CN112185591B - Titanium nitride coated lithium orthosilicate tritium proliferation agent and preparation method and preparation device system thereof - Google Patents
Titanium nitride coated lithium orthosilicate tritium proliferation agent and preparation method and preparation device system thereof Download PDFInfo
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- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
- C01B21/0761—Preparation by direct nitridation of titanium, zirconium or hafnium
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Abstract
The invention provides a TiN coated Li 4 SiO 4 A tritium breeder, a preparation method thereof and a preparation device system are provided, wherein the preparation method comprises the following steps: (1) Make Li 4 SiO 4 The particles are in a fluidized state in a protective atmosphere; (2) Mixing Li on the basis of the continuous operation of the step (1) 4 SiO 4 Particles, titanium source gas and nitrogen source gas; (3) Separating gas and solid to obtain TiN coated Li 4 SiO 4 A tritium breeder. The device system comprises a storage bin, a fluidized bed coating device, a titanium source gasification device, a product collecting device and a tail gas treatment device. The invention overcomes the defect of Li 4 SiO 4 Corrosion to the cladding material and increase the content of the lithium-based ceramic tritium breeder in He-H 2 /H 2 The stability in O environment, the preparation process is simple, and good economic and social benefits are achieved.
Description
Technical Field
The invention belongs to the technical field of nuclear fusion, relates to a preparation method of an advanced lithium-based ceramic tritium breeder with a core-shell structure, and particularly relates to TiN coated Li 4 SiO 4 Tritium breeder, preparation method and preparation device system thereof.
Background
With the environmental deterioration and the continuous expansion of energy demand, the utilization and development of new energy become one of the important issues facing the world at present. Deuterium (D) -tritium (T) nuclear fusion energy (D + T → He + n +17.6 MeV) is considered to be one of important ways for solving the energy crisis of human beings due to the advantages of safety, cleanness, high efficiency and the like. Tritium fuel, however, is naturally less abundant and must be bombarded by neutrons 6 Material of Li for obtaining tritium fuel (a) 1 n+ 6 Li→ 4 He +3T + 4.78MeV). Over decades of development, li is now present 4 SiO 4 The microsphere is selected as one of candidate materials of the solid tritium breeding cladding due to the excellent characteristics of high Li density, good tritium release performance, large compressive strength, good moisture resistance and the like.
However, with the continuous and deep research, people gradually find that in the actual service environment, li 4 SiO 4 The microspheres can corrode the cladding material to form a fragile oxide corrosion layer, which deteriorates the mechanical properties of the cladding material, especially in He-H 2 In the atmosphere cleaning, the corrosion phenomenon is more obvious, and great potential safety hazard is caused to the long-term stable operation of the nuclear reactor.
Based on this, the Japanese atomic energy mechanism is designed to have Er 2 O 3 Coated RAFM steel (Fusion eng. Des.87 (2012) 1777-1787) by design of Er 2 O 3 The coating layer creates a barrier layer between the microsphere and the steel substrate, and blocks Li 4 SiO 4 And the element between the cladding and the steel matrix diffuses and reacts, so that the safety of the cladding is improved. However, as the service time increases, the coating is prone to peeling off due to the large thermal stress between the oxide and the RAFM steel substrate.
CN108751975A discloses a preparation method of tritium-proliferated ceramic pellets in a fusion reactor solid blanket, which has mild conditions, can complete two processes of pelletizing and curing simultaneously in the sedimentation process, simplifies the purification and transfer process of pellet embryo bodies, and has high sphericity, uniform particle size, high porosity and mechanical strength of the obtained product, thereby facilitating industrial production. However, the tritium breeding ceramic pellets are in direct contact with cladding materials during use, and stability of the tritium breeding agent is affected.
CN111217592A discloses a preparation method of tritium-proliferated ceramic spheres with high lithium content based on a molten salt method, which comprises the steps of firstly preparing precursor powder with uniform particle size by adopting a mixed solvothermal method, then preparing a lithium salt solution with a certain concentration, then carrying out ball milling to obtain slurry, obtaining a spherical ceramic biscuit by adopting wet forming, and finally sintering to prepare the lithium orthosilicate ceramic spheres. During sintering, the lithium molten salt is decomposed to form lithium oxide, and finally the lithium oxide is dissolved in the crystal lattice of the lithium orthosilicate in a solid mode, so that impurities are not introduced, and the purpose of improving the lithium atom density can be achieved. The invention solves the problem that the preparation method of tritium propagation ceramic in the prior art is difficult to obtain density and strength at a lower temperature. However, the invention also has the problem that the lithium orthosilicate ceramic balls are in direct contact with the cladding material during the use process, and the phenomenon of corrosion of the cladding material is easily caused.
