阅读说明：本技术 A位含锑元素的max相层状材料、其制备方法及应用 (MAX phase layered material containing antimony element at A position, preparation method and application thereof ) 是由 黄庆 丁浩明 李友兵 于 2021-11-11 设计创作，主要内容包括：本发明公开了一种A位含锑元素的MAX相层状材料、其制备方法及应用。所述MAX相层状材料是一种具有纳米层状化合物,分子式表示为M-(n+)-(1)AX-(n),M选自前过渡金属族元素中的任意一种或两种以上的任意组合,A为锑或含锑合金的任意组合,X为C和/或N元素,n为1、2、3或4。本发明提供的A位含锑元素的MAX相层状材料具有六方晶系结构,空间群为P6-(3)/mmc,晶胞由M-(n+1)X-(n)亚结构层与含锑原子层交替堆垛而成。本发明提供的A位含锑元素的MAX相层状材料在超导、储能、催化、电磁屏蔽、摩擦磨损等领域具有潜在的应用前景。(The invention discloses a MAX phase layered material containing antimony at the A position, a preparation method and application thereof. The MAX phase layered material is a nano layered compound with a molecular formula of M n+ 1 AX n M is any one or any combination of more than two of elements in the early transition metal group, A is any one of antimony or antimony-containing alloyIn combination, X is a C and/or N element and N is 1, 2, 3 or 4. The MAX phase layered material containing antimony element at A site has a hexagonal structure and a space group of P6 3 Unit cell of M n+1 X n The sub-structure layers and the antimony-containing atomic layers are alternately stacked. The MAX phase layered material containing antimony element at the A position has potential application prospect in the fields of superconductivity, energy storage, catalysis, electromagnetic shielding, friction and abrasion and the like.)

1. A MAX phase layered material containing antimony at A site is characterized in that: the molecular formula of the MAX phase layered material is expressed as M_n+1AX_nWherein M is selected from any one or any combination of more than two of elements in the early transition metal group, A is any combination of antimony or antimony-containing alloy, X is any one or any combination of two of C, N elements, and n is 1, 2, 3 or 4.

2. The A-site antimony-containing MAX phase layered material of claim 1 wherein: the M comprises any one or any combination of more than two of Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Mo, Hf, Ta and W.

3. The A-site antimony-containing MAX phase layered material of claim 1 wherein: the A comprises Sb, or an antimony-containing alloy formed by Sb and any one or any combination of more than two of Al, Si, P, S, Ga, Ge, As, In, Sn, Tl, Pb, Bi, Fe, Co, Ni, Cu, Zn, Pd, Ir, Au, Cd, Se and Te.

4. The A-site antimony-containing MAX phase layered material of claim 1 wherein: what is needed isX is C_xN_yWherein x + y is 1-2.

5. The A-site antimony-containing MAX phase layered material of claim 1 wherein: the MAX phase layered material containing antimony element at A position has a hexagonal structure and a space group of P6₃Unit cell of M_n+1X_nThe sub-structure layers and the antimony-containing atomic layers are alternately stacked.

6. A method for the preparation of a MAX phase layered material containing antimony in the A-position as claimed in any of claims 1-5, comprising: mixing M and/or M-containing materials, A and/or A-containing materials and X and/or X-containing materials according to the ratio of (2-4): 1: (1-3), and reacting the obtained mixture at the high temperature of 1000-1700 ℃ for 30-120 min in an inert atmosphere to obtain the MAX phase layered material containing the antimony element at the A position;

or, mixing a precursor MAX phase material, A and/or A-containing material, molten metal salt and inorganic salt according to the proportion of 1: (1-3): (2-3): (3-10), carrying out high-temperature reaction on the obtained mixture in an inert atmosphere at 400-1000 ℃ for 30-120 min, and then carrying out post-treatment to obtain the MAX phase layered material containing the antimony element at the A position;

wherein the molecular formula of the precursor MAX phase material is expressed as M_m+1A’X_mWherein M is selected from group iiib, IV B, V B or VI B early transition metal elements, a' is selected from group iiia or iva elements, X includes C and/or N, and M is 1, 2 or 3.

7. The method of claim 6, wherein: the precursor MAX phase material comprises Ti₃AlC₂、Ti₂AlC、Ti₂AlN、Ti₄AlN₃、V₂AlC、Cr₂AlC、Nb₂AlC、Hf₂AlN、Ta₄AlC₃、Ti₃Any one or a combination of two or more of AlCN.

