CN112875703A - High-entropy two-dimensional material, high-entropy MAX phase material and preparation method thereof - Google Patents

High-entropy two-dimensional material, high-entropy MAX phase material and preparation method thereof Download PDF

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CN112875703A
CN112875703A CN202110023188.1A CN202110023188A CN112875703A CN 112875703 A CN112875703 A CN 112875703A CN 202110023188 A CN202110023188 A CN 202110023188A CN 112875703 A CN112875703 A CN 112875703A
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entropy
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dimensional material
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杨树斌
杜志国
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Beihang University
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Abstract

The invention discloses a high-entropy two-dimensional material, a high-entropy MAX phase material and a preparation method thereof, wherein the high-entropy two-dimensional material has a two-dimensional lamellar structure and consists of M elements and X elements, wherein the M elements are selected from IIIB, IVB, VB, VIB, VIIB and VIIIAt least five metal elements in IB and IIB groups, wherein the X element is at least one non-metal element selected from IIIA, IVA, VA and VIA; the chemical general formula of the high-entropy MAX phase material is M n+1AX n The high-entropy two-dimensional material can be used as a precursor for preparing the high-entropy two-dimensional material, and the component A in the precursor is etched to obtain the high-entropy two-dimensional material.

Description

High-entropy two-dimensional material, high-entropy MAX phase material and preparation method thereof
Technical Field
The invention relates to the field of new materials, in particular to a high-entropy two-dimensional material, a high-entropy MAX phase material and a preparation method thereof.
Background
High-entropy ceramic materials, which generally refer to multi-principal solid solutions formed of 5 or more ceramic components, have recently become one of the hot research spots in the ceramic field due to their novel "high-entropy effect" and excellent properties. In 2015, Rost, Maria, Curtarolo and the like firstly report a high-entropy ceramic material which takes MgO, NiO, CoO, CuO and ZnO as initial raw materials, wherein the rest 3 oxides except CuO and ZnO are rock-salt ore structures. 5 oxides are uniformly mixed, heated in air and kept at 875 ℃ for 12 hours to form the single-phase (MgNiCoCuZn) O high-entropy ceramic. Different from the traditional material, the multi-principal-element high-entropy alloy has complex components, and the atoms of the constituent elements are randomly and disorderly distributed on lattice positions, so that the high-entropy alloy has a high-entropy effect in thermodynamics, a slow diffusion effect in kinetics, a lattice distortion effect in structure and a cocktail effect in performance. The mixing mode of various main elements of the high-entropy alloy leads the mixing entropy of the material to reach the maximum, the high mixing entropy inhibits the formation of intermetallic compounds, and the formation of saturated solid solution with simple crystal structure is promoted. Under the coupling action of various mechanisms, the high-entropy alloy has excellent performances which cannot be compared with many traditional materials, such as outstanding performances in the aspects of mechanics, electromagnetism, high temperature resistance, corrosion resistance and the like, so the high-entropy alloy is regarded as one of key materials expected to solve the bottleneck problem of material performance in the current engineering field. However, the research on the performance of the high-entropy material at present mainly focuses on changing the types of the constituent elements and the crystal structure of the high-entropy material so as to obtain the bulk alloy material, and no report is made on the low-dimensional high-entropy material at present.
Disclosure of Invention
The invention discloses a novel high-entropy two-dimensional material which has a two-dimensional lamellar structure and consists of M elements and X elements, wherein the M elements are selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, and the X elements are selected from at least one non-metal element in IIIA, IVA, VA and VIA.
In some embodiments, the two-dimensional lamellar structure has a thickness of 1nm to 20 nm.
In some embodiments, the two-dimensional sheet structure further has a crystal structure comprising: perovskite type, rock salt type or iron phosphorus sulfide type.
In some embodiments, the X element is at least one of carbon, nitrogen, oxygen, boron, phosphorus, or sulfur.
In some embodiments, the M element comprises one or more of the Pt, Au, V, Hf, W, Mo, Ag, Pd, Au, Ag, Fe, Co, Ni, Cu, or Bi elements.
In some embodiments, the two-dimensional lamellar structure contains functional groups, including: one or more of O, F, Cl, Br, I or OH.
On the other hand, the invention discloses a high-entropy MAX phase material which consists of M element, A element and X element and has a chemical general formula of M n+1AXnWherein, M element is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, A element is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements, X element is selected from at least one of carbon, nitrogen or boron element, and n is 1, 2, 3, 4, 5 or 6.
In some embodiments, when the M element is five metal elements, any one of Sc, Y, or Hf elements is not included therein.
In some embodiments, the high entropy MAX phase material of the invention further has a crystal structure comprising: perovskite type, rock salt type or iron phosphorus sulfide type.
In some embodiments, the M element comprises one or more of the Pt, Au, V, Hf, W, Mo, Ag, Pd, Au, Ag, Fe, Co, Ni, Cu, or Bi elements.
The invention also discloses a preparation method of the high-entropy MAX phase material, which comprises the following steps:
the material preparation step: determining the required amount of raw materials containing each element according to the stoichiometric ratio of each element in the chemical general formula of the high-entropy MAX phase material;
sintering: sintering each raw material at a preset temperature under the condition of protective atmosphere or vacuum to obtain a high-entropy two-dimensional material with a two-dimensional structure;
the high-entropy MAX phase material is composed of an M element, an A element and an X element, and the chemical general formula of the high-entropy MAX phase material is Mn +1AXn, wherein the M element is at least five metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, the A element is at least one element selected from VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA groups, the X element is at least one element selected from carbon, nitrogen or boron, and n is 1, 2, 3, 4, 5 or 6.
In some embodiments, in the step of compounding, the molar ratio of the M element, the A element and the X element in the required amount of the raw material is (n +1): 1.2-2): n.
In some embodiments, when the M element is five metal elements, any one of Sc, Y, or Hf elements is not included therein.
In some embodiments, the sintering temperature in the sintering step is between 600 ℃ and 1700 ℃.
