CN114988425A - MAX phase material with boron element stable X bit as chalcogen element, preparation method and application thereof - Google Patents
MAX phase material with boron element stable X bit as chalcogen element, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an MAX phase material with boron element stable X site as chalcogen element, a preparation method and application thereof, belonging to the technical field of materials. The molecular formula of the MAX phase layered material is expressed as M 2 AX, X is (B) x Ch 1‑x ) X is 0-1, x is not equal to 0, and Ch is S, Se, Te and any combination thereof. The invention provides a novel MAX phase material with X position being chalcogen under the stabilization action of B atom, which adjusts and controls the physical and chemical properties of the X position chalcogen by introducing the X position chalcogen to achieve the purpose of application in the fields of energy storage, catalysis, electrons, thermoelectricity and the like. The novel MAX phase material is simple in preparation method, low in consumption and universal.
Description
Technical Field
The invention relates to an inorganic material, in particular to an MAX phase material with boron element stable X bit as chalcogen element, a preparation method and application thereof, belonging to the technical field of materials.
Background
The MAX phase is a large class of non-van der Waals layered solid materials, and these hexagonal prism compounds have a general chemical formula M n+1 AX n In a hexagonal symmetrical structure (P6) 3 /mmc) where M is a transition metal, a is predominantly a main group element, X is C, N, B, n is 1-3 (m.w. barsum et al, prog.solid State Ch.,2000,28(1-4), 201-. Theoretical calculations predict that there are over 600 MAX phases with thermodynamic stability, of which over 70 have been successfully synthesized. The M, A, and X bits of the MAX phases that have been found include more than 20M-bit elements, nearly 20A-bit elements, and 3X-bit elements. Wherein M is n+1 X n The nanostructure sublayer is composed of covalent bonds 6 X octahedron layer, X element occupies octahedron gap of M element; and A is a monoatomic layer and M n+1 X n The interaction force between the nanostructure sub-layers is weak and is in a state similar to a metal bond. By virtue of its unique covalent M 6 The X octahedron and the metalloid A layer form an alternate arrangement structure, and the MAX phase shows the composite characteristic of metal and ceramic: these MAX phases generally combine the lightweight, high strength, oxidation resistance, creep resistance and good thermal stability of ceramics with high electrical conductivity, high thermal conductivity, relative flexibility of metals and good damage tolerance, high temperature plasticity and processability (j. Gonzalez-Julian et al, j.am.chem.soc.,2021,104(2), 659-. Recent studies have also found that MAX phases have low irradiation activity and good material connection properties (c.wang et al, nat. commun.,2019,10, 622)&X.Zhou et al, Carbon,2016,102, 106-. Therefore, most of the current research on the corresponding application fields of MAX mainly focuses on the direction of high-safety structural materials including high-temperature electrodes, high-speed pantograph, nuclear fuel cladding tube, etc., while relatively little research on the application fields of MAX phase functionalization.