8. The method of claim 6The preparation method is characterized by comprising the following steps: the molten metal salt comprises FeO and Fe₂O₃、CoO、NiO、CuO、ZnO、CdO、Ag₂O、FeCl₂、FeCl₃、CoCl₂、NiCl₂、CuCl₂、CuCl、ZnCl₂、CdCl₂、AgCl、FeBr₂、FeBr₃、CoBr₂、NiBr₂、CuBr₂、CuBr、ZnBr₂、CdBr₂、AgBr、FeI₂、CoI₂、NiI₂、CuI、ZnI₂、CdI₂、AgI、FeSO₄、Fe₂(SO₄)₃、CoSO₄、NiSO₄、CuSO₄、Cu₂SO₄、ZnSO₄、CdSO₄、Ag₂SO₄Any one or a combination of two or more of them.

9. The method of claim 6, wherein: the M and/or M-containing material comprises an alloy containing M simple substance and/or M; and/or the A and/or A-containing material comprises an alloy containing A simple substance and/or A, preferably comprises Sb, CdSb and Ag₂Sb、CoSb、Cu₂Sb、FeSb、FeSb₂Any one or combination of more than two of NiSb, SnSb and ZnSb; and/or the inorganic salt comprises any one or the combination of more than two of NaF, NaK, LiCl, NaCl, KCl, NaBr and KBr.

10. Use of a MAX phase layered material comprising antimony in the a-position according to any of claims 1-5 in the fields of superconductivity, energy storage, catalysis, electromagnetic shielding or tribological wear.

Technical Field

The invention relates to an inorganic material, in particular to a novel MAX phase layered material containing antimony at the A position, a preparation method and application thereof, belonging to the technical field of materials.

Background

M_n+1AX_nThe phase material is a ternary layered nano-layered compound, the M-site element generally refers to an early transition metal element, the A-site element mainly refers to IIIA group and IVA group elements, the X element refers to C and/or N, wherein N is 1, 2 or 3. The crystal structure of the MAX phase is a hexagonal crystal structure with space group P6₃C,/mmc from_n+1X_nThe nanometer sublayer structure and the A atomic layer are stacked alternately, wherein M is_n+1X_nThe nanostructure sublayer is composed of covalent bonds₆And the X octahedron layer is formed, the adjacent MX sublayer structures are in twin crystal phase, and X is positioned in an octahedron gap formed by M-site atoms. Theoretical calculations predict that more than 600 MAX phases are thermodynamically stable, with over 70 pure MAX phases having been successfully synthesized. The M-, A-and X-bit element distributions of the MAX phases that have been found so far include 25M-bit elements, 18A-bit elements (Al, Si, P, S, Ga, Ge, As, In, Sn, Tl, Pb, Bi, Cu, Zn, Pd, Ir, Au, Cd) and 2X-bit elements. The MAX phase has rich chemical element composition, so that the physical and chemical properties of the MAX phase can be changed and adjusted by adjusting the element types and relative contents of the MAX phase, and meanwhile, the diversity of MAX phase materials can be greatly enriched. At present, the preparation of the MAX phase with the A site as Sb element is not successfully realized.

Disclosure of Invention

The invention mainly aims to provide a MAX phase layered material containing antimony at the A site and a preparation method thereof, thereby overcoming the defects in the prior art.

The invention also aims to provide application of the MAX phase layered material containing the antimony element at the A position.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a MAX phase layered material containing antimony element at A position, and the molecular formula of the MAX phase layered material is expressed as M_n+1AX_nWherein M is selected from any one or any combination of more than two of elements in the early transition metal group, A is any combination of antimony or antimony-containing alloy, X is any one or any combination of two of C, N elements, and n is 1, 2, 3 or 4.

In some embodiments, A is Sb, or an antimony-containing alloy of Sb and any one or any combination of two or more of Al, Si, P, S, Ga, Ge, As, In, Sn, Tl, Pb, Bi, Fe, Co, Ni, Cu, Zn, Pd, Ir, Au, Cd, Se, Te, and the like.

