CN111285359A - Preparation method of single-layer/few-layer MXene two-dimensional material - Google Patents
Preparation method of single-layer/few-layer MXene two-dimensional material Download PDFInfo
- Publication number
- CN111285359A CN111285359A CN202010037500.8A CN202010037500A CN111285359A CN 111285359 A CN111285359 A CN 111285359A CN 202010037500 A CN202010037500 A CN 202010037500A CN 111285359 A CN111285359 A CN 111285359A
- Authority
- CN
- China
- Prior art keywords
- layer
- aqueous solution
- mxene
- aqueous
- few
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010410 layer Substances 0.000 title claims abstract description 58
- 239000002356 single layer Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 7
- 230000002687 intercalation Effects 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- -1 amine salt Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- 150000003840 hydrochlorides Chemical class 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910004470 Ta4AlC3 Inorganic materials 0.000 claims description 2
- 229910009594 Ti2AlN Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 16
- 239000000725 suspension Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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 relates to a preparation method of a single-layer/few-layer MXene two-dimensional material. Compared with other methods, the method has the remarkable advantages of high efficiency, quickness, environmental friendliness, small risk coefficient, wide application, easiness in realizing batch production and the like, and the prepared single-layer/few-layer MXene two-dimensional material has excellent conductivity, higher volume capacitance, larger specific surface area, more active sites and wide application in the aspects of lithium ion batteries and supercapacitors.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a preparation method of a single-layer/few-layer MXene two-dimensional material.
Background
MXene is a graphene two-dimensional material emerging in recent years. The transition metal carbon/nitride MXene synthesized by Gogotsi team with hydrofluoric acid (HF) in 2011 provides a new research direction for researchers in various fields. MXene generally employs slave Mn+1AXnPhase selective etching A layer for preparation, ternary MAX phase structureCan be described as two-dimensional Mn+1AXnA sublattice of alternating a layers, wherein M is an early transition metal, a is a third or fourth main group element, and X is C or/and N. MAX is a layered structure material, MAX phase has a hexagonal layered structure and is composed of MX layers and A atomic layers which are alternately arranged, M-X is mainly characterized by mixed covalent/metallic bond, and M-A is characterized by metallic bond and weaker bond. Under a specific chemical environment, the A atomic layer can be selectively corroded to form a stable M-X layer, and terminal functional groups such as-OH, -O, -F and the like are adsorbed on the etched surface, so that the formed two-dimensional material is MXene.
MXene is a brand-new two-dimensional material, and due to the intrinsic nano-layered structure, the large specific surface area, the good hydrophilicity, the excellent conductivity and the excellent catalytic activity of the MXene, the MXene has wide application prospects in various fields such as chemical sensing, supercapacitors, photo (electro) catalysts, transparent conductive films, electronic devices, energy sources, flexible high-strength composite materials and the like. In particular, MXene has good electrochemical storage charge performance due to excellent electronic characteristics, and is considered to be one of electrode materials of electrochemical energy storage devices such as super capacitors and lithium ion batteries.
In the prior art, MXene (generally, multiple layers) is prepared by processes such as a chemical etching method, a salt template method, a hydrothermal alkali method and the like, or a chemical vapor deposition method is adopted to directly prepare the small-layer MXene. The electrochemical device based on the design and assembly of the few-layer MXene shows good electrochemical performance, so how to efficiently prepare the single-layer/few-layer MXene becomes a problem to be solved by a plurality of experts. Compared with other preparation methods, the chemical etching method is the most mature, simplest and most easily-obtained preparation technology of the single-layer/few-layer MXene at present, but the method still has great differences from the ultrasonic stripping method provided by the application in yield, danger and preparation difficulty.
