CN115744906A - In-plane ordered multicomponent MAX phase material and MXene material, and preparation method and application thereof - Google Patents
In-plane ordered multicomponent MAX phase material and MXene material, and preparation method and application thereof Download PDFInfo
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- 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
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses an in-plane ordered multicomponent MAX phase material and MXene material, and a preparation method and application thereof, wherein the chemical formula of the multicomponent MAX phase material is expressed as (M) x 'M” y ) n+1 AX n Wherein n is from 1 to 6,x + y =1,M' and M "are ordered in at least one crystallographic plane; the sum of the element types of M 'and M' is at least three; wherein M 'is selected from at least one or two elements in IVB, VB, VIB, VIIB, VIII, IB and IIB groups, and M' is selected from at least one or two elements in IIIB, zirconium, lanthanide and actinide groups. The component A in the MAX phase material is etched to obtain the in-plane ordered multi-component MXene material, which belongs to a novel super surface due to the ordered structure and the multi-component atomic composition; atoms in the in-plane ordered multicomponent MXene material are further selectively etched to obtain ordered vacancy or multi-vacancy MXene material, and the material also belongs to a novel super surface. Has application prospect in the fields of anticorrosive coatings, high-temperature coatings, nuclear radiation protection, catalysis and the like.
Description
Technical Field
The invention relates to the field of new materials, in particular to a multi-component MAX phase material and MXene material and a preparation method thereof.
Background
Meta-materials refer to artificial composite structures or composite materials having meta-material properties that natural materials do not have, and the design idea is that an artificial structure having a specific function is used as a basic crystal, and ordered structures at atomic level are arranged in order at other levels. The metamaterial shows macroscopic physical characteristics such as electromagnetism, light, sound and the like which are not possessed by the traditional material, particularly certain breakthroughs are realized by precisely designing the geometric shape, the size and the arrangement mode of a microstructure unit, and subversive changes in multiple fields such as communication, stealth, imaging detection and information processing are caused. For example, the information metamaterial can rapidly regulate and control electromagnetic waves, including amplitude regulation, polarization regulation, phase regulation and the like; in addition, various convolution operations can be performed through the information metamaterial, a brand-new framework is provided for communication, the bottleneck of AD/DA is hopefully broken through, a very simple high-speed communication system is realized, and different high-speed modulation communication is realized through space coding, time coding and frequency domain coding; in the field of radar, a brand-new architecture can be provided for radar imaging, the bottleneck that the existing radar imaging system is high in complexity is expected to be broken through, and an extremely simple high-resolution radar imaging system is realized.
The super surface belongs to a two-dimensional metamaterial, and can realize the regulation and control of incident light on a very thin layer of sub-wavelength structure. Compared with a three-dimensional body metamaterial, the existing super surface can be prepared by the technologies of electron beam exposure, focused ion beam etching, laser direct writing, self-assembly, nano imprinting and the like; meanwhile, the ultra-light and ultra-thin integrated type micro-scale light-emitting diode is easy to integrate in micro equipment due to the characteristics of ultra-light and ultra-thin, and the weight and the volume of the equipment are reduced. The super-surface can be used for realizing wave front control (beam deflection, focusing, holography) and polarization conversion and other applications due to excellent phase, amplitude and polarization control capability, and a multifunctional super-surface integrating multiple functions can be realized by a phase staggered arrangement or polarization multiplexing method.
The size of a microstructure of a super surface manufactured by the existing processing technology is in a micron scale, the miniaturization and high frequency of a device are the main directions of the development of the super surface, particularly the size of the microstructure needs to be reduced to be below a nanometer scale by the optical frequency super surface, and the existing processing technology is difficult to realize, so that a plurality of supernormal optical or electromagnetic properties cannot be realized.
Disclosure of Invention
The invention aims to provide a novel in-plane ordered multi-component MAX phase material, which is used as a raw material to obtain an in-plane ordered MXene material, and the MXene material with ordered vacancies or multi-vacancies is obtained by selectively etching atoms in the in-plane ordered MXene material, so that a new technical path is provided for realizing the preparation of a super surface by atomic-level microstructure regulation.
In one aspect, the invention provides an in-plane ordered multicomponent MAX phase material having a chemical formula represented by (M) x 'M” y ) n+ 1 AX n (ii) a Wherein n is between 1 and 6,x+y=1; m 'and M' are arranged in an ordered manner in at least one crystal plane; the sum of the element types of M 'and M' is more than three; m 'is selected from one or more elements in IVB, VB, VIB, VIIB, VIII, IB and IIB, and M' is selected from at least one or more elements in IIIB, zirconium, lanthanide and actinideAnd (4) elements.
In some embodiments, M' is selected from one or more elements of groups IVB, VB, VIB, and VIIB; preferably, M' is selected from one or more elements of titanium, vanadium, chromium, manganese, niobium, molybdenum, technetium, hafnium, tantalum, tungsten or rhenium; and/or, the M' is one or more elements selected from scandium, yttrium, zirconium, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium or ytterbium; and/or A is at least one selected from aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium or lead; and/or, the X is at least one of carbon, nitrogen or boron.
In some embodiments, in the crystal plane perpendicular to the [010] crystal axis and the (001) crystal plane, atoms of M' and M ″ are arranged in a period of 2; and/or, in the multicomponent MAX phase material, the atoms of each element of M 'are randomly distributed at the M' position, and the atoms of each element of M 'are randomly distributed at the M' position.
