High-density tritium storage film and preparation method and tritium absorption method thereof
By employing a high-density tritium storage thin film structure in isotope batteries, and utilizing inexpensive materials and advanced preparation techniques, the problems of high preparation costs and tritium leakage risks have been solved, achieving efficient tritium storage and improved battery power output.
Patent Information
- Application Number
- CN202511725015.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-20
- Publication Date
- 2026-03-03
Smart Images
Figure CN121593069A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of isotope battery source technology, specifically to a high-density tritium storage thin film and its preparation method and tritium absorption method. Background Technology
[0002] An isotope battery is a device that converts the energy released from the decay of radioactive isotopes into electrical energy. Compared to traditional chemical batteries and solar cells, isotope batteries have significant advantages in terms of operating life, energy density, and environmental adaptability. Among isotope batteries are the beta-radiovolt isotope battery (RVIB), which utilizes the interaction between beta particles released from the decay of a beta radioactive source and a semiconductor transducer. This interaction generates a large number of electron-hole pairs within the transducer. These pairs separate under the influence of a built-in electric field and are transported to corresponding electrodes for collection, thus converting energy into electrical output. The core components of an RVIB are the radioactive source and the transducer; commonly used radioactive sources include tritium sources.
[0003] Tritium sources include liquid tritium sources, gaseous tritium sources, and solid tritium sources. Solid tritium sources are those in which tritium gas is fixed in a solid material through physical or chemical methods. Solid tritium sources have many advantages, such as high tritium atom density, small size, and controllable radioactive tritium, and are often used in fields such as isotope batteries.
[0004] Isotope batteries require a tritium source to operate. Due to limitations in chemical properties and manufacturing processes, solid-state tritium sources have low energy density, which significantly restricts the power output of the radioactive source. In existing technologies, increasing the tritium absorption capacity of storage materials is typically achieved by increasing the tritium gas pressure, reaction temperature, tritium absorption time, or by depositing palladium or nickel films on the titanium film surface. However, the following problems exist: 1. As a radioactive gas, tritium, under high temperature, high pressure, and long-term tritium absorption conditions, will cause more tritium to leak from the tritium absorption reaction chamber, affecting the surrounding environment and personnel health; 2. Increasing the tritium absorption time will increase the process production cost, including electricity costs, equipment wear and tear costs, and labor costs; 3. Tritium is expensive, and high temperature or high pressure will cause more tritium leakage. Due to the scarcity and high price of tritium, 1 gram of tritium costs tens of millions of yuan, which will increase the preparation cost of isotope batteries; 4. Palladium, as a precious metal, is expensive, and mass production will significantly increase costs, which is not conducive to industrial production and sales; 5. Plating palladium or nickel films will increase the thickness of the solid tritium source and the overall thickness of the film, which is not conducive to improving the output power of the battery through multilayer structures; 6. Plating palladium or nickel films will increase the thickness of the solid tritium source and the overall thickness of the film, which will reduce the emission power of the tritium source radiating beta rays, thereby reducing the battery power.
[0005] In summary, existing solid-state tritium source preparation technologies for isotope batteries suffer from drawbacks such as high preparation costs and reduced emission power. Therefore, a new technical solution is needed in this field to address these issues. Summary of the Invention
[0006] This invention aims to at least partially solve the technical problems in related technologies. To this end, embodiments of this invention propose a high-density tritium storage film. The oxygen-consuming sacrificial layer uses inexpensive materials and also has catalytic functions, eliminating the need for high-temperature, high-pressure tritium absorption and reducing preparation costs. During the tritium absorption process of the high-density tritium storage film, the oxygen-absorbing sacrificial layer can be pulverized and vaporized, without reducing the output power due to its presence. Furthermore, the oxygen-absorbing sacrificial layer can consume oxygen in the tritium absorption environment, thereby increasing the tritium absorption capacity of the storage layer. Simultaneously, the oxygen-absorbing sacrificial layer ensures the tritium storage layer is isolated from the atmospheric environment, preventing long-term exposure and oxidation. This makes the high-density tritium storage film easier to store and transport for subsequent tritium absorption.
[0007] The high-density tritium storage thin film of the present invention comprises:
[0008] Substrate layer;
[0009] A tritium storage layer, wherein the tritium storage layer is disposed on the substrate layer in the thickness direction of the substrate layer;
[0010] An oxygen-consuming sacrificial layer is disposed on the tritium storage layer, wherein the tritium storage layer and the substrate layer are disposed opposite each other on both sides of the tritium storage layer in the thickness direction of the substrate layer;
[0011] An oxygen-barrier sacrificial layer is disposed on the oxygen-consuming sacrificial layer in the thickness direction of the substrate layer, and the oxygen-barrier sacrificial layer and the tritium storage layer are disposed opposite each other on both sides of the oxygen-consuming sacrificial layer in the thickness direction of the substrate layer.
