CN111477419B - Novel quinary layered magnetic material, preparation method and application thereof - Google Patents
Novel quinary layered magnetic material, preparation method and application thereof Download PDFInfo
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- CN111477419B CN111477419B CN201910068169.3A CN201910068169A CN111477419B CN 111477419 B CN111477419 B CN 111477419B CN 201910068169 A CN201910068169 A CN 201910068169A CN 111477419 B CN111477419 B CN 111477419B
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Abstract
The invention discloses a novel quinary layered magnetic material and a preparation method thereofA method and application. The chemical composition of the quinary layered magnetic material is represented as A2(BxCyDz)E1Wherein A is any one of Ta, Sc, Hf, V, Nb, Mo, Zr, Cr and Ti elements, B is any one of Al, Sn, Ga and In elements, C and D are magnetic elements, C and D are different, x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, x + y + z is 1, and E is any one or the combination of two of C, N elements. The novel quinary layered magnetic material has potential application prospects in the fields of electrochemical catalysis, wave absorption and the like.
Description
Technical Field
The invention relates to a composite inorganic material, in particular to a novel quinary layered magnetic material, a preparation method and application thereof, belonging to the technical field of materials.
Background
The magnetic material has great potential application in the fields of data storage, recording, refrigeration, electron spinning and the like due to the special properties of the magnetic material, and the giant magnetoresistance effect found in the nano-layered magnetic material has attracted great attention of scientists. Taking Fe/MgO/Fe as an example, where single crystal Fe/MgO/Fe magnetic tunnel structures have been predicted to have a large tunnel magnetoresistance with magnetoresistance ratios in excess of 1000%, this very special property is associated with the [001 ] edge]The electron band structure of the directionally bulk iron material is directly related and delays the decay rate of the MgO barrier layer by incorporating a symmetrically related tunnel. The material thereofThe structure is a magnetic layer which is similar to a sandwich structure and is formed by arranging a layer of ferromagnetic element Fe in the middle and arranging a ferromagnetic layer between two insulating layers MgO. The method has huge potential application in the fields of magnetoresistive read heads, Magnetic Random Access Memory (MRAM) spin torque oscillators, detectors and the like. The MAX phase material is a nano-layered ternary compound, and the unit cell of the MAX phase material is formed by Mn+1XnThe unit is stacked alternately with the A atom plane, and n is 1, 2 or 3, which has both metal and ceramic characteristics and exhibits excellent physical, chemical, mechanical, electrical and other properties.
In recent years, the magnetic MAX phase material has attracted great interest to scientists, and from theoretical prediction to experimental synthesis, many theoretical calculations and experimental synthesis emerge like bamboo shoots in spring after rain, and the synthesis and application of the magnetic MAX phase functional material will be a hot spot and a focus of future research on the MAX phase material. At present, the magnetic MAX phase materials mainly focus on MAX phase materials with Mn occupying M-site, and there are only few reports on MAX phase materials with a-site containing magnetic elements. 2011 Dahlqvist et al calculated M by first principlesn+1AlCn(M-Cr, Mn, Fe, Co.) stability of the MAX phase under different magnetic properties of PM, AFM, FM. In 2013, magnetic MAX phase materials (Cr) are experimentally synthesized for the first time by A.S. Ingason and the like1-xMnx)2GeC, the experimental results show that (Cr) can be detected at temperatures above 200K0.75Mn0.25)2Magnetic signal of GeC film. Then, a Per Eklund team of the university of Sweden-Xuezhei prepares a novel Fe-containing MAX phase material Mn with ternary A-site through an element replacement strategy2(GaAuFe) C. The common ternary laminar MAX phase material is easy to synthesize by a common hot-pressing method, while the A position of the MAX phase is changed into three elements from a single element in the ternary to quinary MAX phase materials, the conventional synthesis method needs extremely high temperature and long heat preservation time, extremely stable competitive phases (such as FeC phase) are easy to form in the sintering process, and stoichiometric ratio deviation caused by volatilization of raw materials is easy to form, and all the factors can cause that target products cannot be obtained finally, so that the synthesis of the quinary laminar material by the conventional hot-pressing sintering method is extremely difficult, and at present, the multi-laminar magnetic material containing multiple magnetic elements is extremely difficult to synthesize by the conventional hot-pressing sintering methodThe materials have not been reported.