Disclosure of Invention
The invention aims to provide a preparation method of a single-layer/few-layer MXene two-dimensional material, which specifically comprises the following steps: firstly, preparing a plurality of layers of MXene and dispersing the MXene in water to obtain a plurality of layers of MXene dispersion liquid; and then sequentially carrying out ultrasonic stripping and centrifugation on the multi-layer MXene dispersion liquid to obtain single-layer/few-layer MXene dispersion liquid, and finally drying.
Further, the preparation method of the multilayer MXene comprises the following specific steps: adding MAX powder into the reaction liquid for etching and modifying, and then carrying out solid-liquid separation. The MAX powder is selected from Ti3AlC2、Cr3AlC2、Ti2SiC、Ti2AlN、Ta4AlC3、Ti3(Al0.5,Si0.5)C2、Ti2Al(C0.5,N0.5)、Zr3Al3C5At least one of; the reaction solution is selected from aqueous HF solution, aqueous HCl/fluoride salt solution, and H2SO4Aqueous fluoride salt solution, NH4HF2At least one of an aqueous solution, an organic alkali aqueous solution and an organic amine salt aqueous solution.
Still further, the aqueous HCl/fluoride salt solution is selected from the group consisting of aqueous HCl/LiF, aqueous HCl/NaF, aqueous HCl/KF, and aqueous HCl/CaF2At least one of aqueous solutions; said H2SO4The aqueous solution of the fluoride salt is selected from H2SO4LiF aqueous solution, H2SO4Aqueous NaF solution, H2SO4Aqueous solution of KF and H2SO4/CaF2At least one of aqueous solutions; the organic alkaline water solution is at least one of tetramethylammonium hydroxide aqueous solution (TMAOH), dimethylformamide aqueous solution (DMF), choline aqueous solution, hydrazine hydrate aqueous solution and urea aqueous solution; the organic amine salt aqueous solution is at least one of an isopropylamine aqueous solution and an n-butylamine aqueous solution.
Further, the prepared multi-layer MXene is mixed with dimethyl sulfoxide (DMSO) for intercalation treatment before ultrasonic stripping, solid-liquid separation and washing are carried out after the intercalation treatment, and then the multi-layer MXene is dispersed in water again to form dispersion liquid.
Further, the temperature of the multi-layer MXene dispersion liquid during ultrasonic stripping does not exceed 20 ℃, because MXene can be oxidized due to high temperature, and the target product cannot be obtained. Preferably, the temperature of the ultrasonic stripping of the dispersion is 0 ℃ created by an ice water bath. The ultrasonic power is 50-1000W during ultrasonic stripping, the ultrasonic time is 5-600min, and the atmosphere during ultrasonic stripping is Ar gas.
Further, the ultrasonic peeling device is at least one of an ultrasonic cleaning machine and a cell crushing ultrasonic machine.
Furthermore, after ultrasonic stripping and before centrifugation, the dispersion liquid needs to be subjected to oscillation treatment for 5-20 min. The oscillation operation has at least two purposes, one is to ensure the precipitate to be completely dissolved, and the other is to further promote MXene stripping by oscillation, so that a single-layer/few-layer MXene two-dimensional material is obtained to the maximum extent.
Further, the centrifugation time is 5-120min, the rotation speed is 1000-.
Further, the drying is vacuum freeze drying, wherein the freeze drying temperature is-50 ℃ to-30 ℃, and the freeze drying duration is 12-100 h.
Another object of the present invention is to provide a single/few layer MXene two-dimensional material prepared according to the above method.
Compared with other methods (such as a chemical etching method), the ultrasonic stripping is relatively simple and quick. Carrying out etching/intercalation treatment on MAX phase powder with a layered structure in a chemical environment, and then carrying out ultrasonic washing to obtain MXene suspension, wherein the MXene suspension mainly contains residual MAX particles which are not completely etched/intercalated and multiple layers of MXene nanosheets, and the multiple layers of MXene nanosheets are delaminated to form single-layer or single-layer/few-layer MXene by virtue of a certain-strength ultrasonic treatment effect; meanwhile, through multiple times of centrifugal washing treatment, multiple layers of MXene and residual MAX particles which are not completely etched/intercalated are deposited at the bottom of a centrifugal tube, and are removed with thicker MXene nanosheets through centrifugation and separation, and a single-layer/few-layer MXene dispersion liquid can be obtained by collecting an upper solution; finally, the single-layer/few-layer MXene dispersion liquid is subjected to vacuum freeze drying, and the single-layer/few-layer MXene two-dimensional material powder with excellent performance is finally prepared.
