CN113224306A - V-based MXene @ PANI flexible film and preparation method thereof - Google Patents
V-based MXene @ PANI flexible film and preparation method thereof Download PDFInfo
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- CN113224306A CN113224306A CN202110508945.4A CN202110508945A CN113224306A CN 113224306 A CN113224306 A CN 113224306A CN 202110508945 A CN202110508945 A CN 202110508945A CN 113224306 A CN113224306 A CN 113224306A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 11
- 239000002109 single walled nanotube Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 7
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000011056 performance test Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000005057 refrigeration Methods 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 10
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a V-based MXene @ PANI flexible film and a preparation method thereof, which change the conventional method for stirring and polymerizing polyaniline at low temperature and adopt a method of refrigeration and standing so as to generate a composite material with a special appearance, wherein polyaniline is stacked and grows along with MXene. To meet the requirements of users.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a V-based MXene @ PANI flexible film and a preparation method thereof.
Background
Due to the rise of the electronic product industry, the demand of electronic devices and energy storage is increasing day by day, and in recent years, research on the positive electrodes, the zinc negative electrodes and the electrolyte of the water-based ZIBs has been advanced to a certain extent, but the water-based ZIBs still face huge challenges in the aspects of the positive electrodes and the negative electrodes. Problems such as cathode dissolution, adverse effects from electrostatic interactions, zinc dendrites, corrosion, passivation and byproducts can lead to capacity degradation, low coulombic efficiency, short circuits and the like of the water system ZIBs, which severely limits the development and commercialization of the water system ZIBs. Therefore, it is necessary to summarize the challenges faced by water-based ZIBs and to provide relevant solutions.
MXene has high specific capacity and is an ideal negative electrode material, but due to strong van der Waals interaction, MXene is easy to agglomerate together, which obviously limits the interlayer accessibility of the electrolyte and reduces the electrochemical performance of ZIBs (zinc oxides).
Therefore, the prior art is yet to be further studied.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a preparation method of a V-based MXene @ PANI flexible film, which can effectively inhibit agglomeration of MXene with a two-dimensional lamellar structure and solve the problem of low utilization rate of an active material caused by agglomeration.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a V-based MXene @ PANI flexible film specifically comprises the following steps:
s1: adding the V-base MAX into a reaction kettle containing sodium fluoride and concentrated hydrochloric acid, filling inert gas, etching for 70-74h at 85-95 ℃, centrifugally washing with deionized water until the pH value is 5.8-6.2, and carrying out vacuum freeze drying to obtain V-base MXene powder;
s2, dispersing the MXene powder in a dilute HCl solution, adding an aniline monomer, filling inert gas, and stirring under ice water to obtain a mixed liquid A;
s3: dispersing Ammonium Persulfate (APS) in a dilute HCl solution, and stirring under ice water to obtain a mixed liquid B;
and S4, stopping stirring after a certain time, slowly adding the mixed liquid B in the step S3 into the mixed liquid A in the step S2 along the wall surface, filling inert gas, and refrigerating and standing at 0 ℃ in a refrigerator for 22-26h to obtain dark green liquid.
S5: centrifuging and washing the dark green liquid obtained in the step S4 with deionized water at a high rotating speed, and finally performing vacuum drying and freeze drying to prepare V-based MXene @ PANI powder;
s6: dispersing the prepared V-based MXene @ PANI powder and the single-walled carbon nanotube in a DMF solution according to a certain proportion, introducing inert gas, and performing ultrasonic treatment for a period of time to uniformly disperse the powder;
s7: and (3) carrying out suction filtration on the liquid in the S6 to form a film, and drying the film for 10-12h at 40-60 ℃ in a vacuum drying oven. Preparing a V-based MXene @ PANI flexible film;
s8: and assembling the button cell by using the prepared V-based MXene @ PANI flexible film as a positive electrode, a zinc sheet as a negative electrode and zinc trifluoromethanesulfonate as a water system electrolyte, and performing performance test.
Preferably, the reaction kettle in the step S1 is a polytetrafluoroethylene reaction kettle.
Preferably, the concentration of the concentrated hydrochloric acid in the step S1 is 10-12 mol/L, and the volume is 10-30 ml; the mass ratio of sodium fluoride to VYl MAX is 1: 1.