The chemical and structural diversity of the MAX phase is crucial to optimize its performance for future applications (m.sokol et al, Trends in chem.,2019,1(2),210-The measurement and control of the MAX phase element composition and the electron cloud structure to obtain the MAX phase with brand new physicochemical properties and improve the understanding of people on the MAX phase material crystal structure are always important directions of the efforts of scholars in the field. Experiments have shown that the elements at various positions in the MAX phase play a decisive role in the properties of the material. For example, functional chemical elements are doped into the M site of the MAX phase, and the MAX phase solid solution is formed by regulating and controlling the arrangement mode of the M site elements, which is an important means for exploring the physicochemical properties of the novel MAX phase at present. By introducing Fe, Mn, etc. atoms into Cr 2 AlC、Cr 2 GeC、Cr 2 GaC and V 2 The M position of MAX phase such as AlC can obtain MAX phase and MAX phase solid solution (C.Hamm et al., mater. chem. front.,2018,2,483-490) with magnetic property. The Swedish Linxuepin university Per Eklund team in Nature Materials reports that the twin structure M is maintained by the method of A site element replacement n+1 X n Multiple metal elements (such as Au, Ir, and the like) are simultaneously inserted into the nano sub-layer, so that the physicochemical properties of the MAX phase material, such as the ohmic contact performance of the MAX phase and SiC (H.Fashandi et al, nat. Mat.,2017,16, 814-Asca 818), can be effectively regulated and controlled. However, the chemical diversity of MAX phases has so far been mainly limited to both M-and A-positions, such as the subgroup MAX phases (Ti) 3 ZnC 2 (M.Li et al.,J.Am.Chem.Soc.,2019,141,4730-4737)、Nb 2 CuC (H.M. Ding et al, mater.Res.Lett.,2019,7(12),510- 2 FeC (Y.B. Li et al, appl.Phys.Rev.,2021,8(3),03148)), rare earth metal MAX phase (Lu) 2 SnC (S.Kuchida et al, Physica C,2013,494,77-79)), and a high entropy MAX phase ((Ti, Zr, Hf, Nb, Ta) 2 AlC (W.Bao et al, scr. mater, 2020,183,33-38) and V 2 (Sn, a) C (a ═ Fe, Co, Ni, Mn) (y, Li et al, PNAS,2020,117(2), 820-. A common choice for X bits in the MAX phase is C and/or N, because the compatibility requirements of M and X atoms are high, i.e., the size of the X bit atom should be able to occupy M 6 Center of X octahedron. Dirk Jorrendt et al synthesized and characterized the first boride MAX phase Nb by a solid state method 2 SB (t. Rackl et al, phys. rev. mater, 2019,3(5), 054001). Experiments prove that the physical and mechanical properties of MAX phase are adjusted by the boron atom at X positionThis attempt opens a door to extend the X-site element of the MAX phase, as can superconductivity, thermal conductivity, hardness and breaking strength (t. rackl et al, Solid State sci, 2020,106, 106316). However, the X-bit elements of the MAX phase explored so far are all elements of smaller atomic size (C, N, B).
Disclosure of Invention
In view of the above problems of the prior art, an object of the present invention is to provide a MAX phase material in which X site is a chalcogen element under the stabilization of B atoms.
In order to achieve the above purpose, the invention is realized by the following scheme: a MAX phase material with B element as stable X bit as chalcogen element, wherein the molecular formula of MAX phase layered material is expressed as M 2 AX, X is (B) x Ch 1-x ) X is 0-1, x is not equal to 0, and Ch is S, Se, Te and any combination thereof.
It is extremely difficult to introduce chalcogen into X site alone, and in the invention, B atom with least outer charge number is adopted to stabilize the stable existence of chalcogen atom (such as S, Se, Te, etc.) in X site, so that the formed MAX phase is greatly changed due to the electron cloud density of X site atom, and further the change of structure and performance is regulated and controlled.
In the MAX phase material in which the boron element stabilizes the X site as a chalcogen element, M is preferable 2 M in AX comprises one or more of Zr, Hf, Nb, Ti, V and Ta.
In the MAX phase material in which the boron element stabilizes the X site as a chalcogen element, M is preferable 2 A in AX comprises one or more of S, Se and Te.
In the MAX phase material in which B is a stable element and X is a chalcogen element, the MAX phase material has a hexagonal structure and a space group of P6 3 Per mm, unit cell of M 2 The X unit and the chalcogen atomic layer are stacked alternately.
The invention also provides a preparation method of the MAX phase material with stable X site of boron element as chalcogen element, which comprises the following steps: mixing the M material, the A material and the X material, and reacting at 800-1700 ℃ in an inert atmosphere to obtain the MAX phase material with the stable X site of the boron element as the chalcogen element.
In the preparation method, the molar ratio of the M material, the A material and the X material is 2 (1-1.5) to 1-1.5.
In the above production method, preferably, the M material includes a simple substance M and/or an alloy containing M.
In the above production method, preferably, the a material includes a simple substance a and/or an alloy containing a.
In the above production method, preferably, the X material includes a simple substance X and/or an alloy containing X.
In the preparation method, the preferable reaction time is 30-120 min, and the pressure is 0-70 MPa.
