CN113223776A - 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 inventionProvides a self-supporting MXene/MWCNT flexible composite film, a preparation method and application thereof, belonging to the field of composite materials. The invention is to mix Ti2CTxPerforming 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 again2CTxAnd (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 Mn+1XnTx(N-1, 2 or 3) wherein M represents a transition metal, X represents C or N, TxRepresents 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. Thereby influencing the specific capacitance and rate capability of the MXene electrode material and limiting the expansion of the MXene electrode material in various fields.
The MXene/MWCNT flexible composite film is prepared by using 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 the above, the present invention aims to provide a self-supporting MXene/MWCNT flexible composite film, and a preparation method and applications thereof. 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 Ti2CTxPerforming 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 Ti2CTxMXene 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 film2CTxThe mass ratio of MXene to the multi-walled carbon nano-tube is 1: 5-15.
Preferably, the cycle is repeated 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 1 g: 400 mL.
Preferably, the mass ratio of the acidified MWCNT to the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution is 100: 0.1-5.
Preferably, the Ti2CTxThe 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 Ti2Mixing 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 Ti2CTxA solution;
subjecting the exfoliated Ti to a stripping treatment2CTxCentrifuging the solution to obtain the Ti2CTxMXene 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 Ti2CTxPerforming 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 Ti2CTxMXene colloidal solution to obtain a composite film; laminating the composite filmAnd removing the composite fiber filter membrane after vacuum freeze drying of the membrane to obtain the self-supporting MXene/MWCNT flexible composite membrane.
Has the advantages 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 prepared 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 Ti2CTxPerforming 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 Ti2CTxMXene 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.
The invention is to mix Ti2CTxAnd (3) 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 aperture of the composite fiber Filter membrane is preferably 0.2-0.45 μm.
In the present invention, the Ti is2CTxThe MXene colloidal solution is preferably prepared by a process comprising the steps of:
mixing LiF and HCl solution for reaction to obtain hydrogen fluoride acidic solution;
mixing Ti2Mixing AlC powder and the hydrogen fluoride acidic solution for etching reaction, and sequentially carrying out centrifugal washing on the obtained etching product to obtain a solid material;
mixing the solid material with ethanol, and then carrying out ultrasonic stripping to obtain stripped Ti2CTxA solution;
subjecting the exfoliated Ti to a stripping treatment2CTxCentrifuging the solution to obtain the Ti2CTxMXene colloidal solution.
The method mixes LiF and HCl solution for reaction to obtain the hydrogen fluoride acidic solution.
In the invention, the dosage ratio of the LiF to the HCl solution is preferably 0.6-1.2 g: 20mL, more preferably 1.0 g: 20mL, and the concentration of the HCl solution is preferably 6-9M.
In the invention, the reaction temperature is preferably 35 ℃, and the reaction time is preferably 0.5-1 h.
After obtaining the hydrogen fluoride acidic solution, the invention adds Ti2Mixing 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 is2The grain size of the AlC powder is preferably 200-400 meshes.
In the present invention, the Ti is2The mass ratio of the AlC powder to the LiF is preferably 1: 0.6-1.2, and 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 250 rpm.
After the etching reaction is finished, the obtained etching system is centrifugally washed to obtain the etching product. In the present invention, the speed of the centrifugal water washing is preferably 3500 rpm.
The specific mode of the centrifugal water washing is not particularly limited, 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 Ti2And (C) solution.
In the invention, the power of ultrasonic stripping is preferably 50-1000W, and the ultrasonic stripping has the function of stripping multiple layers of (quasi-accordion-shaped) MXene into a single layer MXene nano-flake.
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 treatment2CTxAfter the solution is dissolved, the invention peels the solutionDetached treated Ti2CTxCentrifuging the solution to obtain the Ti2CTxMXene 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 is2CTxThe concentration of MXene colloidal solution is preferably 0.5 mg/mL.
The present invention does not specifically limit the specific parameters of the first filtration, and may adopt a manner 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 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 3-5: 1, more preferably 3:1, and the dosage ratio of the multiwalled carbon nanotube to the mixed acid is preferably 1 g: 400 mL.
