CN113223776B - Self-supporting MXene/MWCNT flexible composite film and preparation method and application thereof - Google Patents
Self-supporting MXene/MWCNT flexible composite film and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a self-supporting MXene/MWCNT flexible composite film and a preparation method and application thereof, belonging to the field of composite materials. The invention is to mix Ti 2 CT x Performing first filtration on the MXene colloidal solution on a composite fiber filter membrane, performing second filtration on the MWCNT dispersion liquid on the obtained first thin film layer, sequentially and circularly repeating the first filtration and the second filtration on the obtained first MWCNT layer, and finally filtering Ti again 2 CT x And (3) carrying out vacuum freeze drying on the MXene colloidal solution, and removing the composite fiber filter membrane to obtain the self-supporting MXene/MWCNT flexible composite film. The MXene/MWCNT composite film electrode prepared by adopting the vacuum freeze-drying technology has a looser interlayer structure and larger interlayer spacing, the storage and transmission performance of ions between the layers is obviously improved, more electrode/electrolyte interfaces are exposed, an open and firm structure is established, and the structural stability is improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a self-supporting MXene/MWCNT flexible composite film and a preparation method and application thereof.
Background
MXene is a new two-dimensional transition metal carbon/nitride material with the chemical general formula of M n+1 X n T x (N =1, 2 or 3), wherein M represents a transition metal, X represents C or N, T x Represents a surface group (e.g., -O, -OH, or-F). MXene mainly etches an A atomic layer in a MAX phase of a precursor through selective etching to form a two-dimensional layered structure, has the characteristics of metalloid conductivity, excellent hydrophilicity, rich surface functional groups, pseudocapacitance and the like, and has attracted extensive attention of researchers in the fields of electrochemical energy storage such as secondary batteries, supercapacitors, catalysis and the like. However, interlayer stacking phenomenon caused by MXene interlayer van der waals force inhibits effective utilization of surface active sites and hinders rapid transport of ions inside the material. Therefore, the specific capacitance and rate performance of the MXene electrode material are influenced, and the expansion of the MXene electrode material in various fields is limited.
The MXene/MWCNT flexible composite film is prepared by utilizing MXene and MWCNT in the prior art, but the prepared MXene/MWCNT flexible composite film still has the problem of poor electrochemical performance.
Disclosure of Invention
In view of this, the present invention provides a self-supporting MXene/MWCNT flexible composite film, a method for preparing the same, and applications of the same. The self-supporting MXene/MWCNT flexible composite film prepared by the method has a looser interlayer structure and larger interlayer spacing, and the storage and transmission performance of ions between the layers is obviously improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a self-supporting MXene/MWCNT flexible composite film, which comprises the following steps:
mixing Ti 2 CT x The MXene colloidal solution is subjected to first filtration on a composite fiber filter membrane to formA first thin film layer;
performing second filtration on the multi-walled carbon nanotube dispersion liquid on the first thin film layer to form a first MWCNT layer;
sequentially repeating the first and second filtering cycles on the first MWCNT layer, and finally re-filtering the Ti 2 CT x MXene colloidal solution to obtain a composite film;
and removing the composite fiber filter membrane after vacuum freeze drying the composite membrane to obtain the self-supporting MXene/MWCNT flexible composite membrane.
Preferably, ti in the self-supporting MXene/MWCNT flexible composite film 2 CT x The mass ratio of MXene to the multi-wall carbon nano-tube is 1:5-15.
Preferably, the cycle is repeated from 3 to 20 times.
Preferably, the temperature of the vacuum freeze drying is-60 to-80 ℃, and the time is 12 to 24 hours.
Preferably, the multi-walled carbon nanotube dispersion is prepared by a method comprising the steps of:
mixing a multi-walled carbon nanotube and mixed acid, and then sequentially diluting with water, washing and drying to obtain acidified MWCNT, wherein the mixed acid comprises concentrated sulfuric acid and concentrated nitric acid;
mixing sodium dodecyl benzene sulfonate with water to obtain a sodium dodecyl benzene sulfonate aqueous solution;
and mixing the acidified MWCNT with a sodium dodecyl benzene sulfonate aqueous solution to obtain the multi-walled carbon nanotube dispersion liquid.