[0012] Optionally, the material of the oxygen-consuming sacrificial layer includes zinc; and / or
[0013] The thickness of the oxygen-consuming sacrificial layer is 50 nm to 1000 nm.
[0014] Optionally, the material of the oxygen-consuming sacrificial layer may also include cadmium;
[0015] The proportion of cadmium in the oxygen-consuming sacrificial layer is between 5% and 25%.
[0016] Optionally, the high-density tritium storage film also includes:
[0017] A tritium-enhancing layer is disposed between the tritium storage layer and the oxygen-consuming sacrificial layer;
[0018] The material of the tritium-enhancing layer includes hafnium;
[0019] The thickness of the tritium-absorbing layer is 5 nm to 50 nm.
[0020] Optionally, the material of the tritium storage layer includes titanium-based, magnesium-based, zirconium-based, or rare-earth-based materials; and / or
[0021] The thickness of the tritium storage layer is 1 μm to 10 μm; and / or
[0022] The material of the oxygen-barrier sacrificial layer includes zinc; and / or
[0023] The thickness of the oxygen-barrier sacrificial layer is 20 nm to 50 nm.
[0024] Another method for preparing a high-density tritium storage film according to the present invention is used to prepare the above-mentioned high-density tritium storage film, wherein the method for preparing the high-density tritium storage film includes:
[0025] The substrate layer is placed in the film-forming environment;
[0026] The tritium storage layer is prepared on the substrate layer;
[0027] The tritium absorption-enhancing layer is prepared on the tritium storage layer;
[0028] The oxygen-consuming sacrificial layer is prepared on the tritium-absorbing layer;
[0029] The oxygen-barrier sacrificial layer is prepared on the oxygen-consuming sacrificial layer to form the high-density tritium storage film.
[0030] Optionally, the oxygen-consuming sacrificial layer may be made of zinc and cadmium and may be prepared by one of the following techniques: magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating.
[0031] Optionally, the material of the tritium-enhancing layer includes hafnium, and the tritium-enhancing layer is prepared by one of magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating.
[0032] Optionally, the tritium storage layer is made of titanium and is prepared using one of the following techniques: magnetron sputtering, evaporation deposition, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating; and / or
[0033] The oxygen-barrier sacrificial layer comprises zinc and is prepared by one of the following techniques: magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating.
[0034] Another tritium absorption method of the present invention is used for the above-mentioned high-density tritium storage film, the tritium absorption method comprising:
[0035] The high-density tritium storage film is placed in a tritium-absorbing environment, which is then heated to a first preset temperature and evacuated to a preset vacuum level.
[0036] The high-density tritium storage film is placed in the tritium absorption environment for at least 20 minutes, the vacuuming is stopped, the tritium absorption environment is cooled to a second preset temperature, and tritium gas is introduced into the tritium absorption environment to maintain a preset gas pressure.
[0037] The high-density tritium storage film is irradiated with ultraviolet light of a preset power.
[0038] The oxygen-barrier sacrificial layer contains zinc, and the oxygen-consuming sacrificial layer contains cadmium and zinc. Attached Figure Description
[0039] Figure 1 This is a schematic diagram of a high-density tritium storage film in a specific embodiment of the present invention.
[0040] Figure 2 This is a schematic diagram of a high-density tritium storage film after tritium storage in a specific embodiment of the present invention.
[0041] Figure reference numerals: 100-high-density tritium storage film, 110-substrate layer, 120-tritium storage layer, 130-oxygen-consuming sacrificial layer, 140-oxygen-barrier sacrificial layer, 150-tritium absorption-promoting layer. Detailed Implementation
[0042] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.
[0043] The high-density tritium storage film 100 of the present invention will now be described with reference to the accompanying drawings. Figure 1 and Figure 2 As shown, the high-density tritium storage film 100 of this embodiment includes a substrate layer 110, a tritium storage layer 120, an oxygen-consuming sacrificial layer 130, and an oxygen-barrier sacrificial layer 140.
[0044] A tritium storage layer 120 is disposed on the substrate 110 in the thickness direction of the substrate 110, and an oxygen-consuming sacrificial layer 130 is disposed on the tritium storage layer 120. The oxygen-consuming sacrificial layer 130 and the substrate 110 are disposed opposite each other on both sides of the tritium storage layer 120 in the thickness direction of the substrate 110. An oxygen-barrier sacrificial layer 140 is disposed on the oxygen-consuming sacrificial layer 130 in the thickness direction of the substrate 110, and the oxygen-barrier sacrificial layer 140 and the tritium storage layer 120 are disposed opposite each other on both sides of the oxygen-consuming sacrificial layer 130 in the thickness direction of the substrate 110.
