Preparation method of flexible isotope source and isotope battery

Abstract

The invention relates to the technical field of isotopes, particularly provides a preparation method of a flexible isotope source and an isotope battery, and aims to solve the problems that in the prior art, a flexible film with radioactive elements cannot continue to use a conventional process, and introduction of the radioactive element tritium causes degradation of a high polymer material, so that the performance is reduced, and the service life is prolonged. In order to achieve the purpose, the preparation method comprises the following steps: S1, obtaining 14C and 3H alkyne and a 14C-containing carbon source; s2, the 14C and the 3H alkyne react with a tritium source to obtain an intermediate product, the tritium source is tritium gas 3H2 or tritium halide 3HX, and X represents a halogen element; and S3, adding three-dimensional graphene into the intermediate product, and carrying out polymerization reaction on the intermediate product. The flexible isotope source is prepared from the 14C and 3H alkyne, the 14C-containing carbon source and the tritium source, and the three-dimensional graphene is added, so that the performance and the service life of the flexible radioisotope thin film are ensured while the requirements of high tritium generation rate and flexibility of an isotope battery are met.

Description

Technical Field

[0001] The invention relates to the field of isotope technology, and specifically provides a method for preparing a flexible isotope source and an isotope battery. Background Art

[0002] Isotope batteries are devices that convert the energy released by the decay of radioactive isotopes into electrical energy. They were proposed by British physicist Henry Moseley in 1913 and developed in the 1960s as a new type of power source. Compared with traditional chemical batteries and solar cells, isotope batteries have obvious advantages in terms of operating life, energy density, and environmental adaptability, making them have great application prospects in representative fields such as implantable medical devices, positioning beacons, Internet of Things chips, marine and polar power supplies, and space power supplies.

[0003] There are many types of isotope batteries. According to the energy conversion mechanism, they include direct charging type, thermal energy type, electron excitation type, photon excitation type and radiovoltaic type. Compared with other types, the electron excitation type beta radiovoltaic isotope battery (RVIB) uses the interaction between the beta particles released by the decay of the radioactive source and the semiconductor transducer unit material to generate a large number of electron-hole pairs in the semiconductor material, which are finally separated and transported to the corresponding electrode end for collection under the action of the built-in electric field, thereby realizing the conversion and output of electrical energy. The biggest advantage of this battery is that it is based on semiconductor materials and has reached the initial industrialization level in both integrated process and product development; most importantly, its output power is in the μW-mW range, which basically meets the power requirements of low-power electronic devices. At the same time, its easy integration, quiet operation and DC output can meet the needs of various electronic devices and have a wide range of applications.

[0004] Flexible electronic devices are an emerging electronic technology that have greater flexibility and can adapt to different working environments to a certain extent and meet the deformation requirements of the equipment. In order to meet the power supply needs in flexible devices, isotope batteries also need to be flexible. Due to the advantages of low cost, low radiation, and easy processing, the use of tritium as a radioactive source isotope battery is a development direction with great application potential. However, the current conventional loading method of tritium isotope sources is to store tritium in alloys, but the alloy material is rigid and cannot achieve a flexible effect. Therefore, how to prepare a flexible isotope source is a key issue in the development of flexible isotope batteries.

[0005] At present, tritium is usually used to replace the hydrogen element in conventional flexible polymer materials to make a flexible tritium isotope source. However, when preparing a flexible radioactive film with tritium isotopes, the following problems usually exist: 1. In the preparation of flexible films, it is mainly reflected in the kinetic isotope effect. Its primary effect is manifested in that due to the different masses of isotopes, the zero-point energy of the reactants is different, resulting in different reaction rates and catalytic effects. In particular, when hydrogen is replaced by tritium (T) for reaction, due to the two-fold mass difference, the CT bond is not as active as the CH bond during the reaction, and the zero-point vibration energy of the CT bond is lower than that of the CH bond, which means that the CT bond is more difficult to break than the CH bond. The secondary effect is mainly manifested in that when the hybridization state of the C atom connected to the isotope atom changes, the reaction rate changes due to the different effects of the out-of-plane bending vibration in the transition state and the ground state. In the reaction where hydrogen is replaced by tritium, since the bond length of the CT bond is shorter than that of the CH bond, the degree of freedom of the bending state of the CT bond is smaller than that of the CH bond, which makes it more difficult for the C connected to T to change the hybridization. This also makes it impossible to use the existing conventional non-radioactive film preparation process, and it is necessary to develop new processes and catalysts. 2. After the introduction of radioactive nuclides, the decay particles cause the degradation of polymer materials, reducing the performance and life. When the high-energy rays produced by the decay of radioactive nuclides hit the polymer molecules, they will remove electrons from the atomic or molecular orbits to generate free radical cations. These cations are unstable and easily cleaved to form more free radicals. These free radicals attack the polymer main chain, resulting in irregular main chain breakage and a decrease in the molecular weight of the polymer. High-energy rays can also excite electrons to higher energy levels, and when the excited molecules return to the ground state, the energy release may cause the chemical bonds to break, the main chain of the polymer to break, and the molecular weight to decrease. This will lead to the breakage of the main chain and the reduction of the molecular weight, which will increase the solubility of the polymer in the solvent, and the corresponding thermal stability and mechanical properties will decrease, resulting in a reduced service life. This also leads to the introduction of tritium, a radioactive element, in the preparation of flexible radioactive films with tritium isotopes, which will cause the degradation of polymer materials and reduce the performance and life.

[0006] Accordingly, the art needs a new technical solution to solve the above problems. Summary of the invention

[0007] The present invention aims to solve the above technical problems, namely, to solve the problems in the prior art that flexible films with radioactive elements cannot be made using conventional flexible non-radioactive film preparation processes and that the introduction of the radioactive element tritium causes polymer material degradation, thereby reducing performance and service life.

[0008] In a first aspect, the present invention provides a method for preparing a flexible isotope source, characterized in that the preparation method comprises:

[0009] S1: Get14 C and 3 H-substituted alkynes, and obtain 14 C carbon source, the 14 The carbon source of C is carbon-14 compound of the second main group element;

[0010] S2: Make the 14 C and 3 The H-substituted alkyne reacts with a tritium source to obtain an intermediate product, wherein the tritium source is tritium gas 3 H2 or tritium halide 3 HX, wherein X represents a halogen element;

[0011] S3: mixing the intermediate product with three-dimensional graphene and causing the intermediate product to undergo a polymerization reaction to obtain the flexible isotope source, wherein the flexible isotope source is 14 C and 3 H-generation polyolefin or 14 C and 3 H generation polyhaloolefin.