The invention also discloses a preparation method of the high-entropy two-dimensional material, which comprises the following steps:
the high-entropy MAX phase material is prepared by adopting the preparation method of the high-entropy MAX phase material;
etching: and reacting the obtained high-entropy MAX phase material with an etching agent at a preset temperature, so that the etching agent selectively etches the component of the element A in the high-entropy MAX phase material, thereby obtaining the high-entropy two-dimensional material.
In some embodiments, the etchant is a hydrofluoric acid solution, an acid solution + fluoride salt system, or a halogen metal salt.
In some embodiments, the etchant in the etching step is one or more of a halogen simple substance, a halogen hydride, and a nitrogen hydride in a gas phase.
In some embodiments, the etching reaction temperature in the etching step is between 500 ℃ and 1200 ℃.
The invention also discloses another preparation method of the high-entropy two-dimensional material, which comprises the following steps:
the material preparation step: determining the required amount of raw materials containing each element according to the stoichiometric ratio of each element in the chemical general formula of the high-entropy two-dimensional material, wherein the high-entropy two-dimensional material consists of an M element and an X element, the M element is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, and the X element is selected from at least one of oxygen, silicon, phosphorus, sulfur, arsenic, selenium or tellurium;
sintering: sintering each raw material at a preset temperature under the condition of protective atmosphere or vacuum to obtain the high-entropy two-dimensional material with a two-dimensional structure.
In some embodiments, the sintering temperature in the sintering step is between 600 ℃ and 3000 ℃.
The invention also comprises a metallic lithium cathode containing the high-entropy two-dimensional material.
The high-entropy two-dimensional material disclosed by the invention has an ultrathin two-dimensional lamellar structure, and meanwhile, a large amount of metal atoms are exposed on the surface, so that the two-dimensional material is endowed with new performance and has application potential in catalysis, sensors, electronic devices, supercapacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials or superconducting materials.
Drawings
FIG. 1 high entropy MAX phase materials (Ti) in one embodiment of the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC (a) and high entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x (b) SEM photograph of (a).
FIG. 2 shows an exemplary high entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2XRD spectra of AlC and TiNbAlC were compared (a), high entropy MAX phase materials (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC and high entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x XRD patterns of (a) and (b).
FIG. 3 high entropy two-dimensional Material (Ti) in an embodiment of the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The HRTEM photograph (a) and the electron diffraction spectrum (b) of (A) were obtained.
FIG. 4 high entropy two-dimensional Material (Ti) in an embodiment of the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The HRTEM (a) of (a), the position-atom energy relationship of the line-scanned atoms (b), and the stress distribution pattern on the lamellar structure (c and d).
FIG. 5 high entropy two-dimensional Material (Ti) in an embodiment of the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x STEM photograph and atomic map of (a).
FIG. 6 high entropy two-dimensional Material (Ti) in an embodiment of the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The AFM photograph (a) and the thickness analysis chart (b) of (a).
FIG. 7 shows an exemplary high entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC (a) and high entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x (b) SEM photograph of (a).
FIG. 8 shows an exemplary high entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC and high entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x XRD spectrum of (1).
FIG. 9 shows a high-entropy two-dimensional material (Ti) prepared by vapor phase method according to an embodiment of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x TEM photograph and STEM atomic distribution map.
FIG. 10 shows a high-entropy two-dimensional material (Ti) prepared by vapor phase method according to an embodiment of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x AFM pictures (a, c) and corresponding thickness analysis charts (b, d).
FIG. 11 shows an embodiment of the present invention in which the high entropy two-dimensional material is Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3SEM photograph of (a).
FIG. 12 shows an embodiment of the present invention in which the high entropy two-dimensional material is Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3XRD spectrum of (1).
FIG. 13 high entropy two-dimensional material Fe in an embodiment of the invention0.2Co0.2Ni0.2Mn0.2Zn0.2PS3STEM photograph and atomic map of (a).
FIG. 14 high entropy two-dimensional material Fe in an embodiment of the invention0.2Co0.2Ni0.2Mn0.2V0.2PS3SEM photograph of (a).
FIG. 15 high entropy two-dimensional material Fe in an embodiment of the invention0.2Co0.2Ni0.2Mn0.2V0.2PS3XRD spectrum of (1).
FIG. 16 high entropy two-dimensional material Fe in an embodiment of the invention0.2Co0.2Ni0.2Mn0.2V0.2PS3STEM photograph and atomic map of (a).
FIG. 17 shows the results of the performance test of catalytic hydrogen production by high-entropy two-dimensional material in one embodiment of the present invention.
Fig. 18 shows voltage-capacity curves (a) of different sample films for lithium deposition, cycling performance tests (b) of different metal lithium electrodes, rate performance tests (c) and deep charge and deep discharge performance tests (d).
Detailed Description
The technical solution of the present invention will be described below by way of specific examples. 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 intended only to illustrate the invention and are not intended to limit the scope of the 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.
Example 1
The embodiment provides a high-entropy two-dimensional material, which has a two-dimensional lamellar structure and is composed of an M element and an X element, wherein the M element is selected from at least five metal elements in groups IIIB, IVB, VB, VIB, VIIB, VIII, IB, and IIB, and the X element is selected from at least one non-metal element in groups IIIA, IVA, VA, and VIA. The two-dimensional lamellar structure is a material with a two-dimensional lamellar structure, the size of the material reaches a nanometer size (1 nm-100 nm) in one-dimensional direction in a three-dimensional structure, the material with the two-dimensional lamellar structure is called a two-dimensional material, and carrier migration and heat diffusion of the material are limited in a two-dimensional plane, so that the material shows many peculiar properties, for example, the material has high specific surface area, when functional atoms are doped, the functional atoms can also generate a large amount of atom exposure on the two-dimensional lamellar structure (included in the structure of the two-dimensional lamellar structure or on the surface of the lamellar), and thus new performance is endowed to the two-dimensional material.
In some embodiments, the high-entropy two-dimensional material has a thickness of 1-20 atomic layers, or a thickness of 1 nm-20 nm, and has the characteristics of ultra-thin, soft and transparent properties, and has a larger specific surface area for the same material amount.