The invention also comprises a preparation method of the multi-component MAX phase material, which comprises the following steps: 1) Mixing solid powder containing an M 'phase, an M' phase, an A phase and an X phase according to the stoichiometric ratio of a chemical formula, and carrying out ball milling treatment to obtain a mixture; 2) Carrying out heat treatment on the mixture obtained in the step 1) in inert gas shielding gas to obtain a multi-component MAX phase material; preferably, the heat treatment temperature is between 800 ℃ and 3200 ℃.
Still another aspect of the present invention includes a multicomponent MXene material etched from the above multicomponent MAX phase material.
The invention also provides a preparation method of the multi-component MXene material, which comprises the following steps: etching A in the multi-component MAX phase material to obtain the multi-component MXene material, wherein the chemical formula of the multi-component MXene material is (M' x M” y ) n+1 X n (ii) a Or mixing A and all or part of M 'in the multicomponent MAX phase material to obtain the multicomponent MXene material, wherein the chemical formula of the multicomponent MXene material is (M' x M” β ) n+1 X n Wherein beta is more than or equal to 0 and less than y; or, the multicomponent MXene material is obtained by mixing A, all or part of M 'and all or part of M' in the multicomponent MAX phase material, and the obtained multicomponent MXene material has chemical formulaFormula (II) is (M' α M” β ) n+1 X n Wherein alpha is more than or equal to 0 and less than x, and beta is more than or equal to 0 and less than y.
In some embodiments, the etchant used for etching is selected from the group consisting of: one or more of halogen elementary gas, hydrogen halide gas, metal halide salt or ammonium salt of halogen element; or, the etching agent is: hydrofluoric acid or acid solution + fluoride salt system.
The invention also provides application of the multi-component MAX phase material in the fields of anticorrosive coatings, high-temperature coatings, nuclear radiation protection or electric brushes.
The invention also provides application of the multi-component MXene material in an anticorrosive coating, a high-temperature coating, nuclear radiation protection, catalysis, a sensor, an electronic device, a super capacitor, a battery, electromagnetic shielding, a wave-absorbing material or a superconducting material.
The invention also provides a coating material which contains the multi-component MAX phase material and/or the multi-component MXene material.
The invention also provides an electronic device comprising the above multicomponent MAX phase material and/or the above multicomponent MXene material.
The invention also provides an energy storage device which is characterized by comprising the multi-component MAX phase material and/or the multi-component MXene material.
The invention has the beneficial effects that:
the invention provides a novel in-plane ordered multi-component MAX phase material and MXene material and a preparation method thereof, wherein the in-plane ordered multi-component MXene material (two-dimensional material) is obtained by etching a component A in the in-plane ordered multi-component MAX phase material, wherein the component M contains at least three elements, and the material belongs to a novel super surface due to the ordered structure and the multi-component atomic components; atoms in the multi-component MXene material with ordered vacancies in the surface are further selectively etched, so that the MXene material or the multi-vacancy MXene material with ordered vacancies can be obtained, the novel super-surface material also belongs to a class of novel super-surface materials, more single atoms can be exposed due to the existence of abundant vacancies and atoms of multiple components, the novel performance can be endowed to the class of materials, the macroscopic physical characteristics of electromagnetism, light, sound and the like which are not possessed by the traditional materials are presented, the novel super-surface material has application prospects in anticorrosion coatings, high-temperature coatings, nuclear radiation protection, catalysis, sensors, electronic devices, super capacitors, batteries, electromagnetic shielding, wave-absorbing materials or superconducting materials, and subversive changes in multiple fields of communication, stealth, imaging detection, information processing and the like are possibly caused.
Drawings
FIGS. 1 and 2 are views of a multicomponent MAX phase material (M) in example 1 of the present invention x 'M” y ) 2 AX n And MXene materials (M) x 'M” y ) 2 X n Schematic structural diagram of (a);
FIGS. 3 to 5 are Mo, which are multi-component MAX phase materials in example 2 of the present invention 1.33 (Sc n Y 1-n ) 0.67 AlC and multi-component MXene material Mo 1.33 (Sc n Y 1-n ) 0.67 C and ordered vacancy MXene material Mo 1.33 C, a structural schematic diagram;
FIGS. 6 to 8 are views of the multi-component MAX phase materials (Mo) in example 3 of the present invention m W 1-m ) 1.33 (Sc n Y 1-n ) 0.67 AlC, multicomponent MXene material (Mo) m W 1-m ) 1.33 (Sc n Y 1-n ) 0.67 C and ordered vacancy MXene materials (Mo) m W 1-m ) 1.33 C is a structural schematic diagram;
FIGS. 9 to 11 are views of the multi-component MAX phase materials (Mo) in example 4 of the present invention m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 AlC, multicomponent MXene material (Mo) m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 C and ordered vacancy MXene materials (Mo) m W p Cr 1-m-p ) 1.33 C is a structural schematic diagram;
FIG. 12 shows a multicomponent MAX phase material (Mo) in example 5 of the present invention 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 SEM image of AlC;
FIG. 13 shows a multicomponent MAX phase material (Mo) in example 5 of the present invention 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 AlC and ordered MAX phase materials (Mo) 0.67 Y 0.34 ) 2 XRD pattern of AlC;
FIGS. 14 and 15 show (Mo) in example 5 of the present invention 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 STEM graph of AlC and EDS result of corresponding position;
FIG. 16 is a high-resolution TEM image of a spherical aberration electron microscope with the multicomponent MAX phase material perpendicular to the [010] crystal axis crystal plane in example 5;
FIGS. 17 and 18 show MXene materials (Mo) etched in example 6 of the present invention 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 SEM picture of C;
FIGS. 19 to 21 are diagrams illustrating the multicomponent ordered vacancy MXene materials (Mo) obtained by etching in example 7 of the present invention 0.221 W 0.221 Cr 0.221 ) 2 CT x SEM, TEM and high resolution TEM images of;
FIG. 22 shows a multi-component MAX phase material (Mo) in example 8 of the present invention 0.221 W 0.221 V 0.221 Y 0.17 Sc 0.17 ) 2 The structural schematic diagram of AlC;
FIG. 23 shows a multicomponent MAX phase material (Mo) in example 9 of the present invention 0.16 W 0.16 Cr 0.16 V 0.16 Y 0.17 Sc 0.17 ) 2 The structural schematic diagram of AlC;
FIG. 24 shows the multicomponent MAX phase material (Mo) in example 12 of this invention 0.16 W 0.16 Cr 0.16 V 0.16 Y 0.34 ) 2 A schematic structural diagram of AlC;
FIG. 25 shows the multicomponent MAX phase material (Mo) in example 13 of this invention 0.16 W 0.16 Cr 0.16 V 0.16 Sc 0.34 ) 2 And the structure schematic diagram of AlC.