[0012] When the above technical solution is adopted, 14 C and 3 H-substituted alkynes, containing 14 C carbon source and tritium source can be prepared 14 C and 3 H-generation polyolefin or 14 C and 3 H-generation polyhaloolefins have a high tritium substitution rate. Using them as flexible isotope sources can meet the high tritium substitution rate requirements of isotope batteries, and 14 C and 3 H-generation polyolefin also has good flexibility, which can meet the requirements of raw materials for flexible films that need to be folded and bent in isotope batteries, and thus meet the flexibility requirements of isotope batteries. In addition, the present invention adds three-dimensional graphene when the intermediate product undergoes polymerization reaction. There are a large number of π-π bonds in the three-dimensional graphene, and the π-π conjugated structure can capture and quench the active free radicals produced by the radioactive element tritium, preventing the free radicals from further initiating chain reactions and thus aggravating the degradation process. When the main chain of the flexible isotope source is broken by irradiation, the three-dimensional graphene can wrap the flexible isotope source obtained after the intermediate product is polymerized, maintain its stability, and support the structure of the flexible isotope source by adsorption and fixation of the fractured products, preventing the structure from being damaged. In other words, by adding three-dimensional graphene, the main chain breakage of the flexible isotope source caused by the introduction of the radioactive element tritium can be effectively avoided, ensuring the stability of its performance and improving its service life.

[0013] In the optional technical solution of the above preparation method, the tritium source is tritium gas 3When H2, the catalyst in S2 is Lindela catalyst.

[0014] In the optional technical scheme of the above preparation method, the chemical formula of the Lindela catalyst is Pd x M y N z , wherein M is a mixture of calcium carbonate and tungsten oxide, the mixing ratio of the calcium carbonate to the tungsten oxide is (2-8):1, N is tin, aluminum, antimony and a mixture thereof, the value range of x is 1-3, the value range of y is 3-7, and the value range of z is 1-2.

[0015] Since the bond energy of carbon-tritium bond is higher than that of carbon-hydrogen bond, the tritium addition reaction is more difficult than the hydrogenation reaction. Therefore, the catalyst activity is required to be higher than that of ordinary Lindella catalysts, and the existing Lindella catalyst components cannot meet the requirements. In the Lindella catalyst of the present application, palladium provides catalytic activity, and M acts as a dispersant to play a dispersing role. At the same time, the tungsten oxide in M ​​has a high density and a large atomic number, which can effectively shield the decay rays of the radioactive source and prevent the catalytic activity and life of the palladium metal from being affected. N acts as an inhibitor to control the catalytic activity of palladium and prevent excessive tritium addition. In other words, with Pd x M y N z As a catalyst, it can effectively promote 14 C and 3 The H-substituted alkyne reacts with a tritium source to obtain an intermediate product, while also avoiding excessive addition of tritium to ensure the purity of the intermediate product.

[0016] In an optional technical solution of the above preparation method, the catalyst in S3 is a supported titanium-based catalyst or a supported Cr-based catalyst.

[0017] In the optional technical solution of the above preparation method, the tritium source is tritium halide 3 In the case of HX, the catalyst in S2 is a mercury-based catalyst, and the catalyst in S3 is one of a titanium-based catalyst, a zirconium-based catalyst, a copper-based catalyst, and mercuric chloride.

[0018] In the optional technical solution of the above preparation method, the 14 C and 3 H-substituted alkynes are prepared by the following steps:

[0019] S11: Tritium 3 H2 and oxygen O2 are mixed in a first ratio and reacted to obtain tritium water 3 H2O;

[0020] S12: the tritium water 3 H2O is mixed with the carbon source in a second ratio and reacted to obtain the 14C and 3 H-substituted alkyne.

[0021] In the optional technical solution of the above preparation method, the first ratio is the tritium gas 3 The molar ratio of H2 to the oxygen O2 is in the range of (1.5-5.0):1; and / or

[0022] The second ratio is the tritium water 3 The molar ratio of H2O to the carbon source is in the range of (2.0-6.5):1.

[0023] In an optional technical solution of the above preparation method, the reaction of S11 is carried out under the catalytic action of a Pt-based catalyst or a Pd-based catalyst.

[0024] In an optional technical solution of the above preparation method, the preparation method further comprises:

[0025] At the same time or after the reaction in S12 occurs, the tritiated water is added 3 Carbon dioxide CO2 is introduced into the mixture of H2O and the carbon source to recover the tritiated water 3 H2O.

[0026] In the optional technical scheme of the above preparation method, the carbon source is Ba 14 C2 or Ca 14 C2.

[0027] In an optional technical solution of the above preparation method, the molar ratio of the three-dimensional graphene to the intermediate product is 1:9 to 1:3.

[0028] In the case of adopting the above technical solution, the three-dimensional graphene is added according to the above ratio, which can fully absorb the free radicals generated by the introduction of the radioactive element tritium, ensure the stability of the polymer molecular structure of the flexible isotope source, and avoid the degradation of the flexible isotope film due to the radiation during the decay of the radioactive element, resulting in reduced function or even failure. At the same time, the radioactive element in the total molecular weight of the flexible isotope source will not be increased due to excessive three-dimensional graphene. 14 C and 3 The proportion of H decreases, which in turn leads to a decrease in the output power of the final flexible thin film source.

[0029] In a second aspect, the present invention further provides an isotope battery, comprising the flexible isotope source described in any of the aforementioned schemes.

[0030] It should be noted that the isotope battery has all the technical effects of the aforementioned flexible isotope source, which will not be repeated here. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings, in which:

[0032] Figure 1 is a schematic diagram of a polymer molecule wrapped in three-dimensional graphene according to an embodiment of the present invention;

[0033] Figure 2 It is a schematic diagram of a process for preparing three-dimensional graphene according to an embodiment of the present invention. DETAILED DESCRIPTION

[0034] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0035] Further, in the following specification, reference will be made to a number of expressions, which are defined as having the following meanings.

[0036] “ 14 "C" refers to the radioactive isotope of carbon, carbon-14.

[0037] “ 3 H" refers to the radioactive isotope of hydrogen, tritium.

[0038] "Chromium trioxide-activated carbon catalyst" refers to a catalyst with activated carbon as a carrier and chromium trioxide as the active component.

[0039] "Copper phosphate-silicon dioxide catalyst" refers to a catalyst with silicon dioxide as a carrier and copper phosphate as an active component.

[0040] “Mercury oxide-activated carbon catalyst” refers to a catalyst with activated carbon as a carrier and mercury oxide as an active component.