Compared with the prior art, the beneficial effects of the invention are mainly embodied in the following aspects: 1. the preparation method of the single-layer/few-layer MXene two-dimensional material is based on an ultrasonic stripping technology, mechanical impact and local energy accumulation are provided through ultrasonic, conditions are created for formation of MXene interlayer separation, and therefore preparation of the single-layer/few-layer MXene is achieved; 2. the single-layer/few-layer MXene two-dimensional material prepared by the method has excellent conductivity, high volume capacitance, larger specific surface area and more active sites, is more beneficial to full contact of electrolyte and electrode materials when being applied to a lithium ion battery, and can provide an effective ion transmission channel; 3. the method is efficient, rapid, environment-friendly, low in risk coefficient, wide in application and easy to realize batch production.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention;
FIG. 2 is a scanning electron microscope photograph of a multilayered MXene two-dimensional material prepared in example 1 of the present invention;
fig. 3 is a transmission electron microscope photograph of the single-layer/few-layer MXene two-dimensional material prepared in example 3 of the present invention.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further provided with reference to the specific embodiments and the accompanying drawings.
Example 1
The preparation method of the single-layer/few-layer MXene two-dimensional material shown in FIG. 1 specifically comprises the following steps: first, 1.0g of Ti was taken3AlC2And putting the powder into 40mL of HF aqueous solution with the mass concentration of 40%, and stirring and soaking for 36h at constant temperature. And then, carrying out centrifugal separation, washing the obtained solid with deionized water, putting the washed solid into the reaction kettle again, and adding dimethyl sulfoxide for intercalation treatment. Performing solid-liquid separation after intercalation treatment, repeatedly washing the obtained solid, dispersing in deionized water, introducing argon, maintaining for 30min to remove air as far as possible, and ultrasonically stripping the dispersion liquid in an ice-water bath at a power of 500W for 2h to obtain Ti3C2TxAnd (3) suspension. Manually oscillated Ti3C2TxThe suspension is centrifuged for 10min at 3500rpm and 10 deg.C for 1h to obtain single-layer/few-layer Ti3C2TxAnd (3) dispersing the mixture. A single layer/few layers of Ti3C2TxPlacing the dispersion in a vacuum freeze drying oven, and cooling at-50 deg.CFreeze drying for 48 hr to obtain single layer/few layer Ti3C2TxAnd (3) powder.
Example 2
Taking 1.0g of Ti3AlC2Powder, which was placed in 20mL of NH at a concentration of 2mol/L4HF2Stirring and soaking in the aqueous solution for 36h at constant temperature. Then centrifugally separating, washing the obtained solid, dispersing the washed solid in deionized water, introducing argon into the solution to remove air, transferring the solution into an ice water bath, and ultrasonically stripping the solution for 2 hours at the power of 500W to obtain Ti3C2TxAnd (3) suspension. Manually oscillated Ti3C2TxThe suspension is centrifuged for 10min at 3500rpm and 10 deg.C for 1h to obtain single-layer/few-layer Ti3C2TxAnd (3) dispersing the mixture. A single layer/few layers of Ti3C2TxPlacing the dispersion in a vacuum freeze drying oven, and freeze drying at-50 deg.C for 48 hr to obtain single-layer/few-layer Ti3C2TxAnd (3) powder.