The invention also aims to provide application of the MAX phase material with boron element stabilizing X site as chalcogen in energy storage, catalysis, electron, thermoelectricity or preparation of two-dimensional transition metal boride/borosulfide MXene precursor.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a novel MAX phase material with X position being chalcogen under the stabilization action of B atoms, and the electronic structure of the chalcogen is greatly changed compared with the existing MAX phase material due to the introduction of the chalcogen in the X position, so that the physical and chemical properties of the MAX phase material are changed. The physical and chemical properties of the sulfur and selenium element at the X position are regulated and controlled by introducing the sulfur and selenium element at the X position, so that the purpose of the application of the sulfur and selenium element in the fields of energy storage, catalysis, electrons, thermoelectricity and the like is achieved.
2. The invention realizes the preparation of the novel MAX phase material of which the X position is the chalcogen element under the stabilization action of the B atom for the first time, and has simple preparation method, low consumption and universality.
3. The present invention uses chalcogen to change the electronic structure of the MAX phase material over a large range, and it is expected that MAX phase materials with semiconductor properties can be obtained by this method.
Drawings
FIGS. 1a-c show Zr as a MAX phase material in which B is stable and X is a chalcogen element in examples 1-3 of the present invention 2 Se(B x Se 1-x ) The XRD diagram and the total spectrum analysis result diagram of the Reitveld method;
FIGS. 2a-c show Zr as a MAX phase material with B element stabilizing X site as chalcogen element in examples 1-3 of the present invention 2 Se(B x Se 1-x ) SEM image of fracture cross section;
FIGS. 3a-b are views of the observed Zr as a MAX phase material with stable X site chalcogen of boron in examples 2-3 of the present invention 2 Se(B x Se 1-x ) A spherical aberration correction high-resolution transmission electron microscope image and an element contrast analysis image;
FIG. 4 shows the MAX phase material and Zr of example 2-3 of the present invention in which B stabilizes X as chalcogen 2 Results of resistivity testing of the sebmax phase material.
Detailed Description
Example 1: in this embodiment, the MAX phase material with B as the stable X site chalcogen is Zr 2 Se(B 0.9 Se 0.1 ) The block material is prepared by the following steps:
(1) 3.5g of zirconium powder with the granularity of 400 meshes, 1.5g of selenium powder with the granularity of 300 meshes and 0.2g of boron powder with the granularity of 300 meshes are weighed and 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: under the protection of nitrogen in inert atmosphere, the reaction temperature is 1600 ℃, the heat preservation time is 20min, and the pressure is 50 Mpa. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.
(3) Removing graphite paper on the surface of the obtained block, polishing the block to a mirror surface by using abrasive paper with different meshes, putting the mirror surface into a 50 ℃ oven, and taking out the block for 12 hours to obtain a block material.
And (4) detecting the block treated in the step (3) by utilizing X-ray diffraction spectrum (XRD). (R) can be obtained by the Reitveld method full spectrum analysis wp 11.04%), which successfully synthesized Zr 2 Se(B x Se 1-x ) MAX phase materials of type, in this example x is 0.9 (see fig. 1a), with lattice constants a 0.35617nm and c 1.26330 nm. The impurities of zirconium oxide and zirconium boride appearing in the powder may be derived from the oxidation of zirconium element in the preparation process, and the impurities of zirconium oxide and zirconium boride are derived from the by-product obtained by the reaction of zirconium and boronA compound (I) is provided.
When the fracture cross section of the bulk treated in step (3) is observed by using a Scanning Electron Microscope (SEM), the synthesized powder has a typical MAX phase layered structure (see fig. 2 a). As shown in table 1, the above-mentioned presumption can be further verified by energy spectrum analysis, and the bulk is composed of Zr, Se, B, etc. elements, wherein the atomic percentage ratio of Zr element to Se is 2.05, which is in accordance with experimental design and XRD analysis.
Table 1: the result of energy spectrum analysis of the obtained block
Example 2: in this embodiment, the MAX phase material with B as the stable X site chalcogen is Zr 2 Se(B 0.4 Se 0.6 ) The block material is prepared by the following method:
(1) 2.2g of zirconium powder with the granularity of 400 meshes, 1.5g of selenium powder with the granularity of 300 meshes and 0.05g of boron powder with the granularity of 300 meshes are weighed and ground and mixed to obtain a mixture.