The embodiment of the invention also provides a preparation method of the MAX phase layered material containing the antimony element at the A position, which comprises the following steps: mixing M and/or M-containing materials, A and/or A-containing materials and X and/or X-containing materials according to the ratio of (2-4): 1: (1-3), and reacting the obtained mixture at a high temperature of 400-1700 ℃ for 30-120 min in an inert atmosphere to obtain the MAX phase layered material containing the antimony element at the A position;

or, mixing a precursor MAX phase material, A and/or A-containing material, molten metal salt and inorganic salt according to the proportion of 1: (1-3): (2-3): (3-10), carrying out high-temperature reaction on the obtained mixture at 400-1700 ℃ in an inert atmosphere, and then carrying out post-treatment to obtain the MAX phase layered material containing the antimony element at the A position;

wherein the molecular formula of the precursor MAX phase material is expressed as M_m+1A’X_mWherein M is selected from group iiib, IV B, V B or VI B early transition metal elements, a' is selected from group iiia or iva elements, X includes C and/or N, and M is 1, 2 or 3. Further, the precursor MAX phase material comprises Ti₃AlC₂、Ti₂AlC、Ti₂AlN、Ti₄AlN₃、V₂AlC、Cr₂AlC、Nb₂AlC、Hf₂AlN、Ta₄AlC₃、Ti₃Any one or a combination of two or more of alcns, but is not limited thereto. Compared with the prior art, the invention has the advantages that:

(1) the preparation method of the A-site antimony-containing MAX phase layered material provided by the embodiment of the invention realizes the preparation of the novel MAX phase material with A as antimony for the first time, and the preparation method is simple and has universality;

(2) the A-bit element of the MAX phase layered material provided by the embodiment of the invention contains antimony, has the characteristics of metal and ceramic, and has the characteristics of high strength, high hardness, high heat conductivity, high electrical conductivity, oxidation resistance, high temperature resistance, high damage tolerance, processability and the like. The introduction of antimony element leads the electronic structure of the material to be greatly changed compared with the existing MAX phase material, thereby causing the physical and chemical properties of the MAX phase material to be changed, and the antimony element is introduced to regulate and control the physical and chemical properties of the MAX phase material, so that the synthesized novel MAX phase material has potential application prospects in the fields of superconductivity, energy storage, catalysis, electromagnetic shielding, friction and abrasion and the like.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. The drawings in the following description are only some embodiments described in the present invention, and it is obvious to those skilled in the art that other drawings can be obtained based on the drawings without inventive efforts.

FIG. 1 shows a MAX phase layered material Nb containing antimony at A site in example 1 of the present invention₂SbC XRD pattern;

FIG. 2 shows a MAX phase layered material Nb containing antimony at A site in example 1 of the present invention₂SbC XRD pattern Reitveld method fine modification analysis result pattern;

FIG. 3 shows a MAX phase layered material Nb containing antimony at A site in example 1 of the present invention₂SbC, a spherical aberration correction high-resolution transmission electron microscope image and an atomic-scale element distribution image;

FIG. 4 shows a MAX phase layered Ti material containing antimony at A site in example 2 of the present invention₃SbC₂XRD pattern of (a);

FIG. 5 shows a MAX phase layered Ti material containing antimony at A site in example 2 of the present invention₃SbC₂The spherical aberration correction high-resolution transmission electron microscope image and the atomic-scale element distribution diagram are obtained;

FIG. 6 shows a MAX phase layered Ti material containing antimony at A site in example 3 of the present invention₃XRD pattern of SbCN;

FIG. 7 shows a MAX phase layered Ti material containing antimony at A site in example 3 of the present invention₃SbCN edgeA high-resolution transmission electron microscope image and an atomic schematic diagram for correcting the spherical aberration of a crystal ribbon axis;

FIG. 8 shows a MAX phase layered Ti material containing antimony at A site in example 3 of the present invention₃A spherical aberration correction high-resolution transmission electron microscope image and an atomic element distribution image of SbCN.

Detailed Description

The MAX phase material containing antimony element at A position is synthesized by the method, which has very important significance for supplementing the conventional definition of MAX phase, expanding the composition variety and regulating and controlling the chemical properties of the material; secondly, by utilizing the diversity and rich adjustability of the A-site elements of the MAX phase material, a brand new MAX phase material containing the A-site antimony elements can be synthesized, and the material synthesis method is an innovation and also provides a brand new synthesis strategy for the synthesis of other novel MAX phases; in addition, the MAX phase material containing antimony element at A site is synthesized, and the structure and the property of the MAX phase material are regulated and controlled by regulating the content, the position and the type of the element at A site, so that the MAX phase material is applied to the fields of superconduction, energy storage and the like.