Example 3
Taking 1.0g of Ti3AlC2And putting the powder into 20mL of 9mol/L HCl/LiF aqueous solution, and stirring and soaking for 36h at constant temperature. Then centrifugally separating, washing the obtained solid, dispersing the washed solid in deionized water, introducing argon into the solution to remove air, transferring the solution into an ice water bath, and ultrasonically stripping the solution for 2 hours at the power of 500W to obtain Ti3C2TxAnd (3) suspension. Manually oscillated Ti3C2TxThe suspension is centrifuged for 10min at 3500rpm and 10 deg.C for 1h to obtain single-layer/few-layer Ti3C2TxAnd (3) dispersing the mixture. A single layer/few layers of Ti3C2TxPlacing the dispersion in a vacuum freeze drying oven, and freeze drying at-50 deg.C for 48 hr to obtain single-layer/few-layer Ti3C2TxAnd (3) powder.
In order to fully understand the ultrasonic peeling effect and the micro-morphology of the product, the multi-layer MXene two-dimensional material prepared in example 1 and the single-layer/few-layer two-dimensional material prepared in example 3 were subjected to TEM test, and the results are shown in FIGS. 2-3. As can be seen from FIG. 2, the chemical solution etching produces multiple layers of Ti3C2TxThe microstructure is similar to an accordion shape, and the number of layers is large and the layer spacing is small; and the single-layer/few-layer Ti obtained by ultrasonic stripping in the application3C2TxThe two-dimensional material has the characteristic of few layers and has more active sites.
Claims (10)
1. A preparation method of a single-layer/few-layer MXene two-dimensional material is characterized by comprising the following steps: firstly, preparing a plurality of layers of MXene and dispersing the MXene in water to obtain a plurality of layers of MXene dispersion liquid; and then sequentially carrying out ultrasonic stripping and centrifugation on the multi-layer MXene dispersion liquid to obtain single-layer/few-layer MXene dispersion liquid, and finally drying.
2. The method according to claim 1, wherein the multilayered MXene is prepared by the following method: adding MAX powder into the reaction liquid for etching and modifying, and then carrying out solid-liquid separation; the MAX powder is selected from Ti3AlC2、Cr3AlC2、Ti2SiC、Ti2AlN、Ta4AlC3、Ti3(Al0.5,Si0.5)C2、Ti2Al(C0.5,N0.5)、Zr3Al3C5At least one of; the reaction solution is selected from aqueous HF solution, aqueous HCl/fluoride salt solution, and H2SO4Aqueous fluoride salt solution, NH4HF2At least one of an aqueous solution, an organic alkali aqueous solution and an organic amine salt aqueous solution.
3. The method of claim 2, wherein: the HCl/fluoride salt aqueous solution is selected from the group consisting of HCl/LiF aqueous solution, HCl/NaF aqueous solution, HCl/KF aqueous solution, HCl/CaF aqueous solution2At least one of aqueous solutions; said H2SO4The aqueous solution of the fluoride salt is selected from H2SO4LiF aqueous solution, H2SO4Aqueous NaF solution, H2SO4Aqueous solution of KF and H2SO4/CaF2At least one of aqueous solutions; the organic alkali aqueous solution is selected from tetramethylammonium hydroxide aqueous solutionAt least one of liquid, dimethylformamide aqueous solution, choline aqueous solution, hydrazine hydrate aqueous solution and urea aqueous solution; the organic amine salt aqueous solution is at least one of an isopropylamine aqueous solution and an n-butylamine aqueous solution.
4. The method of claim 1, wherein: the prepared multi-layer MXene is required to be mixed with dimethyl sulfoxide for intercalation treatment before ultrasonic stripping, solid-liquid separation and washing are carried out after the intercalation treatment, and then the multi-layer MXene is dispersed in water again to form dispersion liquid.
5. The method of claim 1, wherein: the temperature of the multilayer MXene dispersion liquid during ultrasonic stripping is not more than 20 ℃, the ultrasonic power is 50-1000W, the ultrasonic time is 5-600min, and the ultrasonic stripping is carried out in a protective atmosphere.
