Rapid solid-phase synthesis method of molybdenum antimonide-based material

Abstract

The invention relates to a method for rapidly preparing a molybdenum antimonide-based material by utilizing a method combining mechanical alloying, cold pressing and ultrafast heat treatment, in particular to a method for rapidly preparing the molybdenum antimonide-based material by utilizing a pure solid-phase reaction. The method aims at solving the problems that an existing molybdenum antimonide-based material is long in preparation period, high in energy consumption and complex in process control by adopting a traditional melting-annealing-hot pressing sintering method. The method comprises the following steps: 1, pretreating a molybdenum antimonide-based raw material by using a mechanical alloying method, and carrying out cold pressing on the obtained mechanical alloying powder to form a block body; 2, carrying out ultrafast heat treatment on the cold-pressed block by using an ultrafast heat treatment method based on a Joule heating principle to obtain a final molybdenum antimonide-based material; the molybdenum antimonide-based material comprises but is not limited to Mo < 3 > Sb < 7-x > M < x > (M = Te, Se), Mo < 3-x > Re < x > Sb < 7 >, Mo < 3-x > Ru < x > Sb < 7 >, Mo < 2.5 > Ru < 0.5 > Sb < 7-x > Tex, Ni < x > Mo < 3-y > Ni < y > Sb < 7 >, A < 0.05 > Mo < 3 > Sb < 5.4 > Te < 1.6 > (A = Mn, Fe, Co and Ni). According to the method, the molybdenum antimonide-based material can be simply and rapidly prepared by combining mechanical alloying, cold pressing and ultrafast heat treatment. The method is suitable for large-scale rapid preparation of molybdenum antimonide-based materials in the technical fields of thermoelectric materials, catalytic materials, sodium ion battery electrodes, superconduction and the like.

Description

Technical Field

[0001] The invention relates to a rapid solid phase synthesis method for a molybdenum antimonide-based material, which can be applied to the large-scale rapid preparation of molybdenum antimonide-based materials in the fields of thermoelectric materials, catalytic materials, nano-ion battery electrodes and superconducting technology. Background Art

[0002] As a new type of material with unique properties, molybdenum antimonide has shown its potential and application value in many fields in recent years. At present, molybdenum antimonide has been found to be superconducting at 2.08K. Magnetization measurements show that Mo 3 Sb 7 It is a bulk П-type superconductor. In the field of thermoelectric materials, Mo is doped with atoms with a large number of valence electrons. 3 Sb 7 Being able to adjust the carrier concentration and mobility of the material, thereby improving the ZT value, can optimize its thermoelectric performance and provide a new way to develop high-efficiency thermoelectric materials. In addition, molybdenum antimonide-based materials can also replace platinum group metals as catalysts for hydrogen evolution reactions, effectively reducing the cost of water electrolysis hydrogen production technology. At the same time, molybdenum antimonide-based materials have high theoretical capacity and can provide ultra-high sodium storage capacity for sodium-ion batteries. Their good electrochemical reversibility can maintain stable performance during the charging process, which helps to improve the battery cycle life and has broad application prospects in the field of sodium-ion batteries.

[0003] The current method for preparing molybdenum antimonide-based materials is mainly to melt the raw materials into a liquid state first, and then perform a long annealing for hundreds of hours after cooling. Some will also add steps such as quenching. This method requires multiple long-term heating treatments during the preparation process, which is prone to complex reactions and the introduction of impurity phases. In addition, the melting points of the elements in molybdenum antimonide-based materials are very different, and element volatilization is prone to occur during the heating process. It is difficult to accurately control the phase composition of the product. At the same time, the preparation cycle is long and the energy consumption is high. In addition, there is also a method of obtaining pure molybdenum antimonide single crystals by using the peritectic reaction between metallic molybdenum and liquid antimony, but this method is complex and is not suitable for the application requirements of molybdenum antimonide semiconductor doping in the fields of thermoelectric materials. Therefore, it is urgent to develop a method for quickly realizing the pure phase preparation of molybdenum antimonide-based materials through solid-state reaction. At present, there is no report on the method of quickly preparing molybdenum antimonide-based materials through full solid-phase reaction by mechanical alloying pre-reaction followed by cold pressing and then ultrafast heat treatment. Summary of the invention

[0004] The purpose of the present invention is to solve the problems of complex process, long preparation cycle, high energy consumption and easy inclusion of impurity phase in the existing preparation method of molybdenum antimonide-based materials, and to propose a rapid solid phase synthesis method of molybdenum antimonide-based materials combining mechanical alloying, cold pressing and ultrafast heat treatment.

