more than 6 and the solution is in an ink state to obtain a multilayer MXene;
step 2: preparing graphite oxide dispersion liquid by an improved Hummer's method; the method comprises the following specific steps: 230mL of the solution with a concentration of 18 mol. L is taken-1Cooling concentrated sulfuric acid in ice bath to below 3 deg.C, and cooling at a temperature of 1 g/min-1Adding 10g of natural graphite at the speed of (1), stirring for 30min, and then stirring at the speed of 5 g/min-1Adding 60g of potassium permanganate at the speed of (1), keeping the reaction temperature below 10 ℃ in the adding process, continuing stirring 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 medium-temperature reaction stage, manually stirring until the solution is viscous, adding 800mL of distilled water, continuing stirring until the temperature rises to 91 ℃, continuing adding 800mL of distilled water, stirring for 5min, pouring 1.2L of distilled water, uniformly stirring, and then adding 20 mL/min-1Adding 200mL of hydrogen peroxide until the solution turns golden yellow, and finally centrifugally washing the obtained acidic 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 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, concentration 14 mol. L)-1113mL 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-1The 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 the MXene/graphene/carbon nano tube gel is 2-10 microns, the pore walls are formed by crosslinking of graphene nano sheets and MXene nano sheets, the carbon nano tubes are successfully adsorbed on the surfaces of the MXene and the graphene nano sheets, and the MXene/graphene/carbon nano tube gel, the MXene gel and the MXene nano sheets coexist in a large visual field range.
Example 2: the specific steps for preparing the cathode material of the supercapacitor 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 the testing is finished, 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-1The specific capacitance can reach 312 F.g-1When the scanning rate is increased to 3 V.s-1The 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 (10)
1. The MXene/graphene/carbon nanotube gel is characterized by being formed by mutually crosslinking a two-dimensional MXene sheet layer, a graphene nanosheet and a carbon nanotube, and having a three-dimensional hierarchical porous structure and a pore diameter of 2-10 microns.
2. The method for preparing the MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 1, wherein the preparation method comprises the following steps:
step 1: by using hydrochloric acid and lithium fluoride to react with Ti3AlC2Etching, ultrasonic-assisted stripping, centrifuging, and vacuum-filtering to desired volume to obtain MXene dispersion, MXeThe concentration of ne dispersion is 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 1-12 hours at 50-85 ℃ to obtain the MXene/graphene/carbon nano tube gel with high multiplying power and long service life.
3. The method for preparing MXene/graphene/carbon nanotube gel with high magnification and long service life as claimed in claim 2, wherein the step 1 comprises reacting Ti with hydrochloric acid and lithium fluoride3AlC2The specific steps of etching are as follows: adding lithium fluoride into hydrochloric acid solution, stirring until the lithium fluoride is dissolved, and then adding Ti3AlC2Stirring the powder, transferring the powder into an oil bath after uniform stirring, heating and stirring, cooling to room temperature after reaction, centrifugally washing until the pH value is greater than 6 and the solution is ink-shaped to obtain a multilayer MXene, wherein in the step 1, the ultrasonic-assisted stripping frequency is 30-50 kHz, the ultrasonic-assisted stripping time is 10-120 min, the centrifugal rotation speed after stripping is 3000-5000 rpm, and the centrifugal time after stripping is 10-120 min.
4. 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-1Adding natural graphite at the speed of (1), stirring for 30min, and stirring at the speed of (5 g.min)-1Adding potassium permanganate at a speed of 10 deg.C or below, stirring after the addition is completed, allowing the solution to release heat, allowing the solution to enter a medium temperature reaction stage, stirring manually until the solution is viscous, adding distilled water, and stirringAdding hydrogen peroxide, centrifugally washing until the pH value is more than 6, wherein the concentration of the graphite oxide dispersion liquid in the step 2 is 0.5-20 mg/mL-1。
5. The method for preparing MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 3 or 4, wherein the concentration of the hydrochloric acid solution is 6-12 mol-L-1Said Ti3AlC2The ratio of the mass of (a) to the volume of the hydrochloric acid solution is 0.5 g: (5-20) mL of the above-mentioned Ti3AlC2The mass ratio of the lithium fluoride to the lithium fluoride is 1: (0.5-2), adding lithium fluoride into the hydrochloric acid solution, stirring for 5-60 min, and adding Ti3AlC2Stirring for 5-60 min after powder is obtained, wherein the oil bath reaction temperature is 30-60 ℃, the heating stirring time is 12-48 h, the centrifugal rotation speed is 3000-5000 rpm, and the centrifugal washing time is 1-10 min; the concentration of the concentrated sulfuric acid is 18 mol.L-1The volume of the concentrated sulfuric acid and the mass of the natural graphite are in a ratio of (200-250) mL: 10g, wherein the volume of the concentrated sulfuric acid to the mass of the potassium permanganate is (200-250) mL: 60g, 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, 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 rotating speed is 2000-8000 rpm, and the centrifugal time is 3-20 min.