[0045] According to the high-density tritium storage film 100 of the present invention, the oxygen-consuming sacrificial layer 130 can consume oxygen in the tritium absorption environment and can be vaporized and pulverized during the tritium absorption process of the high-density tritium storage film 100, preventing the tritium storage layer 120 from being oxidized and increasing the tritium absorption capacity of the tritium storage layer 120. At the same time, the oxygen-barrier sacrificial layer 140 can prevent the tritium storage layer 120 from being oxidized, and at the same time, the oxygen-barrier sacrificial layer 140 can be pulverized and vaporized during the tritium absorption process of the high-density tritium storage film 100. In other words, the oxygen-consuming sacrificial layer 130 can consume oxygen in the tritium absorption environment, thereby increasing the tritium absorption capacity of the tritium storage layer 120. At the same time, the oxygen-isolating sacrificial layer 140 can ensure that the tritium storage layer 120 is isolated from the atmospheric environment, preventing the tritium storage layer 120 from being exposed to the atmospheric environment for a long time and preventing the tritium storage layer 120 from being oxidized. This makes the high-density tritium storage film 100 easier to store and transport for a long time, so as to facilitate subsequent tritium absorption.
[0046] like Figure 1 and Figure 2 As shown, to make the technical solution of this application easier to understand, the technical solution of this application will be described in more detail below using a specific embodiment of the high-density tritium storage film 100. Wherein, as Figure 1 The vertical direction shown is the thickness direction of the substrate layer 110. The high-density tritium storage film 100 includes a substrate layer 110, a tritium storage layer 120, an oxygen-consuming sacrificial layer 130, an oxygen-barrier sacrificial layer 140, and a tritium absorption-promoting layer 150.
[0047] In some specific embodiments, such as Figure 1 As shown, the material of the substrate 100 should be selected to match the thermal expansion coefficient and chemical stability of the tritium storage layer material. The substrate 100 is mainly to provide a flat surface so that the tritium storage layer 120 can be deposited uniformly, thereby making the prepared tritium storage layer 120 uniformly distributed and preventing it from affecting subsequent processes.
[0048] In some specific embodiments, such as Figure 1 and Figure 2 As shown, the tritium storage layer 120 is disposed on the substrate 110 in the thickness direction of the substrate 110. Specifically, the tritium storage layer 120 is mainly used to store tritium gas.
[0049] In some specific embodiments, the tritium storage layer 120 is made of titanium. Specifically, titanium is preferably used as the material for the tritium storage layer 120 in this embodiment of the invention. That is, titanium has a strong tritium absorption capacity and can absorb a large amount of tritium.
[0050] In some specific embodiments, the tritium storage layer 120 can also be made of various titanium-based alloys, such as TiFe alloys, TiMo alloys, TiCr alloys, TiMn alloys, TiV alloys, and TiZr alloys. Optionally, the tritium storage layer 120 can also be made of magnesium or magnesium-based alloys as the main tritium absorber, such as MgNi alloys, MgAl alloys, and MgNb alloys. Optionally, the tritium storage layer 120 can also be made of zirconium-based or rare-earth-based materials.
[0051] In some specific embodiments, the thickness of the tritium storage layer 120 is from 1 μm to 10 μm. Specifically, a tritium storage layer 120 of 1 μm to 10 μm can improve the output power.
[0052] In some specific embodiments, such as Figure 1 and Figure 2 As shown, an oxygen-barrier sacrificial layer 140 is disposed on the tritium storage layer 120 along the thickness direction of the substrate layer 110, and the oxygen-barrier sacrificial layer 140 and the substrate layer 110 are disposed opposite each other on both sides of the tritium storage layer 120 along the thickness direction of the substrate layer 110. Specifically, the oxygen-barrier sacrificial layer 140 can prevent the tritium storage layer 120 from being oxidized. That is to say, the oxygen-barrier sacrificial layer 140 can ensure that the tritium storage layer 120 is isolated from the atmospheric environment, avoid long-term exposure of the tritium storage layer 120 to the atmospheric environment, and prevent the tritium storage layer 120 from being oxidized, thereby making the high-density tritium storage film 100 easier to store and transport for a long time, so as to facilitate subsequent tritium absorption.