[0005] The preparation method combining mechanical alloying, cold pressing and ultrafast heat treatment of the present invention is carried out according to the following steps:

[0006] The molybdenum antimonide-based raw materials are pretreated using a mechanical alloying method. First, the raw materials are weighed according to the stoichiometric ratio, and the raw materials, process control agents, and grinding balls are placed in a mechanical alloying tank. The ball milling method is used to ensure that the raw materials are evenly mixed at near room temperature and in a certain atmosphere, and to promote atomic diffusion and alloying reactions between powder particles to generate nanopowders with high surface energy; then the obtained mechanically alloyed powder is placed in a cold pressing mold and pressure is applied for cold pressing. The gaps between the nanomaterials are compressed by cold pressing to obtain dense blocks of different shapes, so that the next solid phase reaction can proceed quickly;

[0007] The cold pressed block is subjected to ultrafast heat treatment based on the Joule heating principle. During the ultrafast heating, ultrashort heat preservation and rapid cooling process, the cold pressed block is subjected to a complete phase transformation in the solid state in an extremely short heat treatment cycle, thereby avoiding the volatilization of elements caused by the large difference in melting point and boiling point between the elements of the molybdenum antimonide-based material, and accurately controlling the phase composition of the product to obtain the final pure phase of the molybdenum antimonide-based material.

[0008] The mechanical alloying method aims to pre-alloy and nano-size the raw materials at near room temperature, including but not limited to ball milling method.

[0009] The process control agent includes but is not limited to ethanol, methanol, acetone and the like.

[0010] The atmosphere environment includes but is not limited to: argon, helium, nitrogen and air.

[0011] The dense blocks of different shapes include but are not limited to: cylindrical, rectangular, triangular prism and other complex shapes.

[0012] The molybdenum antimonide-based materials include but are not limited to Mo 3 Sb 7 、Mo 3 Sb 7-x M x (M=Te,Se), Mo 3-x Re x Sb 7 、Mo 3- x Ru x Sb 7 、Mo 2.5 Ru 0.5 Sb 7–x Te x 、Ni x Mo 3-y Ni y Sb 7, A 0.05 Mo 3 Sb 5.4 Te 1.6 (A=Mn, Fe, Co, Ni).

[0013] The principles and beneficial effects of the present invention are:

[0014] The present invention utilizes mechanical alloying pre-reaction followed by cold pressing and then ultrafast heat treatment to achieve full solid phase reaction to quickly prepare molybdenum antimonide-based materials, which can effectively avoid the generated products containing impurity phases, and has simple process control and low energy consumption. At the same time, it does not have high requirements on equipment and can be quickly prepared on a large scale.

[0015] The reason why the full solid phase reaction effectively avoids the formation of products containing impurity phases is that the present invention uses a method of high-energy ball milling to perform mechanical alloying pretreatment under low temperature conditions on the molybdenum antimonide-based raw materials to obtain nano-scale products. The raw material molybdenum antimonide-based metal powder is subjected to the continuous impact and friction of the grinding balls in a ball mill under a certain atmosphere to achieve a series of processes such as powder deformation, refinement, interatomic diffusion and solid phase reaction. Mechanical alloying mainly achieves solid phase alloying through the action of mechanical force, rather than through the chemical reaction of molten raw materials at high temperature to generate new compounds, which can effectively avoid the impurity phase introduced by complex chemical reactions. The ultrafast heat treatment method based on the Joule heating principle is used for the cold-pressed block to achieve ultrafast heating and cooling rates, significantly shorten the side reactions during the heating and cooling process, and reduce the internal grain growth of the material, ensuring that the material undergoes a complete phase transformation in the solid state throughout the process, avoiding the phenomenon of element volatilization caused by the large difference in melting points between molybdenum antimonide-based materials, accurately controlling the phase composition of the product, and obtaining the final pure phase of molybdenum antimonide-based material.