Preferably, the inert gas is any one of argon and nitrogen.
Preferably, the concentration of the dilute hydrochloric acid in the steps S2 and S3 is 1-3 mol/L; the mass ratio of MXene to APS in the solution A and the solution B is 1: 1; the volume of the aniline in the solution A is 50-200 ul.
Preferably, the temperature of the vacuum freeze drying is minus 30 ℃ to minus 50 ℃, and the time is 10-20 h.
Preferably, the time in step S4 is 5-10 min.
Preferably, the V-based MXene @ PANI material PANI prepared in step S5 grows attached to the V-based MXene.
Preferably, the centrifugal rotating speed is 10000 r/min-15000 r/min.
Preferably, the mass ratio of the V-based MXene @ PANI powder prepared in the step S6 to the single-walled carbon nanotube is 8:2 or 7: 3; the volume of the DMF solution is 10-50 ml; the ultrasonic time is more than 3 h.
Preferably, the concentration of the zinc trifluoromethanesulfonate electrolyte in step S8 is 1mol/L to 3 mol/L.
A V-based MXene @ PANI flexible film prepared by the preparation method of claim 1, comprising an MXene two-dimensional layered structure and a conductive polymer polyaniline.
The composite material ensures good wettability of the material in ZIBs by utilizing rich hydrophilic functional groups in a polyaniline framework, so that the specific surface area can be further improved, charge transfer and ion diffusion are promoted, the electrochemical performance of the composite material is improved, the practicability of the composite material is increased, the characteristics of high active sites and high specific capacity of MXene are fully exerted, meanwhile, the agglomeration of the MXene with a two-dimensional lamellar structure can be effectively inhibited by the single-walled carbon nanotube, and the problem of low utilization rate of the active material caused by the agglomeration is solved.
The invention has the beneficial effects that:
(1) the layered MXene serving as an active material with large surface area and framework can provide an important path for the insertion/extraction of ions, and the chain-shaped polyaniline serving as a connecting bridge and a conductive chain structure can accelerate the charge transfer between different MXene layers. In addition, the introduction of polyaniline can also improve the electrochemical performance of the water-based zinc-ion battery.
(2) The traditional method for polymerizing polyaniline by stirring at low temperature is changed, and a cold storage standing method is adopted, so that a special appearance that polyaniline is stacked and grows along with MXene is generated, the layered structure of V-based MXene is stabilized, and the layered structure is prevented from being stacked, so that the ion embedding/separation in the battery is influenced. In addition, a part of polyaniline is polymerized in the interlayer of V-based MXene, so that the interlayer spacing is enlarged to a certain extent, and ion diffusion is facilitated.
(3) The agglomeration of MXene with a two-dimensional lamellar structure can be effectively inhibited by using the single-walled carbon nanotube, and the problem of low utilization rate of the active material caused by the agglomeration is solved.
(4) The V-based MXene @ PANI flexible film prepared by the application improves the narrow voltage interval of the conventional water system zinc ion battery, and can enable the battery to be charged and discharged in a large voltage interval.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a scanning electron microscope image of V-based MXene @ PANI prepared in comparative example 1;
FIG. 2 is a scanning electron microscope image of V-based MXene @ PANI prepared in example 1;
fig. 3 is a scanning electron microscope image of MXene after etching in example 1;
fig. 4 is a scanning electron microscope image of PANI;
FIG. 5 is an XRD image of V-based MXene @ PANI, MXene and PANI prepared in example 1; a
FIG. 6 is a scanning electron microscope image of V-based MXene @ PANI prepared in example 2;
FIG. 7 is a scanning electron microscope image of V-based MXene @ PANI prepared in example 3;
FIG. 8 is an image of a V-based MXene @ PANI flexible film prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which should be construed as merely illustrative, and not limitative of the remainder of the disclosure.
The raw materials and reagents used in the embodiment of the invention are all conventional chemical products, and can be purchased from commercial channels.
