CN114709379A - Three-dimensional fold structure Ti3C2Mxene and preparation method and application thereof - Google Patents
Three-dimensional fold structure Ti3C2Mxene and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 44
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 32
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 30
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 9
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal chalcogenides Chemical class 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- 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
-
- 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
Abstract
The application discloses three-dimensional fold structure Ti3C2The Mxene and the preparation method and the application thereof comprise the following steps: (S1) obtaining Ti3C2A dispersion of MXene; (S2) adding a cationic surfactant and Ti3C2Mixing MXene dispersion liquid, and reacting to obtain three-dimensional fold structure Ti3C2Mxene. For 2H-MoS2Poor conductivity, volume change, etc., using 1T-MoS2With a three-dimensional corrugated structure Ti3C2And the Mxene is compounded, so that the stacking and agglomeration of materials are inhibited while the conductivity of the materials is improved.
Description
Technical Field
The application relates to a three-dimensional fold structure Ti3C2Mxene, a preparation method and application thereof, belonging to the field of composite materials.
Background
Lithium ion batteries have been widely used due to their high energy density and power density, but with the rapid development of science and technology, the demand of people for energy has also increased rapidly. Commercial carbon-based negative electrodes are increasingly not meeting the future requirements for high energy density, and therefore, the development and design of a high-cycle negative electrode material for improving the lithium storage capacity of a battery are urgently needed.
In recent years, transition metal chalcogenides have been of interest to researchers because of their high theoretical specific capacities. Molybdenum disulfide (MoS)2) Being a typical transition metal chalcogenide, has a plurality of special physicochemical properties, such as large interlayer spacing, a high-activity surface and abundant edge sites, due to the two-dimensional layered structure. These characteristics may provide extremely high pseudocapacitance and fast reaction kinetics. However, 2H-MoS2Is poor in conductivity, so that 2H-MoS2The rate capability and cycle performance of the electrode material still can not meet the application requirements. And 2H-MoS2In contrast, 1T-MoS2Is a metal phase of octahedral structure with a conductivity ratio of 2H-MoS2Height of about 105And the electronic conduction capability is improved. Furthermore, MoS2The volume change can be caused in the circulation process, and the problems of capacity attenuation and the like are caused.
Disclosure of Invention
For 2H-MoS2Poor conductivity, volume change, etc. we used 1T-MoS2Compounding with a conductive substrate, pretreating the MXene nanosheet to form a three-dimensional folded structure to inhibit the stacking of the MXene nanosheet, and designing the 1T-MoS growing on the MXene with the three-dimensional folded structure2And the electrode is used as a negative electrode of the lithium ion battery.
According to an aspect of the present application, there is provided a three-dimensional corrugated structure Ti3C2The method for preparing the Mxene uses the cationic surfactant, and utilizes the electrostatic self-assembly principle to enable the MXene nanosheets to present a three-dimensional folded structure, so that the MXene nanosheets can be prevented from stacking and agglomerating to a great extent, and the specific surface area of the material is improved.
Three-dimensional fold structure Ti3C2Preparation of MxeneThe method comprises the following steps:
(S1) obtaining Ti3C2A dispersion of MXene;
(S2) adding a cationic surfactant and Ti3C2Mixing MXene dispersion liquid, and reacting to obtain three-dimensional fold structure Ti3C2 Mxene。
Optionally, the cationic surfactant comprises a quaternary ammonium salt type cationic surfactant;
preferably, the quaternary ammonium salt type cationic surfactant is one selected from the group consisting of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide (CTAB), octadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.
Alternatively, the Ti3C2In the dispersion of MXene, Ti3C2The concentration of MXene is 0.5 mg/ml-2.5 mg/ml.
Alternatively, in the step (S2), the solution containing the cationic surfactant is dropped into Ti3C2MXene in dispersion.
Optionally, the concentration of the cationic surfactant in the solution containing the cationic surfactant is 0.5 mg/ml-3.5 mg/ml;
preferably, the concentration of the cationic surfactant is 1mg/ml to 2 mg/ml.
Optionally, a solution containing a cationic surfactant, Ti3C2The volume ratio of the MXene dispersion liquid is (5-7.5): (10-15);
preferably, a solution containing a cationic surfactant, Ti3C2The volume ratio of the MXene dispersion liquid is 6-12.
Alternatively, the reaction conditions are as follows:
temperature: 20-30 ℃;
time: 1-10 min.
Preferably, the reaction is carried out with stirring;
stirring speed: 50rpm to 250 rpm.
Alternatively, Ti3C2The dispersion of MXene was obtained as follows:
mixing a mixed solution containing lithium fluoride and hydrochloric acid with Ti3AlC2Mixing and reacting to obtain the Ti3C2A dispersion of MXene.