(2) And pressing the mixture into a sheet by using a graphite mold, and then putting the sheet into a spark plasma sintering system for reaction. The reaction conditions are as follows: the reaction temperature is 1600 ℃, the heat preservation time is 20min, the pressure is 50Mpa, and the protection is carried out in inert atmosphere. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.
(3) Removing graphite paper on the surface of the obtained block, polishing the block to a mirror surface by using abrasive paper with different meshes, putting the mirror surface into a 50 ℃ oven, and taking out the block for 12 hours to obtain a block material.
And (4) detecting the block treated in the step (3) by utilizing X-ray diffraction spectrum (XRD). (R) can be obtained by the Reitveld method full spectrum analysis wp 11.04%), which successfully synthesized Zr2Se (B) x Se 1-x ) MAX phase materials of type, in this example X is 0.4 (see fig. 1b), and have a lattice constant of 0.36920nm for a and 1.25635nm for c. The impurities of zirconium oxide and zirconium boride appearing in the powder are small, wherein the former is probably from the oxidation of zirconium element in the preparation process, and the latter is from a by-product obtained by the reaction of zirconium and boron.
When the fracture section of the block treated in step (3) is observed by using a Scanning Electron Microscope (SEM), it can be seen that the synthesized powder has a layered structure, but the crystal grains are reduced (see fig. 2 b). As shown in table 2, the spectrum analysis can further verify the above presumption that the bulk is composed of Zr, Se, B, etc. elements, wherein the atomic percent ratio of Zr element to Se is 1.28, which is approximately 1.25, and meets the experimental design and XRD analysis. By using a spherical aberration correction high-resolution transmission electron microscope, the X layer atoms in the material can be clearly seen to have obvious contrast (as shown in figure 3a), namely Zr 2 The partial B atoms in the B layer are replaced by Se atoms, which can be well matched with the energy spectrum result of a scanning electron microscope.
Table 2: the result of energy spectrum analysis of the obtained block
Example 3: in this embodiment, the MAX phase material with B as a stable X site chalcogen is Zr 2 Se(B 0.03 Se 0.97 ) The block material is prepared by the following steps:
(1) 2.3g of zirconium powder with the granularity of 400 meshes, 2g of selenium powder with the granularity of 300 meshes and 0.02g of boron powder with the granularity of 300 meshes are weighed and 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 1600 ℃, the heat preservation time is 20min, the pressure is 50Mpa, and the protection is carried out in inert atmosphere. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.
(3) Removing graphite paper on the surface of the obtained block, polishing the block to a mirror surface by using abrasive paper with different meshes, putting the mirror surface into a 50 ℃ oven, and taking out the block for 12 hours to obtain a block material.
And (4) detecting the block treated in the step (3) by utilizing X-ray diffraction spectrum (XRD). (R) can be obtained by the Reitveld method full spectrum analysis wp 14.64%), which successfully synthesized Zr2Se (B) x Se 1-x ) Type MAX phase material, X ═ 0.03 (fig. 1c), with a lattice constant of 0.37447nm, c ═ 1.25045 nm. The impurities of zirconium oxide and zirconium boride appearing in the powder are small, wherein the former is probably from the oxidation of zirconium element in the preparation process, and the latter is from a by-product obtained by the reaction of zirconium and boron.
When the fracture section of the block treated in step (3) is observed by using a Scanning Electron Microscope (SEM), it can be seen that the synthesized powder has a layered structure, but the crystal grains are reduced (see fig. 2 c). As shown in table 3, the above-mentioned presumption can be further verified by energy spectrum analysis, and the bulk is composed of Zr, Se, B, etc. elements, wherein the atomic percentage ratio of Zr element to Se is 1.01, which is close to 1, and meets experimental design and XRD analysis. By using a high-resolution transmission electron microscope for spherical aberration correction, the atomic contrast of the X layer in the material is clearly close to that of the A layer (as shown in figure 3b), namely Zr 2 Almost all the B atoms in the X layer are replaced by Se atoms, which can be well matched with the energy spectrum result of a scanning electron microscope.