[0041] Based on the technical problems raised in the background technology part, the present invention uses 14 C and 3 H-substituted alkynes, containing 14 C carbon source and tritium source prepared 14 C and 3 H-generation polyolefin has a high tritium generation rate and good flexibility, which can well meet the needs of isotope batteries.

[0042] In this embodiment, the preparation method of the flexible isotope source includes:

[0043] S1: Get 14 C and 3 H-substituted alkynes, and obtain 14 C carbon source, including 14 The carbon source of C is a carbon-14 compound of a second main group element.

[0044] In one possible implementation, 14 C and 3 H-substituted alkynes are prepared by the following steps:

[0045] S11: Tritium 3 H2 and oxygen O2 are mixed in a first ratio and reacted to obtain tritium water 3 H2O.

[0046] In S11, the first ratio is tritium gas 3 The molar ratio of H2 to oxygen O2 is in the range of (1.5-5.0):1. For example, tritium gas 3 The molar ratio of H2 to oxygen O2 is 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, etc. Preferably, tritium gas 3 The molar ratio of H2 to oxygen O2 is 1.8:1, which means that tritium 3 H2 and oxygen O2 are fed into the reactor at a molar ratio of 1.8:1 for reaction. 3 The amount of H2 is slightly less than twice the amount of oxygen O2. In this case, the reaction can be ensured and the tritium gas fed into the reactor can be 3 H2 fully participates in the reaction to avoid the generation of tritium gas 3 H2 waste can effectively reduce costs, and after the reaction is completed, the reactor will contain only tritium water. 3 H2O is oxygen O2, which is easy to separate later. At the same time, tritium gas can also be used directly 3 The amount of H2 is used to calculate tritiated water 3 H2O volume, which is convenient for calculation. Of course, tritium 3 The molar ratio of H2 to oxygen O2 can also be other values, as long as the reaction can produce tritium water 3 H2O is enough.

[0047] In one possible embodiment, the reaction in S11 is carried out under the catalytic action of a noble metal catalyst, which may be a Pt-based catalyst or a Pd-based catalyst, wherein a Pt-based catalyst refers to a catalyst loaded with Pt metal, and a Pd-based catalyst refers to a catalyst loaded with Pd metal, and the catalyst carrier may be alumina, silica gel, activated carbon, pumice, diatomaceous earth and other natural products. Obviously, the noble metal catalyst may also be other types of noble metal catalysts such as a gold-based catalyst or a silver-based catalyst. Of course, it may not be a noble metal catalyst. Without departing from the basic principles of the present application, those skilled in the art may flexibly select the specific type of catalyst in S11 according to the specific application scenario, as long as the catalyst can catalyze tritium gas. 3 H2 reacts with oxygen O2 to produce tritium water 3H2O is enough.

[0048] In a possible implementation, the reaction temperature in S11 is 200°C to 500°C, for example, the temperature may be 200°C, 300°C, 350°C, 400°C, 450°C, 500°C, etc. Obviously, other possible temperatures may also be used. Without departing from the basic principles of the present application, those skilled in the art may flexibly select the specific value of the reaction temperature of S11 according to the specific application scenario, as long as the noble metal catalyst has good activity at this temperature and can catalyze tritium gas. 3 H2 reacts with oxygen O2 to produce tritium water 3 H2O is enough.

[0049] For example, the noble metal catalyst in S11 is a Pt-based catalyst, which converts tritium gas into 3 H2 and oxygen O2 are fed into the reactor at a molar ratio of 1.8:1. Under the catalytic action of the Pt-based catalyst, a reaction occurs at 200°C to generate tritiated water. 3 H2O, as shown in Formula 1 below. 3 H2+O2→ 3 H2O Formula 1

[0050] S12: Tritium water 3 H2O and the carbon source are mixed in a second ratio and reacted to obtain the 14 C and 3 H-substituted alkyne.

[0051] In one possible embodiment, the carbon source may be Ba 14 C2 or Ca 14 C2. It should be noted that 14 The carbon source of C can also be carbon-14 compounds of other second main group elements. Carbon-14 compounds are carbon compounds containing 14 C compounds, such as Mg 14 C2, etc. Without departing from the basic principles of this application, those skilled in the art may flexibly select the content according to the specific application scenario. 14 C carbon source, as long as it is based on 14 C carbon source and tritiated water 3 H2O can be prepared 14 C and 3 H can be replaced by acetylene gas.

[0052] In S12, the second ratio is tritium water 3 The molar ratio of H2O to carbon source is in the range of (2.0-6.5):1. For example, tritiated water 3The molar ratio of H2O to carbon source is 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, 5.5:1, 6.0:1, 6.5:1, etc. Preferably, tritiated water 3 The molar ratio of H2O to carbon source is 2:1, which means that tritiated water 3 H2O and carbon source are fed into a reactor (e.g., acetylene generator) at a molar ratio of 2:1, stirred and mixed, and the reaction is obtained. 14 C and 3 H-substituted alkynes. Among them, 14 C and 3 H-substituted alkynes can be 14 C and 3 H-acetylene, or 14 C and 3 H-substituted propyne, etc. Tritium water 3 The mixing of H2O and carbon source in this molar ratio can ensure the progress of the reaction and make full use of the tritiated water fed into the reactor. 3 H2O, and will not be affected by tritium water 3 Excessive H2O causes waste and increases costs. 3 The molar ratio of H2O to carbon source can also be other values, as long as the reaction can obtain 14 C and 3 H-substituted alkyne.

[0053] In a possible embodiment, the reaction temperature in S12 is 20°C to 100°C, for example, the temperature may be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, etc. Obviously, other possible temperatures may also be used. Without departing from the basic principles of the present application, those skilled in the art can flexibly select the specific value of the reaction temperature of S12 according to the specific application scenario, as long as the tritiated water can react at this temperature. 3 H2O can react with carbon source to generate 14 C and 3 H-substituted alkyne.

[0054] In one possible embodiment, after the reaction in S12 occurs, carbon dioxide CO2 is introduced into the reactor. This is because in tritiated water 3 H2O reacts with carbon source to generate 14 C and 3 When H-substituted alkynes are generated, by-products are generated. These by-products are soluble in water and contain 3 H, passing carbon dioxide CO2 into it can precipitate the cations in the carbon source and obtain tritiated water 3 H2O. In this way, expensive tritium water can be produced by introducing carbon dioxide CO2. 3The recycling of H2O can avoid wasting tritium source and effectively reduce costs. Of course, it is also possible to introduce carbon dioxide CO2 into the reactor at the same time as the reaction in S12. Those skilled in the art can flexibly choose the specific time to introduce carbon dioxide CO2 according to the specific application scenario. As long as the cations in the carbon source can be precipitated and tritium water can be recovered, 3 Obviously, when or after the reaction in S12, carbon dioxide CO2 may not be introduced into the reactor.