Alternatively, the lithium fluoride and the Ti3AlC2The mass ratio is 1-1.
Optionally, the concentration of the hydrochloric acid is 6mol/L to 9 mol/L.
Alternatively, the Ti3AlC2The volume ratio of the powder mass to the hydrochloric acid is 1g (20 ml-25 ml).
Alternatively, the reaction conditions are as follows:
temperature: 30-40 ℃;
time: 22-26 h.
Preferably, the reaction is carried out with stirring;
the stirring speed is 100rpm to 300 rpm.
According to yet another aspect of the present application, there is provided a 1T MoS2The preparation method of @ MXene adopts a one-pot method, and is simple and efficient; composite 1T MoS2The conductivity of the whole material is improved.
1T MoS2The preparation method of @ MXene comprises the following steps:
will contain a three-dimensional wrinkled structure Ti3C2Placing a mixture of Mxene, ammonium tetrathiomolybdate and an organic solvent in a closed container, and reacting to obtain 1T MoS2@ MXene composite;
the three-dimensional fold structure Ti3C2Mxene is selected from three-dimensional folded structure Ti prepared by the preparation method3C2At least one of Mxene.
Optionally, the three-dimensional corrugated structure Ti3C2The mass ratio of Mxene to the ammonium tetrathiomolybdate is 1: (1-5);
preferably, the three-dimensional corrugated structure Ti3C2The mass ratio of Mxene to the ammonium tetrathiomolybdate is 1: (2-3).
Optionally, the volume ratio of the mass of the ammonium tetrathiomolybdate to the organic solvent is (0.1-0.3) g: (10-50) ml.
Optionally, the organic solvent comprises a reducing organic solvent.
Optionally, the reducing organic solvent is selected from one of N, N-dimethylformamide, ethylene glycol, 1, 2-propylene glycol, nitrogen methyl pyrrolidone and dimethylacetamide.
Alternatively, the reaction conditions are as follows:
temperature: 180-220 ℃;
time: 10 to 16 hours.
According to a third aspect of the present application, a three-dimensional corrugated structure Ti is provided3C2 Mxene。
The three-dimensional folded structure Ti obtained by the preparation method of any one of the above3C2 Mxene。
According to a fourth aspect of the present application, there is provided a 1T MoS2@MXene。
1T MoS prepared by the preparation method of any one of the above2@ MXene composite material.
According to a fifth aspect of the present application, there is provided a 1T MoS2Application of @ MXene.
1T MoS prepared by the preparation method of any one of the above2Application of @ MXene in negative electrode of lithium ion battery.
In the present application, "MXene" refers to a two-dimensional material.
CTAB is an abbreviation for cetyltrimethylammonium bromide.
DMF is an abbreviation for N, N-dimethylformamide.
The beneficial effects that this application can produce include:
1) the three-dimensional fold structure Ti provided by the application3C2The preparation method of the Mxene enables the MXene nanosheets to be in a three-dimensional folded structure, inhibits the stacking and agglomeration of the MXene nanosheets, greatly improves the specific surface area of the material, and is beneficial to MoS2Exposing moreAn active site.
2) The three-dimensional fold structure Ti provided by the application3C2The preparation method of the Mxene adopts a one-pot method, and the method is simple and efficient; composite 1T MoS2The conductivity of the material is improved.
3) The three-dimensional fold structure Ti provided by the application3C2The application of the Mxene improves the conductivity of the lithium ion battery cathode, so that the lithium ion battery cathode has excellent rate capability and cycle performance.
Drawings
FIG. 1 is a SEM image of example 1, wherein a and b are SEM images of example 1 at different magnifications.
FIG. 2 is a field emission scanning electron micrograph of comparative example 1, wherein a and b are field emission scanning electron micrographs at different magnifications of comparative example 1.
Fig. 3 is an electrochemical performance diagram of the commercial molybdenum disulfide of example 1, comparative example 1, wherein a is a rate performance diagram, and b is a cycle performance diagram.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were all purchased commercially, wherein:
Ti3AlC2purchased from one technology.
CTAB was purchased from the national pharmaceutical group chemicals ltd.
DMF is available from Chemicals, Inc., national drug group.
Constant current charge and discharge test
The constant-current charge and discharge test is a means for testing the charge and discharge curve, the cycle performance and the rate performance of the battery by setting the voltage value to be a specific interval (the voltage interval of the lithium ion battery is 0.01-3V). The electrochemical performance of the electrode was tested using the novyi cell tester BTS5V 10 mA. And (3) testing conditions are as follows: all tests are currently carried out at room temperature 28 ℃.