CN108550404A discloses a fluid state tritium breeding ceramic composite material, which is formed by mixing a liquid phase and a solid phase, and can eliminate the magnetohydrodynamic resistance effect and the corrosion effect on cladding structure materials of the existing liquid metal or molten salt tritium breeding agent, and also can eliminate the problems of low tritium release efficiency, low heat transfer property, fragility, carrier gas channel blockage caused by lithium volatilization and the like. However, the method has higher cost, is difficult to realize large-scale batch production, cannot fundamentally avoid element diffusion between the tritium breeder and the cladding material, and still has the problem of cladding material corrosion after long-term use.
Therefore, how to further design and optimize a barrier layer between the tritium breeding agent and the cladding material and prevent the tritium breeding agent from directly contacting with the cladding material becomes a problem to be solved urgently in the prior art of the tritium breeding cladding module in the nuclear fusion reactor.
Disclosure of Invention
The invention aims to provide TiN coated Li 4 SiO 4 Tritium breeder, method and apparatus system for its preparation, which overcomes Li 4 SiO 4 Corrosion to cladding material, and raising the content of lithium-base ceramic tritium breeder in He-H 2 /H 2 Stability in O environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a TiN coated Li 4 SiO 4 A method of preparing a tritium proliferator, the method comprising the steps of:
(1) Make Li 4 SiO 4 The particles are in a fluidized state in a protective atmosphere;
(2) Mixing Li on the basis of the continuous operation of the step (1) 4 SiO 4 GranulesA titanium source gas and a nitrogen source gas;
(3) Separating gas and solid to obtain TiN coated Li 4 SiO 4 A tritium breeder.
In the present invention, the fluidization state in the step (1) is such that not only Li 4 SiO 4 The particles are uniformly distributed in the reaction space, and air in the reaction space is removed; step (2) said Li 4 SiO 4 Particles of TiN deposited by reaction with the titanium source gas and the nitrogen source gas in a fluidized state, thereby forming particles of Ti and/or Ti 4 SiO 4 TiN coating layers are uniformly formed on the surfaces of the particles to obtain TiN coated Li 4 SiO 4 The core-shell structure of (A) is an advanced tritium breeding agent.
Preferably, the Li in the step (1) 4 SiO 4 The particles are spherical or spheroidal in shape.
Preferably, the Li 4 SiO 4 The particles have an equivalent diameter of from 0.1 to 1.2mm, and may be, for example, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm or 1.2mm, but are not limited to the values recited, and other values not recited within the range of values are equally applicable.
In the present invention, when said Li is 4 SiO 4 When the particles are spherical in shape, the equivalent diameter is Li 4 SiO 4 The actual particle size of the particles; when said Li is 4 SiO 4 When the particles are spheroidal in shape, the equivalent diameter is Li 4 SiO 4 The average particle size of the particles.
Preferably, the gas in the protective atmosphere in step (1) comprises any one of argon, helium or neon or a combination of at least two of them, and typical but non-limiting combinations include a combination of argon and helium, a combination of helium and neon, a combination of argon and neon, or a combination of argon, helium and neon.
In the present invention, the protective atmosphere may be such that the Li 4 SiO 4 The particles keep a fluidized state, and can isolate the air in the environment, so that the subsequent TiN film layer can be coated smoothly.
Preferably, the mixing in step (2) is carried out in such a way thatThe titanium source gas and the nitrogen source gas are respectively and independently introduced into the Li 4 SiO 4 The particles are in a protective atmosphere.
In the invention, the titanium source gas and the nitrogen source gas are respectively and independently introduced into the Li from different inlets at the same time 4 SiO 4 The particles being in a protective atmosphere so that Li is present 4 SiO 4 A TiN film layer is formed on the surface of the particles.
Preferably, the temperature of the mixing in step (2) is 500-900 ℃, for example 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mixing time in step (2) is not less than 1min, for example, 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other non-recited values in the range are also applicable.
Preferably, the titanium source gas in the step (2) is a gas formed by high-temperature gasification of a titanium salt.
Preferably, the titanium salt is titanium dichloride.
Preferably, the carrier gas for high-temperature gasification is the gas in the protective atmosphere in the step (1)
Preferably, the high temperature gasification temperature is 400-800 ℃, for example 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, but is not limited to the recited values, and other unrecited values in the range of values are equally applicable.