[0055] For example, with carbon source as Ba 14 Take C2 as an example, tritium water 3 H2O was fed into the reactor, and then Ba 14 C2 is stirred, tritium water 3 H2O and Ba 14 The molar ratio of C2 is 2:1, and the reaction takes place at 50°C to generate 14 C and 3 H-substituted acetylene is shown in Formula 2 below. Ba 14 C2+ 3 H2O→ 14 C 3 H≡ 14 C 3 H+Ba(O 3 H)2 Formula 2

[0056] The above formula 2 produces 14 C 3 H≡ 14 C 3 H is discharged from the reactor as a gas and collected, Ba(O 3 H)2 can be dissolved in water. At this time, carbon dioxide CO2 is fed into the reactor, and carbon dioxide CO2 reacts with Ba(O 3 H)2 reacts to produce barium carbonate BaCO3 and tritium water 3 H2O, as shown in Formula 3. Barium carbonate BaCO3 is precipitated, and the barium carbonate BaCO3 is filtered by solid-liquid separation, and the remaining tritium water 3 H2O can be reused. Ba(O 3 H)2+CO2→BaCO3+ 3 H2O formula 3

[0057] S2: Make 14 C and 3 The H-substituted alkyne is reacted with a tritium source to obtain an intermediate product.

[0058] In one possible embodiment, the tritium source is tritium gas. 3H2, the catalyst in S2 is Lindela catalyst, and the intermediate product obtained in S2 is 14 C and 3 H-substituted olefins, that is, in S2, 14 C and 3 H-alkynes and tritium 3 H2 reacts with Lindela catalyst at 1MPa pressure and 200℃ to obtain the intermediate product. 14 C and 3 H-substituted olefin, as shown in Formula 4 below. 14 C 3 H≡ 14 C 3 H+ 3 H2→ 14 C 3 H2= 14 C 3 H2 Formula 4

[0059] In one possible embodiment, the chemical formula of the Lindela catalyst is Pd x M y N z , wherein M is a mixture of calcium carbonate and tungsten oxide, the mixing ratio of calcium carbonate to tungsten oxide is (2-8):1, N is tin, aluminum, antimony and a mixture thereof, x is in the range of 1-3, y is in the range of 3-7, and z is in the range of 1-2. The palladium in the Lindela catalyst provides catalytic activity and can promote 14 C and 3 H-alkynes and tritium 3 H2 reacts to form an intermediate 14 C and 3 H-substituted olefins. M, as a dispersant, can play a dispersing role and make palladium evenly dispersed in the catalyst. In addition, the tungsten oxide of M has a high density and a large tungsten atomic number, which can effectively shield the decay rays of the radioactive source and prevent the catalytic activity and life of palladium metal from being affected. This is because the high-energy rays generated when the radioactive element tritium decays can cause the electrons in the palladium catalyst powder to transition from the valence band to the conduction band, forming electron-hole pairs, thereby improving the catalytic activity of the catalyst, and can increase the dislocation density in the palladium catalyst powder, thereby improving the catalytic activity of the Lindela catalyst. However, too many defects may cause structural instability of the catalyst and reduce its service life. Due to the uncontrollability of the radiation effect, it will make it difficult to control the overall activity of the catalyst and affect the life of the catalyst. Therefore, the addition of tungsten oxide in the Lindela catalyst of the present application can shield radiation, improve its catalytic activity, and ensure the service life of the Lindela catalyst. N is an inhibitor, and the catalytic activity of palladium can be controlled by N to prevent excessive addition of tritium and ensure the purity of the intermediate product. In other words, the Pd of the present applicationx M y N z Catalysts have high activity and can effectively promote 14 C and 3 The H-substituted alkyne reacts with a tritium source to obtain an intermediate product, which also has a good service life and can avoid excessive addition of tritium, thereby ensuring the purity of the intermediate product.

[0060] Preferably, the Lindela catalyst is palladium-barium sulfate (chemical formula is Pd-BaSO4), or palladium-calcium carbonate-lead dioxide (chemical formula is Pd-CaCO3-PbO2). Taking the Lindela catalyst as Pd-BaSO4 as an example, the BaSO4 in Pd-BaSO4 can be BaSO4 sold on the market, or can be the tritium water recovered from the above-mentioned S12 3 It is prepared by using BaCO3 produced when H2O is added, that is, it is prepared by using BaCO3 produced in Formula 3. Specifically, sulfuric acid is added to BaCO3 to produce the reaction shown in Formula 5 below: BaCO3+H2SO4→BaSO4+H2O+CO2 Formula 5

[0061] The BaSO4 produced in the above formula 5 can be used as the raw material required for Pd-BaSO4, and CO2 can be recycled and utilized in the above formula 3.

[0062] Of course, other types of Lindela catalysts can also be used, as long as they can catalyze 14 C and 3 H-alkynes and tritium 3 H2 reaction produces 14 C and 3 Without departing from the basic principles of the present application, those skilled in the art can flexibly select the specific type of catalyst in S2 according to the specific application scenario, as long as the catalyst can catalyze 14 C and 3 H-alkynes and tritium 3 H2 reaction produces 14 C and 3 H-substituted olefins are sufficient.

[0063] In one possible embodiment, the tritium source is a tritium halide 3 HX, where X represents a halogen element, which may be fluorine, chlorine, bromine, etc. The halogen element is chlorine, that is, the tritium source is tritium chloride 3 HCl as an example, in this case, the catalyst in S2 is a mercury catalyst, and the intermediate product obtained in S2 is 14 C and 3 H-chloroolefins, that is, in S2, 14 C and 3H-substituted alkynes and tritium chloride 3 HCl reacts with mercury catalyst at 100℃~200℃ to obtain intermediate product 14 C and 3 H-substituted chloroolefin is shown in Formula 6 below. 14 C 3 H≡ 14 C 3 H+ 3 HCl→ 14 C 3 H2= 14 C 3 HCl Formula 6

[0064] It should be noted that the mercury catalyst can be a HgCl2 catalyst. Of course, the mercury catalyst can also be other types of catalysts, as long as the catalyst can catalyze 14 C and 3 H-substituted alkynes and tritium chloride 3 HCl reaction produces 14 C and 3 Without departing from the basic principles of the present application, those skilled in the art can flexibly select the specific type of catalyst in S2 according to the specific application scenario, as long as the catalyst can catalyze 14 C and 3 H-alkynes and tritium 3 H2 reaction produces 14 C and 3 H-substituted olefins are sufficient.