Analysis by scanning electron microscope
Scanning Electron Microscopy (SEM) mainly analyzes the morphology, size, and shape of a sample to be measured by means of secondary electron imaging. In the sample preparation process of the test sample, the sample is generally bonded on a conductive adhesive, and then the gold spraying treatment is carried out to improve the conductivity of the material, so that a high-quality SEM picture can be shot. This patent uses a JEM-7600F field emission scanning electron microscope, a Japanese JEOL company, and carries out a gold spraying treatment for 80 to 100 seconds.
Example 1
1g of lithium fluoride and hydrochloric acid solution with the concentration of 6mol/L-9mol/L are stirred and mixed evenly to obtain solution A, and 1g of Ti3AlC2The powder is slowly added to the solution a over a period of more than 10 minutes; slowly stirring for 24 hours at 35 ℃ and at the rotating speed of 200rpm to obtain a solution B; washing the solution B with deionized water until the ph is more than 6, centrifuging for 5 minutes under the condition that the rotating speed is controlled to be 3500rpm for each centrifugal washing, removing the supernatant to obtain a precipitate for one time of washing, repeating the step until the ph value of the supernatant is more than 6 to obtain a lower-layer precipitate after washing, violently shaking the precipitate for 1min by hand before each centrifugation, adding 150ml of deionized water into the precipitate, and uniformly mixing to obtain a solution C; subjecting the solution C to ultrasonic treatment for 60min, centrifuging at 3500rpm for 1h, and collecting the black upper layer solution to obtain Ti3C2MXene dispersion.
10ml of a 2mg/ml aqueous solution of cetyltrimethylammonium bromide was slowly dropped into 20ml of a 1mg/ml aqueous solution of Ti3C2Stirring in MXene dispersion at 200 rpm; then, the mixture was centrifuged and washed at least 3 times at a centrifugal speed of 3500 rpm. Then freeze-drying for 24h to obtain the three-dimensional fold structure Ti3C2 MXene。
0.2g of (NH)4)2MoS4Dissolving in 30ml DMF solution to obtain solution D; 20mg of three-dimensional corrugated structure Ti3C2MXene is added into the solution D and stirred uniformly to obtain a solution E; transferring the solution D into the inner container of a reaction kettle, and reacting for 10 hours at 200 ℃. After the reaction is finished, washing the mixture for more than 5 times by using deionized water, and drying the mixture in vacuum for 12 hours to obtain the three-dimensional 1T MoS2@ MXene composite material, 1T MoS2@MXene-CTAB。
Comparative example 1
1g of lithium fluoride and hydrochloric acid solution with the concentration of 6mol/L-9mol/L are stirred and mixed evenly to obtain solution A, and 1g of Ti3AlC2The powder is slowly added to the solution a over a period of more than 10 minutes; slowly stirring for 24 hours at 35 ℃ and at the rotating speed of 200rpm to obtain a solution B; washing the solution B with deionized water until the ph is more than 6, centrifuging for 5 minutes under the condition that the rotating speed is controlled to be 3500rpm for each centrifugal washing, removing the supernatant to obtain a precipitate for one time of washing, repeating the step until the ph value of the supernatant is more than 6 to obtain a lower-layer precipitate after washing, violently shaking the precipitate for 1min by hand before each centrifugation, adding 150ml of deionized water into the precipitate, and uniformly mixing to obtain a solution C; subjecting the solution C to ultrasonic treatment for 60min, centrifuging at 3500rpm for 1h, and collecting the black upper layer solution to obtain Ti3C2MXene dispersion.
20ml of Ti with the concentration of 1mg/ml3C2MXene dispersion, centrifugal washing at least 3 times, centrifugal speed 3500 rpm. Then freeze-drying for 24h to obtain non-fold structure Ti3C2 MXene。
0.2g of (NH)4)2MoS4Dissolving in 30ml DMF solution to obtain solution D; 20mg of non-corrugated structure Ti3C2MXene is added into the solution D and stirred uniformly to obtain a solution E; transferring the solution D into the inner container of a reaction kettle, and reacting for 10 hours at 200 ℃. After the reaction is finished, washing the mixture for more than 5 times by using deionized water, and performing vacuum drying for 12 hours to obtain the non-fold structure 1T MoS2@ MXene composite material, 1T MoS2@MXene。
Topography characterization
For the 1T MoS prepared in the example2The @ MXene composite was subjected to SEM topography characterization, as typically shown in FIG. 1. FIG. 1 is a three-dimensional 1T MoS prepared in example 12@ MXene composite material, FIG. 2 is non-folded structure 1T MoS prepared in comparative example 12Scanning electron microscope image of @ MXene composite material shows that MoS in example 12Uniformly grown on the three-dimensional folded structure MXene as in comparative example 1MXene stacking due to no CTAB addition, and MoS2Severe agglomeration occurs.