In some embodiments, the two-dimensional sheet structure of the high-entropy two-dimensional material of the present invention has a crystal structure, including but not limited to a perovskite-type, rock salt-type, or iron phosphorous sulfide-type crystal structure, with different arrangements of atoms corresponding to different crystal forms, corresponding to different exposure of atoms on the surface of the two-dimensional sheet.
In some embodiments, the X element is at least one of carbon, nitrogen, oxygen, boron, phosphorus, or sulfur.
In some embodiments, the high-entropy two-dimensional material M of the present invention includes functional metal atoms, because the high-entropy two-dimensional material has a two-dimensional lamellar structure and high specific surface area, a large amount of atoms are exposed on the two-dimensional lamellar structure, the functional atoms also generate a large amount of atom exposure on the two-dimensional lamellar structure, thereby endowing the two-dimensional material with new properties, for example, the element M of the high-entropy two-dimensional material of the invention contains metal atoms with catalytic performance, including but not limited to Pt, Pd, Au, Ag, Fe, Co, Ni, Cu or Bi, which endows the high-entropy two-dimensional material of the invention with excellent catalytic performance, and for example, the element M of the high-entropy two-dimensional material of the invention contains metal atoms with corrosion resistance, including but not limited to Pt, Au, V, Hf, W, Mo or Ag, which endows the high-entropy two-dimensional material of the invention with excellent corrosion resistance.
Example 2
This example provides a high-entropy MAX phase material, which is composed of M element, A element and X element, and has a chemical formula of M n+1AX n The composite material has a layered structure, wherein M is at least five metal elements selected from groups IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB, A is at least one element selected from elements in groups VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA, X is at least one element selected from carbon, nitrogen or boron, and n is 1, 2, 3, 4, 5 or 6 and respectively corresponds to MAX phases in a '211' configuration, a '312' configuration, a '413' configuration, a '514' configuration, a '615' configuration and a '716' configuration.
Typically, M elements include, but are not limited to: scandium, three or four of yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and lanthanoids (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium); the a elements include, but are not limited to: one or more of aluminum, silicon, phosphorus, sulfur, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, ruthenium, rhodium, palladium, cadmium, indium, tin, antimony, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, or astatine; wherein, MAX phase material of A being at least one element of aluminum, gallium, indium, lead, silicon, germanium, tin or sulfur is easy to prepare.
In some embodiments, the high entropy MAX phase materials of the present invention have a crystal structure including, but not limited to, a perovskite type, a rock salt type, or a phosphorus iron sulfide type.
The high-entropy MAX phase material can be used as a precursor for preparing a high-entropy two-dimensional material, and the high-entropy MAX phase material is reacted with an etching agent to etch away an A element component, so that the high-entropy two-dimensional material with a two-dimensional lamellar structure is obtained. Among them, the high-entropy MAX phase material used for preparing the precursor of the high-entropy two-dimensional material does not include any of Sc, Y or Hf when the M element is five metal elements, because the carbide or nitride of the three transition metals has high activity, is easy to decompose in air or react with acid gas or solution, and is difficult to exist stably. When the high-entropy bi-dimensional material is used as a precursor for preparing the high-entropy bi-dimensional material (high-entropy MXene), the high-entropy bi-dimensional material (high-entropy MXene) cannot be obtained because the high-entropy bi-dimensional material is easily removed by an etching agent.
In some embodiments, the high-entropy MAX phase material M element of the present invention comprises functional metal atoms, for example, the high-entropy MAX phase material M element of the present invention comprises metal atoms with catalytic properties, including but not limited to Pt, Pd, Au, Ag, Fe, Co, Ni, Cu, or Bi, and for example, the high-entropy MAX phase material M element of the present invention comprises metal atoms with corrosion resistance, including but not limited to Pt, Au, V, Hf, W, Mo, or Ag. And after the element A is etched, exposing a large amount of functional metal atoms in the two-dimensional lamellar structure of the obtained high-entropy two-dimensional material to obtain the novel two-dimensional material with a specific function.
In some embodiments, the high-entropy MAX phase material reacts with an etchant, wherein the preferred etchant is an acid, a metal salt or a gas containing halogen, and the surface of the obtained high-entropy two-dimensional material contains corresponding halogen functional groups, including-F, -Cl, -Br and-I, and the halogen functional groups have high activity and are easy to perform a substitution reaction of the functional groups, so that the surface modification of the two-dimensional lamellar structure of the high-entropy two-dimensional material is realized. When a liquid phase method (solution etching) is adopted, the surface of the obtained high-entropy two-dimensional material also comprises-OH or-O.
Example 3
The embodiment provides a preparation method of a high-entropy MAX phase material, which comprises the following steps:
the material preparation step: determining the required amount of raw materials containing each element according to the stoichiometric ratio of each element in the chemical general formula of the high-entropy MAX phase material;
sintering: sintering each raw material at a preset temperature under the condition of protective atmosphere or vacuum to obtain a high-entropy two-dimensional material with a two-dimensional structure; wherein the high-entropy MAX phase material consists of M element, A element and X element, and the chemical general formula is M n+1AX n Wherein, M element is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, A element is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements, X element is at least one of carbon, nitrogen or boron element, and n is 1, 2, 3, 4, 5 or 6.
In some embodiments, in the step of compounding, the molar ratio of the M element, the a element and the X element in the raw material is (n+1):(1.2～2):nThe required amount of each raw material is determined. The raw material of element A is slightly excessive because carbide of MX phase is easily formed during high temperature reaction in the sintering step, and the proper excess of element A can reduce the yield of MX in the reaction process, thereby effectively increasing the purity of MAX phase, and more preferably, the molar ratio of M element, A element and X element is (C) ((M))n+1):(1.2～1.3):n。
In a preferred embodiment, between the batching step and the sintering step, a raw material grinding step is further included: the required amount of raw materials are mixed and ground, preferably, the particle size range of the ground raw materials is between 1nm and 20 μm, more preferably, the particle size range is between 10nm and 500nm, the raw materials are refined and uniformly mixed through grinding, and the formation of the homogeneous MAX phase material in the sintering step is facilitated. In the specific implementation, the grinding step is preferably a ball milling device, and the ball milling is carried out in a ball milling mode, preferably, the ball milling implementation conditions are that the mass ratio of ball materials is 1: 1-30: 1, the ball milling speed is 50 r/min-600 r/min, and the ball milling time is 1-120 h.