Table 3: the result of energy spectrum analysis of the obtained block
Example 4: in this embodiment, the chalcogen MAX phase layered material of the B atom X site is Nb 2 Se(B 0.9 Se 0.1 ) And (3) powder materials. The Nb 2 Se(B 0.9 Se 0.1 ) The preparation method of the powder comprises the following steps:
(1) weighing 3.6g of niobium powder with the granularity of 400 meshes, 1.5g of selenium powder with the granularity of 300 meshes and 0.2g of boron powder with the granularity of 300 meshes, and grinding and mixing the materials to obtain a mixture.
(2) And pressing the mixture into a sheet by using a graphite mold, and then putting the sheet into a spark plasma sintering system for reaction. The reaction conditions are as follows: the reaction temperature is 1600 ℃, 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.
Example 5: in this embodiment, the chalcogen MAX phase layered material of the X site of the B atom is Hf 2 S(B 0.9 S 0.1 ) A bulk material. The Hf is 2 S(B 0.9 S 0.1 ) The preparation method of the block body comprises the following steps:
(1) weighing 4.5g of hafnium powder with the granularity of 400 meshes, 0.45g of sulfur powder with the granularity of 300 meshes and 0.12g of boron powder with the granularity of 300 meshes, 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 1500 ℃, the heat preservation time is 20min, the pressure is 60Mpa, and the protection is carried out in inert atmosphere. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.
(3) Removing graphite paper on the surface of the obtained block, polishing the block to a mirror surface by using abrasive paper with different meshes, putting the mirror surface into a 50 ℃ oven, and taking out the block for 12 hours to obtain a block material.
Example 6: in this embodiment, the MAX phase material with B as the stable X site chalcogen is Zr 2 Se(B 0.5 S 0.5 ) And (3) powder materials. Zr in the reaction solution 2 Se(B 0.5 S 0.5 ) The preparation method of the powder comprises the following steps:
(1) 2.3g of zirconium powder with the granularity of 400 meshes, 1g of selenium powder with the granularity of 300 meshes, 0.20g of sulfur powder with the granularity of 300 meshes and 0.06g of boron powder with the granularity of 300 meshes are weighed, and the materials 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 1600 ℃, 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.
Example 7: in this embodiment, the MAX phase material with B as the stable X site chalcogen is Zr 2 (Se 0.5 S 0.5 )(B 0.5 S 0.5 ) And (3) powder materials. Zr in the reaction solution 2 (Se 0.5 S 0.5 )(B 0.5 S 0.5 ) The preparation method of the powder comprises the following steps:
(1) weighing 4.6g of zirconium powder with the granularity of 400 meshes, 1g of selenium powder with the granularity of 300 meshes, 0.8g of sulfur powder with the granularity of 300 meshes and 0.13g of boron powder with the granularity of 300 meshes, 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 1600 ℃, 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 (3) grinding a 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.
Example 8: in this embodiment, the MAX phase material with B as the stable X site chalcogen is Zr 2 Se(B 0.5 S 0.25 Se 0.25 ) And (3) powder materials. Zr in the reaction solution 2 Se(B 0.5 S 0.25 Se 0.25 ) The preparation method of the powder comprises the following steps:
(1) 5.5g of zirconium powder with the granularity of 400 meshes, 3g of selenium powder with the granularity of 300 meshes, 0.24g of sulfur powder with the granularity of 300 meshes and 0.16g of boron powder with the granularity of 300 meshes are weighed, and the materials 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 1600 ℃, 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.
Example 9: in this example, the chalcogen MAX phase layered material at the X site of the B atom is (Nb) 1/3 Zr 1/3 Hf 1/3 ) 2 S(B 0.9 S 0.1 ) A bulk material. The (Nb) 1/3 Zr 1/3 Hf 1/3 ) 2 S(B 0.9 S 0.1 ) The preparation method of the block body comprises the following steps:
(1) 0.7g of zirconium powder with the granularity of 400 meshes, 0.75g of Nb powder, 1.5g of hafnium powder, 0.45g of sulfur powder with the granularity of 300 meshes and 0.12g of boron powder with the granularity of 300 meshes are weighed, and the materials 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 1500 ℃, the heat preservation time is 20min, the pressure is 60Mpa, and the protection is carried out in inert atmosphere. And taking out the reaction product in the graphite mold after the temperature of the sintering system is reduced to room temperature.