6. The method of claim 5, wherein: the temperature of the multi-layer MXene dispersion liquid during ultrasonic stripping is 0 ℃, and the protective atmosphere is argon.
7. The method of claim 1, wherein: the ultrasonic stripping equipment is at least one of an ultrasonic cleaning machine and a cell crushing ultrasonic machine.
8. The method of claim 1, wherein: after ultrasonic stripping and before centrifugation, the dispersion liquid is required to be subjected to oscillation treatment, and the oscillation time is 5-20 min; the centrifugation time is 5-120min, the rotation speed is 1000-.
9. The method of claim 1, wherein: the drying is vacuum freeze drying, wherein the freeze drying temperature is-50 ℃ to-30 ℃, and the freeze drying duration is 12-100 h.
10. A single-layer/few-layer MXene two-dimensional material is characterized in that: the material is prepared according to the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010037500.8A CN111285359A (en) | 2020-01-14 | 2020-01-14 | Preparation method of single-layer/few-layer MXene two-dimensional material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010037500.8A CN111285359A (en) | 2020-01-14 | 2020-01-14 | Preparation method of single-layer/few-layer MXene two-dimensional material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111285359A true CN111285359A (en) | 2020-06-16 |
Family
ID=71026640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010037500.8A Pending CN111285359A (en) | 2020-01-14 | 2020-01-14 | Preparation method of single-layer/few-layer MXene two-dimensional material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111285359A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905785A (en) * | 2020-08-25 | 2020-11-10 | 浙江工业大学 | Single-layer MXeneTi3C2Pt-loaded catalyst and preparation method and application thereof |
| CN112007675A (en) * | 2020-08-25 | 2020-12-01 | 浙江工业大学 | Catalyst Pd/Nb2C and preparation method and application thereof |
| CN112103504A (en) * | 2020-09-22 | 2020-12-18 | 广东工业大学 | Ternary material loaded few-layer/rod-shaped MXene composite material and preparation method thereof |
| CN112121834A (en) * | 2020-09-30 | 2020-12-25 | 湖北大学 | MXene/CdS composite photocatalyst, preparation method thereof and application thereof in hydrogen production by water cracking |
| CN112142101A (en) * | 2020-09-30 | 2020-12-29 | 湖北大学 | Preparation method of single-layer two-dimensional nano material MXene |
| CN112194134A (en) * | 2020-10-19 | 2021-01-08 | 江西理工大学 | Preparation of few-layer Ti with high etching rate and high stripping rate based on secondary etching method3C2TxMethod of producing a material |
| CN112563515A (en) * | 2020-12-11 | 2021-03-26 | 苏州大学张家港工业技术研究院 | Iron-nitrogen co-doped carbon and MXene compound and preparation method and application thereof |
| CN112624115A (en) * | 2021-01-14 | 2021-04-09 | 山东大学 | Ti for lubricant2CTxNanosheet and preparation method and application thereof |
| CN112695461A (en) * | 2020-12-14 | 2021-04-23 | 杭州肄康新材料有限公司 | Preparation method of MXene material diaphragm applied to lithium ion battery |
| CN112973653A (en) * | 2021-02-23 | 2021-06-18 | 浙江理工大学 | Preparation method of Mxene membrane adsorbing material based on polyamidoxime and uranium extraction method |
| CN113060709A (en) * | 2021-03-26 | 2021-07-02 | 中国科学技术大学 | Ti2Preparation method of N MXene nano material and method for applying N MXene nano material to negative electrode of lithium ion battery |
| CN113451590A (en) * | 2021-06-29 | 2021-09-28 | 合肥工业大学 | Preparation method of MXene-based catalyst with ion/electron double transmission |