In specific implementation, the sintering step is preferably carried out under the conditions that the sintering temperature is between 800 and 1500 ℃, and the sintering time is between 10 and 120 min.
In some embodiments, after the sintering step, a product grinding step is further included: and further grinding the high-entropy MAX phase material obtained after sintering to obtain powder of the high-entropy MAX phase material.
Example 4
The embodiment provides a preparation method of a high-entropy two-dimensional material, which comprises the following steps:
firstly, preparing a high-entropy MAX phase material according to the method in the embodiment 3;
then, an etching step is carried out: and reacting the obtained high-entropy MAX phase material with an etching agent at a preset temperature, so that the etching agent selectively etches the component of the element A in the high-entropy MAX phase material, thereby obtaining the high-entropy two-dimensional material.
In some embodiments, optionally, the etchant is hydrofluoric acid solution, the mass concentration of hydrofluoric acid is 1% -50%, the reaction temperature is 0-100 ℃, and the reaction time is 5 min-100 h; preferably, the mass concentration of hydrofluoric acid is more than 30%, the reaction temperature is more than 50 ℃, the reaction time is more than 10h, and the high-entropy MAX phase material contains more than five transition metal atoms with different radiuses, so that the acting force of the high-entropy MAX phase material is stronger than that of the single-component or double-component MAX phase material compared with the atoms of the A component layer.
In some embodiments, optionally, the etchant is an acid solution + fluoride salt system, wherein the acid solution may be one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, the fluoride salt used may be one or more of lithium fluoride, sodium fluoride, potassium fluoride and ammonium fluoride, the reaction temperature is 0-100 ℃, and the reaction time is 5 min-100 h;
in some embodiments, the etchant is optionally a halogen metal salt, wherein the halogen metal salt can be FeCl3，CoCl2，NiCl3，CuCl2，ZnCl2，CdCl2，FeBr3，CoBr2，NiBr3，CuBr2，ZnBr2，CdBr2，FeI3，CoI2，NiI3，CuI2，ZnI2，CdI2And the metal halide salt and the high-entropy MAX-phase ceramic material are subjected to etching reaction at the temperature of 100-1500 ℃ in a protective atmosphere or in vacuum.
In some embodiments, optionally, the etchant is one or more of a gaseous halogen simple substance, a gaseous halogen hydride, and a gaseous nitrogen hydride, and the simple substance or the gaseous hydride can react with the a component in the MAX-phase material under a certain reaction condition to generate a gaseous product and be removed from the reaction system, so that partial or complete etching of the a component is realized, and a MX-containing two-dimensional material is obtained, and the MX two-dimensional material does not contain solid impurities and has the excellent characteristic of high purity. Preferably, the halogen element, includes Br2Or I2(ii) a Halogen hydrides including HF, HCl, HBr or HI; hydrides of nitrogen family, including NH3Or H3And P. Preferably, the etch reaction temperature is between 500 ℃ and 1200 ℃. The gas-phase etchant reacts with the MAX-phase material, so that a high-purity high-entropy two-dimensional material can be directly obtained, the steps of repeated cleaning, ultrasonic treatment, centrifugal separation, drying and the like in a liquid-phase method (acid liquor etching) are avoided, and the preparation process is greatly simplified.
Example 5
This example was carried out to prepare a high entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC and obtaining a high-entropy two-dimensional material (Ti) by etching Al element therein0.2Nb0.2Ta0.2Zr0.2V0.2)2C is an example to further illustrate the technical characteristics of the invention.
High entropy MAX phase materials (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2The preparation of AlC comprises the following steps:
the material preparation step: according to the chemical general formula (Ti) of the high-entropy two-dimensional material0.2Nb0.2Ta0.2Zr0.2V0.2)2The stoichiometric ratio (molar ratio) of Ti to Nb to Ta to Zr to V to Al to C =1:1:1:1: 2.5:2.5 of AlC is determined according to the requirement of raw materials of Ti to Nb to Ta to Zr to V to Al to C =1:1:1:1:1:3:2.5, wherein 3.8294g of titanium powder, 7.4325g of niobium powder, 14.4760g of tantalum powder, 7.2979g of zirconium powder, 4.0754g of vanadium powder, 6.4757g of aluminum powder and 2.4022g of graphite are weighed;
grinding: putting the raw materials into a planetary ball mill for ball milling and mixing, wherein the ball milling speed is 300rpm and the ball milling time is 20h according to the ball material mass ratio of 1: 1;
sintering: transferring the ball-milled powder into a corundum crucible, heating to 1500 ℃ at the speed of 5 ℃/min under the Ar atmosphere, preserving heat for 1h, cooling along with the furnace, taking out the loose block obtained after cooling, and grinding to obtain the high-entropy MAX phase (Ti0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC powder.
High entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2C, preparing, comprising:
etching: 40ml of concentrated hydrochloric acid and 2g of LiF were mixed uniformly to obtain an etchant, and 1g of the high-entropy MAX phase (Ti) obtained in step (1) in this example was used0.2Nb0.2Ta0.2Zr0.2V0.2)2Placing AlC in an etching agent, reacting for 24h at 50 ℃, and after the reaction is finished, performing centrifugal separation, water washing and drying treatment to obtain the high-entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x (wherein T is x Represents a functional group contained).
