Isotope battery coupled with carbon 14 and tritium radioactive source

Abstract

The invention relates to the technical field of isotopes, particularly provides an isotope battery coupled with C14 and a tritium radioactive source, 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 leads to degradation of a high polymer material and further leads to reduction of performance and service life. In order to achieve the purpose, the flexible isotope source of the isotope battery is prepared by the following steps: S1, obtaining 14C and 3H alkyne and a carbon source containing 14C; s2, enabling the 14C and 3H alkyne to react with a tritium source to obtain an intermediate product; 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, the tritium source and the three-dimensional graphene, so that the requirements of high tritium generation rate and flexibility of an isotope battery can be met, and the performance and the service life of a flexible radioisotope film are ensured.

Description

Technical Field

[0001] The present invention relates to the field of isotope technology, and in particular provides an isotope battery coupling carbon 14 and tritium radioactive sources. Background Art

[0002] An isotope battery is a device that converts the energy released by the decay of radioactive isotopes into electricity. Proposed by British physicist Henry Moseley in 1913 and developed in the 1960s, it represents a new type of power source. Compared to traditional chemical and solar cells, isotope batteries offer significant advantages in terms of operating life, energy density, and environmental adaptability. This makes them promising applications in a variety of areas, including implantable medical devices, positioning beacons, IoT chips, marine and polar power supplies, and space power supplies.

[0003] There are numerous types of isotope batteries, categorized by their energy conversion mechanism, including direct charging, thermal, electron-excitation, and photon-excitation radiovoltaic. Compared to these other types, the electron-excitation beta radiovoltaic isotope battery (RVIB) utilizes the interaction of beta particles released by the decay of a radioactive source with the semiconductor transducer element, generating a large number of electron-hole pairs within the semiconductor material. These pairs are then separated by a built-in electric field and transported to the corresponding electrode terminals for collection, thereby converting and outputting electrical energy. The greatest advantage of this type of battery lies in its semiconductor-based design, which has achieved initial industrialization in both integration processes and product development. Most importantly, its output power is in the μW-mW range, essentially meeting the power requirements of low-power electronic devices. Furthermore, its ease of integration, quiet operation, and DC output meet the needs of various electronic devices and have broad applications.

[0004] Flexible electronic devices are an emerging electronic technology that offer greater flexibility and can adapt to varying working environments to a certain extent, meeting the deformation requirements of the device. To meet the power supply needs within flexible devices, isotope batteries must also be flexible. Due to their low cost, low radiation, and ease of processing, using tritium as a radioactive source isotope battery is a development direction with great application potential. However, the current conventional method of loading tritium isotope sources is to store tritium in alloys, but alloy materials are rigid and cannot achieve flexibility. Therefore, how to prepare a flexible isotope source is a key issue in the development of flexible isotope batteries.

[0005] Currently, tritium is commonly used to replace hydrogen in conventional flexible polymer materials to create flexible tritium isotope sources. However, the preparation of flexible radioactive films containing tritium isotopes often faces the following challenges: 1. The primary effect of the kinetic isotope effect is that the different zero-point energies of the reactants, due to the different masses of the isotopes, lead to different reaction rates and catalytic effects. Specifically, when hydrogen is replaced by tritium (T), due to the two-fold mass difference, the C-T bond is less active than the C-H bond during the reaction. The zero-point vibrational energy of the C-T bond is lower than that of the C-H bond, which means that the C-T bond is more difficult to break than the C-H bond. The secondary effect manifests primarily in the change in the hybridization state of the carbon atom to which the isotope atom is attached. This is due to the different effects on out-of-plane bending vibrations in the transition state and the ground state, causing a change in reaction rate. In the reaction of hydrogen replaced by tritium, the C-T bond is shorter than the C-H bond, and the degree of freedom of the bending state of the C-T bond is smaller than that of the C-H bond, making it more difficult for the carbon atom to undergo hybridization changes. This makes it impossible to continue using existing conventional non-radioactive film preparation processes, requiring the development of new processes and catalysts. 2. The decay particles from the introduction of radioactive nuclides cause degradation of polymer materials, reducing performance and lifespan. When high-energy radiation produced by the decay of radioactive nuclides hits polymer molecules, it removes electrons from atomic or molecular orbitals, generating free radical cations. These cations are unstable and easily break down, forming more free radicals. These free radicals attack the polymer backbone, causing irregular chain breakage and a decrease in polymer molecular weight. High-energy radiation can also excite electrons to higher energy levels. When the excited molecules return to the ground state, the energy released may cause chemical bonds to break, breaking the polymer backbone and reducing the molecular weight. This will lead to backbone breakage and a decrease in molecular weight, increasing the solubility of the polymer in the solvent, while correspondingly reducing thermal stability and mechanical properties, resulting in a shortened service life. This also means that when preparing flexible radioactive films with tritium isotopes, the introduction of tritium, a radioactive element, will cause degradation of polymer materials, reducing performance and lifespan.