Example 1
A preparation method of a V-based MXene @ PANI flexible film specifically comprises the following steps:
s1: adding 1g of V-base MAX into a reaction kettle containing 1g of sodium fluoride and 25ml of concentrated hydrochloric acid with the concentration of 12mol/L, filling inert gas, stirring and etching for 70-74h at the temperature of 85-95 ℃, centrifugally washing with deionized water until the PH is 5.8-6.2, and carrying out vacuum freeze drying at the temperature of-30-50 ℃ to obtain V-base MXene powder;
s2, dispersing 0.2g of the obtained MXene powder in 30ml of 1mol/LHCl solution, adding 50ul of aniline monomer, filling inert gas, and stirring under ice water to obtain a mixed liquid A;
s3: dispersing 0.2g of Ammonium Persulfate (APS) in 20ml of 1mol/L HCl solution, and stirring under ice water to obtain a mixed liquid B;
and S4, stopping stirring after 5-10 min, slowly adding the mixed liquid B in the step S3 into the mixed liquid A in the step S2 along the wall surface, filling inert gas, and refrigerating and standing for 22-26h at 0 ℃ in a refrigerator to obtain dark green liquid.
S5: and (4) centrifugally washing the dark green liquid obtained in the step (S4) at the rotating speed of 12000r/min by using deionized water, and finally carrying out vacuum freeze drying at the temperature of-30 to-50 ℃ to prepare V-based MXene @ PANI powder.
S6: dispersing 21mg of prepared V-based MXene @ PANI powder and 9mg of single-walled carbon nanotube in 30ml of DMF solution, and introducing inert gas N2And carrying out ultrasonic treatment for 3.5 hours to uniformly disperse the materials.
S7: and (3) filtering the liquid in the S6 into a film on a celgard 2400 diaphragm by suction, and drying for 10-12h at 40-60 ℃ in a vacuum drying oven. And preparing the V-based MXene @ PANI flexible film.
S8: and assembling the button cell by using the prepared V-based MXene @ PANI flexible film as a positive electrode, a zinc sheet as a negative electrode and 1.3mol/L zinc trifluoromethanesulfonate as an aqueous electrolyte, and performing a performance test.
Example 2
A preparation method of a V-based MXene @ PANI flexible film specifically comprises the following steps:
s1: 1g of the V-base MAX is added to a reaction mixture containing 1g of sodium fluoride and 30ml of concentrated 12mol/L hydrochloric acidFilling inert gas N into the kettle2Stirring and etching for 70-74h at 85-95 ℃, centrifugally washing with deionized water until the pH is 5.8-6.2, and carrying out vacuum freeze drying at-30 to-50 ℃ to obtain V-based MXene powder;
s2 dispersing 0.4g of MXene powder in 30ml of 1mol/L HCl solution, adding 100ul of aniline monomer, and introducing inert gas N2Stirring the mixture under ice water to obtain a mixed liquid A;
s3: dispersing 0.4g of Ammonium Persulfate (APS) in 20ml of 1mol/L HCl solution, and stirring under ice water to obtain a mixed liquid B;
s4, stopping stirring after 5-10 min, slowly adding the mixed liquid B in the step S3 into the mixed liquid A in the step S2 along the wall surface, and filling inert gas N2And then, refrigerating and standing for 22-26h at 0 ℃ in a refrigerator to obtain the dark green liquid.
S5: and (4) centrifugally washing the dark green liquid obtained in the step (S4) with deionized water at the rotating speed of 14000r/min, and finally carrying out vacuum freeze drying at the temperature of minus 30-minus 50 ℃ to prepare V-based MXene @ PANI powder.
S6: dispersing the prepared 24mg of V-based MXene @ PANI powder and 6mg of single-walled carbon nanotube into 30ml of DMF solution according to the mass ratio of 8:2, and introducing inert gas N2And carrying out ultrasonic treatment for 4h to uniformly disperse the mixture.
S7: and (3) filtering the liquid in the S6 into a film on a celgard 2400 diaphragm by suction, and drying for 10-12h at 40-60 ℃ in a vacuum drying oven. And preparing the V-based MXene @ PANI flexible film.
S8: and assembling the button cell by using the prepared V-based MXene @ PANI flexible film as a positive electrode, a zinc sheet as a negative electrode and 1.5mol/L zinc trifluoromethanesulfonate as an aqueous electrolyte, and performing a performance test.