[0053] In some specific embodiments, the oxygen-barrier sacrificial layer 140 is made of zinc. Specifically, zinc can react with water and oxygen in the atmosphere to form a dense layer of basic zinc carbonate, protecting the internal oxygen-barrier sacrificial layer 140 and tritium storage layer 120 from oxidation. In other words, the oxygen-barrier sacrificial layer 140 ensures that the tritium storage layer 120 is isolated from the atmospheric environment, preventing long-term exposure and oxidation. This makes the high-density tritium storage film 100 easier to store and transport for extended periods, facilitating subsequent tritium absorption. Zinc is inexpensive and outperforms traditional palladium in both laboratory preparation and large-scale industrial production.
[0054] In some specific embodiments, the thickness of the oxygen-barrier sacrificial layer 140 is 20 nm to 50 nm. A 20 nm to 50 nm oxygen-barrier sacrificial layer 140 can form a dense basic zinc carbonate film, thereby protecting the interior of the high-density tritium storage film 100 from further oxidation. A thicker film is unnecessary and would only increase processing time and cost.
[0055] In some specific embodiments, such as Figure 1 and Figure 2 As shown, the oxygen-consuming sacrificial layer 130 is disposed between the tritium storage layer 120 and the oxygen-barrier sacrificial layer 140. Specifically, during the tritium absorption process of the high-density tritium storage film 100, a small amount of oxygen will still exist in the tritium absorption environment. To prevent the tritium storage layer 120 from being oxidized, the oxygen-consuming sacrificial layer 130 can consume all the oxygen in the tritium absorption environment. In other words, if the surface of the tritium storage layer 120 is oxidized, the amount of tritium absorbed by the tritium storage layer 120 will be greatly reduced, thereby reducing the output power of the high-density tritium storage film 100 after tritium absorption.
[0056] In some specific embodiments, the thickness of the oxygen-consuming sacrificial layer 130 is 50 nm to 1000 nm. Specifically, the 50 nm to 1000 nm oxygen-consuming sacrificial layer 130 can consume the residual oxygen content in the tritium absorption environment to a level that no longer affects the tritium storage material. Thicker films are unnecessary and would only increase processing time and cost.
[0057] In some specific embodiments, the oxygen-consuming sacrificial layer 130 is made of zinc. Specifically, a portion of the zinc in the oxygen-consuming sacrificial layer 130 can react with oxygen in the tritium absorption environment to produce zinc oxide powder. After the oxygen in the tritium absorption environment is consumed, the remaining zinc in the oxygen-consuming sacrificial layer 130 can be vaporized and extracted from the tritium absorption environment. In other words, zinc can absorb oxygen in the tritium absorption environment, preventing titanium oxidation. The generated zinc oxide powder falls onto the tritium storage layer 120, which can act as a photocatalyst for tritium absorption, reducing the dissociation energy of tritium gas and promoting tritium absorption by the tritium storage layer 120. Furthermore, after the tritium storage layer 120 has absorbed all its tritium, the zinc oxide powder on its surface can be easily removed. Moreover, zinc is inexpensive and performs better than traditional palladium in both laboratory preparation and large-scale industrial production.
[0058] In some specific embodiments, such as Figure 1 and Figure 2 As shown, the oxygen-consuming sacrificial layer 130 also includes cadmium. Specifically, cadmium is added to the zinc-containing oxygen-consuming sacrificial layer 130. Both cadmium and zinc can react with oxygen in the tritium-absorbing environment, thereby consuming the oxygen in the tritium-absorbing environment. At the same time, compared with pure zinc, the alloy composed of cadmium and zinc has a lower boiling point, that is, a lower vaporization temperature. In other words, the addition of cadmium to the zinc-containing oxygen-consuming sacrificial layer 130 is mainly to lower the vaporization temperature of zinc.
[0059] Preferably, the proportion of cadmium in the oxygen-consuming sacrificial layer 130 is 5% to 25%. Specifically, cadmium and zinc are elements in the same group, both with half-filled outer electron shells, stable properties, few active electrons, and low metallic bond energies, resulting in low melting and boiling points. Cadmium has a larger atomic radius than zinc; adding cadmium increases lattice instability and lowers the overall bond energy in the oxygen-consuming sacrificial layer 130, thereby reducing its boiling point. If the proportion of cadmium in the oxygen-consuming sacrificial layer 130 is less than 5%, the effect on lowering the boiling point is not significant. If the proportion of cadmium in the oxygen-consuming sacrificial layer 130 is greater than 25%, a large amount of cadmium will be scattered in the tritium storage layer 120, hindering the absorption of light by zinc oxide and thus reducing the catalytic performance of zinc oxide.