[0006] Accordingly, this field requires 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 containing radioactive elements cannot be prepared using conventional flexible non-radioactive film preparation processes and that the introduction of the radioactive element tritium causes degradation of polymer materials, thereby reducing performance and service life.

[0008] The present invention provides an isotope battery coupling carbon 14 and tritium radioactive sources, wherein the isotope battery comprises a flexible isotope film, wherein the flexible isotope film is prepared from a flexible isotope source, and the flexible isotope source is prepared by the following steps:

[0009] S1: Acquisition 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;

[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 polyhaloolefins.

[0012] In the case of adopting the above technical solution, the isotope battery includes a flexible isotope film, which is prepared by a flexible isotope source. 14 C and 3 H-substituted alkynes, containing 14 C carbon source and tritium source prepared 14 C and 3 H-generation polyolefin or 14 C and 3 H-generation polyhalogenated olefins have a high tritium substitution rate, which can meet the high tritium substitution rate requirements of isotope batteries, and 14 C and 3 H-generation polyolefins and 14 C and 3H-generation polyhalogenated olefins also have good flexibility and 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. 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 a chain reaction and thereby exacerbating 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 polymerization of the intermediate product, maintain its stability, and support the structure of the flexible isotope source by adsorbing and fixing the 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.

[0013] In the optional technical solution of the above isotope battery, the tritium source is tritium gas 3 When H2 is used, the catalyst in S2 is a Lindela catalyst.

[0014] In the optional technical solution of the above isotope battery, the chemical formula of the Lindella 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, tritium addition reaction is more difficult than hydrogenation reaction. Therefore, the catalyst activity is required to be higher than that of ordinary Lindela catalyst, and the existing Lindela catalyst components cannot meet the requirements. In the Lindela 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 Acts as a catalyst to effectively 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 and ensuring the purity of the intermediate product.

[0016] In the optional technical solution of the above-mentioned isotope battery, 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 isotope battery, 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-mentioned isotope battery, 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 react to obtain tritium water 3 H2O;

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

[0021] In the optional technical solution of the above isotope battery, 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 the optional technical solution of the above-mentioned isotope battery, the reaction of S11 is carried out under the catalysis of a Pt-based catalyst or a Pd-based catalyst.

[0024] In the optional technical solution of the above isotope battery, the steps further include:

[0025] At the same time or after the reaction in S12 occurs, the tritiated water 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 solution of the above isotope battery, the carbon source is Ba 14 C2 or Ca 14 C2.

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

[0028] When the above technical solution is adopted, the three-dimensional graphene is added according to the above proportion. This 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 prevent the flexible isotope film from being degraded by radiation during the decay of the radioactive element, resulting in reduced function or even failure. At the same time, the excessive amount of three-dimensional graphene will not lead to a decrease in the proportion of radioactive elements 14C and 3H in the total molecular weight of the flexible isotope source, thereby reducing the output power of the final flexible film source. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The preferred embodiments of the present invention are described below with reference to the accompanying drawings, in which:

[0030] Figure 1 is a schematic diagram of a three-dimensional graphene-wrapped polymer molecule according to an embodiment of the present invention;

[0031] 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

[0032] 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 scope of protection of the present invention.