Disclosure of Invention
The invention mainly aims to provide a novel quinary layered magnetic material, a preparation method and application thereof, thereby overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a novel quinary layered magnetic material, and the chemical composition of the quinary layered magnetic material is represented as A2(BxCyDz)E1Wherein A is any one of Ta, Sc, Hf, V, Nb, Mo, Zr, Cr and Ti, B is any one of Al, Sn, Ga and In, C and D are magnetic elements, C and D are different, and E is any one of C, N elements or the combination of two elements.
Further, the atomic number of the element B is x, the atomic number of the element C is y, the atomic number of the element D is z, 0 < x < 1, 0 < z < 1, 0 < y < 1, and x + y + z is 1.
Further, C is any one of Mn and Fe magnetic elements, but is not limited thereto.
Further, D is any one of Co and Ni magnetic elements, but is not limited thereto.
Further, a includes any one of Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and the like, but is not limited thereto.
Further, said E may preferably be CaNbWherein a + b is 1.
Further, the unit cell of the novel quinary layered magnetic material is represented by A2E1Unit and (B)xCyDz) The units are stacked alternately.
Further, the form of the novel five-membered layered magnetic material includes any one or a combination of two or more of powder, bulk, thin film, and the like, but is not limited thereto.
The embodiment of the invention also provides a preparation method of the novel quinary layered magnetic material, which comprises the following steps: a molten salt method, a discharge plasma method, but not limited thereto.
In some embodiments, the method of making comprises:
mixing A and/or A-containing materials, B and/or B-containing materials, C and/or C-containing materials, D and/or D-containing materials, E and/or E-containing materials and inorganic salts according to the ratio of (2-4): 1: (0.01-0.99): (0.01-0.99): 1: (0-3), reacting the obtained mixture in an inert atmosphere at the high temperature of 500-1300 ℃ for 60-720 min, and performing post-treatment to obtain a novel five-membered layered magnetic material;
the chemical composition of the quinary layered magnetic material is represented as A2(BxCyDz)E1Wherein A is any one of Ta, Sc, Hf, V, Nb, Mo, Zr, Cr and Ti elements, B is any one of Al, Sn, Ga and In elements, C and D are magnetic elements, C and D are different, x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, x + y + z is 1, and E is any one or the combination of two of C, N elements.
Further, C is any one of Mn and Fe magnetic elements, but is not limited thereto.
Further, D is any one of Co and Ni magnetic elements, but is not limited thereto.
Further, the a-containing material includes an a-containing alloy, and is not limited thereto.
Further, the B-containing material includes a B-containing alloy, and is not limited thereto.
Further, the C-containing material includes a C-containing alloy, and is not limited thereto.
Further, the D-containing material includes an alloy containing D, and is not limited thereto.
Further, the E-containing material includes an E-containing alloy, and is not limited thereto.
Further, the inorganic salt includes NaF, KF, NaCl, KCl, NaBr, KBr, NaI, Na2SO4、K2SO4、Na2CO3、K2CO3And the like, and is not limited thereto.
Further, the A and/or A-containing material, the B and/or B-containing material, the C and/or C-containing material, the D and/or D-containing material and the E and/or E-containing material are powder, and the particle size is 500 nm-100 mu m.
Further, the inorganic salt is powder, and the particle size is 500 nm-1 mm.
In some embodiments, the post-treatment comprises: after the high-temperature reaction is finished, washing the obtained reaction product for several times by using deionized water and alcohol, and then drying at 40-80 ℃ for 1-24 hours to obtain the novel five-membered layered magnetic material.
The embodiment of the invention also provides a potential application prospect of the novel quinary layered magnetic material in the fields of electrochemical catalysis, wave absorption and the like.
Furthermore, the novel quinary layered magnetic material has ferromagnetic property within the temperature range of 2-250K, the coercive force of the material is more than 150Oe, and the magnetization intensity of the material is higher than that of a ternary layered material with a single magnetic element.
Furthermore, the wave-absorbing performance and the electro-catalysis performance of the novel quinary layered magnetic material are superior to those of a ternary layered material with a single magnetic element, the novel quinary layered magnetic material can achieve effective absorption in the whole X wave band, and the novel quinary layered magnetic material has potential application prospects in the wave-absorbing field and the electrochemical catalysis field.