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 mode of the water dilution and washing is not particularly limited in the invention, and the washing can be ensured to be neutral by adopting a mode known by the technical personnel in the field.
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 invention, the mass ratio of the sodium dodecyl benzene sulfonate to water is preferably 0-0.15: 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 invention, the mass ratio of the acidified MWCNT to the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution is preferably 100: 0.1-5.
In the present invention, the concentration of the multiwalled carbon nanotube dispersion is preferably 0.05 mg/mL.
The specific parameters of the second filtration are not particularly limited in the present invention, and 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 again2CTxMXene colloidal solution to obtain the composite film.
In the present invention, the number of times of the cycle repetition is preferably 3 to 20 times, and 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 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 film2CTxThe mass ratio of MXene to the multi-walled carbon nanotube is preferably 1: 5-15.
In the invention, the outermost layer of the self-supporting MXene/MWCNT flexible composite film is MXene because Ti2CTxAfter MXene colloidal solution is filtered and dried, the formed filter membrane is not easy to break, has good flexibility and can form a very flexible film.
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 Ti2Adding 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 mixture into 4 50mL centrifuge tubes, centrifuging at the speed of 3500rpm, and washing the mixture with 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) stripping the Ti treated in the step (4)2CTxTransferring 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): putting 1g MWCNT in 400mL mixed acid with the volume ratio of 65% concentrated sulfuric acid to 98% concentrated nitric acid being 3:1, and performing ultrasonic treatment 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)Ti2CTxthe MXene colloidal solution was filtered through a composite fiber membrane (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. Repeating the above operation for 10 times, and filtering Ti2CTxMXene 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-Ti2CTx/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-Ti2CTx/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 by the conventional vacuum drying technique, the MXene/MWCNT composite film electrode prepared by the freeze drying technique has a looser interlayer structure and a larger interlayer distance, the storage and transport performance of ions between the interlayers is significantly improved, the vacuum drying technique causes material wrinkles and damages the material structure, further causes the MXene structure to collapse, the structure of the sample is not damaged during the freeze drying process, the material components are firmly supported on the azimuths thereof, and voids are left when ice sublimes, thereby maintaining 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-Ti2CTx/CNT。
For the electrochemical performance test of the flexible composite films prepared in the embodiment 1 and the comparative examples 1-2, 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 looser 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 (10)
1. A preparation method of a self-supporting MXene/MWCNT flexible composite film is characterized by comprising the following steps:
mixing Ti2CTxPerforming 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 Ti2CTxMXene 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.
2. The preparation method according to claim 1, wherein Ti in the self-supporting MXene/MWCNT flexible composite film2CTxThe mass ratio of MXene to the multi-walled carbon nano-tube is 1: 5-15.
3. The method according to claim 1 or 2, wherein the cycle is repeated 3 to 20 times.
4. The preparation method according to claim 1, wherein the temperature of the vacuum freeze drying is-60 to-80 ℃ and the time is 12 to 24 hours.
5. 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.
6. The preparation method of claim 5, 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 multiwalled carbon nanotube to the mixed acid is 1 g: 400 mL.
7. The method according to claim 5, wherein the mass ratio of the acidified MWCNT to the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate is 100:0.1 to 5.
8. The method according to claim 1, wherein the Ti is2CTxThe 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 Ti2Carrying 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 Ti2CTxA solution;
subjecting the exfoliated Ti to a stripping treatment2CTxCentrifuging the solution to obtain the Ti2CTxMXene colloidal solution.
9. The self-supporting MXene/MWCNT flexible composite film prepared by the preparation method of any one of claims 1 to 8.
10. Use of the self-supporting MXene/MWCNT flexible composite film of claim 9 as an electrode material.
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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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| CN114121496A (en) * | 2021-10-28 | 2022-03-01 | 中国科学院深圳先进技术研究院 | Flexible composite electrode, preparation method thereof and flexible energy storage device |
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| CN116026195A (en) * | 2023-03-02 | 2023-04-28 | 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 |
| CN117180980A (en) * | 2023-08-29 | 2023-12-08 | 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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| CN117180980A (en) * | 2023-08-29 | 2023-12-08 | 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 |
| 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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