Preferably, the nitrogen source gas in step (2) is nitrogen.
Preferably, the titanium source gas is introduced in step (2) at a flow rate of 50-200mL/min, such as 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, 120mL/min, 130mL/min, 140mL/min, 150mL/min, 160mL/min, 170mL/min, 180mL/min, 190mL/min or 200mL/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the nitrogen source gas in step (2) is introduced at a flow rate of 50-200mL/min, such as 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, 120mL/min, 130mL/min, 140mL/min, 150mL/min, 160mL/min, 170mL/min, 180mL/min, 190mL/min or 200mL/min, but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the gas-solid separation method in step (3) comprises any one or a combination of at least two of gravity settling, centrifugal settling or filtration, and typical but non-limiting combinations include a combination of gravity settling and centrifugal settling, a combination of centrifugal settling and filtration, a combination of gravity settling and filtration, or a combination of gravity settling, centrifugal settling and filtration.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Making the spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere; the gas in the protective atmosphere comprises any one or a combination of at least two of argon, helium or neon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 500-900 ℃, and the mixing time is more than or equal to 1min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 400-800 ℃, and the gas speed is 50-200mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50-200mL/min;
(4) Obtaining TiN coated Li after gravity settling, centrifugal settling or filtering 4 SiO 4 A tritium breeder.
In a second aspect, the present invention provides a TiN-coated Li prepared by the preparation method of the first aspect 4 SiO 4 Tritium breeder, said TiN coated Li 4 SiO 4 The tritium breeder may have a TiN layer thickness of 1nm or more, for example, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm or 5nm, andnot only the recited values are intended to be limiting, but other values not recited within the numerical range are also intended to be applicable.
In the present invention, the TiN coated Li 4 SiO 4 The tritium breeder departs from the traditional idea of creating a barrier layer by depositing an oxide coating on a cladding material by depositing Li 4 SiO 4 A corrosion-resistant and stable TiN shell is constructed on the surface, an inert protective layer is formed between the tritium breeder and the cladding material to achieve the purpose of corrosion resistance, and meanwhile, the hydrophobic TiN film isolates the tritium breeder from H in the scavenging gas 2 /H 2 The direct contact of O achieves the purpose of improving the stability of the tritium breeder, thereby solving the key problems of coating falling and tritium breeder breakage and finally obtaining the advanced lithium-based ceramic tritium breeder.
In a third aspect, the present invention provides a method for preparing TiN coated Li 4 SiO 4 The device system for the tritium breeder comprises a storage bin, a fluidized bed coating device, a titanium source gasification device, a product collection device and a tail gas treatment device;
the storage bin is used for providing Li for the fluidized bed coating device 4 SiO 4 Particles;
the fluidized bed coating device is used for mixing Li in protective atmosphere 4 SiO 4 Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN coated Li 4 SiO 4 A tritium breeder;
the titanium source gasification device is used for providing titanium source gas for the fluidized bed coating device;
the product collecting device is used for collecting TiN coated Li generated in the fluidized bed coating device 4 SiO 4 A tritium proliferating agent;
the tail gas treatment device is used for removing tail gas generated in the fluidized bed coating device.
Compared with the prior art, the invention has the following beneficial effects:
(1) The inert TiN film blocks Li in the present invention 4 SiO 4 The tritium breeder is directly contacted with the cladding material, thereby fundamentally avoiding Li, O, fe and Cr elementsThe diffusion and reaction between elements obviously improve the safety of the cladding material;
(2) The inert TiN film of the present invention blocks Li 4 SiO 4 Tritium breeder and H in sweep gas 2 /H 2 The direct contact of O obviously improves the stability of the proliferation agent in the cladding;
(3) The invention prepares TiN coated Li 4 SiO 4 The tritium breeding agent has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy large-scale batch production.
Drawings
FIG. 1 is a process for preparing TiN coated Li according to the present invention 4 SiO 4 A device system for tritium breeder;
FIG. 2 is TiN coated Li prepared by the method provided in example 1 4 SiO 4 EDS profile of tritium breeder;
FIG. 3 is a TiN coated Li obtained by the preparation method provided in example 1 4 SiO 4 SEM images of tritium proliferators.
Wherein: 1-a storage bin; 2-fluidized bed coating device; 3-a titanium source gasification device; 4-a product collection device; 5-tail gas treatment device.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The present invention provides a method for preparing TiN coated Li as shown in figure 1 4 SiO 4 The device system of tritium breeder, the device system includes feed bin 1, fluidized bed cladding device 2, titanium source gasification equipment 3, product collection device 4 and tail gas processing apparatus 5.