Therefore, the technical principle of the inventor is as follows: the introduction of antimony element into the A-site atomic layer of the MAX phase material can cause the electronic structure of the MAX phase material to be greatly changed compared with the existing MAX phase material, thereby causing the physical and chemical properties of the MAX phase material to be changed, and having potential application prospects in the fields of superconductivity, energy storage, catalysis, biology, microwave devices and the like.

According to an aspect of an embodiment of the present invention, there is provided a MAX phase layered material containing antimony element in a position a, where a molecular formula of the MAX phase layered material is represented as M_n+1AX_nWherein M is selected fromAny one or any combination of more than two of the elements in the early transition metal group, A is any combination of antimony or antimony-containing alloy, X is any one or any combination of two of C, N elements, and n is 1, 2, 3 or 4.

In some embodiments, M includes any one or a combination of two or more of Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Mo, Hf, Ta, W, and the like, without limitation.

In some embodiments, A is Sb, or an antimony-containing alloy of Sb and any one or any combination of two or more of Al, Si, P, S, Ga, Ge, As, In, Sn, Tl, Pb, Bi, Fe, Co, Ni, Cu, Zn, Pd, Ir, Au, Cd, Se, Te, and the like.

In some embodiments, X is C_xN_yWherein x + y is 1-2.

Furthermore, the MAX phase layered material containing antimony element at the A position has a hexagonal structure and a space group of P6₃Unit cell of M_n+1X_nThe sub-structure layers and the antimony-containing atomic layers are alternately stacked.

Another aspect of the embodiments of the present invention provides a method for preparing a MAX phase layered material containing antimony at a site, including: mixing M and/or M-containing materials, A and/or A-containing materials and X and/or X-containing materials according to the ratio of (2-4): 1: (1-3), uniformly mixing, and reacting the obtained mixture at the high temperature of 1000-1700 ℃ for 30-120 min in an inert atmosphere to obtain the MAX phase layered material containing the Sb element at the A position;

or, mixing a precursor MAX phase material, A and/or A-containing material, molten metal salt and inorganic salt according to the proportion of 1: (1-3): (2-3): (3-10), carrying out high-temperature reaction on the obtained mixture in an inert atmosphere at 400-1000 ℃ for 30-120 min, and then carrying out post-treatment to obtain the MAX phase layered material containing the antimony element at the A position;

wherein the molecular formula of the precursor MAX phase material is expressed as M_m+1A’X_mWherein M is selected from group iiib, IV B, V B or VI B early transition metal elements, a' is selected from group iiia or iva elements, X includes C and/or N, and M is 1, 2 or 3. The MAX prepared by the inventionThe molecular formula of the phase-layered material is expressed as M_n+1AX_nWherein M is any one or any combination of more than two of elements in the transition metal group, A is any combination of antimony or antimony-containing alloy, X is any one or any combination of two of C, N elements, and n is 1, 2, 3 or 4.

In some embodiments, the precursor MAX phase material comprises Ti₃AlC₂、Ti₂AlC、Ti₂AlN、Ti₄AlN₃、V₂AlC、Cr₂AlC、Nb₂AlC、Hf₂AlN、Ta₄AlC₃、Ti₃Any one or a combination of two or more of AlCN and the like, but is not limited thereto.

In some embodiments, the molten metal salt comprises FeO, Fe₂O₃、CoO、NiO、CuO、ZnO、CdO、Ag₂O、FeCl₂、FeCl₃、CoCl₂、NiCl₂、CuCl₂、CuCl、ZnCl₂、CdCl₂、AgCl、FeBr₂、FeBr₃、CoBr₂、NiBr₂、CuBr₂、CuBr、ZnBr₂、CdBr₂、AgBr、FeI₂、CoI₂、NiI₂、CuI、ZnI₂、CdI₂、AgI、FeSO₄、Fe₂(SO₄)₃、CoSO₄、NiSO₄、CuSO₄、Cu₂SO₄、ZnSO₄、CdSO₄、Ag₂SO₄And the like, but not limited thereto.

In some embodiments, the M-containing material includes, but is not limited to, elemental M-containing and/or an alloy of M.

Further, the material containing a includes an alloy containing a simple substance a and/or a, but is not limited thereto.

Further, the A and/or A-containing material (Sb and its alloy) comprises Sb, CdSb, Ag₂Sb、CoSb、Cu₂Sb、FeSb、FeSb₂Any one or a combination of two or more of NiSb, SnSb, ZnSb, and the like, but not limited thereto.