(3) Removing graphite paper on the surface of the obtained block, polishing the block to a mirror surface by using abrasive paper with different meshes, putting the mirror surface into a 50 ℃ oven, and taking out the block for 12 hours to obtain a block material.
Resistivity Performance test
Taking Zr in the prior art 2 SeB MAX phase Material and Zr in example 2 2 Se(B 0.4 Se 0.6 ) MAX phase Material and Zr in example 3 2 Se(B 0.03 Se 0.97 ) The resistivity of the MAX phase material was tested and the results are shown in figure 4. From the figure, Zr 2 The SeB phase has good electrical properties and room temperature resistance of about 7.6x10 -7 Ω · m, but the resistivity of the material increases by orders of magnitude as the X-site atoms are occupied by chalcogen.
In conclusion, the invention provides a novel MAX phase material of chalcogen with X site under the stabilization action of B atom, and the physical and chemical properties of the MAX phase material are regulated by introducing the chalcogen with X site, so that the purpose of application in the fields of energy storage, catalysis, electronics, thermoelectricity and the like is achieved. The novel MAX phase material is simple in preparation method, low in consumption and universal.
The above description is illustrative of the present invention and is not to be construed as limiting thereof, as numerous modifications and variations therein are possible to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A MAX phase material with B element as stable X bit as chalcogen element, wherein the molecular formula of the MAX phase layered material is expressed as M 2 AX, X is (B) x Ch 1-x ) X is 0-1, x is not equal to 0, and Ch is S, Se, Te and any combination thereof.
2. The boron stabilized MAX phase material for use as a chalcogen of claim 1 wherein M is a transition metal 2 M in AX comprises one or more of Zr, Hf, Nb, Ti, V and Ta.
3. The boron stabilized X-site chalcogen MAX phase material of claim 1, wherein M is a chalcogen 2 A in AX comprises one or more of S, Se and Te.
4. A method of preparation of a MAX phase material of any of claims 1 to 3 in which boron stabilizes the X site as a chalcogen, the method comprising: mixing the M material, the A material and the X material, and reacting at 800-1700 ℃ in an inert atmosphere to obtain the MAX phase material with the stable X site of the boron element as the chalcogen element.
5. The method of claim 4, wherein the molar ratio of M material to A material to X material is 2 (1-1.5) to (1-1.5).
6. The production method according to claim 4 or 5, wherein the M material includes M simple substance and/or an alloy containing M.
7. The production method according to claim 4 or 5, wherein the material A comprises elemental A and/or an alloy containing A.
8. The production method according to claim 4 or 5, wherein the X material includes X element and/or an alloy containing X.
9. The preparation method according to claim 4, wherein the reaction time is 30-120 min and the pressure is 0-70 MPa.
10. Use of a MAX phase material stabilized by elemental boron with the X site being a chalcogen as claimed in any of claims 1-3 for energy storage, catalysis, electronics, thermoelectricity or for the preparation of two-dimensional transition metal boride/borosulfide MXene precursors.
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| CN113233470A (en) * | 2021-05-21 | 2021-08-10 | 中国科学院宁波材料技术与工程研究所 | Two-dimensional transition metal boride material, and preparation method and application thereof |
| CN114276148A (en) * | 2022-01-03 | 2022-04-05 | 西北工业大学 | Hexagonal layered boride ceramic h-MAB material and preparation method thereof |
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| CN113233470A (en) * | 2021-05-21 | 2021-08-10 | 中国科学院宁波材料技术与工程研究所 | Two-dimensional transition metal boride material, and preparation method and application thereof |
| CN114276148A (en) * | 2022-01-03 | 2022-04-05 | 西北工业大学 | Hexagonal layered boride ceramic h-MAB material and preparation method thereof |
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