Compared with the prior art, the invention has the advantages that:
(1) the preparation method of the novel quinary layered magnetic material provided by the embodiment of the invention realizes the synthesis of the quinary layered magnetic material containing two magnetic elements for the first time, the two magnetic elements and the element B are positioned on the same atomic layer, and through the mutual solid solution effect between the elements, the three elements are successfully placed at the same position, so that the variety of the layered material is expanded, and a foundation is laid for the preparation of the later higher layered material; in addition, the introduction of the magnetic element regulates and controls the property of the material, so that the material is changed from the application of the traditional structural material to the application of the functional material;
(2) the quinary layered magnetic material is synthesized for the first time by adopting a molten salt method, and the method has the advantages of low synthesis temperature, short reaction time, no need of high-consumption equipment, low preparation cost and suitability for large-scale industrial production;
(3) the novel quinary layered magnetic material provided by the embodiment of the invention has the characteristics of metal ceramics, compared with a ternary layered magnetic material with a single magnetic element, the introduction of multiple magnetic elements can increase the magnetic property, improve the magnetic loss, the coercive force and the Curie temperature, so that the material can be used in a harsher environment, and the application range of the material is expanded;
(4) the novel quinary layered magnetic material provided by the embodiment of the invention has obvious electrocatalytic performance which is improved by about 20 times compared with a ternary layered material, and has potential application in electrocatalytic hydrogen production;
(5) the novel quinary layered magnetic material provided by the embodiment of the invention has excellent wave-absorbing performance, can achieve effective electromagnetic wave absorption in the whole X wave band, has the highest reflection loss of-41 dB and the absorption efficiency of 99.99 percent, and has the wave-absorbing performance far superior to that of a ternary layered magnetic material.
Drawings
FIG. 1 shows a novel five-membered layered magnetic material V in example 1 of the present invention2(SnxMnyCoz) XRD pattern of C.
FIG. 2a and FIG. 2b are schematic diagrams of a novel quinary layered magnetic material V according to example 1 of the present invention2(SnxMnyCoz) Scanning Electron Micrograph (SEM) and elemental distribution map (EDS) of C.
FIG. 3 shows a novel quinary layered magnetic material V in example 2 of the present invention2(SnxFeyCoz) XRD pattern of C.
FIG. 4a and FIG. 4b are schematic diagrams of a new type of five-membered layered magnetic material V in example 2 of the present invention2(SnxFeyCoz) Scanning Electron Micrograph (SEM) and elemental distribution map (EDS) of C.
FIG. 5 shows a novel quinary layered magnetic material V in example 3 of the present invention2(SnxFeyNiz) XRD pattern of C.
FIG. 6a and FIG. 6b are schematic diagrams of a novel quinary layered magnetic material V in example 3 of the present invention2(SnxFeyNiz) Scanning Electron Micrograph (SEM) and elemental distribution map (EDS) of C.
FIG. 7 shows a novel quinary layered magnetic material V in example 4 of the present invention2(SnxCoyNiz) XRD pattern of C.
FIG. 8a and FIG. 8b are schematic diagrams of a new type of quinary layered magnetic material V in example 4 of the present invention2(SnxCoyNiz) Scanning Electron Micrograph (SEM) and elemental distribution map (EDS) of C.
FIG. 9a is Ta as a new type five-membered layered magnetic material in example 5 of the present invention2(SnxFeyNiz) A ZFC curve chart of the C powder material,
FIG. 9b shows a ternary layered magnetic material V2ZFC profile of fecs.
FIG. 10a is a diagram showing a new type of a five-membered layered magnetic material Ta in example 6 of the present invention2(SnxFeyCoz) M-H curve diagram of C powder material at 200K, FIG. 10b is ternary layered magnetic material Nb2M-H plot of FeC at 200K.
FIG. 11a shows a new type of five-membered layered magnetic material Nb in example 7 of this invention2(SnxMnyCoz) C powder material and ternary laminated Nb2FeC reflection loss plot, Nb in FIG. 11b2(SnxMnyCoz) And C, a reflection loss chart of the powder material under the conditions of different thicknesses of the X wave band.
FIG. 12a shows a new type of five-membered layered magnetic material Nb in example 7 of this invention2(SnxMnyCoz) Electrocatalysis test curve of C powder material, FIG. 12b is Nb2Electrocatalytic picture of FeC material.