Further, the inorganic salt includes any one or a combination of two or more of NaF, NaK, LiCl, NaCl, KCl, NaBr, KBr, and the like, but is not limited thereto.

The embodiment of the invention also provides application of any one of the MAX phase layered materials containing antimony at the A site in the fields of superconductivity, energy storage and the like.

The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.

Example 1: in this embodiment, the MAX phase layered material with the A site being antimony element is Nb₂SbC powdered material.

The Nb₂SbC the preparation method of the powder is as follows:

(1) metal Nb powder (purity 99.99 wt.%), Sb powder (purity 99.99 wt.%), graphite powder (1, 300 mesh) with particle size of 500 mesh and molar ratio of 2:1:1 are weighed, and the materials are ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1000 ℃, the heat preservation time is 30min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) And crushing, grinding and sieving the reaction product to obtain a powder sample.

Detecting the powder treated in step (3) by X-ray diffraction spectrum (XRD) (as shown in figure 1). The theoretical simulation result obtained by the Reitveld method full spectrum analysis is highly consistent with the experimental result (R)_wp9.8%), proving that the method successfully synthesizes Nb₂Type SbC MAX phase material (fig. 2) has a lattice constant of a 0.3314nm and c 1.3239 nm. Small amount of NbSb present in the powder₂Alloy phase impurities, which are by-products in the reaction.

FIG. 3 is a MAX phase Nb₂SbC high resolution transmission electron micrograph and atomic element distribution map. It is clear from this that the two alternating stacked nanostructures consist of Nb₂Layer C and ProSbAnd (4) sub-layer composition. And the atomic position can be clearly distinguished through atomic-level energy spectrum surface scanning analysis and line scanning analysis, and Nb, Sb is approximately equal to 2:1, and Nb are quantitatively analyzed through energy spectrum₂SbC, the stoichiometric ratios of the elements match. The chemical expression of the obtained novel MAX phase material is Nb₂SbC。

Example 2: in this embodiment, the MAX phase layered material with the A site being antimony element is Ti₃SbC₂A bulk material.

The Ti₃SbC₂The preparation method of the block body comprises the following steps:

(1) weighing metal Ti powder (purity 99.99 wt.%), Sb powder (purity 99.99 wt.%), graphite powder (300 mesh) with particle size of 500 mesh and molar ratio of 3:1:2, and grinding and mixing the materials to obtain a mixture.

(2) And pressing the mixture into a sheet by using a graphite mold, and putting the sheet into a spark plasma sintering system for reaction. The reaction conditions are as follows: the reaction temperature is 1300 ℃, the heat preservation time is 50min, and the inert atmosphere is used for protection. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.

(3) Washing the reaction product with deionized water and alcohol: and grinding the graphite layer on the surface of the reaction product, putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.

FIG. 4 shows Ti after the treatment of step (3)₃SbC₂The XRD pattern of the bulk sample is typical of the characteristic peak pattern of the MAX phase XRD pattern of type 211. FIG. 5 shows a MAX phase Ti₃SbC₂The spherical aberration correction high-resolution transmission electron microscope image and the atomic-scale element distribution image. It is clear from this that the two alternately stacked nanostructures consist of Ti₃C₂Layer and atomic layer of Sb. And the atomic position can be clearly distinguished through atomic-level energy spectrum surface scanning analysis and line scanning analysis, and Ti, Sb and Ti are quantitatively analyzed through energy spectrum₃SbC₂The stoichiometric ratio of the elements in (A) is consistent. So obtained new MAX phase material chemical tableIs expressed as Ti₃SbC₂。

Example 3: in this embodiment, the MAX phase layered material with the A site being antimony element is Ti₃A SbCN bulk material.

The Ti₃The preparation method of the SbCN block body comprises the following steps:

(1) weighing the components in a molar ratio of 2:1:1 TiN powder (purity 99.99 wt.%), Ti powder (purity 99.99 wt.%), Sb powder (purity 99.99 wt.%), and graphite powder (300 mesh) with a particle size of 500 mesh, which are ground and mixed to obtain a mixture.

(2) And pressing the mixture into a sheet by using a graphite mold, and putting the sheet into a spark plasma sintering system for reaction. The reaction conditions are as follows: the reaction temperature is 1700 ℃, the heat preservation time is 30min, and the inert atmosphere is used for protection. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.