Detailed Description
The technical solution of the present invention is explained below by specific embodiments with reference to the accompanying drawings. It is to be understood that one or more of the steps mentioned in the present invention does not exclude the presence of other methods or steps before or after the combined steps, or that other methods or steps may be inserted between the explicitly mentioned steps. It should also be understood that these examples are for illustration only and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method well known to those skilled in the art.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations such as "comprises" or "comprising", etc., will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
The invention provides an in-plane ordered multi-component MAX phase material with a chemical formula of (M) x 'M” y ) n+1 AX n Wherein n is 1 to 6,x + y =1; m 'and M' are arranged in an ordered manner in at least one crystal plane; wherein M 'is selected from at least one element of groups IVB, VB, VIB, VIIB, VIII, IB and IIB, and M' is selected from at least two elements of groups IIIB, zirconium, lanthanides or actinides.
The invention also provides another in-plane ordered multicomponent MAX phase material, which has a chemical formula represented by (M) x 'M” y ) n+ 1 AX n Wherein n is between 1 and 6,x+y=1,M 'and M' are ordered in at least one crystal plane; m 'is selected from at least two elements of groups IVB, VB, VIB, VIIB, VIII, IB and IIB, and M' is selected from at least one element of group IIIB, zirconium, lanthanides or actinides.
Fig. 1 shows a schematic structural diagram (for convenience of illustration, n =1 is shown) of a multicomponent MAX phase material of the present invention, fig. 1a and 1b show schematic diagrams of a crystal plane perpendicular to the [010] crystal axis in side view and a (001) crystal plane in top view, respectively, and as can be seen from fig. 1a and 1b, the atoms of M 'and M "are arranged in order, and in particular, as can be seen from the schematic diagram of a crystal plane perpendicular to the [010] crystal axis in side view in fig. 1a, the atoms of M' and M" are arranged in order according to a period of 2.
In some embodiments, M' is selected from one or more elements of groups IVB, VB, VIB and VIIB, preferably at least one of the elements titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), niobium (Nb), molybdenum (Mo), technetium (Tc), hafnium (Hf), tantalum (Ta), tungsten (W) or rhenium (Re); the elements can be sintered and synthesized at relatively low temperature of 1200-2000 ℃.
In some embodiments, M "is selected from at least one of scandium (Sc), yttrium (Y), zirconium (Zr), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), lutetium (Lu), or ytterbium (Yb).
In some embodiments, a is selected from at least one of group VIIB, VIII, IB, IIB, IIIA, IVA, VA, or VIA elements, preferably a is selected from at least one of aluminum (Al), silicon (Si), phosphorus (P), sulfur (S), gallium (Ga), germanium (Ge), arsenic (As), cadmium (Cd), indium (In), tin (Sn), thallium (Tl), or lead (Pb); x is at least one of carbon (C), nitrogen (N) or boron (B).
In some embodiments, M' comprises one to four elements, M "comprises two elements; x =2/3,y =1/3,n =1, 2 or 3, and in the crystal plane perpendicular to the [010] crystal axis and the (001) crystal plane, the atoms of M' and M ″ are arranged in a cycle of 2.
In some embodiments, M' comprises two to four elements, M "comprises one element; x =2/3,y =1/3,n =1, 2 or 3, and in the crystal plane perpendicular to the [010] crystal axis and the (001) crystal plane, the atoms of M' and M ″ are arranged in order with a period of 2.
The embodiment also provides an in-plane ordered multi-component MXene materialThe MAX phase materials of the examples are etched away of the A component and are represented by the formula (M) x 'M” y ) n+1 X n The schematic structure is shown in fig. 2.
Example 2
This example provides a multicomponent MAX phase material, whose chemical formula is Mo 1.33 (Sc n Y 1-n ) 0.67 AlC, wherein n is more than 0 and less than 1, and a schematic structural diagram is shown in FIG. 3, it can be seen that two elements, sc and Y, are distributed on the M' position.
This embodiment also provides an in-plane ordered multicomponent MXene material, which is prepared from the MAX phase material Mo 1.33 (Sc n Y 1-n ) 0.67 Al in AlC is etched away, and the chemical formula of the Al is Mo 1.33 (Sc n Y 1-n ) 0.67 C, the schematic structure is shown in FIG. 4, and it is more clearly shown from FIGS. 4a and 4b that the two elements Sc and Y are randomly distributed on the M "bit and perpendicular to [010]]Crystal planes of the crystal axis and (001) crystal planes are distributed in order.