[0016] The reason for the simple process control and short preparation cycle is that the present invention performs pre-alloying and structural nano-ization of antimony-based raw materials at near room temperature by a mechanical alloying method, and can simply and accurately control the alloying process by adjusting parameters such as the speed and time of the ball mill, and the raw materials can be uniformly mixed at the atomic level without the need for long-term high-temperature smelting for dozens of hours. The obtained nanostructured powder is subsequently loaded into a cold pressing mold and pressure is applied for cold pressing. The gaps between the alloyed nano powders can be compressed by cold pressing, increasing the contact area between the powders and promoting the solid phase reaction during ultrafast heat treatment. At the same time, cold pressing has low equipment requirements and can meet the application of various shapes of antimony-based materials. The ultrafast heat treatment method based on the Joule heating principle can be used for the cold-pressed block to achieve rapid temperature rise and fall and heat preservation treatment at the millisecond level, and the final antimony-based material can be obtained without long-term annealing for hundreds of hours, so the antimony-based material can be simply and quickly prepared.

[0017] The invention adopts mechanical alloying and ultrafast heat treatment to realize the rapid preparation of molybdenum antimonide-based materials, has simple process control, low equipment requirements and energy consumption, and is suitable for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is the X-ray diffraction pattern obtained in Example 1. DETAILED DESCRIPTION

[0019] Specific implementation method 1: The rapid solid phase synthesis method of molybdenum antimonide-based materials combining mechanical alloying, cold pressing and ultrafast heat treatment of the present invention is carried out according to the following steps;

[0020] 1. Use mechanical alloying to pretreat the molybdenum antimonide-based raw materials. First, weigh the raw materials according to the stoichiometric ratio, and place the raw materials, process control agents and grinding balls into the mechanical alloying tank. The ball milling method is used to ensure that the raw materials are evenly mixed at near room temperature and a certain atmosphere, and to promote atomic diffusion and alloying reactions between powder particles to generate nanopowders with high surface energy; then the obtained mechanically alloyed powder is loaded into a cold pressing mold and pressure is applied for cold pressing. The gaps between the nanomaterials are compressed through cold pressing to obtain dense blocks of different shapes, so that the next solid-phase reaction can proceed quickly;

[0021] Second, the cold-pressed block is subjected to ultrafast heat treatment based on the Joule heating principle. During the ultrafast heating, ultrashort insulation and rapid cooling process, a very short heat treatment cycle is used to achieve a complete phase transformation of the cold-pressed block in the solid state, thereby avoiding the volatilization of elements caused by the large differences in melting and boiling points between the elements of the molybdenum antimonide-based material, accurately controlling the phase composition of the product, and obtaining the final pure phase of the molybdenum antimonide-based material.

[0022] The mechanical alloying method aims to pre-alloy and nano-size the raw materials at near room temperature, including but not limited to ball milling method.

[0023] The process control agent includes but is not limited to ethanol, methanol, acetone and the like.

[0024] The atmosphere environment includes but is not limited to: argon, helium, nitrogen and air.

[0025] The dense blocks of different shapes include but are not limited to: cylindrical, rectangular, triangular prism and other complex shapes.

[0026] The molybdenum antimonide-based materials include but are not limited to Mo 3 Sb 7 、Mo 3 Sb 7-x M x (M=Te,Se), Mo 3-x Re xSb 7 、Mo 3- x Ru x Sb 7 、Mo 2.5 Ru 0.5 Sb 7–x Te x 、Ni x Mo 3-y Ni y Sb 7 , A 0.05 Mo 3 Sb 5.4 Te 1.6 (A=Mn, Fe, Co, Ni).

[0027] The principles and beneficial effects of the present invention are:

[0028] The present invention utilizes mechanical alloying pre-reaction followed by cold pressing and then ultrafast heat treatment to achieve full solid phase reaction to quickly prepare molybdenum antimonide-based materials, which can effectively avoid the generated products containing impurity phases, and has simple process control and low energy consumption. At the same time, it does not have high requirements on equipment and can be quickly prepared on a large scale.