(3) Washing the reaction product with deionized water and alcohol: and grinding the graphite layer on the surface of the reaction product, putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.

FIG. 6 shows Ti after the treatment of step (3)₃XRD pattern of SbCN bulk sample. FIG. 7 is Ti₃SbCN edgeA high-resolution transmission electron microscope image and an atomic schematic diagram for correcting the spherical aberration of a crystal band axis. FIG. 8 shows a MAX phase Ti₃A spherical aberration correction high-resolution transmission electron microscope image and an atomic element distribution image of SbCN. It is clear from this that the two alternately stacked nanostructures consist of Ti₃A CN layer and an Sb atom layer. And the atomic position can be clearly distinguished through atomic-level energy spectrum surface scanning analysis and line scanning analysis, and Ti, Sb and Ti are quantitatively analyzed through energy spectrum₃The stoichiometric ratios of the elements in SbCN were matched. So that the obtained novel MAX phase material has a chemical expression of Ti₃SbCN。

Example 4: in this example, the A site is antimonyThe MAX phase layered material is Ti₃SbC₂And (3) powder materials.

The Ti₃SbC₂The preparation method of the powder comprises the following steps:

(1) metal Ti powder (purity 99.99 wt.%), Sb powder (purity 99.99 wt.%), and graphite powder (300 mesh) with particle size 500 mesh and molar ratio of 3:1:2 are weighed, and the materials are ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1500 ℃, the heat preservation time is 120min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and (3) putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, then washing off the residual salt in the reaction product, and then carrying out suction filtration. And finally, cleaning the treated reaction product by using ethanol, putting the cleaned reaction product into a drying oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a powder product.

Example 5: in this embodiment, the MAX phase layered material with the A site being antimony element is Nb₄SbC₃And (3) powder materials.

The Nb₄SbC₃The preparation method of the powder comprises the following steps:

(1) metal Nb powder (purity 99.99 wt.%), Sb powder (purity 99.99 wt.%), and graphite powder (300 mesh) with particle size of 500 mesh are weighed according to a molar ratio of 4:1:3, and the materials are ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1400 ℃, the heat preservation time is 120min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and (3) putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, then washing off the residual salt in the reaction product, and then carrying out suction filtration. And finally, cleaning the treated reaction product by using ethanol, putting the cleaned reaction product into a drying oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a powder product.

Example 6: in this embodiment, the MAX phase layered material with the A site being antimony and iron is Ta₂(Sb_xFe_1-x) C, powder material. The Ta₂(Sb_xFe_1-x) The preparation method of the powder C comprises the following steps:

(1) metal Ta powder (purity 99.99 wt.%) with particle size of 500 mesh and FeSb powder with 300 mesh are weighed according to molar ratio of 2:1:1₂Powder (purity 99.99 wt.%), 300 mesh graphite powder, which were ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1700 ℃, the heat preservation time is 120min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) And crushing, grinding and sieving the reaction product to obtain a powder sample.

Example 7: in this embodiment, the MAX phase layered material with the A site being antimony element is Nb₂(Sb_xCu_1-x) C, powder material.

The Nb₂(Sb_xCu_1-x) The preparation method of the powder C comprises the following steps:

(1) weighing metal Nb powder (purity 99.99 wt.%) with particle size of 500 meshes and CuSb powder with particle size of 300 meshes in a molar ratio of 2:1:1₂Powder (purity 99.99 wt.%), 300 mesh graphite powder, which were ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1700 ℃, the heat preservation time is 120min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) And crushing, grinding and sieving the reaction product to obtain a powder sample.

Example 8: in this embodiment, the MAX phase layered material with the A site being antimony element is Ti₂(Sb_xNi_1-x) C, powder material.

The Ti₂(Sb_xNi_1-x) The preparation method of the powder C comprises the following steps:

(1) weighing Ti with the particle size of 500 meshes in the molar ratio of 1:2:1:3:3₂AlC powder and NiCl₂Powder (purity 99.99 wt.%), 300 mesh antimony powder (purity 99.99 wt.%), LiCl (purity 99 wt.%), KCl (purity 99 wt.%), which were mixed by grinding to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 400 ℃, the heat preservation time is 120min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and (3) putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, then washing off the residual salt in the reaction product, and then carrying out suction filtration. And (3) putting the reaction product obtained by suction filtration into an oven at 40 ℃, and taking out after 12 hours to obtain a powder product.