For high entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC and high entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x (high-entropy MXene) was subjected to Scanning Electron Microscope (SEM) tests, and the results are shown in FIGS. 1a and b, and (Ti) can be seen by comparison0.2Nb0.2Ta0.2Zr0.2V0.2)2The shape of AlC is a three-dimensional block structure, and the high-entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x Is a soft, ultrathin and large-area two-dimensional nano-sheet, which shows high entropy MAX (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2The component A in the high-entropy MAX phase is etched by reacting AlC in the hydrochloric acid + LiF etching agent, and a corresponding high-entropy two-dimensional material (high-entropy MXene) is obtained. For high entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC and high entropy two dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The results of X-ray diffraction (XRD) analysis of each component are shown in FIG. 2, and when comparing FIG. 2b, the raw material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2The (002) peak in AlC appeared at 12.6 degrees, while the (002) peak in the target product reacted with the hydrochloric acid + LiF etchant shifted to 7.2 degrees towards a low angle, and other diffraction peaks corresponding to the high-entropy MAX phase disappeared, indicating that the hydrochloric acid + LiF etchant completely etched in the reaction process (Ti + LiF etchant)0.2Nb0.2Ta0.2Zr0.2V0.2)2Al element in AlC generates MXene (Ti) with lamellar structure0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x Resulting in an enlargement of the interlayer spacing, which is in accordance with (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The results of the scanning electron micrographs are consistent, and the comparison of the XRD spectrogram of FIG. 2a shows that the synthesized high-entropy MAX phase (Ti) is0.2Nb0.2Ta0.2Zr0.2V0.2)2The diffraction peaks of AlC are respectively consistent with the reported TiNbAlC of a single phase, and impurity peaks of other carbides do not appear, which indicates that the obtained high-entropy MAX phase (Ti) is obtained0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC as a single phase, (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The high resolution electron microscopy HRTEM picture and the electron diffraction spectrogram are shown in figures 3a and b, which show that the obtained high-entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x Is of a single crystal rock salt crystal structure. The results of line scanning of the lattice atoms along the high resolution HRTEM (fig. 4 a) are shown in fig. 4b, where the energy intensities of the sequentially exposed metal atoms are different, with higher energy intensities representing heavier metal atoms and relatively lower energy intensities representing relatively lighter metal atoms, thus demonstrating that the metal atoms scanned along the lines are sequentially Zr, Ta, Zr, Nb, V, Ta, which are exposed at the surface of the two-dimensional lamellar structure. Fig. 4c and d show stress distribution diagrams on the two-dimensional lamellar structure obtained by high-resolution electron microscope analysis, wherein dark colors represent positions with higher stress, and light colors represent positions with lower stress, which illustrate that on the microstructure, the surface exposed metal atoms of the two-dimensional lamellar structure of the high-entropy two-dimensional material are distributed in high and low, which is a characteristic of the two-dimensional lamellar structure caused by the stress distribution of the two-dimensional lamellar layer due to different metal atoms with different atomic radii. (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x Scanning Transmission Electron Microscope (STEM) and atom distribution diagram, the two-dimensional nanosheet has uniform Ti, Nb, Ta, Zr, V, C, O and F element distribution, and the obtained target product is the one containing O and F functional groups (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x High entropy two dimensional material (high entropy MXene). The high entropy two-dimensional material (Ti) prepared in this example was tested by atomic force microscopy AFM (as shown in FIGS. 6a and b)0.25Nb0.25Ta0.25Zr0.25)2CT x The atomic layer of (a) is between 7.7nm and 19nm, indicating (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x Has the structural characteristics of ultra-thin and soft. Note that, the high-entropy MAX phase material (Ti) is used0.2Nb0.2Ta0.2Zr0.2V0.2)2The XRD spectrogram of AlC powder can also see that the impurity content is less than 2%, the impurity content is greater than 98 vo 1%, and the impurity content has no impurity peak, which indicates that the prepared product (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2The AlC content has a very high purity.
Example 6
This example provides a specific example of preparing a high-entropy two-dimensional material by vapor phase etching of high-entropy MAX, using the high-entropy MAX phase (Ti phase) prepared in example 60.2Nb0.2Ta0.2Zr0.2V0.2)2AlC is a precursor, commercial liquefied HI gas is used as an etchant to react and prepare a two-dimensional material, and the selected reactor is a tube furnace and comprises the following steps:
1) placing powdered (Ti) in the tube furnace0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC；
2) Introducing HI gas into the tubular furnace for a period of time, and sealing the reaction cavity after the reaction cavity in the reaction device is filled with the HI gas;
3) heating the interior of the reaction device to 700 ℃, preserving heat for 30min, and carrying out etching reaction to obtain a target product high-entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x 。
And after the reaction device is naturally cooled to the room temperature, taking out the target product. To (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2High-entropy two-dimensional material (Ti) obtained after reaction of AlC and HI0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The two target products were subjected to SEM test, and as a result, as shown in FIGS. 7a and b, the target product after reaction (FIG. 7 b) showed a distinct accordion-like layered structure having a distinct layer-by-layer expanded structure, which is distinct from the raw material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2Lamellar bulk morphology of AlC (fig. 7 a). To (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC and high entropy MXene (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x XRD analysis was carried out, and the results are shown in FIG. 8, which shows that the starting material (Ti) was obtained by comparison0.2Nb0.2Ta0.2Zr0.2V0.2)2The (002) peak in AlC appeared at 12.6 deg. and the (002) peak in the target product after reaction with HI gas shifted to 7.6 deg. toward a low angle, indicating that HI gas etched in the gas phase reaction (Ti0.2Nb0.2Ta0.2Zr0.2V0.2)2Al element in AlC generates a high-entropy two-dimensional material (Ti) with a lamellar structure0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x This leads to an enlargement of the layer spacing, which is consistent with the scanning electron micrograph results. High entropy two-dimensional material (Ti) of target product0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The STEM photograph of (A) has a large number of two-dimensional ultrathin nanosheets, as shown in FIG. 9a, indicating that the nanosheets are accordion-like (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x A large number of two-dimensional nanosheets can be obtained by simple stripping, and as can be seen from the atomic distribution diagram in FIGS. 9 b-h, the two-dimensional nanosheets have uniform Ti, Nb, Ta, Zr, V, C and I element distribution, which indicates that the obtained target product is a high-entropy two-dimensional material (Ti) containing I functional groups0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x . Through AFM (atomic force microscope) test (as shown in FIGS. 10 a-d), the high-entropy two-dimensional material (Ti) prepared in the embodiment is obtained0.25Nb0.25Ta0.25Zr0.25)2CT x The thickness of (a) is 1nm to 3.5 nm. High-entropy two-dimensional material (Ti) prepared by gas phase method0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x FromAnd gas phase is easier to enter the gaps of the layered MAX phase material, and compared with liquid phase etching, the method is easier to prepare and obtain a large amount of single-layer ultrathin high-entropy two-dimensional materials. It should be noted that the elements in the high-entropy MAX phase and the high-entropy two-dimensional material prepared in examples 5 and 6 are chemically stable elements, and can stably exist in the air and are easy to store.