Preferably, the mass fraction of the concentrated sulfuric acid is 65%, the mass fraction of the concentrated nitric acid is 98%, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid is 3-5:1, and the dosage ratio of the multiwalled carbon nanotube to the mixed acid is 1g:400mL.
Preferably, the mass ratio of the acidified MWCNT to the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution is 100.
Preferably, the Ti 2 CT x The MXene colloidal solution is prepared by the method comprising the following steps:
mixing LiF and HCl solution for reaction to obtain hydrogen fluoride acidic solution;
mixing Ti 2 Mixing AlC powder and the hydrogen fluoride acidic solution for etching reaction, and centrifugally washing the obtained etching product to obtain a solid material;
mixing the solid material with ethanol, and then carrying out ultrasonic stripping to obtain stripped Ti 2 CT x A solution;
subjecting the exfoliated Ti to a stripping treatment 2 CT x Centrifuging the solution to obtain the Ti 2 CT x MXene colloidal solution.
The invention also provides the self-supporting MXene/MWCNT flexible composite film prepared by the preparation method of the technical scheme.
The invention also provides the application of the self-supporting MXene/MWCNT flexible composite film in the technical scheme as an electrode material.
The invention provides a preparation method of a self-supporting MXene/MWCNT flexible composite film, which comprises the following steps: mixing Ti 2 CT x Performing first filtration on the MXene colloidal solution on a composite fiber filter membrane to form a first film layer; performing second filtration on the multi-walled carbon nanotube dispersion liquid on the first thin film layer to form a first MWCNT layer; sequentially repeating the first and second filtrations cyclically on the first MWCNT layer, and finally refiltering the Ti 2 CT x MXene colloidal solution to obtain a composite film; and removing the composite fiber filter membrane after vacuum freeze drying the composite membrane to obtain the self-supporting MXene/MWCNT flexible composite membrane.
Has the beneficial effects that:
1. the electronic structure of the surface of an MXene sheet layer is regulated and controlled by the doping of the multi-walled carbon nanotube (MWCNT) through effective synergistic effect, the utilization rate of the specific surface area is improved, the MWCNT is applied to electrodes of secondary batteries and super capacitors, the rapid transmission of electrolyte can be realized, no binder is needed in the preparation of the electrodes, and the flexibility is good.
2. The self-supporting MXene/MWCNT composite electrode film is prepared by adopting an alternate filtering strategy, the mutual connection of the structures not only exposes more electrode/electrolyte contact interfaces, but also establishes an open and firm structure and provides good structural stability.
3. Compared with the self-supporting MXene/MWCNT composite film electrode prepared by the traditional vacuum drying technology, the MXene/MWCNT composite film electrode prepared by the freeze drying technology has the advantages that the interlayer structure is looser, the interlayer spacing is larger, and the storage and transmission performance of ions between the layers is obviously improved.
4. The traditional drying technology can cause material wrinkles, destroy the material structure, further cause MXene structure collapse, the structure of the sample can not be destroyed in the freeze drying process, the material molecules are firmly supported by ice, and when the ice is sublimated, gaps are left, and the physical and chemical structural integrity of the product is kept.
The invention also provides the self-supporting MXene/MWCNT flexible composite film prepared by the preparation method of the technical scheme. The self-supporting MXene/MWCNT flexible composite film prepared by the method has a looser interlayer structure and larger interlayer spacing, and has higher specific capacitance when being used as an electrode material.
Drawings
Fig. 1 is SEM images of the flexible composite thin films manufactured in example 1 and comparative example 1, wherein (a) is a SEM image of the flexible composite thin film manufactured in comparative example 1, and (b) is a SEM image of the flexible composite thin film manufactured in example 1;
FIG. 2 is a constant current charge/discharge diagram of the flexible composite films obtained in example 1 and comparative examples 1 to 2 at a current density of 1A/g.