Example 9: in this embodiment, the MAX phase layered material with the A site being antimony element is Cr₂(Sb_xCo_1-x) C, powder material.

The Cr is₂(Sb_xCo_1-x) The preparation method of the powder C comprises the following steps:

(1) weighing Cr with the granularity of 500 meshes and the molar ratio of 1:3:1:10₂The method comprises the following steps of grinding and mixing AlC powder, CoO powder (purity 99.99 wt.%), 300-mesh antimony powder (purity 99.99 wt.%), and NaI (purity 99 wt.%), so as to obtain a mixture. (2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1000 ℃, the heat preservation time is 30min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and (3) putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, then washing off the residual salt in the reaction product, and then carrying out suction filtration. And (3) putting the reaction product obtained by suction filtration into an oven at 40 ℃, and taking out after 12 hours to obtain a powder product.

Example 10: in this embodiment, the MAX phase layered material with the A site being antimony element is Ti₂(Sb_xTe_1-x) C, powder material.

The Ti₂(Sb_xTe_1-x) The preparation method of the powder C comprises the following steps:

(1) weighing Ti with the particle size of 500 meshes in the molar ratio of 1:2.5:1:1:5₂AlC powder and CdCl₂Powder (purity 99.99 wt.%), 300-mesh antimony powder (purity 99.99 wt.%), 300-mesh Te powder (purity 99.99 wt.%), and NaBr (purity 99 wt.%), which are ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 800 ℃, the heat preservation time is 50min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and (3) putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, then washing off the residual salt in the reaction product, and then carrying out suction filtration. And (3) putting the reaction product obtained by suction filtration into an oven at 40 ℃, and taking out after 12 hours to obtain a powder product.

Example 11: in this embodiment, the MAX phase layered material with the A site being antimony element is V₂SbC powdered material.

The V is₂SbC the preparation method of the powder is as follows:

(1) weighing V with the granularity of 500 meshes and the molar ratio of 1:3:1:6₂The preparation method comprises the following steps of grinding and mixing AlC powder, AgCl powder (purity 99.99 wt.%), SnSb powder of 300 meshes and NaF (purity 99 wt.%), so as to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 800 ℃, the heat preservation time is 90min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring and ultrasonically cleaning for 30 minutes, and then carrying out suction filtration. And (3) treating the reaction product obtained by suction filtration with 2mol/L nitric acid solution, and washing off the residual metal simple substance in the reaction process. And finally, carrying out suction filtration on the treated reaction product, cleaning the reaction product by using ethanol, putting the reaction product into a drying oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a powder product.

Example 12: in this embodiment, the MAX phase layered material with the A site being antimony element is Ti₃(Sb_xSn_1-x)C₂And (3) powder materials. The Ti₃(Sb_xSn_1-x)C₂The preparation method of the powder comprises the following steps:

(1) weighing Ti with the particle size of 500 meshes and the molar ratio of 1:2:1:3₃AlC₂Powder, CoCl₂Powder (purity 99.99 wt.%), 300 mesh SnSb powder, NaCl (purity 99 wt.%), and the above materials were ground and mixed to obtain a mixture.

(2) The mixture is put into an alumina crucible and then put into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 800 ℃, the heat preservation time is 90min, and the inert atmosphere is used for protection. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.

(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring and ultrasonically cleaning for 30 minutes, and then carrying out suction filtration. And (3) treating the reaction product obtained by suction filtration with 2mol/L hydrochloric acid solution, and washing off the residual metal simple substance in the reaction process. And finally, carrying out suction filtration on the treated reaction product, cleaning the reaction product by using ethanol, putting the reaction product into a drying oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a powder product.

The inventor of the present invention also conducted related experiments by replacing the corresponding raw materials and process conditions in the foregoing examples 1-12 with other raw materials and process conditions mentioned in the present specification, and the results all show that MAX phase layered materials containing antimony at a-site can be obtained. In summary, compared with the existing MAX phase material, the novel MAX phase material containing the antimony element at the a-site provided by the embodiment of the present invention has a series of advantages of high strength, high thermal conductivity, high electrical conductivity, oxidation resistance, high temperature resistance, high damage tolerance, processability, etc., and the preparation process is simple and easy to operate, and has potential application prospects in the fields of superconductivity, energy storage, catalysis, biology, microwave devices, etc.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.