Example 7
The invention provides another preparation method for preparing a high-entropy two-dimensional material by direct sintering, which comprises the following steps:
the material preparation step: determining the required amount of raw materials containing each element according to the stoichiometric ratio of each element in the chemical general formula of the high-entropy two-dimensional material, wherein the high-entropy two-dimensional material consists of an M element and an X element, the M element is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, and the X element is selected from at least one of oxygen, silicon, phosphorus, sulfur, arsenic, selenium or tellurium;
sintering: sintering each raw material at a preset temperature under the condition of protective atmosphere or vacuum to obtain the high-entropy two-dimensional material with a two-dimensional structure.
In some embodiments, in the sintering step, the sintering temperature is between 600 ℃ and 3000 ℃, and the sintering time is between 10min and 120 min.
Example 8
This example was carried out to prepare a high-entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3For example, a method for preparing a high-entropy two-dimensional material by direct sintering is described, wherein M comprises: fe. Five elements of Co, Ni, Mn and Zn, wherein X comprises: p and S, and the preparation steps comprise:
the material preparation step: according to the chemical general formula Fe of a high-entropy two-dimensional material0.2Co0.2Ni0.2Mn0.2Zn0.2PS3The weight ratio of Fe to Co to Ni to Mn to Zn to P to S =1:1:1:1:1: 5:15, wherein raw materials of iron powder, cobalt powder, nickel powder, manganese powder, zinc powder, phosphorus powder and sulfur powder are weighed;
grinding: putting the raw materials into a planetary ball mill for ball milling and mixing, wherein the ball milling speed is 500rpm and the ball milling time is 20h according to the ball material mass ratio of 1: 20;
sintering: transferring the ball-milled powder into a corundum crucible, heating to 1200 ℃ at the speed of 5 ℃/min under the Ar atmosphere, preserving heat for 1h, cooling along with the furnace, taking out the loose block obtained after cooling, and grinding to obtain the high-entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3And (3) powder.
For high-entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3SEM test of the powder, the result is shown in FIG. 11, and it can be seen that Fe passes0.2Co0.2Ni0.2Mn0.2Zn0.2PS3The structure is shown in figure 12, which shows that the prepared product is a pure single-phase crystal structure (perovskite crystal), and the high-entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3The STEM diagram of (a) as shown in fig. 13 shows that the nanosheet of the two-dimensional lamellar structure has uniform distribution of Fe, Co, Ni, Mn, Zn, P and S elements.
Example 9
This example shows another high entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2V0.2PS3The preparation method is similar to that in the example 8, except that in the material preparation step, the Zn powder in the raw material is replaced by V powder, and in the sintering step, the temperature is raised to 1700 ℃ at the speed of 5 ℃/min under the Ar atmosphere, and the temperature is kept for 1 h.
For the obtained high-entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2V0.2PS3SEM test results are shown in FIG. 14, and the high-entropy two-dimensional material Fe in the present example is similar to the high-entropy two-dimensional material prepared in example 80.2Co0.2Ni0.2Mn0.2V0.2PS3Also has obvious two-dimensional lamellar structure, and the XRD test structure is shown in figure 15, which indicates that the prepared product is pure single-phase crystalBulk structure (perovskite crystal), high entropy two-dimensional material Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3The STEM diagram of (a) as shown in fig. 16 shows that the nanosheet of the two-dimensional lamellar structure has uniform distribution of Fe, Co, Ni, Mn, V, P and S elements.
It is to be noted that examples 8 and 9 give examples in which the X element is P and S, and elements of the same group as P and S, such as N and O, As and Se and Sb and Te elements, can also form a high-entropy two-dimensional material of perovskite-type crystals due to having similar properties.
Example 10
This example provides an application of a high-entropy two-dimensional material in catalytic hydrogen production in the field of catalysis, and provides the high-entropy two-dimensional material Fe prepared in examples 8 and 90.2Co0.2Ni0.2Mn0.2Zn0.2PS3And Fe0.2Co0.2Ni0.2Mn0.2V0.2PS3As an example of the catalyst, a comparative example was a monopropellant NiPS3And FePS3(two-dimensional single crystal compound), a three-electrode system is adopted in the test, a graphite rod with the diameter of 0.6mm is used as a counter electrode, a saturated calomel electrode is used as a reference electrode (all potentials are converted into RHE relative to a reversible hydrogen electrode), a glassy carbon electrode with the diameter of 3mm is used as a working electrode after being treated, and the working electrode is polished by alumina slurry before sample coating. The preparation of the working electrode is that 4mg of catalyst, 0.8 mL of water, 0.2 mL of ethanol and 0.08mL of Nafion solution with the mass fraction of 5% are mixed, the mixture is ultrasonically treated into uniform slurry, a liquid transfer gun is used for taking 5 mu L of slurry to be dropped on the surface of a glassy carbon electrode, and the slurry is directly used as the working electrode after being dried. The Linear Sweep Voltammetry (LSV) test (electrochemical workstation model CHI 760E) has a sweep rate of 10 mV/s and an electrolyte of 1 mol/L KOH in water.