Example 3
A preparation method of a V-based MXene @ PANI flexible film specifically comprises the following steps:
s1: adding 2g of V-base MAX into a reaction kettle containing 2g of sodium fluoride and 35ml of concentrated hydrochloric acid with the concentration of 12mol/L, and filling inert gas N2Stirring and etching at 85-95 ℃ for 70-74h, centrifugally washing with deionized water until the pH is 5.8-6.2, and vacuum freezing at-30 to-50 DEG CDrying to obtain V-based MXene powder;
s2 dispersing 0.6g of MXene powder in 30ml of 1mol/L HCl solution, adding 150ul of aniline monomer, and introducing inert gas N2Stirring the mixture under ice water to obtain a mixed liquid A;
s3: dispersing 0.6g of Ammonium Persulfate (APS) in 20ml of 1mol/L HCl solution, and stirring under ice water to obtain a mixed liquid B;
s4, stopping stirring after 5-10 min, slowly adding the mixed liquid B in the step S3 into the mixed liquid A in the step S2 along the wall surface, and filling inert gas N2And then, refrigerating and standing for 22-26h at 0 ℃ in a refrigerator to obtain the dark green liquid.
S5: and (4) centrifugally washing the dark green liquid obtained in the step (S4) at the rotating speed of 13000r/min by using deionized water, and finally carrying out vacuum freeze drying at the temperature of minus 30-minus 50 ℃ to prepare V-based MXene @ PANI powder.
S6: dispersing the prepared 21mg of V-based MXene @ PANI powder and 9mg of single-walled carbon nanotubes in 30ml of DMF solution according to the mass ratio of 7:3, and introducing inert gas N2And carrying out ultrasonic treatment for 4h to uniformly disperse the mixture.
S7: and (3) filtering the liquid in the S6 into a film on a celgard 2400 diaphragm by suction, and drying for 10-12h at 40-60 ℃ in a vacuum drying oven. And preparing the V-based MXene @ PANI flexible film.
S8: and assembling the button cell by using the prepared V-based MXene @ PANI flexible film as a positive electrode, a zinc sheet as a negative electrode and 2mol/L zinc trifluoromethanesulfonate as a water system electrolyte, and performing performance test.
Comparative example 1
A preparation method of a V-based MXene @ PANI flexible film specifically comprises the following steps:
s1: adding 1g of V-base MAX into a polytetrafluoroethylene reaction kettle containing 1g of sodium fluoride and 30ml of 12mol/L concentrated hydrochloric acid, etching for 70-74h at 85-95 ℃, centrifuging and washing by using deionized water until the PH is 5.8-6.2, and carrying out vacuum freeze drying at-47 ℃ to obtain V-base MXene;
s2, dispersing 0.4g of V-based MXene powder in 20-30ml of 1mol/L HCl solution, adding 100ul of aniline monomer, and charging N2Stirring under gas and ice waterObtaining mixed liquid A; specifically, polymerization of aniline monomer at low temperature is ensured;
s3: dispersing 0.4g of ammonium persulfate in 20-30ml of 1mol/L HCl solution, and stirring under ice water to obtain a mixed liquid B;
and S4, slowly adding the mixed liquid B in the step S3 into the mixed liquid A in the step S2 under the stirring state at the temperature of 0-5 ℃, filling inert gas, and continuously stirring for 22-26h to obtain dark green liquid.
S5: and (4) centrifugally washing the dark green liquid obtained in the step (S4) with deionized water at a high rotation speed of 13000r/min, and finally performing vacuum drying and freeze drying at-47 ℃ to prepare V-based MXene @ PANI powder.
S6: dispersing the prepared 21 mgV-based MXene @ PANI powder and 9mg of single-walled carbon nanotubes in 30ml of DMF solution according to the mass ratio of 7:3, introducing inert gas N2, and performing ultrasonic treatment for 4 hours to uniformly disperse the powder.
S7: and (3) filtering the liquid in the S6 into a film on a celgard 2400 diaphragm by suction, and drying for 10-12h at 40-60 ℃ in a vacuum drying oven. And preparing the V-based MXene @ PANI flexible film.
S8: and assembling the button cell by using the prepared V-based MXene @ PANI flexible film as a positive electrode, a zinc sheet as a negative electrode and 2mol/L zinc trifluoromethanesulfonate as a water system electrolyte, and performing performance test.