This example also provides an ordered multi-vacancy transition metal carbide, which is obtained by further etching off Sc and Y elements from the MXene material of this example, and the chemical formula of the carbide is represented by Mo 1.33 C, the schematic structural diagram of which is shown in FIG. 5, it can be seen that Mo is obtained 1.33 C has orderly arranged vacancies; when Sc and Y elements are not completely etched, a multi-component MXene material with vacant sites is obtained, and the chemical formula of the multi-component MXene material is Mo 1.33 (Sc n Y 1-n ) β C, wherein beta is more than 0 and less than 0.67.
Further, in the present embodiment, for Mo 1.33 (Sc n Y 1-n ) 0.67 Etching Y atom in C to obtain Mo 1.33 Sc 0.67n C。
Further, the selective etching of Mo obtained in this example is continued 1.33 C etching to remove part of Mo to obtain Mo α C, wherein alpha is more than 0 and less than 1.33.
Example 3
The present embodiment provides aA multicomponent MAX phase material having a chemical formula represented by (Mo) m W 1-m ) 1.33 (Sc n Y 1-n ) 0.67 AlC, wherein 0 < M < 1,0 < n < 1, and a schematic structural diagram thereof is shown in FIG. 6, it can be seen that two elements of Mo and W are distributed on the M 'site, and two elements of Sc and Y are distributed on the M' site.
This example also provides an in-plane ordered multicomponent MXene material, which is the MAX phase material (Mo) of this example m W 1-m ) 1.33 (Sc n Y 1-n ) 0.67 Al in AlC is etched away, and the chemical formula of the Al is represented as (Mo) m W 1-m ) 1.33 (Sc n Y 1-n ) 0.67 C, the schematic structure is shown in FIG. 7, it is more clearly shown from FIGS. 7a and 7b that the two elements Mo and W are randomly distributed on the M 'position, and the two elements Sc and Y are randomly distributed on the M' position and perpendicular to [010]]The crystal planes of the crystal axis and the (001) crystal plane are distributed in order.
This example also provides an ordered multi-vacancy transition metal carbide, which is obtained by further etching off Sc and Y elements from the MXene material of this example, and the chemical formula is represented by (Mo) m W 1-m ) 1.33 C, a schematic view of the structure is shown in FIG. 8, it can be seen that (Mo) is obtained m W 1-m ) 1.33 C has orderly arranged vacancies; when Sc and Y elements are not completely etched, a multi-component MXene material with vacant sites is obtained, and the chemical formula of the multi-component MXene material is expressed as (Mo) m W 1-m ) 1.33 (Sc n Y 1-n ) β C, wherein beta is more than 0 and less than 0.67.
Further, in the present embodiment, the pair (Mo) m W 1-m ) 1.33 (Sc n Y 1-n ) 0.67 Etching Y or Sc atoms in C to form vacancies at Y or Sc positions to obtain (Mo) m W 1-m ) 1.33 (Sc n ) 0.67 C or (Mo) m W 1-m ) 1.33 (Y 1-n ) 0.67 C。
Further, the etchant was continuously selected for (Mo) obtained in this example m W 1-m ) 1.33 C is etched, part of Mo and/or W is etched away, new vacancies are formed, and the (Mo) is obtained m W 1-m ) α C, wherein alpha is more than 0 and less than 1.33.
Example 4
This example provides a multicomponent MAX phase material having the chemical formula (Mo) m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 AlC, wherein 0 < M < 1,0 < n < 1,0 < p < 1, and FIG. 9 shows a schematic structure thereof, it can be seen that three elements of Mo, W, and Cr are distributed on the M 'site, and two elements of Sc and Y are distributed on the M' site.
This example also provides an in-plane ordered multicomponent MXene material, which is the MAX phase material (Mo) of this example m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 Al in AlC is etched away, and the chemical formula of the Al is represented as (Mo) m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 C, the schematic structure is shown in FIG. 10, it is more clearly shown from FIGS. 10a and 10b that three elements of Mo, W and Cr are randomly distributed on M 'bit, and two elements of Sc and Y are distributed on M' bit and perpendicular to [010]]The crystal plane of the crystal axis and the (001) crystal plane are distributed in order.
This example also provides an ordered multi-vacancy transition metal carbide, which is obtained by further etching off Sc and Y elements from the MXene material of this example, and the chemical formula is shown as (Mo) m W p Cr 1-m-p ) 1.33 C, a schematic view of the structure is shown in FIG. 11, and it can be seen that (Mo) is obtained m W p Cr 1-m-p ) 1.33 C has orderly arranged vacant sites, and Mo, W and Cr are randomly arranged at the M' site; when Sc and Y elements are not completely etched, a multi-component MXene material with vacant sites is obtained, and the chemical formula of the multi-component MXene material is expressed as (Mo) m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) β And C, wherein beta is more than 0 and less than 0.67.
Further, in the present embodiment, the pair (Mo) m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 Etching Y or Sc atoms in C to form vacancies at Y or Sc positions to obtain (Mo) m W p Cr 1-m-p ) 1.33 Sc 0.67n C or (Mo) m W p Cr 1-m-p ) 1.33 (Y 1-n ) 0.67 C。
Further, the etchant was continuously selected for (Mo) obtained in this example m W p Cr 1-m-p ) 1.33 C is etched, part of Mo, W and/or Cr is etched away to form new vacancies, and then (Mo) is obtained m W p Cr 1-m-p ) α C, wherein alpha is more than 0 and less than 1.33.