Electrochemical performance test
For the 1T MoS prepared in the example2The @ MXene composite constant current charge and discharge test is typically shown in FIG. 3, wherein a is the graph of example 1(1T MoS)2@ MXene-CTAB), comparative example 1(1T MoS)2@ MXene) and commercial MoS2(MoS2) Comparative rate performance plots, it can be seen from the plots that the rate performance of example 1 is significantly better than that of comparative example 1 and commercial MoS2And the specific capacity is higher. b is a graph of example 1, comparative example 1 and commercial MoS2Comparative cycling performance plots, it can be seen that example 1 has better cycling stability, comparative example 1 and commercial MoS2The cycle stability is poor. The result shows that the addition of the three-dimensional folded MXene induced by CTAB can improve MoS to a certain extent2The electrochemical performance of (2).
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. Three-dimensional fold structure Ti3C2A method for preparing Mxene, which is characterized by comprising the following steps:
(S1) obtaining Ti3C2A dispersion of MXene;
(S2) adding a cationic surfactant and Ti3C2Mixing MXene dispersion liquid, and reacting to obtain three-dimensional fold structure Ti3C2Mxene。
2. The production method according to claim 1, wherein the cationic surfactant comprises a quaternary ammonium salt type cationic surfactant;
preferably, the quaternary ammonium salt type cationic surfactant is selected from one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide (CTAB), octadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, and tetradecyl trimethyl ammonium chloride;
preferably, the Ti3C2In the dispersion of MXene, Ti3C2The concentration of MXene is 0.5 mg/ml-2.5 mg/ml.
3. The production method according to claim 1, wherein, in the step (S2), the solution containing the cationic surfactant is dropped into the Ti3C2MXene in a dispersion;
preferably, the concentration of the cationic surfactant in the solution containing the cationic surfactant is 0.5 mg/ml-3.5 mg/ml;
preferably, the concentration of the cationic surfactant is 1 mg/ml-2 mg/ml;
preferably, a solution containing a cationic surfactant, Ti3C2The volume ratio of the MXene dispersion liquid is (5-7.5): (10-15);
preferably, a solution containing a cationic surfactant, Ti3C2The volume ratio of the MXene dispersion liquid is 6-12.
4. The method according to claim 1, wherein the reaction conditions are as follows:
temperature: 20-30 ℃;
time: 1 min-10 min;
preferably, the reaction is carried out with stirring;
stirring speed: 50rpm to 250 rpm.
5. The method according to claim 1, wherein the Ti is Ti3C2The dispersion of MXene was obtained as follows:
mixing a mixed solution containing lithium fluoride and hydrochloric acid with Ti3AlC2Mixing and reacting to obtain the Ti3C2A dispersion of MXene;
preferably, the lithium fluoride is in contact with the Ti3AlC2The mass ratio is 1-1;
preferably, the concentration of the hydrochloric acid is 6-9 mol/L;
preferably, the Ti3AlC2The volume ratio of the powder mass to the hydrochloric acid is 1g (20 ml-25 ml);
preferably, the reaction conditions are as follows:
temperature: 30-40 ℃;
time: 22h to 26 h;
preferably, the reaction is carried out with stirring;
the stirring speed is 100rpm to 300 rpm.
6. 1T MoS2The preparation method of @ MXene is characterized by comprising the following steps of:
will contain a three-dimensional wrinkled structure Ti3C2Placing a mixture of Mxene, ammonium tetrathiomolybdate and an organic solvent in a closed container, and reacting to obtain 1T MoS2@ MXene composite;
the three-dimensional fold structure Ti3C2Mxene is selected from three-dimensional folded structure Ti prepared by the preparation method of claims 1-53C2At least one of Mxene;
preferably, the three-dimensional corrugated structure Ti3C2The mass ratio of Mxene to the ammonium tetrathiomolybdate is 1: (1-5);
preferably, the three-dimensional corrugated structure Ti3C2The mass ratio of Mxene to the ammonium tetrathiomolybdate is 1: (2-3);
preferably, the volume ratio of the mass of the ammonium tetrathiomolybdate to the organic solvent is (0.1-0.3) g: (10-50) ml;
preferably, the organic solvent comprises a reducing organic solvent;
the reducing organic solvent is selected from one of N, N-Dimethylformamide (DMF), ethylene glycol, 1, 2-propylene glycol, N-methylpyrrolidone and dimethylacetamide.
7. The method according to claim 6, wherein the reaction conditions are as follows:
temperature: 180-220 ℃;
time: 10 to 16 hours.
8. The three-dimensional wrinkled structure Ti obtained by the preparation method of any one of claims 1 to 53C2Mxene。
9. 1T MoS prepared by the preparation method of any one of claims 6 to 72@ MXene composite material.
10. 1T MoS prepared by the preparation method of any one of claims 6 to 72Application of @ MXene in negative electrode of lithium ion battery.
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