| CN113462014A (en) * | 2021-06-23 | 2021-10-01 | 南通大学 | Super-hydrophobic sponge with photo-thermal effect and preparation method thereof |
| CN113603970A (en) * | 2021-08-26 | 2021-11-05 | 浙江理工大学 | Synergistic flame-retardant polypropylene composite material and preparation method thereof |
| CN114094279A (en) * | 2021-11-02 | 2022-02-25 | 惠州锂威新能源科技有限公司 | Composite diaphragm and preparation method thereof |
| CN114195151A (en) * | 2021-12-13 | 2022-03-18 | 河北科技大学 | Preparation method of single-layer MXene material |
| CN114220669A (en) * | 2021-11-19 | 2022-03-22 | 常州大学 | MXene porous nanosheet and thermal shock preparation method and application thereof |
| CN114388760A (en) * | 2022-01-14 | 2022-04-22 | 北京化工大学 | Metal oxide nanosheet material, preparation method thereof and lithium ion battery |
| CN114436261A (en) * | 2022-03-07 | 2022-05-06 | 安徽大学 | Two-dimensional Ti3C2TxSelf-crimping fiber of material, preparation method and application thereof |
| CN114507383A (en) * | 2022-03-23 | 2022-05-17 | 陕西科技大学 | Preparation method of esterified cellulose loaded MXene high-toughness film |
| CN114854030A (en) * | 2022-02-11 | 2022-08-05 | 上海应用技术大学 | Preparation method of single-layer MXene nanosheet/ZIF-67 composite material |
| CN114853019A (en) * | 2022-04-27 | 2022-08-05 | 中国石油大学(北京) | Hydrogen sulfide gas-sensitive nano composite material and preparation method and application thereof |
| CN116425160A (en) * | 2023-04-21 | 2023-07-14 | 四川金时新能科技有限公司 | Nb (Nb) alloy 4 C 3 T x MXene material and rapid preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106571244A (en) * | 2016-11-02 | 2017-04-19 | 南京工业大学 | Two-dimensional transition metal carbon (nitrogen) compound and two-dimensional transition metal sulfide nano-composite powder, and preparation and application thereof |
| CN107098344A (en) * | 2017-04-28 | 2017-08-29 | 武汉理工大学 | A kind of preparation method of two-dimensional layer MXene materials |
| CN108584959A (en) * | 2018-05-04 | 2018-09-28 | 浙江大学 | A kind of preparation method for being layered two-dimentional transition metal carbide or the carbonization Tritanium/Trititanium of carbonitride-two improving antibiotic property |
| CN109850899A (en) * | 2019-01-22 | 2019-06-07 | 河海大学 | A kind of two dimensional crystal Nb2CTxThe preparation method of nano material |
| CN110534741A (en) * | 2019-09-06 | 2019-12-03 | 浙江大学 | A kind of fast preparation method and application of few layer MXenes |
-
2020
- 2020-01-14 CN CN202010037500.8A patent/CN111285359A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106571244A (en) * | 2016-11-02 | 2017-04-19 | 南京工业大学 | Two-dimensional transition metal carbon (nitrogen) compound and two-dimensional transition metal sulfide nano-composite powder, and preparation and application thereof |
| CN107098344A (en) * | 2017-04-28 | 2017-08-29 | 武汉理工大学 | A kind of preparation method of two-dimensional layer MXene materials |
| CN108584959A (en) * | 2018-05-04 | 2018-09-28 | 浙江大学 | A kind of preparation method for being layered two-dimentional transition metal carbide or the carbonization Tritanium/Trititanium of carbonitride-two improving antibiotic property |
| CN109850899A (en) * | 2019-01-22 | 2019-06-07 | 河海大学 | A kind of two dimensional crystal Nb2CTxThe preparation method of nano material |
| CN110534741A (en) * | 2019-09-06 | 2019-12-03 | 浙江大学 | A kind of fast preparation method and application of few layer MXenes |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007675A (en) * | 2020-08-25 | 2020-12-01 | 浙江工业大学 | Catalyst Pd/Nb2C and preparation method and application thereof |
| CN111905785A (en) * | 2020-08-25 | 2020-11-10 | 浙江工业大学 | Single-layer MXeneTi3C2Pt-loaded catalyst and preparation method and application thereof |