Detailed Description
In view of the deficiencies of the prior art, the present inventors have attempted to transform the synthetic concept. The synthesis temperature can be effectively reduced, the volatilization of raw materials can be inhibited, the reaction time can be shortened, and the competitive phase can be inhibited by a molten salt method or SPS sintering, so that the method is an effective way for synthesizing the quinary layered material. In addition, the quinary layered magnetic material is formed by introducing two magnetic elements, so that the magnetic property and the magnetic structure can be improved, the magnetic property is enhanced, and in addition, the novel quinary layered magnetic material can have potential application in the fields of wave absorption and electro-catalysis by combining the layered structure and the thermal stability.
The novel quinary layered magnetic material synthesized by the invention has very important significance for the expansion of the types of the layered magnetic materials and the regulation and control of the magnetic property; secondly, by utilizing the characteristic that an alloying effect forms an alloy compound at low temperature, a molten salt method and a traditional powder metallurgy method are combined, a series of novel quinary layered magnetic materials can be synthesized, the method is an innovation in material synthesis means, and a brand new synthesis strategy is provided for synthesis of other novel layered magnetic materials. In addition, the novel quinary layered magnetic material is synthesized, and the structure and the property of the novel quinary layered magnetic material can be regulated and controlled by regulating the content, the position and the type of the magnetic element, so that the novel quinary layered magnetic material has potential application prospects in the fields of electrochemical catalysis, wave absorption and the like.
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
Example 1: in this embodiment, the novel five-membered layered magnetic material is V2(SnxMnyCoz) C, powder material.
The V is2(SnxMnyCoz) The preparation method of the powder C comprises the following steps:
(1) v powder, Sn powder, Co powder, MnCo alloy powder, carbon powder and inorganic salt (NaCl + KCl) are mixed according to a molar ratio of 4: 1: 0.99: 0.99: 1: 3, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1300 ℃, the heat preservation time is 60min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIG. 1 shows the preparation of V by the molten salt process2(SnxMnyCoz) XRD pattern of cmax phase powder material. As can be seen from the XRD patterns, the diffraction peaks of the resulting phases appear as typical XRD peaks of the lamellar MAX phase material. Except for V2(SnxMnyCoz) In addition to phase C, Sn simple substance, VCxAnd some alloy phases (CoSn)2,CoMnSn4)。
FIG. 2a and FIG. 2b are the resulting new five-membered layered magnetic material V2(SnxMnyCoz) Scanning electron pictures (SEM) and elemental distribution maps (EDS) of C. As can be seen from the figure, the resulting V2(SnxMnyCoz) C exhibits a typical layered structure of MAX phase materials. The EDS energy spectrum shows that the alloy contains five elements of V, Sn, Co, Mn and C, and V: (Sn + Mn + Co) is approximately equal to 2:1, so that the material can be judged to contain two elements of Mn and Co, and a novel five-element layered magnetic material containing two magnetic elements (Mn and Co) is obtained, and the chemical expression of the five-element layered magnetic material is V2(SnxMnyCoz) C, wherein x + y + z is 1.
Example 2: in this embodiment, the novel five-membered layered magnetic material is V2(SnxFeyCoz) C, powder material.
The V is2(SnxFeyCoz) The preparation method of the powder C comprises the following steps:
(1) mixing VC powder, Sn powder, Fe powder, Co powder and carbon powder according to a molar ratio of 2: 1: 0.01: 0.01: 1, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 500 ℃, the heat preservation time is 720min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and 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 washing the reaction product with ethanol, putting the reaction product into an oven at 80 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIG. 3 shows a new type five-membered layered magnetic material V prepared by molten salt method2(SnxFeyCoz) XRD pattern of C. As can be seen from the XRD patterns, the diffraction peaks of the resulting phases appear as XRD peaks typical of the lamellar MAX phase materials. Except for V2(SnxFeyCoz) In addition to phase C, Sn simple substance, VCxAnd some alloy phases (CoSn)2,FeSn2)。
FIG. 4a and FIG. 4b are the resulting new five-membered layered magnetic material V2(SnxFeyCoz) Scanning electron pictures (SEM) and elemental distribution maps (EDS) of C. As can be seen from the figure, the resulting V2(SnxFeyCoz) The C material has a typical layered structure, which shows that the novel layered structure material is obtained. EDS energy spectrum shows that the novel quinary layered magnetic material contains five elements of V, Sn, Co, Fe and C, and V (Sn + Fe + Co) is approximately equal to 2:1, so that the novel quinary layered magnetic material can be judged to simultaneously contain two magnetic elements of Fe and Co, and the novel quinary layered material containing two magnetic elements (Fe and Co) is obtained, and the chemical expression of the novel quinary layered material is V2(SnxFeyCoz) C, wherein x + y + z is 1.