[0033] Furthermore, in the following description, reference will be made to a number of expressions, which are defined as having the following meanings.

[0034] “ 14 C" refers to the radioactive isotope of carbon, carbon-14.

[0035] “ 3 H" refers to the radioactive isotope tritium of hydrogen.

[0036] "Chromium trioxide-activated carbon catalyst" refers to a catalyst with activated carbon as the carrier and chromium trioxide as the active component.

[0037] "Copper phosphate-silica catalyst" refers to a catalyst with silica as the carrier and copper phosphate as the active component.

[0038] "Mercury oxide-activated carbon catalyst" refers to a catalyst with activated carbon as the carrier and mercury oxide as the active component.

[0039] 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, tritium source and three-dimensional graphene prepared 14 C and 3H-generation polyolefin has a high tritium substitution rate and good flexibility, which can well meet the needs of isotope batteries.

[0040] In this embodiment, the steps for preparing the flexible isotope source specifically include:

[0041] S1: Acquisition 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.

[0042] In one possible implementation, 14 C and 3 H-substituted alkynes are prepared by the following steps:

[0043] S11: Tritium 3 H2 and oxygen O2 are mixed in a first ratio and react to obtain tritium water 3 H2O.

[0044] In S11, the first ratio is tritium gas 3 The molar ratio of H2 to oxygen O2 is in the range of (1.5 to 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 gas 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, it can ensure the progress of the reaction and enable the tritium gas fed into the reactor to 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 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 The amount of H2O is easy to calculate. Of course, tritium 3 The molar ratio of H2 to oxygen O2 can also be other values, as long as the reaction can produce tritiated water 3 H2O is enough.

[0045] In one possible embodiment, the reaction in S11 is carried out under the catalytic action of a noble metal catalyst, which can 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. The carrier of the catalyst can be alumina, silica gel, activated carbon, pumice, diatomaceous earth and certain natural products. Obviously, the noble metal catalyst can 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 this application, those skilled in the art can 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 3 H2O is enough.

[0046] In one possible embodiment, 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 are also possible. 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 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.

[0047] 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 a temperature of 200°C to generate tritiated water. 3 H2O, as shown in Formula 1 below. 3 H2+O2→ 3 H2O formula 1

[0048] 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 alkynes.

[0049] 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 14C compounds, such as Mg 14 C2, etc. Without departing from the basic principles of this application, those skilled in the art can flexibly select the content of 14 C carbon source, as long as it is based on the 14 C carbon source and tritiated water 3 H2O can be prepared 14 C and 3 H can be used to replace acetylene gas.

[0050] 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 3 The 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. 14 C and 3 H-substituted alkynes can be 14 C and 3 H-acetylene, or 14 C and 3 H-substituted propyne, etc. Tritiated 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 be obtained. 14 C and 3 H-substituted alkyne can be used.

[0051] In one 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 is heated at this temperature. 3 H2O can react with carbon source to produce 14 C and 3H-substituted alkyne can be used.

[0052] 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, the introduction of carbon dioxide CO2 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. 3 The 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 occurs. Those skilled in the art can flexibly choose the specific time of introducing 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 occurs, carbon dioxide CO2 may not be introduced into the reactor.

[0053] 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 was added 14 C2 is stirred, tritium water 3 H2O and Ba 14 The molar ratio of C2 is 2:1, and the reaction occurs at 50°C to produce 14 C and 3 H replaces acetylene, as 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

[0054] The above formula 2 produces 14 C 3 H≡ 14 C 3 H is discharged from the reactor in the form of 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 form barium carbonate BaCO3 and tritium water 3H2O, as shown in formula 3. Barium carbonate BaCO3 is precipitated and filtered through solid-liquid separation, leaving tritium water. 3 H2O can be reused. Ba(O 3 H)2+CO2→BaCO3+ 3 H2O formula 3

[0055] S2: Make 14 C and 3 The H-substituted alkyne reacts with a tritium source to obtain an intermediate product.