[0065] The tritium source is tritium chloride 3 For example, HCl can be added to tritiated water 3 Tritium chloride is obtained by passing chlorine gas Cl2 into H2O 3 HCl, as shown in Formula 7 below. 3 H2O+Cl2→ 3 HCl+ 3 HClO Formula 7 3 HClO→ 3 HCl+O2 Formula 8

[0066] As shown in Formula 7 above, tritiated water 3 H2O reacts with chlorine gas Cl2 to generate target tritium chloride 3 HCl, and by-products 3 HClO, the 3 HClO decomposes under light, as shown in formula 8 above, 3 HClO decomposes to produce tritium chloride. 3HCl, after being separated from oxygen O2, can be used as the raw material of S2, and oxygen O2 can be used as the synthetic tritium water in the above formula 1 3 The raw material of H2O.

[0067] In the above formula 7, when using tritium water 3 Preparation of Tritium Chloride from H2O and Chlorine Gas Cl2 3 HCl, to each liter of tritiated water 3 1.1m3~2m3 of chlorine gas Cl2 is introduced into H2O, which can ensure the progress of the reaction and make full use of tritium water. 3 H2O, increasing tritium chloride 3 The yield of HCl will not be too high due to excessive Cl2 concentration, which will cause danger. 3 Other volumes of chlorine gas Cl2 can also be introduced into H2O, as long as the reaction can produce tritium chloride. 3 Without departing from the basic principles of this application, tritium chloride can be prepared by other methods. 3 HCl, which can be flexibly selected by technicians in this field according to specific application scenarios, as long as the tritium chloride required in S2 can be obtained. 3 HCl is enough.

[0068] In one possible embodiment, the tritium source is mixed with the tritium obtained in S1 in S2. 14 C and 3 The H-substituted alkyne is fed into the reactor at a molar ratio of (3.0-10.0):1, and an addition reaction occurs to generate an intermediate product. In S2, the tritium source fed into the reactor reacts with 14 C and 3 The molar ratio of the H-substituted alkyne can be 3.0:1, 4.0:1, 5.0:1, 6.0:1, 7.0:1, 8.0:1, 9.0:1, 10.0:1, etc. Preferably, the tritium source and 14 C and 3 The molar ratio of H-substituted alkyne is 4.0:1, which means that the tritium source and 14 C and 3 The H-substituted alkyne is fed into the reactor at a molar ratio of 4:1 for reaction. The tritium source in the reactor is excessive, which can ensure the full progress of the reaction and make full use of the tritium source fed into the reactor. 14 C and 3 H-substituted alkynes will not cause waste and increase costs. Of course, the tritium source and 14 C and 3 The molar ratio of the H-substituted alkyne may also be other values ​​as long as the desired intermediate product can be obtained by the reaction.

[0069] S3: mixing the intermediate product with three-dimensional graphene and polymerizing the intermediate product to obtain a flexible isotope source, wherein the flexible isotope source is 14 C and 3 H-generation polyolefin or 14 C and 3 H generation polyhaloolefin.

[0070] In S3, after the gas phase stirred bed reactor is purged with an inert gas, the intermediate product ( 14 C and 3 H-olefins or 14 C and 3 H-substituted halogenated olefin) is fed into the cleaned gas-phase stirred bed reactor in the form of gas, and three-dimensional graphene and the intermediate product ( 14 C and 3 H-olefins or 14 C and 3 H-substituted halogenated olefins) are mixed, and then a gas phase polymerization reaction is carried out under the action of a catalyst at a temperature of 100° C. to 200° C. and a gas pressure of 1.5 MPa to 3.5 MPa to obtain 14 C and 3 H-generation polyolefin or 14 C and 3 H generation polyhaloolefin. 14 C and 3 H generation polyolefins 14 C and 3 The tritium substitution rate of H-generation polyhaloolefins is relatively high, and using them as flexible isotope sources can meet the high tritium substitution rate requirements of isotope batteries, and, 14 C and 3 H generation polyolefins 14 C and 3 The H-generation polyhaloolefin also has good flexibility, which can meet the requirements of raw materials for flexible films that need to be folded and bent in isotope batteries, thereby meeting the flexibility requirements of isotope batteries.

[0071] In addition, during the polymerization reaction, the present application also adds three-dimensional graphene to the reactor, such as Figure 1 As shown, Figure 1 In the figure, the Y-shaped structure represents three-dimensional graphene, and the linear structure represents polymer molecules ( 14 C and 3 H-generation polyolefin or 14 C and 3 H-generation polyhalogenated olefins). There are a large number of π-π bonds in the three-dimensional graphene, and the π-π conjugated structure can capture and quench active free radicals. These active free radicals are polymer molecules obtained by the polymerization reaction when the high-energy rays generated by the decay of the radioactive element tritium hit the polymerization reaction. 14 C and3 H-generation polyolefin or 14 C and 3 H-generation polyhalogenated olefins can prevent the chain reaction caused by active free radicals and aggravate the degradation process. 14 C and 3 H-generation polyolefin or 14 C and 3 When the main chain of the H-generation polyhalogenated olefin is broken by radiation, the three-dimensional graphene can wrap it and maintain its stability. In addition, the three-dimensional graphene has a huge specific surface area. There is a van der Waals force between the polymer molecules and the surface of the three-dimensional graphene. Under the action of the van der Waals force, the polymer molecules can be 14 C and 3 H-generation polyolefin or 14 C and 3 H-generation polyhaloolefins and their fracture products are adsorbed on the surface of three-dimensional graphene, and support the structure of the flexible isotope source by adsorbing and fixing the polymer molecules and fracture products, preventing the structure from being damaged. In other words, by adding three-dimensional graphene, the main chain breakage of the flexible isotope source caused by the introduction of the radioactive element tritium can be effectively avoided, ensuring the stability of its performance and improving its service life. Through a series of studies and experiments, the inventors of this application have found that by adding three-dimensional graphene, the yield of the flexible isotope source can be as high as 92% to 95%, and the service life can be increased to 8 to 13 years. Compared with not adding three-dimensional graphene, the thermal stability can be increased by 34% to 60%.

[0072] It should be noted that the aforementioned inert gas can be any one of argon, helium, neon, krypton, xenon, and radon, or a mixture of multiple gases.