Detailed Description
The invention provides a preparation method of a self-supporting MXene/MWCNT flexible composite film, which comprises the following steps of;
mixing Ti 2 CT x Performing first filtration on the MXene colloidal solution on a composite fiber filter membrane to form a first film layer;
performing second filtration on the multi-walled carbon nanotube dispersion liquid on the first thin film layer to form a first MWCNT layer;
sequentially repeating the first and second filtrations cyclically on the first MWCNT layer, and finally refiltering the Ti 2 CT x MXene colloidal solution to obtain a composite film;
and removing the composite fiber filter membrane after freeze drying the composite membrane to obtain the self-supporting MXene/MWCNT flexible composite membrane.
In the invention, ti 2 CT x And performing first filtration on the MXene colloidal solution on the composite fiber filter membrane to form a first membrane layer.
In the invention, the composite fiber Filter membrane is preferably vacuum filtration Filter paper membrane Filter (MCE), and the pore diameter of the composite fiber Filter membrane is preferably 0.2-0.45 μm.
In the present invention, the Ti is 2 CT x The MXene colloidal solution is preferably prepared by a process comprising the steps of:
mixing LiF and HCl solution to react to obtain hydrogen fluoride acidic solution;
mixing Ti 2 Mixing AlC powder with the hydrogen fluoride acidic solution for etching reaction, and sequentially carrying out centrifugal water washing on obtained etching products to obtain a solid material;
mixing the solid material with ethanol, and carrying out ultrasonic stripping to obtain stripped Ti 2 CT x A solution;
subjecting the exfoliated Ti to a stripping treatment 2 CT x Centrifuging the solution to obtain the Ti 2 CT x MXene colloidal solution.
The method mixes LiF and HCl solution for reaction to obtain the hydrogen fluoride acidic solution.
In the present invention, the ratio of the amount of LiF to the amount of HCl solution is preferably 0.6 to 1.2g:20mL, more preferably 1.0g:20mL, and the concentration of the HCl solution is preferably 6-9M.
In the present invention, the reaction temperature is preferably 35 ℃ and the reaction time is preferably 0.5 to 1 hour.
After obtaining the hydrogen fluoride acidic solution, the invention adds Ti 2 Mixing AlC powder with the hydrogen fluoride acidic solution for etching reaction, and centrifugally washing the obtained etching product to obtain a solid material.
In the present invention, the Ti is 2 AlC powderThe particle size of the powder is preferably 200 to 400 mesh.
In the present invention, the Ti is 2 The mass ratio of the AlC powder to the LiF is preferably 1.6 to 1.2, more preferably 1:1.
In the invention, the temperature of the etching reaction is preferably 35 ℃, the time is preferably 24-72 h, the etching reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 250rpm.
After the etching reaction is finished, the obtained etching system is centrifugally washed by water to obtain the etching product. In the present invention, the speed of the centrifugal water washing is preferably 3500rpm.
The specific mode of the centrifugal water washing is not particularly limited in the invention, and the centrifugal water washing is carried out by adopting a mode well known by the technical personnel in the field until the pH value is 6-7.
After the solid material is obtained, the solid material is mixed with ethanol and then is subjected to ultrasonic stripping to obtain stripped Ti 2 And (C) solution.
In the invention, the power of the ultrasonic stripping is preferably 50-1000W, and the ultrasonic stripping has the function of stripping multiple layers of (quasi-accordion-shaped) MXene into single-layer MXene nano-flakes.
In the invention, inert gas is preferably introduced during the ultrasonic stripping process to prevent MXene from being oxidized during the stripping process.
Obtaining a Ti subjected to exfoliation treatment 2 CT x After solution, the invention strips the treated Ti 2 CT x Centrifuging the solution to obtain the Ti 2 CT x MXene colloidal solution. The present invention is not limited to specific parameters for the centrifugation, and may be performed in a manner known to those skilled in the art.
In the present invention, the Ti is 2 CT x The concentration of MXene colloidal solution is preferably 0.5mg/mL.
The present invention does not specifically limit the specific parameters of the first filtration, and the first filtration may be performed by a method known to those skilled in the art, such as suction filtration.
After the first thin film layer is formed, the multi-walled carbon nanotube dispersion liquid is subjected to second filtration on the first thin film layer to form a first MWCNT layer.