It can be seen from the above embodiments that the M component in the multi-component MAX phase material of the present invention contains at least three different elements, and the in-plane ordered multi-component MXene material (two-dimensional material) is obtained by etching the a component in the in-plane ordered multi-component MAX phase material, and belongs to a new class of super-surfaces due to its ordered structure and multi-component atomic composition; atoms in the multi-component MXene material with ordered vacancies in the surface are further selectively etched to obtain the MXene material with ordered vacancies or the MXene material with multiple vacancies, which also belongs to a novel super-surface material, because of the existence of abundant vacancies and atoms of multiple components, more single atoms can be exposed, the material can be endowed with new performance, presents macroscopic physical characteristics such as electromagnetism, light, sound and the like which are not possessed by the traditional material, has application prospects in anticorrosion coatings, high-temperature coatings, nuclear radiation protection, catalysis, sensors, electronic devices, super capacitors, batteries, electromagnetic shielding, wave absorbing materials or superconducting materials, and possibly induces subversive change in multiple fields such as communication, stealth, imaging detection, information processing and the like.
The implementation of the technical route of the invention comprises screening the etchant, and optionally, the etchant comprises: one or more of halogen elementary gas, hydrogen halide gas, metal halide salt or ammonium salt of halogen element; or, the etching agent is: hydrofluoric acid or acid solution + fluoride salt system, but the invention is not so limited. Through limited experiments, the optimal etchant and etching conditions for different atoms can be obtained, and atomic scale regulation and control can be realized on the MXene two-dimensional material by changing the etchant and the etching conditions.
The M 'and M' positions in the embodiment can be replaced by other types of atoms to obtain a multi-component MAX phase material with abundant types, and a base material is provided for further atom selective etching, so that a wider variety of novel super-surface materials are obtained. The following description will be made by specific experimental examples.
Example 5
This example provides a multicomponent in-plane ordered MAX phase material to produce the (Mo) shown in example 4 m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 The preparation method of AlC is illustrated by the following steps:
uniformly mixing transition metal powder, aluminum powder and crystalline flake graphite according to a stoichiometric ratio of 2, 1.3 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 The results of Scanning Electron Microscope (SEM) observation of AlC are shown in FIG. 12 (Mo) 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 The shape of the AlC is a three-dimensional blocky structure. For high entropy ordered MAX (Mo) 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 AlC and ordered MAX (Mo) 0.67 Y 0.34 ) 2 AlC, the results of comparative analysis by X-ray diffraction (XRD) are shown in FIG. 13, (Mo) 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 The (002) peak of AlC was located at 13.15 DEG, and (Mo) 0.67 Y 0.34 ) 2 The position of the (002) peak of AlC is 12.90 degrees, and the result shows that the simultaneous introduction of W, cr and Sc elements reduces the (002) interplanar spacing. This is also confirmed by the change in the average atomic radius, mo 0.443 W 0.443 Cr 0.443 Y 0.34 Sc 0.34 And Mo 1.33 Y 0.67 Are 291.6 and 298.8, respectively, a decrease in the average atomic radius results in a decrease in the (002) interplanar spacing. The results of Scanning Transmission Electron Microscopy (STEM) and X-ray energy spectroscopy (EDS) at the corresponding position are shown in FIGS. 14 and 15, in which Mo, W, cr, Y, sc, al and C are uniformly distributed, and the results of atomic percentage show that the contents of Mo, W, cr, Y and Sc are close to the charging ratio. Perpendicular to [010]The high-resolution TEM result of crystal axis crystal plane is shown in FIG. 16, wherein M is 1 And M 2 The sites present an ordered distribution, and M 1 And M 2 The atomic ratio is 2:1.
example 6
This example provides a multicomponent in-plane ordered MXene material (Mo) m W p Cr 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 And C, etching by taking the MAX phase material prepared in the embodiment 5 as a raw material, wherein the preparation method comprises the following steps:
1g of the MAX phase (Mo) obtained above was taken 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 And placing AlC in a tube furnace, introducing a mixed gas of etching gas and inert gas into the tube furnace, heating to a preset temperature, preserving heat for a period of time, cooling to normal temperature, and taking out to obtain a powder product.
In some embodiments, the etching gas is selected to include a halogen elemental gas or a hydrogen halide gas, including: br 2 、Cl 2 、I 2 Or HF, HCl, HBr, HI.
In some embodiments, the etchant is a metalA halide salt comprising: feCl 3 、CoCl 2 、NiCl 3 、CuCl 2 、ZnCl 2 ，CdCl 2 、FeBr 3 、CoBr 2 、NiBr 3 、CuBr 2 、ZnBr 2 、CdBr 2 、FeI 3 、CoI 2 、NiI 3 、CuI 2 、ZnI 2 Or CdI 2 Or, an ammonium salt of a halogen element, comprising: NH (NH) 4 F、NH 4 HF 2 、NH 4 Cl、NH 4 Br or NH 4 And I, placing the solid etchant in a tube furnace, and heating to decompose the solid etchant into halogen elemental gas or hydrogen halide gas to realize etching.
Preferably, the tube furnace is heated to a predetermined temperature of 400 ℃ to 1200 ℃ for a holding time of 5min to 12h, and the inert gas is argon. Because the multi-component MAX phase material has a plurality of different atoms and the etching conditions corresponding to the different atoms are different, through limited experiments, different atoms can be etched by selecting different types of etching agents, etching time, heating temperature and heat preservation time, and the regulation and control of material components and position atomic levels are realized.