The catalytic activity of the high-entropy two-dimensional material is tested in 0.5mol/L sulfuric acid electrolyte at a sweep rate of 10 mV/s. FIG. 17a shows the LSV test results, which show that NiPS is comparable to the control sample3And FePS3In contrast, the high-entropy two-dimensional material Fe of the invention0.2Co0.2Ni0.2Mn0.2Zn0.2PS3And Fe0.2Co0.2Ni0.2Mn0.2V0.2PS3The current density and the initial potential of the sample are both obviously improved, which shows that when the high-entropy two-dimensional material is used as an oxygen generation catalyst, the current density is higher than that of other two-dimensional materials under the same potential, the catalytic activity of the surface is high, and Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3The activity of the sample is higher, and the high-entropy two-dimensional material Fe is0.2Co0.2Ni0.2Mn0.2Zn0.2PS3And Fe0.2Co0.2Ni0.2Mn0.2V0.2PS3The increase in activity of the sample, in addition to the current density and the initial potential, the tafel slope values can reflect the kinetics of the electrocatalytic process, with lower slopes demonstrating faster current density increases with decreasing overpotential. FIG. 17b is a Tafel plot based on LSV test fitting, which shows that sample Fe0.2Co0.2Ni0.2Mn0.2Zn0.2PS3Has the lowest slope (52 mV/dec) which is far lower than that of a control NiPS3(83 mV/dec) and FePS3(196 mV/dec), which indicates that the catalytic performance is best, consistent with LSV results. The reason why the high-entropy two-dimensional material shows excellent catalytic performance is that, compared with a massive catalyst, the high-entropy two-dimensional material has a two-dimensional lamellar structure with an ultra-high specific surface area, and exposes metal atoms with high catalytic activity on the two-dimensional lamellar structure, so that a large number of metal atoms with high catalytic activity are on the high-entropy two-dimensional material.
Example 11
The embodiment is providedA metal lithium electrode comprising a high-entropy two-dimensional material (Ti) prepared in example 5 was provided0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x To illustrate by way of example, the lithium metal electrode in this example was prepared by electrodeposition, in particular by deposition of lithium metal in a two-electrode system, in which lithium metal was the counter electrode, using the (Ti) electrode prepared in example 50.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The membrane is a working electrode, the electrolyte is a 1M solution of LiTFSI, and the solvent is 1, 3-Dioxolane (DOL): ethylene glycol dimethyl ether (DME) =1: 1. The control sample is of four components (Ti) under the same conditions0.25Nb0.25Ta0.25Zr0.25)2CT x And two-component TiNbCT x . Wherein (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The membrane is formed by ultrasonically dispersing the prepared powder in a solution, coating the solution on a carrier and drying the carrier, and the thickness of the membrane is 1-2 mu m. FIG. 18a shows the current density at 50 μ A cm-2Below, (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x Film, (Ti)0.25Nb0.25Ta0.25Zr0.25)2CT x Film and TiNbCT x Voltage-capacity curves of lithium deposited on films, from which it can be seen that the high entropy two dimensional material (Ti) of the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The membrane had the lowest overpotential (18 mV), control (Ti)0.25Nb0.25Ta0.25Zr0.25)2CT x Film and TiNbCT x The overpotential of the membrane was 15.4 mV and 26.3 mV, respectively, indicating a high entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x The energy barrier of lithium deposited on the surface of the film is lowest, and metallic lithium is moreHigh entropy two-dimensional material (Ti) which is easy to be used in the invention0.2Nb0.2Ta0.2Zr0.2V0.2)2CT x A uniformly dispersed deposited lithium layer is formed thereon.
In order to verify the electrochemical performance of the metal lithium electrode containing the high-entropy two-dimensional material as the negative electrode of the secondary lithium battery, the metal lithium electrode of the invention was assembled into a CR-2032 type button-type symmetrical battery (hereinafter, referred to as the symmetrical battery of the invention), in which the thickness of the metal lithium layer was 10 μm, under the same conditions, (Ti)0.25Nb0.25Ta0.25Zr0.25)2CT x Film and TiNbCT x The resulting metallic lithium electrode of the film deposition was used as a control (comparative symmetrical cells 1 and 2, respectively). Wherein the electrolyte adopts 1M LiPF6Dissolving in Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) solution, wherein the volume ratio of the solvent is EC: DEC: EMC =1:1:1, and the diaphragm adopts a polypropylene microporous diaphragm.
The inventive symmetrical cell was compared to comparative symmetrical cells 1 and 2 at 1mA/cm2Current density of 1mAh/cm2The electrochemical test is carried out under the surface capacity, the obtained test result is shown in fig. 18b, a cycle process of 300 hours can be seen, the polarization potential of the electrode is stabilized at about 25mV, and the polarization potential of the symmetrical batteries 1 and 2 is about 120 mV under the same condition, which shows that the metal lithium electrode of the invention has excellent cycle stability and the function of inhibiting the growth of lithium dendrites when being used as a negative electrode of a lithium battery. The electric quantity density of the metal lithium battery is improved to 2 mA/cm2、4 mA/cm2、5 mA/cm2、10mA/cm2Then to 1mA/cm2And 10mA/cm2As shown in fig. 18c, after 100 hours, the polarization potential of the metal lithium electrode of the present invention is stabilized at about 60mV, which shows that the metal lithium electrode of the present invention has excellent cycling stability and the effect of inhibiting the growth of lithium dendrite as a negative electrode of a lithium battery. The metal lithium electrode of the invention is 5mAh/cm2、1mAh/cm2、20mAh/cm2The electrochemical test was performed at a surface capacity of (1) as shown in FIG. 18dThe stable charge-discharge curve shows that the metal lithium electrode still has excellent cycle stability and the function of inhibiting the growth of lithium dendrite under the condition of high lithium metal loading. The reason why the high-entropy two-dimensional material shows excellent cycling stability and inhibits the growth of lithium dendrites is that a large number of metal atoms are exposed on a two-dimensional lamellar structure of the high-entropy two-dimensional material in the charging and discharging process, and the characteristic that the surface of the two-dimensional material has high stress can induce the nucleation growth of the metal lithium on the two-dimensional lamellar structure, namely the high-entropy two-dimensional material can be used as a nucleating agent, so that the growth behavior of the metal lithium is effectively regulated and controlled, and the potential safety hazard problem caused by the growth of the sharp lithium dendrites is effectively avoided.