[0060] In some specific embodiments, the tritium absorption-enhancing layer 150 is disposed between the tritium storage layer 120 and the oxygen-consuming sacrificial layer 130. Specifically, the tritium absorption-enhancing layer 150 can synergistically interact with the oxide powder of the oxygen-consuming sacrificial layer 130 or the oxide powder of the oxygen-barrier sacrificial layer 140. That is, under ultraviolet light irradiation, it can play a synergistic catalytic role, thereby efficiently promoting the dissociation of tritium gas molecules into tritium atoms, so that the tritium atoms can be quickly absorbed by the tritium storage layer 120, thereby effectively reducing the requirements for high pressure and high temperature of tritium gas.
[0061] Preferably, the material of the tritium adsorption layer 150 includes hafnium. Specifically, in the catalytic reaction, the d and f orbitals of hafnium can participate in electron transfer. That is, during tritium adsorption, the redistribution of the electron cloud at the interface between the hafnium film and zinc oxide nanopowder leads to electron recombination, thereby changing the electronic density of states of zinc oxide, adjusting the band gap width of zinc oxide, and thus improving the electron availability and activity of the zinc oxide powder and hafnium film surface, enhancing the dissociation and diffusion of tritium molecules by the hafnium film and zinc oxide nanopowder. In addition, compared with titanium films, hafnium films have good hardness and wear resistance, thus protecting titanium films from damage. For example, when a high-density tritium storage film is bonded to a transducer, the titanium film may be damaged. The good hardness and wear resistance of the hafnium film can ensure that the titanium film is not damaged, thereby extending the battery's lifespan. Furthermore, hafnium films also have tritium adsorption properties and can store tritium under synergistic catalysis without reducing the source's output power. Hafnium membranes have a much smaller tritium absorption rate than titanium membranes, thus exhibiting excellent resistance to hydrogen embrittlement and pulverization. Under normal storage conditions, hafnium membranes have lower tritium permeability than titanium membranes, which can reduce tritium leakage in titanium membranes loaded with tritium.
[0062] Preferably, the thickness of the tritium absorption-enhancing layer 150 is between 5 nm and 50 nm. Specifically, if the thickness of the tritium absorption-enhancing layer 150 is less than 5 nm, it cannot provide protection. If the thickness of the tritium absorption-enhancing layer 150 is greater than 50 nm, the electron cloud of the hafnium film cannot be completely recombinated with the electrons of the zinc oxide nanopowder, thus the tritium absorption-enhancing effect cannot be achieved.
[0063] In some specific embodiments, the preparation method of the high-density tritium storage film 100 of the present invention is used to prepare the above-mentioned high-density tritium storage film 100. The preparation method of the high-density tritium storage film 100 includes: placing a substrate layer 110 in a film-forming environment and preparing a tritium storage layer 120 on the substrate layer 110.
[0064] In some specific embodiments, the tritium storage layer 120 is made of titanium and is fabricated on the substrate layer 110 using magnetron sputtering technology, with a vacuum level of less than 1×10⁻⁶ in the film-forming environment. -3 Pa can reduce the content of impurity molecules, making the coating composition closer to the ideal ratio, thereby improving film purity and enhancing adhesion. Preheating the substrate 110 to between 25°C and 300°C can enhance the migration ability of atoms on the surface of the substrate 110, making the atomic distribution more uniform. At the same time, the preheated substrate 110 is more likely to form physical adsorption with atoms, thereby improving the adhesion of the film. In addition, excessively high preheating temperature will vaporize the zinc film. The power of the titanium target is adjusted to between 1kW and 10kW. Too low a power will result in a low deposition rate, resulting in poor adhesion and film density. Too high a power will result in an excessively fast deposition rate, increasing the defect density in the tritium reservoir layer 120. Argon gas is introduced into the film formation environment at a rate between 15sccm and 50sccm. Too low an introduction rate will not provide sufficient sputtering gas and will not be able to deposit a film, while too high an introduction rate will affect the deposition of the target material. The preparation time is 1h to 15h.
[0065] It should be noted that the principle of preparing the tritium storage layer 120 using magnetron sputtering technology is as follows: In the magnetron sputtering coating machine, the target material (titanium) is bombarded by argon ions to knock down the target material (titanium) atoms. Then, under the action of an electric field, the titanium atoms can be deposited on the surface of the substrate layer 110, thereby completing the coating.
[0066] In some specific embodiments, the tritium storage layer 120 can also be prepared using one of the following techniques: evaporation coating technology, ion plating technology, low-pressure chemical vapor deposition technology, plasma-enhanced chemical vapor deposition technology, and electroplating technology.