In a specific embodiment, 5g of solid iodine is selected and placed in a tube furnace, argon is introduced into the tube furnace, the temperature is raised to 800 ℃ and kept for 1h, after the tube furnace is cooled to room temperature, powder is obtained, the obtained powder is characterized, as shown in fig. 17, the powder is obvious in accordion-shaped appearance, which is related to the etching of the Al element, and the (Mo) is obtained 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 C。
In another specific embodiment, gaseous HCl gas is selected as the etchant, a mixed gas of HCl and argon (HCl volume fraction is 10%) is introduced into a tube furnace, the temperature is raised to 600 ℃, the mixture is kept for 1 hour, after cooling to room temperature, powder is obtained, and the obtained powder is characterized, as shown in fig. 18, it can be seen that the powder has an obvious accordion-like morphology, which is related to the etching of Al elementObtained is (Mo) 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 C。
Example 7
This example provides an ordered vacancy multicomponent MXene material (Mo) 0.221 W 0.221 Cr 0.221 ) 2 CT x The preparation method comprises the following steps:
25ml of hydrofluoric acid with a mass fraction of 10% was used as an etchant, and 1g of the high-entropy MAX phase (Mo) obtained in example 5 was used 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 Placing AlC in an etchant, replacing the etchant under the same condition every 24 hours at room temperature, continuously reacting for 72 hours, and after the reaction is finished, performing centrifugal separation, water washing and drying treatment to obtain the entropy MXene two-dimensional material (Mo) in the accordion-shaped ordered vacancies 0.221 W 0.221 Cr 0.221 ) 2 CT x Then 1g of accordion-shaped ordered vacancy entropy (Mo) is taken 0.221 W 0.221 Cr 0.221 ) 2 CT x Adding 20ml DMF, ultrasonic treating for 30min, centrifuging, washing with water and drying to obtain two-dimensional (Mo) 0.221 W 0.221 Cr 0.221 ) 2 CT x A nanosheet.
Scanning electron microscope SEM test is carried out on the obtained nano-sheet, the result is shown in figure 19, and the appearance of the nano-sheet is accordion-shaped, which indicates the occurrence of etching reaction. The results of TEM (transmission electron microscope) are shown in FIG. 20, and the prepared (Mo) is observed 0.221 W 0.221 Cr 0.221 ) 2 CT x Is a two-dimensional flexible sheet. The result of high-resolution TEM using a spherical aberration electron microscope is shown in FIG. 21, and the prepared (Mo) is observed 0.221 W 0.221 Cr 0.221 ) 2 CT x Has an ordered double vacancy structure.
Example 8
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Mo) m W p V 1-m-p ) 1.33 (Sc n Y 1-n ) 0.67 M is more than 0 and less than 1, n is more than 0 and less than 1, p is more than 0 and less than 1,three elements of Mo, W and V are distributed on the M 'position, and two elements of Sc and Y are distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and crystalline flake graphite according to a stoichiometric ratio of 2, 1.3 0.221 W 0.221 V 0.221 Y 0.17 Sc 0.17 ) 2 And (4) AlC. The structure diagram is shown in FIG. 22, and it is more clearly shown in FIGS. 22a and 22b that the three elements Mo, W and V are randomly distributed on the M 'position, and the two elements Sc and Y are distributed on the M' position and perpendicular to [010]]The crystal plane of the crystal axis and the (001) crystal plane are distributed in order.
Hydrofluoric acid with the mass fraction of 10% is taken as an etching agent, and the obtained high-entropy MAX phase (Mo) is taken 0.221 W 0.221 Cr 0.221 Y 0.17 Sc 0.17 ) 2 Placing the AlC in an etching agent, and continuously reacting for 36 hours to obtain the multicomponent MXene material with Al and part of Y etched.
Example 9
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Mo) m W p Cr q V 1-m-p-q ) 1.33 (Sc n Y 1-n ) 0.67 AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, p is more than 0 and less than 1, q is more than 0 and less than 1, the four elements of Mo, W, cr and V are distributed on the M 'position, and the two elements of Sc and Y are distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and flake graphite according to a stoichiometric ratio of 2Placing the mixture powder in an agate ball milling tank for ball milling treatment, wherein the ball milling rotation speed is 600rpm, the ball milling time is 20 hours, then placing the ball milled mixture powder in a mould for 5MPa, cold pressing the mixture powder, placing the mixture powder in a tubular furnace, heating the mixture powder to 1500 ℃ under the protection of argon, preserving the heat for 10 hours, and naturally cooling the mixture powder to room temperature to obtain the high-entropy ordered MAX phase (Mo) 0.16 W 0.16 Cr 0.16 V 0.16 Y 0.17 Sc 0.17 ) 2 And (4) AlC. The structure diagram is shown in FIG. 23, and it is more clearly shown in FIGS. 23a and 23b that the four elements Mo, W, cr and V are randomly distributed on the M 'position, and the two elements Sc and Y are distributed on the M' position and perpendicular to [010]]Crystal planes of the crystal axis and (001) crystal planes are distributed in order.