[0029] The reason why the full solid phase reaction effectively avoids the formation of products containing impurity phases is that: the present invention uses a method of high-energy ball milling to perform mechanical alloying pretreatment under low temperature conditions on the molybdenum antimonide-based raw materials to obtain nano-scale products. The raw material molybdenum antimonide-based metal powder is subjected to the continuous impact and friction of the grinding balls in a ball mill under a certain atmosphere to achieve a series of processes such as powder deformation, refinement, interatomic diffusion and solid phase reaction. Mechanical alloying is mainly achieved by physical means, rather than by chemical reaction to generate new compounds, which can effectively avoid the introduction of impurity phases due to complex chemical reactions. The ultrafast heat treatment method based on the Joule heating principle is used for the cold-pressed block to achieve ultrafast heating and cooling rates, significantly shorten the side reactions during the heating and cooling process, and reduce the internal grain growth of the material, ensuring that the material undergoes a complete phase transformation in the solid state throughout the process, avoiding the phenomenon of element volatilization caused by the large difference in melting points between molybdenum antimonide-based materials, accurately controlling the phase composition of the product, and obtaining the final pure phase of molybdenum antimonide-based material.

[0030] The reason for the simple process control and short preparation cycle is that the present invention performs pre-alloying and structural nano-ization of antimony molybdenum-based raw materials at near room temperature by a mechanical alloying method, and can simply and accurately control the alloying process by adjusting parameters such as the ball mill speed and time, and the raw materials can be uniformly mixed at the atomic level without long-term high-temperature smelting. Subsequently, the obtained nanostructured powder is loaded into a cold pressing mold and pressure is applied for cold pressing. The gaps between the alloyed nano powders can be compressed by cold pressing, increasing the contact area between the powders and promoting the solid phase reaction during ultrafast heat treatment. At the same time, cold pressing has low equipment requirements and can meet the application of various shapes of antimony molybdenum-based materials. The ultrafast heat treatment method based on the Joule heating principle can achieve rapid temperature rise and fall at the millisecond level for the cold-pressed block, and the final antimony molybdenum-based material can be obtained without long-term annealing for hundreds of hours, so the antimony molybdenum-based material can be simply and quickly prepared.

[0031] The invention adopts mechanical alloying and ultrafast heat treatment to realize the rapid preparation of molybdenum antimonide-based materials, has simple process control, low equipment requirements and energy consumption, and is suitable for mass production.

[0032] Specific implementation method 2: This implementation method is different from specific implementation method 1 in that: the mechanical alloying process described in step 1 is: first, the raw materials are weighed according to the stoichiometric ratio, and then the raw materials, process control agent and grinding balls are placed in a ball mill in a glove box filled with argon gas, and then the ball mill is sealed and taken out and placed in a ball mill for mechanical alloying, and parameters such as the ball milling speed is set to not less than 100 rpm and the ball milling time is not less than 1 min.

[0033] Specific implementation method three: This implementation method is different from specific implementation methods one or two in that: the cold pressing pressure described in step one is not less than 50 MPa.

[0034] Specific embodiment 4: This embodiment is different from specific embodiments 1 to 3 in that the molybdenum antimonide-based material described in step 2 includes but is not limited to: Mo 3 Sb 7 、Mo 3 Sb 7-x M x (M=Te,Se), Mo 3-x Re x Sb 7 、Mo 3-x Ru x Sb 7 、Mo 2.5 Ru 0.5 Sb 7–x Te x 、Ni x Mo 3-y Ni y Sb7 , A 0.05 Mo 3 Sb 5.4 Te 1.6 (A=Mn, Fe, Co, Ni).

[0035] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the ultrafast heat treatment process described in step 2 is: the ultrafast heat treatment is carried out in an ultrafast high temperature furnace, the atmosphere of the ultrafast high temperature furnace is a vacuum or other protective atmosphere, and the vacuum degree of the furnace chamber is not less than 1.0×10 -3 Pa, other protective atmospheres include but are not limited to argon, helium and nitrogen, etc. First, heat to 600~800℃ at a speed of not less than 50℃ / s, keep at this temperature for not less than 5s, and then quickly cool to room temperature at a speed of not less than 50℃ / s.