[0067] In some specific embodiments, a tritium uptake-enhancing layer 150 is prepared on the tritium reservoir layer 120. The tritium uptake-enhancing layer 150 is made of hafnium and is prepared using magnetron sputtering. The power of the hafnium target is adjusted to between 1 kW and 3 kW. Too low a power will result in a low deposition rate, leading to poor adhesion and film density. Too high a power will result in an excessively fast deposition rate, increasing the defect density within the tritium uptake-enhancing layer 150. The vacuum level of the film-forming environment is below 1 × 10⁻⁶. -3Pa can reduce the content of impurity molecules, making the coating composition closer to the ideal ratio, thereby improving the purity of the film and enhancing the adhesion.
[0068] It should be noted that the principle of preparing the tritium-enhanced layer 150 using magnetron sputtering technology is the same as that of preparing the tritium-storage layer 120, and will not be repeated here.
[0069] In some specific embodiments, the tritium absorption layer 150 can also be prepared using one of the following techniques: evaporation coating technology, ion plating technology, low-pressure chemical vapor deposition technology, plasma-enhanced chemical vapor deposition technology, or electroplating technology.
[0070] In some specific embodiments, an oxygen-consuming sacrificial layer 130 is prepared on the tritium absorption-promoting layer 150. The oxygen-consuming sacrificial layer 130 is made of zinc and cadmium. The oxygen-consuming sacrificial layer 130 is prepared using magnetron sputtering technology. The power of the zinc target is adjusted to between 1 kW and 5 kW. Too low a power will result in a low deposition rate, leading to poor adhesion and film density. Too high a power will result in an excessively fast deposition rate, increasing the defect density within the oxygen-consuming sacrificial layer 130. The power of the cadmium target is adjusted to between 1 kW and 3 kW. Too low a power will result in a low deposition rate, leading to poor adhesion and film density. Too high a power will result in an excessively fast deposition rate, increasing the defect density within the oxygen-consuming sacrificial layer 130. The vacuum level of the film-forming environment is below 1 × 10⁻⁶. -3 Pa can reduce the content of impurity molecules, making the coating composition closer to the ideal ratio, thereby improving the purity of the film and enhancing the adhesion.
[0071] It should be noted that the principle of preparing the oxygen-consuming sacrificial layer 130 using magnetron sputtering technology is the same as that of preparing the tritium storage layer 120, and will not be repeated here.
[0072] In some specific embodiments, the oxygen-consuming sacrificial layer 130 can also be prepared using one of the following techniques: evaporation coating technology, ion plating technology, low-pressure chemical vapor deposition technology, plasma-enhanced chemical vapor deposition technology, or electroplating technology.
[0073] In some specific embodiments, an oxygen-barrier sacrificial layer 140 is prepared on the oxygen-consuming sacrificial layer 130 to form a high-density tritium storage film 100.
[0074] In some specific embodiments, the oxygen-barrier sacrificial layer 140 comprises zinc, and is prepared by magnetron sputtering technology in a film-forming environment with a vacuum degree of less than 1×10⁻⁶. -3Pa can reduce the content of impurity molecules, making the coating composition closer to the ideal ratio, thereby improving the purity of the film and enhancing the adhesion. The power of the zinc target is adjusted to between 1 kW and 5 kW. Too low a power will result in a low deposition rate, resulting in poor adhesion and film density. Too high a power will result in an excessively fast deposition rate, increasing the defect density within the oxygen-barrier sacrificial layer 140. Placing the high-density tritium storage film 100 containing the oxygen-barrier sacrificial layer 140 in an atmospheric environment for at least 10 minutes will form an oxide film for subsequent zinc oxide powder catalysis. It should be noted that the principle of preparing the oxygen-barrier sacrificial layer 140 using magnetron sputtering technology is as follows: In a magnetron sputtering coating machine, argon ions bombard the target material (zinc), knocking down the target (zinc) atoms. Then, under the action of an electric field, zinc atoms can be deposited on the surface of the tritium storage layer 120, thus completing the coating.
[0075] In some specific embodiments, the oxygen-barrier sacrificial layer 140 can also be prepared using one of the following techniques: evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating.
[0076] The preparation process of the high-density tritium storage thin film 100 is as follows:
[0077] 1. Select titanium, zinc and cadmium targets with 99.999% purity as sputtering targets, install them on the magnetron sputtering equipment, and put the substrate 110 into an ultrasonic cleaner. Use acetone as the cleaning agent and clean at a frequency of 5kHz for 10 minutes to remove surface oil and other impurities.
[0078] 2. After placing the cleaned substrate layer 110 into the magnetron sputtering chamber, start the vacuum system and evacuate the magnetron sputtering chamber of the magnetron sputtering device until the vacuum level is below 1×10⁻⁶. -4 Pa, while heating the substrate to 110 to 50°C, thereby completing the vacuum degassing process;
[0079] 3. Turn on the ion source power supply (1000W) and clean the surface of the substrate layer 110 for 2 hours to enhance the bonding force between the substrate layer 110 and the tritium storage layer 120. Then turn off the ion source power supply (1000W).