| CN111905785B (en) * | 2020-08-25 | 2023-02-28 | 浙江工业大学 | Single-layer MXeneTi 3 C 2 Pt-loaded catalyst and preparation method and application thereof |
| CN112103504A (en) * | 2020-09-22 | 2020-12-18 | 广东工业大学 | Ternary material loaded few-layer/rod-shaped MXene composite material and preparation method thereof |
| CN112121834A (en) * | 2020-09-30 | 2020-12-25 | 湖北大学 | MXene/CdS composite photocatalyst, preparation method thereof and application thereof in hydrogen production by water cracking |
| CN112142101A (en) * | 2020-09-30 | 2020-12-29 | 湖北大学 | Preparation method of single-layer two-dimensional nano material MXene |
| CN112121834B (en) * | 2020-09-30 | 2023-03-10 | 湖北大学 | MXene/CdS composite photocatalyst, preparation method thereof and application thereof in hydrogen production by water cracking |
| CN112194134A (en) * | 2020-10-19 | 2021-01-08 | 江西理工大学 | Preparation of few-layer Ti with high etching rate and high stripping rate based on secondary etching method3C2TxMethod of producing a material |
| CN112563515A (en) * | 2020-12-11 | 2021-03-26 | 苏州大学张家港工业技术研究院 | Iron-nitrogen co-doped carbon and MXene compound and preparation method and application thereof |
| CN112695461B (en) * | 2020-12-14 | 2021-11-23 | 深圳市元鼎智能创新有限公司 | Preparation method of MXene material diaphragm applied to lithium ion battery |
| CN112695461A (en) * | 2020-12-14 | 2021-04-23 | 杭州肄康新材料有限公司 | Preparation method of MXene material diaphragm applied to lithium ion battery |
| CN112624115A (en) * | 2021-01-14 | 2021-04-09 | 山东大学 | Ti for lubricant2CTxNanosheet and preparation method and application thereof |
| CN112973653A (en) * | 2021-02-23 | 2021-06-18 | 浙江理工大学 | Preparation method of Mxene membrane adsorbing material based on polyamidoxime and uranium extraction method |
| CN112973653B (en) * | 2021-02-23 | 2022-07-19 | 浙江理工大学 | Preparation method of Mxene membrane adsorbing material based on polyamidoxime and uranium extraction method |
| CN113060709A (en) * | 2021-03-26 | 2021-07-02 | 中国科学技术大学 | Ti2Preparation method of N MXene nano material and method for applying N MXene nano material to negative electrode of lithium ion battery |
| CN113462014A (en) * | 2021-06-23 | 2021-10-01 | 南通大学 | Super-hydrophobic sponge with photo-thermal effect and preparation method thereof |
| CN113451590A (en) * | 2021-06-29 | 2021-09-28 | 合肥工业大学 | Preparation method of MXene-based catalyst with ion/electron double transmission |
| CN113451590B (en) * | 2021-06-29 | 2023-03-17 | 合肥工业大学 | Preparation method of MXene-based catalyst with ion/electron double transmission |
| CN113603970A (en) * | 2021-08-26 | 2021-11-05 | 浙江理工大学 | Synergistic flame-retardant polypropylene composite material and preparation method thereof |
| CN114094279A (en) * | 2021-11-02 | 2022-02-25 | 惠州锂威新能源科技有限公司 | Composite diaphragm and preparation method thereof |
| CN114220669A (en) * | 2021-11-19 | 2022-03-22 | 常州大学 | MXene porous nanosheet and thermal shock preparation method and application thereof |
| CN114220669B (en) * | 2021-11-19 | 2023-07-25 | 常州大学 | MXene porous nano-sheet and thermal shock preparation method and application thereof |
| CN114195151A (en) * | 2021-12-13 | 2022-03-18 | 河北科技大学 | Preparation method of single-layer MXene material |
| CN114388760A (en) * | 2022-01-14 | 2022-04-22 | 北京化工大学 | Metal oxide nanosheet material, preparation method thereof and lithium ion battery |
| CN114854030A (en) * | 2022-02-11 | 2022-08-05 | 上海应用技术大学 | Preparation method of single-layer MXene nanosheet/ZIF-67 composite material |