Example 10
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Mo) m W p Tc q Ta 1-m-p-q ) 1.33 (Sc n Y 1-n ) 0.67 And AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, p is more than 0 and less than 1, q is more than 0 and less than 1, the four elements of Mo, W, tc and Ta are distributed on the M 'position, and the two elements of Sc and Y are distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and flake graphite according to a stoichiometric ratio of 1.3 0.16 W 0.16 Tc 0.16 Ta 0.16 Y 0.17 Sc 0.17 ) 2 And (4) AlC. MXene material (Mo) can be obtained after the Al element in the material is etched by the etchant 0.16 W 0.16 Tc 0.16 Ta 0.16 Y 0.17 Sc 0.17 ) 2 C; by further etching the metal atoms Y and Sc, ordered vacancies can be obtainedMXene material (Mo) 0.16 W 0.16 Tc 0.16 Ta 0.16 ) 2 C。
Example 11
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Fe) m Co p Ni q Cu 1-m-p-q ) 1.33 (Sc n Y 1-n ) 0.67 And AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, p is more than 0 and less than 1, q is more than 0 and less than 1, four elements of Fe, co, ni and Cu are distributed on the M 'position, and two elements of Sc and Y are distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and flake graphite according to a stoichiometric ratio of 2 0.16 Co 0.16 Ni 0.16 Cu 0.16 Y 0.17 Sc 0.17 ) 2 And (4) AlC. MXene material (Fe) can be obtained after Al element in the Al element is etched by an etchant 0.16 Co 0.16 Ni 0.16 Cu 0.16 Y 0.17 Sc 0.17 ) 2 C; by further etching the metal atoms Y and Sc, MXene materials (Fe) with ordered vacancies can be obtained 0.16 Co 0.16 Ni 0.16 Cu 0.16 ) 2 C。
Example 12
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Mo) m W n Cr p V 1-m-n-p ) 1.33 Y 0.67 And AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, p is more than 0 and less than 1, the four elements of Mo, W, cr and V are distributed on the M 'position, and the element Y is distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and flake graphite according to a stoichiometric ratio of 1.3 0.16 W 0.16 Cr 0.16 V 0.16 Y 0.34 ) 2 And (4) AlC. The structure diagram is shown in FIG. 24, and it is more clearly shown in FIGS. 24a and 24b that the four elements Mo, W, cr and V are randomly distributed on the M 'position, the element Y is distributed on the M' position and is perpendicular to [010]]Crystal planes of the crystal axis and (001) crystal planes are distributed in order.
Example 13
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Mo) m W n Cr p V 1-m-n-p ) 1.33 Sc 0.67 And AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, p is more than 0 and less than 1, the four elements of Mo, W, cr and V are distributed on the M 'position, and the Sc element is distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and crystalline flake graphite according to a stoichiometric ratio of 2 0.16 W 0.16 Cr 0.16 V 0.16 Sc 0.34 ) 2 And (4) AlC. The schematic structure is shown in FIG. 25, and it is more clearly shown in FIGS. 25a and 25b that the four elements Mo, W, cr and V are randomly distributed at the M' positionThe Sc element is distributed on the M' position and is vertical to [010]The crystal plane of the crystal axis and the (001) crystal plane are distributed in order.
Example 14
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Ti) m Mn n V 1-m-n ) 1.33 Sc 0.67 And AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, the three elements of Ti, mn and V are distributed on the M 'position, and the Sc element is distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and crystalline flake graphite according to a stoichiometric ratio of 2, 1.3, wherein the transition metal powder comprises Ti, mn and V, the ratio of Ti to Mn to V to Sc =0.444 is 0.44 Mn 0.44 V 0.44 Sc 0.67 And (4) AlC. After Al element in the MXene is etched by the etchant, MXene material Ti can be obtained 0.44 Mn 0.44 V 0.44 Sc 0.67 C。
Example 15
This example provides another in-plane ordered multicomponent MAX phase material having the formula (Nb) m Hf 1-m ) 1.33 Zr 0.67 And Al, wherein M is more than 0 and less than 1, nb and Hf are distributed on the M 'position, and Zr is distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and flake graphite according to a stoichiometric ratio of 1.3The temperature is 10h, and the high-entropy ordered MAX phase Nb is obtained after the natural cooling to the room temperature 0.67 Hf 0.67n Zr 0.67 And (4) AlC. MXene material Nb can be obtained after Al element in the Al element is etched by the etchant 0.67 Hf 0.67 Zr 0.67 C。
Example 16
This example provides another in-plane ordered multicomponent MAX phase material having the chemical formula (Nb) m Re 1-m ) 1.33 (Zr n Ce 1-n ) 0.67 And AlC, wherein M is more than 0 and less than 1, n is more than 0 and less than 1, two elements of Nb and Re are distributed on the M 'position, and elements of Zr and Ce are distributed on the M' position. The preparation method comprises the following steps:
uniformly mixing transition metal powder, aluminum powder and flake graphite according to a stoichiometric ratio of 2 0.34 Re 0.34 Zr 0.17 Ce 0.17 ) 2 And (4) AlC. MXene material (Nb) can be obtained after etching Al element in the Al element by an etchant 0.34 Re 0.34 Zr 0.17 Ce 0.17 ) 2 C; MXene materials containing ordered vacancies can be obtained by further selectively etching the metal atoms in the MXene materials.
Example 17
The embodiment provides an electronic device, which is a hydrogen evolution catalytic device, wherein an MXene material containing vacancies after etching is prepared into a dispersion liquid, the dispersion liquid is dripped on a glassy carbon electrode, and the solution is evaporated to obtain the hydrogen evolution catalytic device containing the MXene material.