As shown in FIGS. 2-4, V-based MXene @ PANI materials successfully prepared by the invention with gradually changed morphology.
As shown in fig. 1, fig. 2, fig. 6 and fig. 7, it can be seen from examples 1 to 3 and comparative example 1 that a conventional method for polymerizing polyaniline by low-temperature stirring is changed, and a method of refrigerating and standing is adopted, so that a composite material with a special morphology is generated, polyaniline stacks grow attached to MXene, and thus a layered structure of V-based MXene is stabilized, and stacking of the layered structure is prevented, so that ion insertion/extraction in a battery is influenced. In addition, a part of polyaniline is polymerized in the interlayer of V-based MXene, so that the interlayer spacing is enlarged to a certain extent, and ion diffusion is facilitated. As shown in FIG. 5, the 002 face peak of the resulting V-based MXene @ PANI shifted to the left, demonstrating the expansion of the interlayer spacing.
The agglomeration of MXene with a two-dimensional lamellar structure can be effectively inhibited by using the single-walled carbon nanotube, and the problem of low utilization rate of the active material caused by the agglomeration is solved.
As shown in FIG. 8, the V-based MXene @ PANI flexible film obtained by folding has the advantage that the V-based MXene @ PANI material has good flexibility.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and it should be understood by those skilled in the art that various modifications or changes can be made by those skilled in the art without inventive efforts based on the technical solutions of the present invention.
Claims (7)
1. A preparation method of a V-based MXene @ PANI flexible film is characterized by comprising the following steps: the method specifically comprises the following steps:
s1: adding the V-base MAX into a reaction kettle containing sodium fluoride and concentrated hydrochloric acid for etching, centrifugally washing with deionized water until the PH is 5.8-6.2, and carrying out vacuum freeze drying to obtain V-base MXene;
s2, dispersing 0.1-0.5g MXene powder in 20-30ml of 1mol/L HCl solution, adding 50-150ul aniline monomer, filling inert gas, and stirring under ice water to obtain a mixed liquid A;
s3: dispersing 0.1-0.5g of APS in 20-30ml of 1mol/L HCl solution, and stirring under ice water to obtain a mixed liquid B;
s4, stopping stirring after 30-35min, slowly adding the mixed liquid B in the step S3 into the mixed liquid A in the step S2 along the wall surface, filling inert gas, refrigerating and standing in a refrigerator at 0 ℃ for 22-26h to obtain dark green liquid;
s5: centrifuging and washing the dark green liquid obtained in the step S4 with deionized water at a high rotating speed, and finally performing vacuum drying and freeze drying to prepare V-based MXene @ PANI powder;
s6: dispersing the prepared V-based MXene @ PANI powder and the single-walled carbon nanotube in a DMF solution according to a certain proportion, introducing inert gas, and performing ultrasonic treatment for a period of time to uniformly disperse the powder;
s7: and (3) carrying out suction filtration on the liquid in the S6 to form a film, and drying the film for 10-12h at 40-60 ℃ in a vacuum drying oven. Preparing a V-based MXene @ PANI flexible film;
s8: and assembling the button cell by using the prepared V-based MXene @ PANI flexible film as a positive electrode, a zinc sheet as a negative electrode and zinc trifluoromethanesulfonate as a water system electrolyte, and performing performance test.
2. The method according to claim 1, wherein the reaction vessel in step S1 is a polytetrafluoroethylene reaction vessel.
3. The method according to claim 1, wherein the inert gas is any one of argon and nitrogen.
4. The method of claim 1, wherein the vacuum freeze-drying temperature is from-30 ℃ to-50 ℃.
5. The method of claim 4, wherein the temperature of the vacuum freeze-drying is-47 ℃.
6. The method of claim 1, wherein the ratio of the Vy-base MAX to the sodium fluoride in the step S1 is 1:1 by mass, and the etching condition is etching at 85-95 ℃ for 70-74 h.
7. The V-based MXene @ PANI flexible film is prepared by the preparation method of claim 1, and comprises an MXene two-dimensional layered structure and conductive polymer polyaniline, wherein the V-based MXene @ PANI material PANI stack grows attached to the V-based MXene.
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