| CN114436261A (en) * | 2022-03-07 | 2022-05-06 | 安徽大学 | Two-dimensional Ti3C2TxSelf-crimping fiber of material, preparation method and application thereof |
| CN114507383A (en) * | 2022-03-23 | 2022-05-17 | 陕西科技大学 | Preparation method of esterified cellulose loaded MXene high-toughness film |
| CN114507383B (en) * | 2022-03-23 | 2023-12-15 | 广州旭璟科技有限公司 | Preparation method of esterified cellulose loaded MXene high-toughness film |
| CN114853019A (en) * | 2022-04-27 | 2022-08-05 | 中国石油大学(北京) | Hydrogen sulfide gas-sensitive nano composite material and preparation method and application thereof |
| CN116425160A (en) * | 2023-04-21 | 2023-07-14 | 四川金时新能科技有限公司 | Nb (Nb) alloy 4 C 3 T x MXene material and rapid preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111285359A (en) | Preparation method of single-layer/few-layer MXene two-dimensional material | |
| Wei et al. | Recent advances of emerging 2D MXene for stable and dendrite‐free metal anodes | |
| CN110690420B (en) | Composite material cathode, battery and preparation method thereof | |
| CN109167066A (en) | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material | |
| JP6599106B2 (en) | Negative electrode material for lithium secondary battery and method for producing the same, composition for negative electrode active material layer for lithium secondary battery using the negative electrode material, negative electrode for lithium secondary battery, and lithium secondary battery | |
| CN106941167B (en) | Porous composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN112072126A (en) | Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof | |
| TWI443901B (en) | Method for making anode of lithium ion battery | |
| KR101778652B1 (en) | Negative active material having expanded graphite for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof | |
| CN105060289A (en) | Method for preparing fewer-layer graphene on basis of biomass waste | |
| CN113346054B (en) | Preparation method and application of MXene-carbon nanocage-sulfur composite material | |
| Wang | A review on MXene: synthesis, properties and applications on alkali metal ion batteries | |
| CN103579631A (en) | Preparation method for copper foil current collector and application | |
| CN112447977A (en) | Si/C nanowire manufacturing method and Si/C nanowire lithium ion battery electrode manufacturing method | |
| CN109755515B (en) | Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof | |
| CN112142101A (en) | Preparation method of single-layer two-dimensional nano material MXene | |
| CN111573676B (en) | Preparation method of one-dimensional titanium carbide nano roll | |
| CN102916178A (en) | Preparation method of carbon cladding modified lithium manganate anode material | |
| CN110534710B (en) | Silicon/carbon composite material and preparation method and application thereof | |
| CN105826528B (en) | A kind of porous silicon-carbon/carbon-copper composite material and its preparation method and application | |
| CN114335458B (en) | Ti3C2Tx@g-C3N4 composite material and preparation method and application thereof | |
| CN106571444A (en) | Method for manufacturing negative electrode plate of secondary battery | |
| CN115832294A (en) | Method for preparing biomass-based hard carbon composite negative electrode through magnetron sputtering | |
| KR20210154797A (en) | Current collector comprising graphene layer and lithium ion battery and supercapacitor containing the electron collector | |
| CN115477303A (en) | Method for preparing thin-layer dispersed two-dimensional MXenes material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200616 |
|
| RJ01 | Rejection of invention patent application after publication |