In the present invention, the multi-walled carbon nanotube dispersion is preferably prepared by a method comprising the steps of:
mixing a multi-walled carbon nanotube and mixed acid, and then sequentially diluting with water, washing and drying to obtain acidified MWCNT, wherein the mixed acid comprises concentrated sulfuric acid and concentrated nitric acid;
mixing sodium dodecyl benzene sulfonate (SDS) with water to obtain a sodium dodecyl benzene sulfonate aqueous solution;
and mixing the acidified MWCNT with a sodium dodecyl benzene sulfonate aqueous solution to obtain the multi-walled carbon nanotube dispersion liquid.
The invention mixes the multi-wall carbon nano-tube and mixed acid, and then sequentially dilutes, washes and dries with water to obtain the acidified MWCNT, wherein the mixed acid comprises concentrated sulfuric acid and concentrated nitric acid.
In the present invention, the mass fraction of the concentrated sulfuric acid is preferably 65%, the mass fraction of the concentrated nitric acid is preferably 98%, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid is preferably 3 to 5:1, and more preferably 3:1, and the usage ratio of the multiwalled carbon nanotube to the mixed acid is preferably 1g:400mL.
In the present invention, the mixing is preferably ultrasonic for 6h at room temperature, and the power of the ultrasonic is not particularly limited in the present invention.
The specific manner of diluting with water and washing is not particularly limited in the present invention, and the washing can be performed to be neutral by using a manner known to those skilled in the art.
In the present invention, the drying is preferably performed in a drying oven at 60 ℃ for 24 hours.
The invention mixes sodium dodecyl benzene sulfonate (SDS) with water to obtain the sodium dodecyl benzene sulfonate water solution. In the present invention, the mass ratio of the sodium dodecylbenzenesulfonate to water is preferably 0 to 0.15:1000, the dosage of the sodium dodecyl benzene sulfonate is not 0, and the sodium dodecyl benzene sulfonate is used for modifying MWCNT and dispersing MWCNT.
After the acidified MWCNT and the sodium dodecyl benzene sulfonate aqueous solution are obtained, the acidified MWCNT and the sodium dodecyl benzene sulfonate aqueous solution are mixed to obtain the multi-walled carbon nanotube dispersion liquid.
In the present invention, the mass ratio of the acidified MWCNT to the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate is preferably 100.
In the present invention, the concentration of the multiwalled carbon nanotube dispersion is preferably 0.05mg/mL.
The present invention does not specifically limit the specific parameters of the second filtration, and the second filtration may be performed by a method known to those skilled in the art, such as suction filtration.
After forming the first MWCNT layer, the invention circularly repeats the first filtration and the second filtration on the first MWCNT layer in sequence, and finally filters the Ti again 2 CT x MXene colloidal solution to obtain the composite film.
In the present invention, the number of times the cycle is repeated is preferably 3 to 20 times, more preferably 10 times.
After the composite film is obtained, the composite fiber filter membrane is removed after the composite film is subjected to freeze drying, and the self-supporting MXene/MWCNT flexible composite film is obtained.
In the present invention, the temperature of the freeze-drying is preferably-60 to-80 ℃ and the time is preferably 12 to 24 hours.
The specific mode for removing the composite fiber filter membrane is not particularly limited in the present invention, and a mode known to those skilled in the art can be adopted.
The invention also provides the self-supporting MXene/MWCNT flexible composite film prepared by the preparation method of the technical scheme.
In the invention, ti in the self-supporting MXene/MWCNT flexible composite film 2 CT x The mass ratio of MXene to multi-wall carbon nanotubes is preferably 1:5-15.
In the invention, the outermost layer of the self-supporting MXene/MWCNT flexible composite film is MXene because Ti 2 CT x After MXene colloidal solution is filtered and dried, the formed filter membrane is not easy to break, has good flexibility and can form flexibleVery good films.
The invention also provides the application of the self-supporting MXene/MWCNT flexible composite film in the technical scheme as an electrode material.