[0073] In this embodiment, the intermediate product obtained in S2 is 14 C and 3 When H replaces olefins, the reaction occurring in S3 is shown in Formula 9, that is, 14 C and 3 The H-substituted olefin is polymerized to obtain 14 C and 3 The intermediate product obtained in S2 is 14 C and 3 When the halogenated olefin is substituted by H, the reaction occurring in S3 is shown in Formula 10, that is, 14 C and 3 The H-substituted halogenated olefins are polymerized to obtain 14 C and 3 H generation polyhaloolefin. n 14 C 3 H2= 14 C 3H2→-[ 14 C 3 H2- 14 C 3 H2] n - Formula 9 n 14 C 3 H2= 14 C 3 HCl → -[ 14 C 3 H2- 14 C 3 HCl] n - Formula 10

[0074] In one possible embodiment, the tritium source is tritium gas. 3 H2, which means that the intermediate product is 14 C and 3 When H is used to generate olefins, the catalyst in S3 is a supported titanium catalyst or a supported Cr catalyst, wherein the supported titanium catalyst may be triethylaluminum-titanium tetrachloride, etc., triethylaluminum-titanium tetrachloride is referred to as ZN catalyst, and the supported Cr catalyst may be chromium trioxide-activated carbon catalyst, etc. Of course, the catalyst in S3 may also be a titanium catalyst such as titanium tetrachloride, or other types of catalysts. Without departing from the basic principles of the present application, those skilled in the art may flexibly select according to specific application scenarios, as long as they can be used. 14 C and 3 H-olefin polymerization 14 C and 3 H generation polyolefin can be used.

[0075] In one possible embodiment, the tritium source is a tritium halide 3 HX, which means the intermediate product is 14 C and 3 When the halogenated olefin is substituted, the catalyst in S3 is one of a titanium catalyst, a zirconium catalyst, a copper catalyst, and mercuric chloride, wherein the titanium catalyst can be a titanium chloride catalyst, the zirconium catalyst can be a zirconium dioxide catalyst, the copper catalyst can be a copper chloride catalyst, etc. Of course, the catalyst in S3 can also be other types of catalysts, such as mercuric chloride-activated carbon catalyst, etc. Without departing from the basic principles of the present application, those skilled in the art can flexibly select according to the specific application scenario, as long as it can be used. 14 C and 3 H-substituted halogenated olefins polymerization 14 C and 3 H-substituted polyhaloolefins are sufficient.

[0076] In a possible embodiment, the molar ratio of the three-dimensional graphene to the intermediate product obtained in S2 is 1:9 to 1:3. Within this ratio range, the free radicals generated by the introduction of the radioactive element tritium can be fully absorbed to ensure the stability of the polymer molecular structure of the flexible isotope source, and the flexible isotope film can be prevented from being degraded by radiation during the decay of the radioactive element, resulting in reduced function or even failure. At the same time, the radioactive element in the total molecular weight of the flexible isotope source will not be increased due to excessive three-dimensional graphene. 14 C and 3 The proportion of H decreases, which in turn leads to a decrease in the output power of the final flexible thin film source. Preferably, the molar ratio of three-dimensional graphene to the intermediate product is 1:6. At this ratio, the yield of the flexible isotope source can be increased to 86%, the service life can be increased to 10 years, and the thermal stability can be increased by 52% compared with no addition of three-dimensional graphene.

[0077] In a possible implementation, Figure 2 As shown, three-dimensional graphene can be prepared by the following steps:

[0078] S31: triptycene is reacted with raw material 1: 4,4'-di-tert-butyl bipyridine and raw material 2: diboron in the presence of raw material 3: catalyst methoxy(cyclooctadiene)iridium dimer to generate borated triptycene.

[0079] In S31, the molar ratio of triptycene to 4,4'-di-tert-butyl bipyridine and diboron in the catalyst methoxy(cyclooctadiene) iridium dimer is a1:b1:c1:d1, wherein a1 is 0.5 to 3, b1 is 0.1 to 0.8, c1 is 1 to 4, and d1 is 0.1 to 0.5. Preferably, a1:b1:c1:d1 is 1:0.2:1.7:0.1.

[0080] The reaction in S31 can be carried out using tetrahydrofuran as solvent. After adding triptycene, raw material 1, raw material 2 and raw material 3 into the solvent, stirring at 50° C. to 150° C. and reacting for 8 h to 24 h, for example, stirring at 80° C. and reacting for 10 h, borated triptycene can be obtained.

[0081] S32: The borated triptycene prepared in S31 is reacted with raw material 4: brominated graphene under the action of raw material 5: catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride, and then the target product three-dimensional graphene is generated under the catalytic action of light and I2. Wherein, the type of light for illumination can be visible light, the illumination duration can be 0.3h~2h, and the illumination intensity can be 1000lux~5000lux. Preferably, the illumination duration is 0.8h and the illumination intensity can be 2000lux, that is, the borated triptycene and brominated graphene are first reacted under the action of catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride, and then three-dimensional graphene can be prepared under the irradiation of visible light with an illumination intensity of 2000lux and the catalytic action of I2.

[0082] In S32, the molar ratio of triptycene borate, graphene bromide and 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride is a2:b2:c2, wherein a2 is 0.2 to 4, b2 is 1 to 6, and c2 is 0 to 0.6. Preferably, a2:b2:c2 is 1:3.1:0.1.

[0083] The reaction in S32 can use a mixture of water and tetrahydrofuran as a solvent, wherein the volume ratio of water to tetrahydrofuran (THF) can be 1:10 to 1:2. After adding the borated triptycene, raw material 4, and raw material 5 to the solvent, the reaction is stirred at 50°C to 70°C for 10h to 30h, for example, at 55°C for 20h, so that graphene replaces the boric acid of the borated triptycene, and then the target product three-dimensional graphene is generated under light and the catalytic action of I2.

[0084] Based on the flexible isotope source prepared above ( 14 C and 3 H-generation polyolefin or 14 C and 3 H-generation polyhalogenated olefin), the flexible isotope source obtained in the above S3 is calendered by the gap between multiple horizontal rollers rotating in opposite directions, and the calendering pressure range is 400-800N. During the calendering process, the flexible isotope source is subjected to shear force and tensile stress at the same time, and is oriented along the calendering direction to form a flat flexible isotope film with a thickness of approximately 0.01mm-0.5mm. Then, a cutting machine (such as a PE film cutting machine, etc.) is used to cut the flexible isotope film into the size required for the flexible isotope battery, for example, 2cm×4cm, etc., and then a beta radiation voltaic battery flexible transducer device is attached, and a flexible isotope battery can be made after bonding and packaging.