Example 3: in this embodiment, the novel five-membered layered magnetic material is V2(SnxFeyNiz) C, powder material.
The V is2(SnxFeyNiz) The preparation method of the powder C comprises the following steps:
(1) will V2O5The powder, Sn powder, Fe powder, FeNi alloy powder, carbon powder and KCl inorganic salt are mixed according to the mol ratio of 2.5: 1: 0.99: 0.50: 1: weighing the materials according to the proportion of 1.5, and grinding and mixing the materials to obtain a mixture.
(2) The powder mixture was placed in a graphite mold and then sintered by SPS. The sintering conditions are as follows: the temperature is kept at 1100 ℃ for 120min, the heating rate is 100 ℃/min, the argon is used for protection, and the pressure is 37 MPa. And after the reaction is finished, taking out the product.
(3) Removing graphite paper on the surface of the obtained block, polishing the block to a mirror surface by using sand paper with different meshes, putting the mirror surface into an oven at 50 ℃, and taking out the block for 12 hours to obtain a block material.
FIG. 5 is a graph of V obtained by SPS sintering2(SnxFeyNiz) XRD pattern of novel quinary layered magnetic powder material. As can be seen from the XRD patterns, the diffraction peaks of the obtained phases are XRD peaks typical of lamellar MAX phase materials. Except for V2(SnxFeyNiz) In addition to C new phase, Sn simple substance, VCxAnd some impurity alloy phases (FeSn)2,NixSny,VFe)。
FIG. 6a and FIG. 6b are the resulting new five-membered layered magnetic material V2(SnxFeyNiz) Scanning electron pictures (SEM) and elemental distribution maps (EDS) of C powder. As can be seen from the figure, the resulting V2(SnxFeyNiz) C presents typical layered structure properties, which indicates that the obtained new material is a layered structure. EDS energy spectrum shows that the novel five-element layered magnetic material contains five elements of V, Sn, Ni, Fe and C, and V (Sn + Fe + Ni) is approximately equal to 2:1, so that the novel material can be judged to simultaneously contain two magnetic elements of Fe and Ni, and the novel five-element layered magnetic material is successfully prepared by combining XRD, SEM and EDS data analysis, wherein the chemical expression of the novel five-element layered magnetic material is V2(SnxFeyNiz) C, wherein x + y + z is 1.
Example 4: in this embodiment, the novel five-membered layered magnetic material is V2(SnxNiyCoz) C, powder material.
The V is2(SnxNiyCoz) The preparation method of the powder C comprises the following steps:
(1) mixing VC powder, Sn powder, NiCo alloy powder, Ni powder, carbon powder and inorganic salt (KI + NaCl) according to a molar ratio of 3: 1: 0.50: 0.99: 1: 2, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 900 ℃, the heat preservation time is 420min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and 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 washing the reaction product with ethanol, putting the reaction product into an oven at 60 ℃, and taking out the reaction product after 6 hours to obtain a solid product.
FIG. 7 is a graph of V obtained by SPS sintering2(SnxNiyCoz) XRD pattern of C quinary layered magnetic material. As can be seen from the XRD patterns, the diffraction peaks of the resulting phases appear as typical XRD peaks of the lamellar MAX phase material. Except for V2(SnxNiyCoz) In addition to phase C, Sn simple substance, VCxAnd some impurity alloy phases (CoSn)2,NixSny)。
FIGS. 8a and 8b are the resulting five-membered layered magnetic material V, respectively2(SnxNiyCoz) Scanning electron pictures (SEM) and elemental distribution maps (EDS) of C. As can be seen from the figure, the resulting V2(SnxNiyCoz) The particles of C exhibit a lamellar stacking structure. EDS energy spectrum shows that the novel five-element layered magnetic material contains five elements of V, Sn, Ni, Co and C, and V (Sn + Co + Ni) is approximately equal to 2:1, so that the novel Co and Ni magnetic element can be judged to be contained in the novel material, and the XRD, SEM and EDS data analysis are combined to show that the novel five-element layered magnetic material containing two magnetic elements (Ni and Co) is successfully prepared and obtained, and the chemical expression is V2(SnxNiyCoz) C, wherein x + y + z is 1.