[0080] 4. Adjust the opening of the argon plate valve to control the flow rate to 22 sccm, adjust the power of the titanium target to 5 kW, and deposit the film for 3 hours. After setting, start the film deposition. A 1 μm thick titanium film can be deposited on the surface of the substrate layer 110. Turn off the power of the titanium target.
[0081] 5. After the substrate 110 and the titanium film have cooled to room temperature, adjust the power of the zinc target to 4 kW and the power of the cadmium target to 1.5 kW. Deposit for 30 minutes to deposit a 200 nm zinc-cadmium film on the surface of the titanium film.
[0082] 6. Next, turn off the power to the cadmium target, adjust the power of the zinc target to 5kw, and coat for 10 minutes to coat a 40nm zinc film on the surface of the zinc-cadmium film. After coating, it can be placed directly in the indoor environment for a long time.
[0083] In some specific embodiments, the tritium absorption method is used for the aforementioned high-density tritium storage film 100. The tritium absorption method includes: placing the high-density tritium storage film 100 in a tritium absorption environment. The tritium absorption environment is heated to a first preset temperature, which causes the oxygen-consuming sacrificial layer 130 and the oxygen-barrier sacrificial layer 140 to decompose and vaporize. The tritium absorption environment is then evacuated to a preset vacuum level (at which the content of impurity gas molecules can be reduced; simultaneously, the boiling points of zinc and cadmium can be lowered to achievable temperatures). The preset vacuum level is 8 × 10⁻⁶. -4 Up to 1×10 -4 Pa. Placing the high-density tritium storage film 100 in a tritium-absorbing environment for at least 20 minutes ensures the complete decomposition and vaporization of the oxygen-consuming sacrificial layer 130 and the oxygen-barrier sacrificial layer 140, preventing these layers from remaining in the tritium storage layer 120 and affecting its tritium absorption. Stopping the vacuuming process is primarily to prevent the introduced tritium gas from being extracted, thus avoiding waste. Simultaneously, if the vacuuming process continues, the preset pressure cannot be maintained within the tritium-absorbing environment, preventing the tritium storage layer 120 from absorbing more tritium. The tritium-absorbing environment is cooled to a second preset temperature, and tritium gas is continuously introduced to maintain a preset pressure, which is between 10 kPa and 50 kPa. The high-density tritium storage film 100 is irradiated with ultraviolet light of a preset power, between 10 W and 100 W.
[0084] In some specific embodiments, the material in the oxygen-barrier sacrificial layer 130 includes zinc, and the material in the oxygen-consuming sacrificial layer 130 includes cadmium and zinc. The first preset temperature is between 300°C and 400°C. Specifically, as the temperature in the hydrogen absorption environment gradually increases, the high-density tritium storage film 100 undergoes various reactions: ① When the temperature is heated to 140°C, the basic zinc carbonate generated by the high-density tritium storage film 100 begins to decompose, yielding water vapor, carbon dioxide, and zinc oxide. The water vapor and carbon dioxide are discharged from the hydrogen absorption environment during vacuuming, while the remaining zinc oxide adheres to the surface of the zinc-cadmium film in the form of nanoparticles. ② When the temperature reaches 200°C to 250°C, a small amount of oxygen in the hydrogen absorption environment reacts with the zinc and cadmium on the surface of the zinc-cadmium film, thereby absorbing the oxygen. This accelerates the vacuuming process, reduces oxygen contamination in the tritium absorption chamber, and prevents oxidation of the titanium film, which reduces the tritium absorption effect. ③ When the temperature reaches 300°C to 400°C, the zinc-cadmium alloy at 8×10 -4 Up to 1×10 -4 Under pressure of Pa, the zinc-cadmium alloy is vaporized, and the vaporized zinc-cadmium alloy is discharged from the hydrogen-absorbing environment through the vacuum pipe.
[0085] In addition, at the start of tritium absorption, a 10W to 100W ultraviolet lamp is turned on to irradiate the hafnium film.
[0086] In some specific embodiments, the second preset temperature is between 150°C and 400°C.
[0087] The tritium absorption method is as follows:
[0088] 1. When the high-density tritium storage membrane 100 needs to absorb tritium, place the high-density tritium storage membrane 100 into the tritium absorption chamber and evacuate to 1×10⁻⁶. -4 Pa, heating the high-density tritium storage film 100 to above 380°C at a rate of 7°C / min, and then holding it at that temperature for 20 min, so that the high-density tritium storage film 100 is left with a substrate layer 110, a titanium film and a hafnium film;
[0089] 2. After the tritium absorption chamber is cooled to 300°C, tritium gas is introduced to maintain the pressure at 40 kPa.