[0085] In order to more clearly illustrate the preparation method of the present invention, the following carbon source is Ba 14 C2. Tritium source is tritium gas 3H2 or tritium chloride 3 Taking HCl as an example, and combining Examples 1 to 6 and a comparative example, the preparation method of the present invention and possible implementation methods of the flexible isotope film are specifically described.

[0086] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available.

[0087] Thermal stability: The thermal shrinkage of the flexible isotope film was tested according to the test method of shrinkage rate in 5.6.3 of the national standard GB / T 13519-2016, and the thermal stability of the flexible isotope film was evaluated based on the thermal shrinkage rate.

[0088] Embodiment 1:

[0089] Will 3 H2 and oxygen are mixed in a ratio of 1.8:1 and introduced into a reactor. Under the catalytic action of a Pt catalyst, the reaction in the above formula 1 is carried out at 200°C to obtain tritiated water. 3 H2O.

[0090] The tritiated water 3 H2O is fed into the acetylene generator, and then the carbon source Ba is added 14 C2 is stirred and tritium water is added 3 H2O and Ba 14 The molar ratio of C2 is 2:1. The reaction in the above formula 2 is carried out at 50°C to obtain 14 C and 3 H-substituted acetylene.

[0091] The triphenylene, 4,4'-di-tert-butyl bipyridine and diboron are put into a solvent tetrahydrofuran, and a catalyst methoxy (cyclooctadiene) iridium dimer is added to the mixed solution, and the mixture is stirred at 80°C for reaction to generate borated triphenylene, wherein the molar ratio of triphenylene, 4,4'-di-tert-butyl bipyridine, diboron and methoxy (cyclooctadiene) iridium dimer is 1:0.2:1.7:0.1. Then the borated triphenylene and brominated graphene are put into a mixed solution of solvent water and tetrahydrofuran, and a catalyst 1,1'-di(diphenylphosphino) ferrocene palladium dichloride is added to the mixed solution, and the mixture is stirred at 55°C for reaction to allow graphene to replace the boric acid of the borated triphenylene, and then the target product three-dimensional graphene is generated under the irradiation of visible light with an illumination intensity of 2000 lux and the catalytic action of I2. The ratio of triptycene borate, graphene bromide and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride is 1:3.1:0.1.

[0092] The obtained 14 C and 3 H-acetylene and tritium3 H2 is fed into the reactor at a molar ratio of 1:4, and the reactor is filled with Lindela catalyst Pd-BaSO4. At the same time, the three-dimensional graphene prepared as above is fed into the reactor. 14 C and 3 The ratio of H-substituted acetylene is 1:6. The addition reaction in the above formula 4 is carried out at a pressure of 1 MPa and a temperature of 200°C to obtain 14 C and 3 H generation ethylene.

[0093] After purging the gas-phase stirred bed reactor with argon, the obtained 14 C and 3 The H-generation ethylene is fed into a gas phase stirred bed reactor in the form of gas. A chromium trioxide-activated carbon catalyst is placed in the gas phase stirred bed reactor. The polymerization reaction in the above formula 9 is carried out at a temperature of 110° C. and a pressure of 3.5 MPa to obtain 14 C and 3 H generation polyethylene.

[0094] The obtained 14 C and 3 The yield of H-generation polyethylene was 94.4%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 10 years. Compared with the flexible isotope film prepared from a flexible isotope source without adding three-dimensional graphene, the heat shrinkage rate is reduced from 40% to 19.2%, and the thermal stability is improved by 52%.

[0096] Embodiment 2:

[0097] The only difference from Example 1 is that the three-dimensional graphene fed into the reactor is 14 C and 3 The ratio of H-acetylene is 1:3. 14 C and 3 The yield of H-generation polyethylene was 92%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 13 years. Compared with the flexible isotope film prepared from a flexible isotope source without adding three-dimensional graphene, the heat shrinkage rate is reduced from 40% to 18%, and the thermal stability is improved by 55%.

[0099] Embodiment 3:

[0100] The only difference from Example 1 is that the three-dimensional graphene fed into the reactor is 14 C and 3The ratio of H-substituted acetylene is 1:9. 14 C and 3 The yield of H-generation polyethylene was 95%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 8 years. Compared with the flexible isotope film prepared from a flexible isotope source without adding three-dimensional graphene, the heat shrinkage rate is reduced from 40% to 16%, and the thermal stability is increased by 60%.

[0102] Embodiment 4:

[0103] The difference from Example 1 is that 3 The molar ratio of H2 to oxygen is 1.5:1, tritium water 3 H2O and Ba 14 The molar ratio of C2 is 6.5:1, 14 C and 3 H-acetylene and tritium 3 The molar ratio of H2 is 1:3.

[0104] The obtained 14 C and 3 The yield of H-generation polyethylene was 95%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 9 years. Compared with the flexible isotope film prepared from a flexible isotope source without adding three-dimensional graphene, the heat shrinkage rate is reduced from 45% to 25%, and the thermal stability is improved by 44.4%.

[0106] Embodiment 5:

[0107] The difference from Example 1 is that 3 The molar ratio of H2 to oxygen is 5.0:1, tritium water 3 H2O and Ba 14 The molar ratio of C2 is 4.5:1, 14 C and 3 H-acetylene and tritium 3 The molar ratio of H2 is 1:10.

[0108] The obtained 14 C and 3 The yield of H-generation polyethylene was 95.6%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 8 years. Compared with the flexible isotope film prepared from a flexible isotope source without adding three-dimensional graphene, the heat shrinkage rate is reduced from 47% to 26%, and the thermal stability is improved by 44.7%.

[0110] Embodiment 6:

[0111] The difference from Example 1 is that 3 The molar ratio of H2 to oxygen is 1.8:1, tritium water 3 H2O and Ba 14 The molar ratio of C2 is 2:1, and the obtained 14 C and 3 H-substituted acetylene.

[0112] Then, according to the tritium water 3 The tritiated water was prepared by passing 1.1 m3 of chlorine gas Cl2 into H2O. 3 Chlorine gas Cl2 is introduced into H2O to produce tritium chloride as shown in the above formula 7 and formula 8. 3 HCl.

[0113] The obtained 14 C and 3 H-acetylene and tritium chloride 3 HCl was fed into a reactor at a molar ratio of 1:1, and a HgCl2 catalyst was placed in the reactor. The addition reaction in the above formula 6 was carried out at a pressure of 1 MPa and a temperature of 200°C to obtain 14 C and 3 H-chloroethylene.