6. The method for preparing MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 2, wherein the acid treatment in 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 5 g: (50-250) mL, wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid in the mixed acid is 1: (0.2-5), wherein the temperature of the oil bath reflux reaction is 8 DEGStarting a timed reaction for 0.5-4 h at 0-120 ℃ when reflux occurs, wherein the concentration of the carbon nano tube dispersion liquid in the step 3 is 0.5-10 mg/mL-1。
7. The method for preparing the MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 2, wherein the volume ratio of the MXene dispersion liquid to the graphite oxide dispersion liquid in the step 4 is 70: (20-40), wherein the volume ratio of the MXene dispersion liquid to the carbon nanotube dispersion liquid in the step 4 is 70: (0.5-2).
8. The method for preparing MXene/graphene/carbon nanotube gel with high magnification and long service life according to claim 2, wherein the mass ratio of the L-cysteine to the MXene dispersion in the step 4 is (20-40): 70, the mass ratio of the vitamin C to the MXene dispersion liquid in the step 4 is (20-40): 70.
9. the application of the high-rate and long-life MXene/graphene/carbon nanotube gel as claimed in claim 1, wherein the MXene/graphene/carbon nanotube gel is used for preparing a supercapacitor negative electrode material.
10. The application of the MXene/graphene/carbon nanotube gel with high magnification and long service life as claimed in claim 9, 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031867A (en) * | 2021-12-14 | 2022-02-11 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | MXene-graphene-PVC composite material and preparation method thereof |
| CN114854237A (en) * | 2022-04-13 | 2022-08-05 | 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 |
| CN114864297A (en) * | 2022-05-25 | 2022-08-05 | 河南工业大学 | Preparation method of MXene/zinc oxide/graphene composite material |
| CN115246640A (en) * | 2022-03-04 | 2022-10-28 | 成都大学 | Three-dimensional HCNTs @ Ti 3 C 2 T x MXene hybrid aerogel microspheres and preparation method and application thereof |
| CN115772342A (en) * | 2022-11-26 | 2023-03-10 | 安徽省迪盛织造整理有限公司 | Preparation method of MXene-graphene modified waterborne polyurethane conductive coating |
| CN116314794A (en) * | 2023-02-10 | 2023-06-23 | 中国石油大学(华东) | Layered porous lithium battery conductive material, preparation method, conductive agent and battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103151505A (en) * | 2013-03-01 | 2013-06-12 | 中国科学院过程工程研究所 | Lithium-titanate composite negative pole material and preparation method thereof |
| CN109205596A (en) * | 2018-10-26 | 2019-01-15 | 上海应用技术大学 | A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation |
| CN109671576A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof |
| CN109928713A (en) * | 2019-04-09 | 2019-06-25 | 天津大学 | MXene hydrogel and its liquid phase assemble method |
| US20200279696A1 (en) * | 2017-09-25 | 2020-09-03 | Lg Chem, Ltd. | Pseudocapacitor anode material and method for preparing the same |
| CN113035576A (en) * | 2021-03-11 | 2021-06-25 | 浙江大学 | Graphene oxide modified MXene aerogel-loaded manganese dioxide composite electrode material and preparation and application thereof |
-
2021
- 2021-07-16 CN CN202110805929.1A patent/CN113628893B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103151505A (en) * | 2013-03-01 | 2013-06-12 | 中国科学院过程工程研究所 | Lithium-titanate composite negative pole material and preparation method thereof |
| US20200279696A1 (en) * | 2017-09-25 | 2020-09-03 | Lg Chem, Ltd. | Pseudocapacitor anode material and method for preparing the same |
| CN109205596A (en) * | 2018-10-26 | 2019-01-15 | 上海应用技术大学 | A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation |
| CN109671576A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof |
| CN109928713A (en) * | 2019-04-09 | 2019-06-25 | 天津大学 | MXene hydrogel and its liquid phase assemble method |
| CN113035576A (en) * | 2021-03-11 | 2021-06-25 | 浙江大学 | Graphene oxide modified MXene aerogel-loaded manganese dioxide composite electrode material and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUN YAN ETC: "Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031867A (en) * | 2021-12-14 | 2022-02-11 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | MXene-graphene-PVC composite material and preparation method thereof |
| CN115246640A (en) * | 2022-03-04 | 2022-10-28 | 成都大学 | Three-dimensional HCNTs @ Ti 3 C 2 T x MXene hybrid aerogel microspheres and preparation method and application thereof |
| 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 |
| CN114854237A (en) * | 2022-04-13 | 2022-08-05 | 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 |
| 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 |
| CN114864297A (en) * | 2022-05-25 | 2022-08-05 | 河南工业大学 | Preparation method of MXene/zinc oxide/graphene composite material |
| CN115772342A (en) * | 2022-11-26 | 2023-03-10 | 安徽省迪盛织造整理有限公司 | Preparation method of MXene-graphene modified waterborne polyurethane conductive coating |
| CN116314794A (en) * | 2023-02-10 | 2023-06-23 | 中国石油大学(华东) | Layered porous lithium battery conductive material, preparation method, conductive agent and battery |
| CN116314794B (en) * | 2023-02-10 | 2024-04-09 | 中国石油大学(华东) | Layered porous lithium battery conductive material, preparation method, conductive agent and battery |
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