[0036] Example 1: The present invention uses a method combining mechanical alloying, cold pressing and ultrafast heat treatment to prepare Mo 3 Sb 7 , follow the steps below;

[0037] 1. Pre-treat the molybdenum antimonide-based raw materials using the mechanical alloying method. First, weigh the raw materials Mo and Sb according to the stoichiometric ratio of 3:7, and put the raw materials, process control agents and grinding balls into the mechanical alloying tank. The ball milling method is used to ensure that the raw materials are evenly mixed at near room temperature and a certain atmosphere, and to promote atomic diffusion and alloying reactions between powder particles to generate nanopowders with high surface energy; then the obtained mechanical alloyed powder is placed in a cold pressing mold and a pressure of not less than 50MPa is applied for cold pressing. The gaps between the nanomaterials are compressed by cold pressing to obtain dense blocks of different shapes, so that the next solid phase reaction can proceed quickly.

[0038] Step 1: The mechanical alloying process is as follows: metal raw materials Mo and Sb are mixed according to the chemical formula Mo 3 Sb 7 The ingredients were prepared in a stoichiometric ratio of 3:7, and then the raw materials, process control agents and grinding balls were placed in a ball mill in an argon-filled glove box. The ball mill was then sealed, taken out and placed in a ball mill for mechanical alloying. The ball milling program was set to 30min×30, with a total of 30 ball milling cycles. Each rotation cycle was paused for 15min, and then the next cycle of ball milling was carried out, achieving a total ball milling time of 15 hours.

[0039] The cold pressing process described in step 1 is: loading the mechanical alloying powder into a cold pressing mold, and using a cold press to apply a pressure of 150 MPa to press the powder into a block.

[0040] Second, the cold-pressed block is subjected to ultrafast heat treatment based on the Joule heating principle. During the ultrafast heating, ultrashort insulation and rapid cooling process, a very short heat treatment cycle is used to achieve a complete phase transformation of the cold-pressed block in the solid state, thereby avoiding the volatilization of elements caused by the large differences in melting and boiling points between the elements of the molybdenum antimonide-based material, accurately controlling the phase composition of the product, and obtaining the final pure phase of the molybdenum antimonide-based material.

[0041] The ultrafast heat treatment process described in step 2 is as follows: the ultrafast heat treatment is carried out in an ultrafast high temperature furnace, the atmosphere of the ultrafast high temperature furnace is a vacuum or Ar gas protective atmosphere, and the vacuum degree of the furnace chamber is less than 2.2×10 -3 Pa, when the heating furnace is Ar gas protective atmosphere, the Ar gas pressure is -0.07Mpa; firstly, it is heated to 650℃ at a speed of 60℃ / s and kept warm for 30s, and then cooled to room temperature at a speed of 60℃ / s.

[0042] Figure 1 is the X-ray diffraction pattern obtained in Example 1, such as Figure 1 As shown, by comparing the standard XRD spectrum, it can be seen that the obtained material is a single phase of molybdenum antimonide.

[0043] Example 2: The present invention uses a method combining mechanical alloying, cold pressing and ultrafast heat treatment to prepare Mo 3 Sb 5.4 Te 1.6 , follow the steps below;

[0044] 1. Use mechanical alloying to pretreat the molybdenum antimonide-based raw materials. First, weigh the raw materials Mo, Sb and Te according to the stoichiometric ratio of 3:5.4:1.6, and put the raw materials, process control agents and grinding balls into the mechanical alloying tank. The ball milling method is used to ensure that the raw materials are evenly mixed at near room temperature and a certain atmosphere environment, and to promote atomic diffusion and alloying reactions between powder particles to generate nanopowders with high surface energy; then the obtained mechanically alloyed powder is placed in a cold pressing mold and a pressure of not less than 50MPa is applied for cold pressing. The gaps between the nanomaterials are compressed by cold pressing to obtain dense blocks of different shapes, so that the next solid phase reaction can proceed quickly;

[0045] Step 1 The mechanical alloying process is as follows: metal raw materials Mo, Sb and Te are mixed according to the chemical formula Mo 3 Sb 5.4 Te 1.6The ingredients were prepared in a stoichiometric ratio of 3:5.4:1.6, and then the raw materials, process control agents and grinding balls were placed in a ball mill in an argon-filled glove box. The ball mill was then sealed, taken out and placed in a ball mill for mechanical alloying. The ball milling program was set to 60min×15, with a total of 15 ball milling cycles. Each rotation cycle was paused for 15min, and then the next cycle of ball milling was carried out, achieving a total ball milling time of 15 hours.

[0046] The cold pressing process described in step 1 is: loading the mechanical alloying powder into a cold pressing mold, and using a cold press to apply a pressure of 200 MPa to press the powder into a block.