[0114] After purging the gas-phase stirred bed reactor with argon, the obtained 14 C and 3 The H-generation vinyl chloride is fed into a gas phase stirred bed reactor in the form of gas. A gold chloride-activated carbon catalyst is placed in the gas phase stirred bed reactor. The polymerization reaction in the above formula 10 is carried out at a temperature of 120° C. and a pressure of 3.5 MPa to obtain 14 C and 3 H generation polyvinyl chloride.

[0115] The obtained 14 C and 3 The yield of H-type polyvinyl chloride was 93%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 12 years. Compared with the flexible isotope film prepared from a flexible isotope source without adding three-dimensional graphene, the heat shrinkage rate is reduced from 62% to 28%, and the thermal stability is improved by 54.8%.

[0117] Comparative Example:

[0118] Will 3H2 and oxygen are mixed in a ratio of 1.8:1 and introduced into a reactor. Under the catalytic action of a Pt catalyst, the reaction in the above formula 1 is carried out at 200°C to obtain tritiated water. 3 H2O.

[0119] The tritiated water 3 H2O is fed into the acetylene generator, and then the carbon source Ba is added 14 C2 is stirred and tritium water is added 3 H2O and Ba 14 The molar ratio of C2 is 2:1. The reaction in the above formula 2 is carried out at 50°C to obtain 14 C and 3 H-substituted acetylene.

[0120] The obtained 14 C and 3 H-acetylene and tritium 3 H2 was fed into the reactor at a molar ratio of 1:4, and the reactor was filled with Lindela catalyst Pd-BaSO4. The addition reaction in the above formula 4 was carried out at a pressure of 1 MPa and a temperature of 200°C to obtain 14 C and 3 H generation ethylene.

[0121] After purging the gas-phase stirred bed reactor with argon, the obtained 14 C and 3 The H-generation ethylene is fed into a gas phase stirred bed reactor in the form of gas. A chromium trioxide-activated carbon catalyst is placed in the gas phase stirred bed reactor. The polymerization reaction in the above formula 9 is carried out at a temperature of 110° C. and a pressure of 3.5 MPa to obtain 14 C and 3 H generation polyethylene.

[0122] The obtained 14 C and 3 The yield of H-generation polyethylene was 96%. 14 C and 3 The service life of the flexible isotope film prepared from H-generation polyethylene is about 1.4 years.

[0124] It should be noted that, in the above embodiments, although the intermediate product is 14 C and 3 H-ethylene or 14 C and 3 H-generation vinyl chloride, flexible isotope source 14 C and 3 H generation polyethylene or 14 C and 3The H-generation polyvinyl chloride is used as an example to illustrate this, but it is obviously only an exemplary illustration. The flexible isotope source can also be 14 C and 3 H-generation polypropylene and other materials with high tritium generation rate and flexibility 14 C and 3 H-generation polyolefin or 14 C and 3 Without departing from the basic principles of the present application, those skilled in the art can flexibly select according to the specific application scenario, as long as the high tritium generation rate and flexibility requirements of the isotope battery can be met.

[0125] Although the various steps in the above embodiment are described in the above-mentioned chronological order, those skilled in the art can understand that in order to achieve the effect of this embodiment, different steps do not have to be executed in such an order. They can be executed simultaneously (in parallel) or in a reverse order. These simple changes are within the scope of protection of this application.

[0126] So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims

1. A method for preparing a flexible isotope source, characterized in that: The preparation method comprises: S1: Get 14 C and 3 H-substituted alkynes, and obtain 14 C carbon source, the 14 The carbon source of C is carbon-14 compound of the second main group element; S2: Make the 14 C and 3 The H-substituted alkyne reacts with a tritium source to obtain an intermediate product, wherein the tritium source is tritium gas 3 H2 or tritium halide 3 HX, wherein X is a halogen element; S3: mixing the intermediate product with three-dimensional graphene and causing the intermediate product to undergo a polymerization reaction to obtain the flexible isotope source, wherein the flexible isotope source is 14 C and 3 H-generation polyolefin or 14 C and 3 H generation polyhaloolefin.

2. The preparation method according to claim 1, characterized in that: The tritium source is tritium gas 3 When H2, the catalyst in S2 is Lindela catalyst.

3. The preparation method according to claim 2, characterized in that: The chemical formula of the Lindela catalyst is Pd x M y N z , wherein M is a mixture of calcium carbonate and tungsten oxide, the molar ratio of the calcium carbonate to the tungsten oxide is (2-8):1, N is tin, aluminum, antimony and a mixture thereof, the value range of x is 1-3, the value range of y is 3-7, and the value range of z is 1-2.

4. The preparation method according to claim 2, characterized in that: The catalyst in S3 is a supported titanium-based catalyst or a supported Cr-based catalyst.

5. The preparation method according to claim 1, characterized in that: The tritium source is tritium halide 3 In the case of HX, the catalyst in S2 is a mercury-based catalyst, and the catalyst in S3 is one of a titanium-based catalyst, a zirconium-based catalyst, a copper-based catalyst, and mercuric chloride.

6. The preparation method according to any one of claims 1 to 5, characterized in that Said 14 C and 3 H-substituted alkynes are prepared by the following steps: S11: Tritium 3 H2 and oxygen O2 are mixed in a first ratio and reacted to obtain tritium water 3 H2O; S12: the tritium water 3 H2O is mixed with the carbon source in a second ratio and reacted to obtain the 14 C and 3 H-substituted alkyne.

7. The preparation method according to claim 6, characterized in that: The first ratio is the tritium gas 3 The molar ratio of H2 to the oxygen O2 is in the range of (1.5-5.0):1; and / or The second ratio is the tritium water 3 The molar ratio of H2O to the carbon source is in the range of (2.0-6.5):

1.

8. The preparation method according to claim 7, characterized in that: The reaction in S11 is carried out under the catalytic action of a Pt-based catalyst or a Pd-based catalyst.

9. The preparation method according to claim 6, characterized in that: The preparation method further comprises: At the same time or after the reaction in S12 occurs, the tritiated water is added 3 Carbon dioxide CO2 is introduced into the mixture of H2O and the carbon source to recover the tritiated water 3 H2O.

10. The preparation method according to any one of claims 1 to 5, characterized in that: The carbon source is Ba 14 C2 or Ca 14 C2.

11. The preparation method according to any one of claims 1 to 5, characterized in that: The molar ratio of the three-dimensional graphene to the intermediate product is 1:9 to 1:

3.

12. An isotope battery, characterized in that: The isotope battery comprises the flexible isotope source according to any one of claims 1 to 11.

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