Example 5: in this embodiment, the novel five-membered layered magnetic material is Ta2(SnxFeyNiz) C, powder material.
The Ta2(SnxFeyNiz) The preparation method of the powder C comprises the following steps:
(1) mixing TaC powder, SnS powder, Ni powder, FeNi alloy powder, carbon powder and K2SO4The inorganic salt is added into the mixture according to a molar ratio of 3.5: 1: 0.30: 0.70: 1: 3, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 800 ℃, the heat preservation time is 500min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and 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 washing the reaction product with ethanol, putting the reaction product into an oven at 60 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIG. 9a is the new type five-element layered magnetic material Ta obtained in this example2(SnxFeyNiz) ZFC curve diagram of C powder, FIG. 9b is ternary layered magnetic material V2The ZFC curve chart of FeC shows that the obtained novel five-element layered magnetic material has high magnetization intensity, represents that the magnetization intensity is strong, and shows ferromagnetism within the temperature range of 2-250K. In addition, the Curie temperature of the quinary magnetic material is about 250K, and the Curie temperature of the ternary layered magnetic material is about 200K, which is 50K lower than that of the quinary magnetic material, so that the quinary layered magnetic material has a wider use temperature range and is more suitable for being used as a magnetic electronic device.
Example 6: in this embodiment, the novel five-membered layered magnetic material is Ta2(SnxFeyCoz) C, powder material.
The Ta2(SnxFeyCoz) The preparation method of the powder C comprises the following steps:
(1) mixing Ta powder, Sn powder, CoO powder, Fe powder, carbon powder and Na2SO4The inorganic salt is added into the mixture according to a molar ratio of 4: 1: 0.80: 0.99: 1: 2, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 300min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and 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 washing the reaction product with ethanol, putting the reaction product into an oven at 70 ℃, and taking out the reaction product after 1h to obtain a solid product.
FIG. 10a is the new type five-element layered magnetic material Ta obtained in this example2(SnxFeyCoz) C at 200K, FIG. 10b is the ternary layered magnetic material Nb2The M-H curve of FeC at 200K shows that the material has typical hard magnetic property with the coercive force of 487Oe, while the coercive force of the ternary layered material Nb2FeCd is about 15Oe, and the material has soft magnetic property with the saturation magnetic magnetization far lower than that of a quinary layered magnetic material. The quinary layered magnetic material has stronger magnetism, and the synergistic enhancement effect of the two magnetic elements improves the magnetic property of the material, so that the quinary layered magnetic material can be used in the fields of magnetic separation and the like.
Example 7: in this embodiment, the novel quinary layered magnetic material is Nb2(SnxMnyCoz) C, powder material.
The Nb2(SnxMnyCoz) The preparation method of the powder C comprises the following steps:
(1) mixing NbC powder and SnO2The powder, Mn powder, FeCo powder, carbon powder and NaI inorganic salt are mixed according to a molar ratio of 3: 1: 0.99: 0.01: 1: 3, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1200 ℃, the heat preservation time is 300min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and 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 washing the reaction product with ethanol, putting the reaction product into an oven at 60 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIG. 11a is a reflection loss diagram of the five-element layered material and the three-element layered material, and it can be seen from the diagram that the minimum reflection loss of the three-element layered material is about-15 dB, and the effective absorption loss is less than 99%, while the minimum reflection loss of the five-element layered magnetic material is about-41 dB, which shows that the effective absorption is over 99.99%, and the wave-absorbing performance is far better than that of the three-element layered magnetic material. FIG. 11b is a return loss diagram of the quinary layered material under different thickness conditions of the X wave band, and it can be seen from the diagram that the quinary layered material can achieve effective absorption (< -10dB) in the whole X wave band, and can be used as a candidate wave-absorbing material.
Fig. 12a is an electrocatalytic diagram of a quinary layered magnetic material, and fig. 12b is an electrocatalytic diagram of a ternary layered magnetic material. As can be seen from the figure, under the same test conditions, the response current density of the quinary layered material under a lower excitation voltage (1.6) is about 12mA/cm2While the response current density of the ternary layered material under a higher excitation voltage (1.8V) is only about 0.6mA/cm2About 1/20, indicating that the electrocatalytic performance of the five-element layered magnetic material is far superior to that of the three-element layered magnetic material under the same conditions.