In the invention, the stock bin 1 is used for providing Li for the fluidized bed coating device 2 4 SiO 4 Particles; the fluidized bed coating device 2 is used for mixing Li in protective atmosphere 4 SiO 4 Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN coated Li 4 SiO 4 Tritium breeder, in particular, the fluidized bedThe coating device 2 is a fluidized bed; the titanium source gasification device 3 is used for providing titanium source gas for the fluidized bed coating device 2, and specifically, the titanium source gasification device 3 is a conical fluidized bed; the product collecting device 4 is used for collecting TiN coated Li generated in the fluidized bed coating device 2 4 SiO 4 A tritium breeder, specifically, the product collection device 4 is a storage tank; the tail gas treatment device 5 is used for treating tail gas generated in the fluidized bed coating device 2, and specifically, the tail gas treatment device 5 is a conventional compensation ignition device.
Example 1
This example provides a TiN coated Li 4 SiO 4 A preparation method of a tritium breeding agent, which is carried out in the device system provided by the invention and shown in figure 1, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.6mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of argon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 700 ℃, and the mixing time is 30min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 600 ℃, the carrier gas is argon, and the gas speed is 125mL/min; the nitrogen source gas is nitrogen, and the gas speed is 125mL/min;
(4) Obtaining TiN coated Li after gravity settling 4 SiO 4 A tritium breeder.
FIG. 2 is a view of the TiN coated Li obtained by the preparation method provided in this example 4 SiO 4 EDS diagram of tritium breeder, where TiN content reaches 8.2at.%.
FIG. 3 is the TiN coated Li obtained by the preparation method provided in this example 4 SiO 4 The SEM image of the tritium breeder shows that a layer of nano TiN film is uniformly coated on the surface of the crystal grain of the microsphere as shown in figure 3.
The preparation method provided in this example can obtain TiN coated Li 4 SiO 4 The thickness of the TiN layer of the tritium breeder is 2nm.
Example 2
This example provides a TiN coated Li 4 SiO 4 The preparation method of the tritium breeding agent is carried out in the device system provided by the invention and shown in the figure 1, and comprises the following steps:
(1) Spherical Li having a particle diameter of 0.9mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of helium;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 800 ℃, and the mixing time is 45min; the titanium source gas is formed by gasifying titanium dichloride at high temperature of 700 ℃, the carrier gas is helium, and the gas speed is 160mL/min; the nitrogen source gas is nitrogen, and the gas speed is 160mL/min;
(4) Obtaining TiN coated Li after centrifugal sedimentation 4 SiO 4 A tritium breeder.
TiN-coated Li obtained in this example 4 SiO 4 The thickness of the TiN film of the tritium breeder is 2.5nm, and the obtained TiN coated Li 4 SiO 4 The element composition and the micro-morphology of the tritium breeder are similar to those of example 1, and therefore, the details are not repeated herein.
Example 3
This example provides a TiN coated Li 4 SiO 4 The preparation method of the tritium breeding agent is carried out in the device system provided by the invention and shown in the figure 1, and comprises the following steps:
(1) Spherical Li having a particle diameter of 0.3mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of neon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 600 ℃, and the mixing time is 15min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 500 ℃, the carrier gas is neon, and the gas speed is 85mL/min; the nitrogen source gas is nitrogen, and the gas speed is 85mL/min;
(4) Filtering to obtain TiN coated Li 4 SiO 4 A tritium breeder.
TiN-coated Li obtained in the example 4 SiO 4 The thickness of the TiN film of the tritium breeder is 1.5nm, and the obtained TiN coated Li 4 SiO 4 The element composition and the micro-morphology of the tritium breeder are similar to those of example 1, and therefore, the details are not repeated herein.
Example 4
This example provides a TiN coated Li 4 SiO 4 The preparation method of the tritium breeding agent is carried out in the device system provided by the invention and shown in the figure 1, and comprises the following steps:
(1) Spherical Li having a particle diameter of 1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of argon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 Mixing the granules in a protective atmosphere at 900 deg.C for 1min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 800 ℃, the carrier gas is argon, and the gas speed is 200mL/min; the nitrogen source gas is nitrogen, and the gas speed is 200mL/min;
(4) Obtaining TiN coated Li after gravity settling 4 SiO 4 A tritium breeder.
TiN-coated Li obtained in this example 4 SiO 4 The thickness of the TiN film of the tritium breeder is 1nm, and the obtained TiN coated Li 4 SiO 4 The elemental composition and the microscopic morphology of the tritium breeder are similar to those of example 1, and therefore are not described herein.