It should be noted that, this embodiment illustrates a metal lithium electrode containing a high-entropy two-dimensional material, in this embodiment, metal lithium is deposited on the surface of the high-entropy two-dimensional material, that is, the high-entropy two-dimensional material is distributed on the surface of the metal lithium layer, because the metal lithium electrode continuously performs a dissolving-depositing process of the metal lithium during charging and discharging, the high-entropy two-dimensional material can perform its nucleation function only in the metal lithium electrode, that is, in other embodiments, the metal lithium electrode of the present invention, the high-entropy two-dimensional material may also be distributed inside the metal lithium layer.
The above embodiments are provided only to illustrate some embodiments of the technical features of the present invention, and the present invention includes embodiments not limited thereto, and it will be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept of the present invention, and the scope of the present invention should be determined by what is defined in the claims.

Claims (23)

1. The high-entropy two-dimensional material is characterized by having a two-dimensional lamellar structure and consisting of M elements and X elements, wherein the M elements are selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, and the X elements are selected from at least one non-metal element in IIIA, IVA, VA and VIA.
2. The high-entropy two-dimensional material of claim 1, wherein the thickness of the two-dimensional sheet structure is in a range from 1nm to 20 nm.
3. A high entropy two-dimensional material as claimed in claim 1, wherein the two-dimensional sheet structure further has a crystal structure comprising: perovskite type, rock salt type or iron phosphorus sulfide type.
4. The high-entropy two-dimensional material of claim 1, wherein the X element is at least one of carbon, nitrogen, oxygen, boron, phosphorus, or sulfur.
5. The high-entropy two-dimensional material of claim 1, wherein the M element includes one or more of Pt, Au, V, Hf, W, Mo, Ag, Pd, Au, Ag, Fe, Co, Ni, Cu, or Bi elements.
6. The high-entropy two-dimensional material of claim 1, wherein the two-dimensional sheet structure contains functional groups including: one or more of O, F, Cl, Br, I or OH.
7. A high-entropy MAX phase material is characterized by consisting of M element, A element and X element, and the chemical general formula of the material is M n+ 1AX n Wherein the M element is at least five metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, the A element is at least one element selected from VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA groups, the X element is at least one element selected from X element which is carbon, nitrogen or boron,nis 1, 2, 3, 4, 5 or 6.
8. A high entropy MAX phase material as claimed in claim 7 wherein, where the M element is five metal elements, any of Sc, Y or Hf elements are excluded.
9. A high entropy MAX phase material as claimed in claim 7, further having a crystal structure comprising: perovskite type, rock salt type or iron phosphorus sulfide type.
10. A high entropy MAX phase material as claimed in claim 7 wherein the M element comprises one or more of Pt, Au, V, Hf, W, Mo, Ag, Pd, Au, Ag, Fe, Co, Ni, Cu or Bi elements.
11. A method for preparing a high-entropy MAX phase material is characterized by comprising the following steps:
the material preparation step: determining the required amount of raw materials containing each element according to the stoichiometric ratio of each element in the chemical general formula of the high-entropy MAX phase material;
sintering: sintering each raw material at a preset temperature under the condition of protective atmosphere or vacuum to obtain a high-entropy two-dimensional material with a two-dimensional structure;
wherein the high-entropy MAX phase material consists of M element, A element and X element, and the chemical general formula of the high-entropy MAX phase material is M n+1AX n Wherein the M element is at least five metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, the A element is at least one element selected from VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA groups, the X element is at least one element selected from carbon, nitrogen or boron,nis 1, 2, 3, 4, 5 or 6.
12. A method of preparing a high entropy MAX phase material as claimed in claim 11 wherein in the compounding step the molar ratio of M, a and X elements in the required amount of the raw material is (M: (M) (M))n+1):(1.2～2):n。
13. A method of preparation of a high entropy MAX phase material as claimed in claim 11, wherein when the M element is five metal elements, none of Sc, Y or Hf elements are included.
14. A method for the preparation of a high entropy MAX phase material as claimed in claim 11, wherein in the sintering step, the sintering temperature is between 600 ℃ and 1700 ℃.
15. A preparation method of a high-entropy two-dimensional material is characterized by comprising the following steps:
the method of preparing a high entropy MAX phase material according to any one of claims 11 to 14, producing a high entropy MAX phase material;
etching: and reacting the obtained high-entropy MAX phase material with an etching agent at a preset temperature, so that the etching agent selectively etches the component of the element A in the high-entropy MAX phase material, thereby obtaining the high-entropy two-dimensional material.
16. The method of producing a high-entropy two-dimensional material according to claim 15, wherein the etchant is a hydrofluoric acid solution, an acid solution + fluoride salt system, or a halogen metal salt.
17. The method for preparing a high-entropy two-dimensional material as claimed in claim 15, wherein in the etching step, the etchant is one or more of a simple halogen, a halogen hydride, and a nitrogen hydride in a gas phase.
18. The method for preparing a high-entropy two-dimensional material as claimed in claim 17, wherein, in the etching step, the etching reaction temperature is between 500 ℃ and 1200 ℃.
19. A preparation method of a high-entropy two-dimensional material is characterized by comprising the following steps:
the material preparation step: determining the required amount of raw materials containing elements according to the stoichiometric ratio of each element in the chemical general formula of the high-entropy two-dimensional material, wherein the high-entropy two-dimensional material consists of M elements and X elements, the M elements are at least five metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, and the X elements are at least one of oxygen, silicon, phosphorus, sulfur, arsenic, selenium or tellurium;
sintering: and sintering each raw material at a preset temperature under the condition of protective atmosphere or vacuum to obtain the high-entropy two-dimensional material with the two-dimensional structure.
20. A method for producing a high-entropy two-dimensional material according to claim 20, wherein, in the sintering step, the sintering temperature is between 600 ℃ and 3000 ℃.
21. A metallic lithium negative electrode comprising the high entropy two dimensional material of any of claims 1 to 6.
22. Use of the high-entropy two-dimensional material of any one of claims 1 to 6 in catalysis, sensors, electronic devices, supercapacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials, or superconducting materials.
23. The use of the high-entropy two-dimensional material prepared by the method of any one of claims 13 to 20 in catalysis, sensors, electronic devices, supercapacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials, or superconducting materials.
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