The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
In order to further illustrate the present invention, the self-supporting MXene/MWCNT flexible composite film provided by the present invention and the preparation method and application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Adding 1g LiF into 20mL of 6M HCl solution, and stirring and reacting in a 100mL polytetrafluoroethylene beaker for 30min to prepare hydrogen fluoride acidic solution;
(2) Mixing ceramic material MAX phase 1g Ti 2 Adding AlC powder (200 meshes) into the solution in the step (1), stirring at the speed of 250rpm and the temperature of 35 ℃, and reacting for 72 hours;
(3) Adding 60mL of deionized water in the step (2) after the reaction is finished, putting the deionized water into 4 50mL centrifuge tubes, centrifuging at the speed of 3500rpm, and cleaning the deionized water until the pH value is 6;
(4) Adding alcohol with the purity of 99.99 percent into the step (3), and transferring the mixture into a gas collecting bottle for ultrasonic stripping treatment. Meanwhile, inert gas is introduced to prevent MXene from being oxidized in the stripping process;
(5) The Ti stripped in the step (4) 2 CT x Transferring the solution into a 50mL centrifuge tube, manually shaking for further layering, centrifuging to obtain a supernatant, wherein the color of the supernatant is dark brown to obtain 0.5mg/mL MXene dispersion;
(6) Acidized multi-walled carbon nanotubes (MWCNTs): 1g of MWCNT is placed in 400mL of mixed acid of 65% concentrated sulfuric acid and 98% concentrated nitric acid with the volume ratio of 3:1, and ultrasonic treatment is carried out for 6h at room temperature;
(7) Diluting the mixed solution after ultrasonic treatment with appropriate amount of distilled water, repeatedly washing by vacuum filtration method, and washing with water to neutrality;
(8) Drying the product after washing in a drying oven at 60 ℃ for 24h to obtain the product, namely the acidified MWCNT;
(9) Adding sodium dodecyl benzene sulfonate (SDS) surfactant into distilled water to prepare 50mL of surfactant solution;
(10) Adding the acidified multi-walled carbon nanotube into a surfactant solution, and ultrasonically dispersing uniformly to prepare a uniformly dispersed multi-walled carbon nanotube dispersion liquid (with the concentration of 0.05 mg/mL);
(11)Ti 2 CT x the MXene colloidal solution was filtered through a composite fiber filter (pore size 0.45 μm) to form a continuous membrane layer. The multiwall carbon nanotube dispersion is then filtered over the thin film layer to form a MWCNT layer. Then repeating the above operation 10 times, and finally filtering Ti 2 CT x MXene colloidal solution;
(12) Drying the composite film in a vacuum freezing box at-60 ℃ for 24h, and then removing the composite fiber filter membrane to obtain the self-supporting MXene/MWCNT flexible composite film marked as LT-Ti 2 CT x /CNT。
(13) The prepared self-supporting electrode composite film has better flexibility and can be well rolled up
There was no damage mark on the glass rod (2).
Comparative example 1
The same as example 1, except that the composite film was vacuum dried at 120 ℃ for 12 hours to obtain a flexible composite film, noted HT-Ti 2 CT x /CNT。
Fig. 1 is an SEM image of the flexible composite film obtained in example 1 and comparative example 1, wherein (a) is an SEM image of the flexible composite film obtained in comparative example 1, and (b) is an SEM image of the flexible composite film obtained in example 1, it can be seen that compared to the self-supporting MXene/MWCNT composite film electrode obtained in the conventional vacuum drying technique, the MXene/MWCNT composite film electrode prepared in the freeze drying technique has a looser interlayer structure and a larger interlayer distance, the storage and transport properties of ions between the interlayers are significantly improved, the vacuum drying technique causes material wrinkles and damages the material structure, further causes MXene structure collapse, the structure of the sample is not damaged during freeze drying, the material components are strongly supported on their azines, and voids are left when ice sublimes, thus preserving the physical and chemical structural integrity of the product.