[0090] 3. Turn on the ultraviolet lamp, adjust the power to 20W, and irradiate the titanium film. Keep it warm for 5 hours to complete the tritium absorption.
[0091] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.
[0092] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.
[0093] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.
[0094] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can mean that the first feature is in direct contact with the second feature, or that the first feature is in indirect contact with the second feature through an intermediate medium. Furthermore, "above," "over," and "on top" of the second feature can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.
[0095] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0096] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.
Claims
1. A high-density tritium storage thin film, characterized in that, include: Substrate layer; A tritium storage layer, wherein the tritium storage layer is disposed on the substrate layer in the thickness direction of the substrate layer; An oxygen-consuming sacrificial layer is disposed on the tritium storage layer, wherein the oxygen-consuming sacrificial layer and the substrate layer are disposed opposite each other on both sides of the tritium storage layer in the thickness direction of the substrate layer; An oxygen-barrier sacrificial layer is disposed on the oxygen-consuming sacrificial layer in the thickness direction of the substrate layer, and the oxygen-barrier sacrificial layer and the tritium storage layer are disposed opposite each other on both sides of the oxygen-consuming sacrificial layer in the thickness direction of the substrate layer.
2. The high-density tritium storage thin film according to claim 1, characterized in that, The material of the oxygen-consuming sacrificial layer includes zinc; and / or The thickness of the oxygen-consuming sacrificial layer is 50 nm to 1000 nm.
3. The high-density tritium storage thin film according to claim 2, characterized in that, The oxygen-consuming sacrificial layer also includes cadmium; The proportion of cadmium in the oxygen-consuming sacrificial layer is between 5% and 25%.
4. The high-density tritium storage thin film according to claim 1, characterized in that, Also includes: A tritium-enhancing layer is disposed between the tritium storage layer and the oxygen-consuming sacrificial layer; The material of the tritium-enhancing layer includes hafnium; The thickness of the tritium-absorbing layer is 5 nm to 50 nm.
5. The high-density tritium storage thin film according to any one of claims 1-4, characterized in that, The material of the tritium reservoir includes titanium-based, magnesium-based, zirconium-based, or rare earth-based materials; and / or The thickness of the tritium reservoir layer is 1 μm to 10 μm; and / or The material of the oxygen-barrier sacrificial layer includes zinc; and / or The thickness of the oxygen-barrier sacrificial layer is 20 nm to 50 nm.
6. A method for preparing a high-density tritium storage thin film, characterized in that, The method for preparing the high-density tritium storage film is used to prepare the high-density tritium storage film according to any one of claims 1-5, wherein the method for preparing the high-density tritium storage film includes: The substrate layer is placed in the film-forming environment; The tritium storage layer is prepared on the substrate layer; The tritium absorption-enhancing layer is prepared on the tritium storage layer; The oxygen-consuming sacrificial layer is prepared on the tritium-absorbing layer; The oxygen-barrier sacrificial layer is prepared on the oxygen-consuming sacrificial layer to form the high-density tritium storage film.
7. The method for preparing a high-density tritium storage thin film according to claim 6, characterized in that, The oxygen-consuming sacrificial layer is made of zinc and cadmium and is prepared by one of the following techniques: magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating.
8. The method for preparing a high-density tritium storage thin film according to claim 6, characterized in that, The tritium-enhancing layer is made of hafnium and is prepared by one of the following techniques: magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating.
9. The method for preparing a high-density tritium storage thin film according to any one of claims 6-8, characterized in that, The tritium storage layer is made of titanium and is prepared using one of the following techniques: magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and electroplating; and / or The oxygen-barrier sacrificial layer comprises zinc and is prepared by one of the following techniques: magnetron sputtering, evaporation coating, ion plating, low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, or electroplating.
10. A method for absorbing tritium, characterized in that, The tritium absorption method is used for a high-density tritium storage film according to any one of claims 1-5, the tritium absorption method comprising: The high-density tritium storage film is placed in a tritium-absorbing environment, which is then heated to a first preset temperature and evacuated to a preset vacuum level. The high-density tritium storage film is placed in the tritium absorption environment for at least 20 minutes, the vacuuming is stopped, the tritium absorption environment is cooled to a second preset temperature, and tritium gas is introduced into the tritium absorption environment to maintain a preset gas pressure. The high-density tritium storage film is irradiated with ultraviolet light of a preset power. The oxygen-barrier sacrificial layer contains zinc, and the oxygen-consuming sacrificial layer contains cadmium and zinc.