In a specific embodiment, the following will be mentioned(Mo) obtained in example 7 0.221 W 0.221 Cr 0.221 ) 2 CT x The solution is prepared into 2mg/mL dispersion liquid which is dripped on an L-glassy carbon electrode to prepare the hydrogen evolution catalytic device.
Example 18
The embodiment provides a protective coating, which is prepared by grinding and refining a multi-component MAX phase material, adding the grinded material into a liquid matrix, uniformly mixing, coating the liquid matrix into a film, and curing and forming the film to obtain a MAX phase material-containing coating which can be used as a thermal barrier coating, an anticorrosive coating or an electromagnetic shielding coating.
The multicomponent MXene material is added into a liquid matrix to obtain a protective coating containing the multicomponent MXene material, and the two-dimensional MXene material can form an ultrathin protective film in the coating and can also be used as a thermal barrier coating, an anticorrosive coating or an electromagnetic shielding coating and the like.
Example 19
The embodiment provides an energy storage device, which is a battery, wherein a negative electrode material comprises metallic lithium and the multi-component MXene material, and the surface tension of molten metallic lithium can be reduced by doping the multi-component MXene material, so that an ultrathin metallic lithium composite material is obtained and is used as the negative electrode material of the battery.
The multi-component MAX phase material or MXene material can also be applied to other types of energy storage devices, such as a super capacitor.
The multi-component MAX phase material or MXene material can also be used as a modified material to be added into other matrixes to form a composite material, for example, the composite material is compounded with a high polymer material and the like.
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (12)
1. An in-plane ordered multicomponent MAX phase material, wherein said multicomponent MAX phase material has the chemical formula (M) x 'M” y ) n+1 AX n ；
Wherein n is between 1 and 6,x + y =1;
m 'and M' are arranged orderly in at least one crystal plane;
the sum of the element types of M 'and M' is more than three;
m 'is selected from one or more elements in groups IVB, VB, VIB, VIIB, VIII, IB and IIB, and M' is selected from at least one or more elements in groups IIIB, zirconium, lanthanides and actinides.
2. Multicomponent MAX phase material according to claim 1, wherein M' is selected from one or more elements of groups IVB, VB, VIB and VIIB; preferably, M' is selected from one or more elements of titanium, vanadium, chromium, manganese, niobium, molybdenum, technetium, hafnium, tantalum, tungsten or rhenium;
and/or, the M' is one or more elements selected from scandium, yttrium, zirconium, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium or ytterbium;
and/or A is selected from at least one of aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium or lead;
and/or X is at least one of carbon, nitrogen or boron.
3. Multicomponent MAX phase material according to any of claims 1 to 2 characterized in that in the crystallographic plane perpendicular to the [010] crystal axis and the (001) crystallographic plane, the atoms of M' and M "are ordered according to a period of 2;
and/or, in the multi-component MAX phase material, each element atom of M 'is randomly distributed in M' position, and each element atom of M 'is randomly distributed in M' position.
4. A method for the preparation of a multicomponent MAX phase material according to any of claims 1 to 3 comprising the steps of:
1) Mixing solid powder containing an M 'phase, an M' phase, an A phase and an X phase according to the stoichiometric ratio of a chemical formula, and carrying out ball milling treatment to obtain a mixture;
2) Carrying out heat treatment on the mixture obtained in the step 1) in inert gas shielding gas to obtain a multi-component MAX phase material; preferably, the heat treatment temperature is between 800 ℃ and 3200 ℃.
5. A multicomponent MXene material etched from the multicomponent MAX phase material of any one of claims 1 to 3.
6. The preparation method of the multicomponent MXene material is characterized by comprising the following steps:
etching A in the multicomponent MAX phase material of any one of claims 1 to 3 to obtain the multicomponent MXene material, which is represented by formula (M' x M” y ) n+1 X n ；
Or, the multicomponent MXene material obtained by mixing A and all or part of M 'in the multicomponent MAX phase material of any one of claims 1 to 4, and having a chemical formula of (M' x M” β ) n+1 X n Wherein beta is more than or equal to 0 and less than y;
or, obtaining the multicomponent MXene material by mixing A, all or part of M ' and all or part of M ' in the multicomponent MAX phase material as defined in any one of claims 1 to 4, wherein the multicomponent MXene material has a chemical formula of (M ' α M” β ) n+1 X n Wherein alpha is more than or equal to 0 and less than x, and beta is more than or equal to 0 and less than y.
7. The method according to claim 6, wherein the etching is performed with an etchant selected from the group consisting of: one or more of halogen elementary gas, hydrogen halide gas, metal halide salt or ammonium salt of halogen element; or, the etching agent is: hydrofluoric acid or acid solution + fluoride salt system.
8. Use of a multicomponent MAX phase material according to any of claims 1 to 3 in the field of anti-corrosion coatings, high temperature coatings, nuclear radiation protection or electrical brushes.
9. Use of the multicomponent MXene material of claim 5 in anticorrosion coatings, high temperature coatings, nuclear radiation protection, catalysis, sensors, electronics, supercapacitors, batteries, electromagnetic shielding, wave absorbing materials or superconducting materials.
10. A coating material comprising a multicomponent MAX phase material according to any one of claims 1 to 3 and/or a multicomponent MXene material according to claim 5.
11. An electronic device comprising a multicomponent MAX phase material according to any of claims 1 to 3 and/or a multicomponent MXene material according to claim 5.
12. An energy storage device comprising a multicomponent MAX phase material according to any of claims 1 to 3 and/or a multicomponent MXene material according to claim 5.
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