Example 5
This example provides a TiN coated Li 4 SiO 4 A preparation method of a tritium breeding agent, which is carried out in the device system provided by the invention and shown in figure 1, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.1mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of helium;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 500 ℃, and the mixing time is 60min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 400 ℃, the carrier gas is helium, and the gas speed is 50mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50mL/min;
(4) Obtaining TiN coated Li after centrifugal sedimentation 4 SiO 4 A tritium breeder.
TiN-coated Li obtained in this example 4 SiO 4 The thickness of the TiN film of the tritium breeder is 3nm, and the obtained TiN coated Li 4 SiO 4 The element composition and the micro-morphology of the tritium breeder are similar to those of example 1, and therefore, the details are not repeated herein.
Comparative example 1
This comparative example provides Li 4 SiO 4 A method for treating a tritium breeding agent, wherein the method is carried out in the device system shown in figure 1, and the method comprises the following steps:
(1) Making the particle diameter of the ball Li 0.6mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of argon;
(2) Introducing nitrogen into Li on the basis of continuous operation of the step (1) 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 700 ℃, and the mixing time is 30min; the gas introducing speed of the nitrogen is 250mL/min;
(3) Obtaining Li after gravity settling 4 SiO 4 A tritium breeder.
Li obtained in example 1 and comparative example 1 4 SiO 4 The tritium breeder was separately placed in a container made of low activation steel, heated to 650 ℃ under an argon atmosphere and kept at the temperature for 10 days, and then the surface of the low activation steel was analytically tested, and as a result, it was found that the low activation steel was loaded with Li obtained in example 1 4 SiO 4 Low activation steel with tritium breeder showed no significant corrosion, but was loaded with Li from comparative example 1 4 SiO 4 Obvious corrosion phenomenon is found in the low-activation steel of the tritium breeder, which indicates that Li 4 SiO 4 The tritium breeder obviously inhibits the corrosion of low-activation steel after coating a TiN layer.
It can be seen that the inert TiN film in the present invention hinders Li 4 SiO 4 The tritium breeder is directly contacted with the cladding material, so that the diffusion and reaction among Li, O, fe and Cr elements are fundamentally avoided, and the safety of the cladding material is remarkably improved; the inert TiN film blocks Li in the present invention 4 SiO 4 Tritium breeder and H in sweep gas 2 /H 2 The direct contact of O obviously improves the stability of the proliferation agent in the cladding; the invention prepares TiN coated Li 4 SiO 4 The tritium breeding agent has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy large-scale batch production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (10)
1. TiN coated Li 4 SiO 4 A process for the preparation of a tritium breeder, characterized in that it comprises the following steps:
(1) Making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere;
(2) On the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li at a gas speed of 50-200mL/min 4 SiO 4 The mixing temperature of the particles in the protective atmosphere is 500-900 ℃, and the mixing time is more than or equal to 1min;
(3) Separating gas from solid to obtain TiN coated Li 4 SiO 4 A tritium breeder.
2. The method according to claim 1, wherein the gas in the protective atmosphere in step (1) comprises any one of argon, helium or neon or a combination of at least two of them.
3. The production method according to claim 1, wherein the titanium source gas in the step (2) is a gas formed by high-temperature gasification of a titanium salt.
4. The method of claim 3, wherein the titanium salt is titanium dichloride.
5. The method according to claim 3, wherein the carrier gas for high-temperature gasification is a gas in the protective atmosphere in step (1).
6. The method according to claim 3, wherein the high-temperature gasification temperature is 400 to 800 ℃.
7. The method according to claim 1, wherein the nitrogen source gas in the step (2) is nitrogen.
8. The method of claim 1, wherein the gas-solid separation in step (3) comprises any one or a combination of at least two of gravity settling, centrifugal settling and filtration.
9. The method of any one of claims 1 to 8, comprising the steps of:
(1) Making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere; the gas in the protective atmosphere comprises any one or a combination of at least two of argon, helium or neon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 500-900 deg.C, and the mixing time is not less than 1min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 400-800 ℃, and the gas speed is 50-200mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50-200mL/min;
(4) Obtaining TiN coated Li after gravity settling, centrifugal settling or filtering 4 SiO 4 A tritium breeder.
10. TiN-coated Li prepared by the preparation method as described in any one of claims 1 to 9 4 SiO 4 Tritium breeder characterized in that said TiN coats Li 4 SiO 4 The thickness of the TiN layer of the tritium breeding agent is more than or equal to 1nm.
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