Comparative example 2
Same as example 1, except that the composite film was naturally dried at room temperature for 12 hours to obtain a flexible composite film, which was designated as RT-Ti 2 CT x /CNT。
For the electrochemical performance test of the flexible composite films prepared in the example 1 and the comparative examples 1 to 2, fig. 2 is a constant current charge-discharge diagram at a current density of 1A/g, and it can be seen that the mass specific capacitance of the flexible composite film after vacuum drying, natural drying and freeze drying treatment is 72.5F/g, 85.8F/g and 99.7F/g, respectively, and it can be seen that the self-supporting MXene/MWCNT flexible composite film prepared by the invention has a more loose interlayer structure and a larger interlayer spacing, and has a higher specific capacitance when used as an electrode material.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A preparation method of a self-supporting MXene/MWCNT flexible composite film is characterized by comprising the following steps:
mixing Ti 2 CT x Performing first filtration on the MXene colloidal solution on a composite fiber filter membrane to form a first film layer;
performing second filtration on the multi-walled carbon nanotube dispersion liquid on the first thin film layer to form a first MWCNT layer;
sequentially repeating the first and second filtrations cyclically on the first MWCNT layer, and finally refiltering the Ti 2 CT x MXene colloidal solution to obtain a composite film;
removing the composite fiber filter membrane after vacuum freeze drying the composite membrane to obtain the self-supporting MXene/MWCNT flexible composite membrane; the temperature of the vacuum freeze drying is-60 to-80 ℃, and the time is 12 to 24 hours;
ti in the self-supporting MXene/MWCNT flexible composite film 2 CT x The mass ratio of MXene to the multi-wall carbon nano-tube is 1:5-15.
2. The method according to claim 1, wherein the cycle is repeated 3 to 20 times.
3. The method of claim 1, wherein the multi-walled carbon nanotube dispersion is prepared by a method comprising:
mixing a multi-walled carbon nanotube and mixed acid, and then sequentially diluting with water, washing and drying to obtain acidified MWCNT, wherein the mixed acid comprises concentrated sulfuric acid and concentrated nitric acid;
mixing sodium dodecyl benzene sulfonate with water to obtain a sodium dodecyl benzene sulfonate aqueous solution;
and mixing the acidified MWCNT with a sodium dodecyl benzene sulfonate aqueous solution to obtain the multi-walled carbon nanotube dispersion liquid.
4. The preparation method of claim 3, wherein the mass fraction of the concentrated sulfuric acid is 65%, the mass fraction of the concentrated nitric acid is 98%, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid is 3-5:1, and the dosage ratio of the multi-walled carbon nanotubes to the mixed acid is 1g:400mL.
5. The method according to claim 3, wherein the mass ratio of the acidified MWCNT to the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate is 100.
6. The method of claim 1, wherein the Ti2CTx MXene colloidal solution is prepared by a method comprising the steps of:
mixing LiF and HCl solution to react to obtain hydrogen fluoride acidic solution;
mixing Ti 2 Carrying out etching reaction on AlC powder and the hydrogen fluoride acidic solution, and carrying out centrifugal washing on an obtained etching product to obtain a solid material;
mixing the solid material with ethanol, and then carrying out ultrasonic stripping to obtain stripped Ti 2 CT x A solution;
subjecting the exfoliated Ti to a stripping treatment 2 CT x Centrifuging the solution to obtain the Ti 2 CT x MXene colloidal solution.
7. The self-supporting MXene/MWCNT flexible composite film prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the self-supporting MXene/MWCNT flexible composite film of claim 7 as an electrode material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110508389.0A CN113223776B (en) | 2021-05-11 | 2021-05-11 | Self-supporting MXene/MWCNT flexible composite film and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110508389.0A CN113223776B (en) | 2021-05-11 | 2021-05-11 | Self-supporting MXene/MWCNT flexible composite film and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN113223776A CN113223776A (en) | 2021-08-06 |
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| CN116026195B (en) * | 2023-03-02 | 2023-11-21 | 中国工程物理研究院激光聚变研究中心 | MXene composite film flying piece and preparation method thereof |
| CN117180980B (en) * | 2023-08-29 | 2024-03-08 | 华北电力大学（保定） | Composite nanofiltration membrane for efficiently intercepting ammonium sulfate and ammonium nitrate and simultaneously adsorbing and removing mercury ions and preparation method thereof |
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| 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 |
| CN112072126A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof |
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| CN112072126A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof |
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