[0056] In one possible embodiment, the tritium source is tritium gas. 3 H2, 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-substituted alkynes and tritium gas 3 H2 reacts with Lindela catalyst at a pressure of 1 MPa and a temperature of 200°C to obtain an intermediate product. 14 C and 3 The H-substituted olefin is 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

[0057] 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-substituted alkynes and tritium gas 3 H2 reacts to form an intermediate 14 C and 3H-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 the 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 jump from the valence band to the conduction band, forming electron-hole pairs, thereby improving the catalytic activity of the catalyst. The catalytic activity of the Lindela catalyst can be improved by increasing the dislocation density in the palladium catalyst powder. However, too many defects may cause the structure of the catalyst to be unstable and reduce its service life. Due to the uncontrollable nature of the radiation effect, it will be 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 acts as an inhibitor. The catalytic activity of palladium can be controlled by N, preventing excessive addition of tritium and ensuring the purity of the intermediate product. In other words, the Pd x 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, can avoid excessive addition of tritium, and ensure the purity of the intermediate product.

[0058] Preferably, the Lindella catalyst is palladium-barium sulfate (chemical formula: Pd-BaSO4) or palladium-calcium carbonate-lead dioxide (chemical formula: Pd-CaCO3-PbO2). Taking the Lindella 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 can be prepared by using BaCO3 produced by adding H2O, that is, by using the 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

[0059] 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.

[0060] Of course, other types of Lindela catalysts can also be used, as long as they can catalyze 14 C and 3 H-substituted alkynes and tritium gas 3 H2 reaction produces 14 C and 3Without departing from the basic principles of this 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-substituted alkynes and tritium gas 3 H2 reaction produces 14 C and 3 H-substituted olefins can be used.

[0061] In one possible embodiment, the tritium source is a tritium halide 3 HX, where X represents a halogen element, which can be fluorine, chlorine, bromine, etc. The halogen element is chlorine, that is, the tritium source is tritium chloride. 3 Take HCl as an example. In this case, the catalyst in S2 is mercury catalyst, and the intermediate product obtained in S2 is 14 C and 3 H-substituted chloroolefins, that is, in S2, 14 C and 3 H-substituted alkynes and tritium chloride 3 HCl reacts with mercury catalyst at a temperature of 100°C to 200°C to obtain an 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

[0062] 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 this 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-substituted alkynes and tritium gas 3 H2 reaction produces 14 C and 3 H-substituted olefins can be used.

[0063] The tritium source is tritium chloride 3For 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

[0064] As shown in formula 7 above, tritiated water 3 H2O reacts with chlorine gas Cl2 to generate target tritium chloride 3 HCl, and a by-product 3 HClO, the 3 HClO decomposes under light, as shown in formula 8 above. 3 HClO decomposes to produce tritium chloride. 3 HCl, 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.

[0065] In the above formula 7, when using tritium water 3 Preparation of Tritium Chloride from H2O and Chlorine Cl2 3 HCl, to each liter of tritiated water 3 1.1m H2O was introduced into 3 ~2m 3 Chlorine Cl2, which can ensure the progress of the reaction and make full use of tritium water 3 H2O, to increase tritium chloride 3 The yield of HCl will not be too high due to excessive Cl2, 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, those skilled in the art can flexibly choose according to the specific application scenario, as long as the tritium chloride required in S2 can be obtained 3 HCl is enough.

[0066] 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 with14 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 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.

[0067] S3: mixing the intermediate product with three-dimensional graphene and causing the intermediate product to undergo a polymerization reaction 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 polyhaloolefins.

[0068] In S3, after the gas phase stirred bed reactor is purged with inert gas, the intermediate product ( 14 C and 3 H-substituted olefins or 14 C and 3 H-substituted halogenated olefins) are 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-substituted 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 1.5MPa to 3.5MPa to obtain 14 C and 3 H-generation polyolefin or 14 C and 3 H-generation polyhaloolefins. 14 C and 3 H generation polyolefins and 14 C and 3 The tritium substitution rate of H-generation polyhalogenated olefins is relatively high, and using them as flexible isotope sources can meet the high tritium substitution rate requirements of isotope batteries, and, 14 C and3 H generation polyolefins and 14 C and 3 H-generation polyhalogenated olefins also have good flexibility, which can meet the raw material requirements of flexible films that need to be folded and bent in isotope batteries, thereby meeting the flexibility requirements of isotope batteries.