Example 8: in this embodiment, the novel five-membered layered magnetic material is V2(SnxMnyFez)CaNbAnd (3) powder materials.
The V is2(SnxMnyFez)CaNbThe preparation method of the powder comprises the following steps:
(1) mixing VC powder and SnO2The powder, the Mn powder, the Fe powder and the carbon nitrogen powder are mixed according to the mol ratio of 1.5: 1: 0.1: 0.99: 1, grinding and mixing the materials to obtain a mixture.
(2) And placing the mixture into a corundum crucible, and placing the corundum crucible into a high-temperature tubular furnace for reaction. The reaction conditions are as follows: the reaction temperature is 950 ℃, the heat preservation time is 420min, and the inert atmosphere is used for protection. And taking out the reaction product in the crucible after the temperature of the tube furnace is reduced to the room temperature.
(3) Washing the reaction product with deionized water and alcohol: and 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 24 hours to obtain a solid product.
The structure of the novel quinary layered magnetic material obtained in example 8 of the present invention was identical to the products of examples 1 to 7.
In addition, the inventor also replaces the corresponding raw materials and process conditions in the previous examples 1 to 8 with other raw materials and process conditions mentioned in the specification to perform relevant experiments, and the results show that the novel five-membered layered magnetic material can be obtained.
Compared with the existing ternary MAX phase material, the novel quinary layered magnetic material provided by the embodiment of the invention has the advantages of simple preparation process, low cost, high Curie temperature, hard magnetic property, excellent wave-absorbing performance, excellent electrochemical catalytic performance and potential application prospect in the fields of electrochemical catalysis, wave absorption and the like.
It should be understood that the above description is only an example of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent flow transformations that are made by the present specification and drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a novel quinary layered magnetic material is characterized by comprising the following steps:
mixing A and/or A-containing materials, B and/or B-containing materials, C and/or C-containing materials, D and/or D-containing materials, E and/or E-containing materials and inorganic salts according to the molar ratio of (2-4) 1 (0.01-0.99) to (0-3), reacting the obtained mixture at the high temperature of 500-1300 ℃ for 60-720 min in an inert atmosphere, and performing post-treatment after the high-temperature reaction is finished, namely washing the obtained reaction product for several times by deionized water and alcoholDrying at 40-80 ℃ for 1-24 h to obtain the novel quinary layered magnetic material, wherein the inorganic salt is selected from NaF, KF, NaCl, KCl, NaBr, KBr, NaI and Na2SO4、K2SO4、Na2CO3、K2CO3Any one or a combination of two or more of them;
the chemical composition of the quinary layered magnetic material is represented as A2(BxCyDz)E1Wherein A is any one of Ta, Sc, Hf, V, Nb, Mo, Zr, Cr and Ti, B is any one of Al, Sn, Ga and In, C is Mn or Fe, D is Co or Ni, and E is CaNbWherein a + b =1, 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z =1, E is any one or combination of two of C, N elements, and the unit cell of the novel five-membered layered magnetic material is formed by A2E1Unit and (B)xCyDz) The units are stacked alternately; the novel quinary layered magnetic material has ferromagnetic property within the temperature range of 2-250K, and the coercive force is more than 150 Oe.
2. The method of claim 1, wherein: the form of the novel quinary layered magnetic material is selected from any one or the combination of more than two of powder, block and film.
3. The method of claim 1, wherein: the material containing A is an alloy containing A.
4. The method of claim 1, wherein: the B-containing material is an alloy containing B.
5. The method of claim 1, wherein: the C-containing material is a C-containing alloy.
6. The method of claim 1, wherein: the D-containing material is an alloy containing D.
7. The method of claim 1, wherein: the E-containing material is an E-containing alloy.
8. The method of claim 1, wherein: the material A and/or the material containing A, the material B and/or the material containing B, the material C and/or the material containing C, the material D and/or the material containing D, and the material E and/or the material containing E are powder, and the particle size is 500 nm-100 mu m.
9. The method of claim 1, wherein: the inorganic salt is powder, and the particle size is 500 nm-1 mm.
10. Use of a novel five-membered layered magnetic material prepared by the method of any one of claims 1 to 9 in the field of electrochemical catalysis or wave absorption.
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