[0047] Second, the cold-pressed block is subjected to ultrafast heat treatment based on the Joule heating principle. During the ultrafast heating, ultrashort insulation and rapid cooling process, a very short heat treatment cycle is used to achieve a complete phase transformation of the cold-pressed block in the solid state, thereby avoiding the volatilization of elements caused by the large differences in melting and boiling points between the elements of the molybdenum antimonide-based material, accurately controlling the phase composition of the product, and obtaining the final pure phase of the molybdenum antimonide-based material.

[0048] The ultrafast heat treatment process described in step 2 is as follows: the ultrafast heat treatment is carried out in an ultrafast high temperature furnace, the atmosphere of the ultrafast high temperature furnace is a vacuum or Ar gas protective atmosphere, and the vacuum degree of the furnace chamber is less than 2.2×10 -3 Pa, when the heating furnace is an Ar gas protective atmosphere, the Ar gas pressure is -0.07Mpa; firstly, it is heated to 750℃ at a speed of 80℃ / s and kept warm for 60s, and then cooled to room temperature at a speed of 80℃ / s.

[0049] The obtained Mo 3 Sb 5.4 Te 1.6 It is single phase.

[0050] Example 3: The present invention uses a method combining mechanical alloying, cold pressing and ultrafast heat treatment to prepare Mo 2.2 Ru 0.8 Sb 7 , follow the steps below;

[0051] 1. Use mechanical alloying to pretreat the molybdenum antimonide-based raw materials. First, weigh the raw materials Mo, Sb and Ru according to the stoichiometric ratio of 2.2:0.8:7, and put the raw materials, process control agents and grinding balls into the mechanical alloying tank. The ball milling method is used to ensure that the raw materials are evenly mixed at near room temperature and a certain atmosphere environment, and to promote atomic diffusion and alloying reactions between powder particles to generate nanopowders with high surface energy; then the obtained mechanically alloyed powder is placed in a cold pressing mold and a pressure of not less than 50MPa is applied for cold pressing. The gaps between the nanomaterials are compressed by cold pressing to obtain dense blocks of different shapes, so that the next solid phase reaction can proceed quickly;

[0052] Step 1: The mechanical alloying process is as follows: metal raw materials Mo, Sb and Ru are mixed according to the chemical formula Mo 2.2 Ru 0.8 Sb 7 The ingredients were prepared in a stoichiometric ratio of 2.2:0.8:7, and then the raw materials, process control agents and grinding balls were placed in a ball mill in an argon-filled glove box. The ball mill was then sealed, taken out and placed in a ball mill for mechanical alloying. The ball milling program was set to 30min×30, with a total of 30 ball milling cycles. Each rotation cycle was paused for 15min, and then the next cycle of ball milling was carried out, achieving a total ball milling time of 15 hours.

[0053] The cold pressing process described in step 1 is: loading the mechanical alloying powder into a cold pressing mold, and using a cold press to apply a pressure of 350 MPa to press the powder into a block.

[0054] Second, the cold-pressed block is subjected to ultrafast heat treatment based on the Joule heating principle. During the ultrafast heating, ultrashort insulation and rapid cooling process, a very short heat treatment cycle is used to achieve a complete phase transformation of the cold-pressed block in the solid state, thereby avoiding the volatilization of elements caused by the large differences in melting and boiling points between the elements of the molybdenum antimonide-based material, accurately controlling the phase composition of the product, and obtaining the final pure phase of the molybdenum antimonide-based material.

[0055] The ultrafast heat treatment process described in step 2 is as follows: the ultrafast heat treatment is carried out in an ultrafast high temperature furnace, the atmosphere of the ultrafast high temperature furnace is a vacuum or Ar gas protective atmosphere, and the vacuum degree of the furnace chamber is less than 2.2×10 -3 Pa, when the Ar gas protective atmosphere in the heating furnace is -0.07Mpa; firstly, heat to 800℃ at a speed of 90℃ / s and keep warm for 120s, then cool to room temperature at a speed of 90℃ / s.

[0056] The obtained Mo 2.2 Ru 0.8 Sb 7 It is single phase.

Claims

1. A rapid solid phase synthesis method for molybdenum antimonide-based materials, characterized in that: The method proceeds as follows: The molybdenum antimonide-based raw materials are pretreated using a mechanical alloying method. First, the raw materials are weighed according to the stoichiometric ratio, and the raw materials, process control agents, and grinding balls are placed in a mechanical alloying tank. The ball milling method is used to ensure that the raw materials are evenly mixed at near room temperature and in a certain atmosphere, and to promote atomic diffusion and alloying reactions between powder particles to generate nanopowders with high surface energy; then the obtained mechanically alloyed powder is placed in a cold pressing mold and pressure is applied for cold pressing. The gaps between the nanomaterials are compressed by cold pressing to obtain dense blocks of different shapes, so that the next solid phase reaction can proceed quickly; The cold pressed block is subjected to ultrafast heat treatment based on the Joule heating principle. During the ultrafast heating, ultrashort heat preservation and rapid cooling process, the cold pressed block is subjected to a complete phase transformation in the solid state in an extremely short heat treatment cycle, thereby avoiding the volatilization of elements caused by the large difference in melting point and boiling point between the elements of the molybdenum antimonide-based material, and accurately controlling the phase composition of the product to obtain the final pure phase of the molybdenum antimonide-based material. The mechanical alloying method aims to pre-alloy and nano-size the raw materials at near room temperature, including but not limited to ball milling method.

2. The process control agent includes but is not limited to: ethanol, methanol, acetone, etc.

3. The atmosphere includes but is not limited to: argon, helium, nitrogen and air, etc. The dense blocks of different shapes include but are not limited to: cylindrical, rectangular, triangular prism and other complex shapes.

4. The molybdenum antimonide-based materials include but are not limited to Mo3Sb7, Mo3Sb 7-x M x (M=Te,Se), Mo 3-x Re x Sb7、Mo 3- x Ru x Sb7、Mo 2.5 Ru 0.5 Sb 7–x Te x 、Ni x Mo 3-y Ni y Sb7, A 0.05 Mo3Sb 5.4 Te 1.6 (A=Mn, Fe, Co, Ni).

5. The rapid solid phase synthesis method of molybdenum antimonide-based materials according to claim 1, characterized in that: The mechanical alloying process described in step 1 is as follows: first, the raw materials are weighed according to the stoichiometric ratio, and then the raw materials, process control agent and grinding balls are placed in a ball mill in a glove box filled with argon gas, and then the ball mill is sealed and taken out and placed in a ball mill for mechanical alloying, and parameters such as the ball milling speed is set to not less than 100 rpm and the ball milling time is not less than 1 min.

6. The rapid solid phase synthesis method of molybdenum antimonide-based materials according to claim 1, characterized in that: The mechanical alloying process described in step 1 is as follows: first, the raw materials are weighed according to the stoichiometric ratio, and then the raw materials, process control agent and grinding balls are placed in a ball mill in a glove box filled with argon gas, and then the ball mill is sealed and taken out and placed in a ball mill for mechanical alloying, and parameters such as the ball milling speed is set to not less than 100 rpm and the ball milling time is not less than 1 min.

7. The rapid solid phase synthesis method of molybdenum antimonide-based materials according to claim 1, characterized in that: The molybdenum antimonide-based materials in step 2 include but are not limited to Mo3Sb7, Mo3Sb 7-x M x (M=Te,Se), Mo 3-x Re x Sb7、Mo 3-x Ru x Sb7、Mo 2.5 Ru 0.5 Sb 7–x Te x 、Ni x Mo 3-y Ni y Sb7, A 0.05 Mo3Sb 5.4 Te 1.6 (A=Mn, Fe, Co, Ni).

8. The rapid solid phase synthesis method of molybdenum antimonide-based materials according to claim 1, characterized in that: The ultrafast heat treatment process described in step 2 is as follows: the ultrafast heat treatment is carried out in an ultrafast high temperature furnace, the atmosphere of the ultrafast high temperature furnace is a vacuum or other protective atmosphere, and the vacuum degree of the furnace chamber is not less than 1.0×10 -3 Pa, other protective atmospheres include but are not limited to argon, helium and nitrogen, etc. First, heat to 600~800℃ at a speed of not less than 50℃ / s, keep at this temperature for not less than 5s, and then quickly cool to room temperature at a speed of not less than 50℃ / s.

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