[0069] 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). Polymer molecules obtained by the polymerization reaction when high-energy rays produced by the decay of the radioactive element tritium hit 14 C and 3 H-generation polyolefin or 14 C and 3 The active free radicals generated by H-generation of polyhalogenated olefins will further trigger a chain reaction, leading to the polymerization of molecules. 14 C and 3 H-generation polyolefin or 14 C and 3 The main chain of H-generation polyhalogenated olefins breaks and aggravates the degradation process. There are a large number of π-π bonds in three-dimensional graphene, forming a π-π conjugated system. When the active free radical is close to the conjugated structure, its unpaired electron will interact with the π electron cloud of the conjugated system to form a delocalized state. Through the overlap of the π orbitals, the electrons of the free radical are dispersed to a larger spatial area, significantly reducing its single electron energy, thereby inhibiting its oxidation or chain reaction ability. At the same time, the conjugated system can act as an energy acceptor or donor. Through excited state electron transfer or photoactivation process, the high energy of the free radical can be transferred to the conjugated structure, prompting it to return to the ground state or form a stable form. In addition, three-dimensional graphene usually has a large volume structure, and its large volume structure can hinder the diffusion of free radicals to the active site and reduce the probability of collision with the reactants. In other words, the π-π conjugated system in three-dimensional graphene can efficiently capture and quench active free radicals through the synergistic effect of the triple mechanism of electron delocalization, energy transfer, and steric protection. Moreover, in the polymer molecule 14 C and 3 H-generation polyolefin or 14 C and 3 When the main chain of H-generation polyhalogenated olefin is broken by radiation, three-dimensional graphene can wrap it and maintain its stability. At the same time, 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 3H-generation polyolefin or 14 C and 3 H-generation polyhalogenated olefins and their fracture products are adsorbed on the surface of three-dimensional graphene, and through the adsorption and fixation of polymer molecules and fracture products, they play a supporting role in the structure of the flexible isotope source, 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 improved by 34% to 60%.

[0070] 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.

[0071] In this embodiment, the intermediate product obtained in S2 is 14 C and 3 When H replaces olefins, the reaction in S3 is shown in the following formula 9, which is 14 C and 3 The H-substituted olefin undergoes polymerization to obtain 14 C and 3 The intermediate product obtained in S2 is 14 C and 3 When H is used to substitute halogenated olefins, the reaction occurring in S3 is shown in the following formula 10, which is: 14 C and 3 H-substituted halogenated olefins undergo polymerization to obtain 14 C and 3 H-generation polyhaloolefins. n 14 C 3 H2= 14 C 3 H2→-[ 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

[0072] In one possible embodiment, the tritium source is tritium gas. 3 H2, which means the intermediate product is14 C and 3 When H replaces olefins, the catalyst in S3 is a supported titanium catalyst or a supported Cr catalyst, wherein the supported titanium catalyst can be triethylaluminum-titanium tetrachloride, etc., triethylaluminum-titanium tetrachloride is referred to as ZN catalyst, and the supported Cr catalyst can be chromium trioxide-activated carbon catalyst, etc. Of course, the catalyst in S3 can also be a titanium catalyst such as titanium tetrachloride, or other types of catalysts. Without departing from the basic principles of this application, those skilled in the art can flexibly choose according to the specific application scenario, as long as it can be used. 14 C and 3 H-substituted olefin polymerization 14 C and 3 H-generation polyolefin can be used.

[0073] In one possible embodiment, the tritium source is a tritium halide 3 When HX, it means that 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 choose 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 can be used.

[0074] In one possible embodiment, the molar ratio of 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 reduced proportion of H leads to a decrease in the output power of the resulting 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 improved by 52% compared to without the addition of three-dimensional graphene.

[0075] In one possible implementation, Figure 2 As shown, three-dimensional graphene can be prepared by the following steps:

[0076] S31: Tributylene 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.

[0077] In S31, the molar ratio of triptycene to 4,4'-di-tert-butylbipyridine and bis(diboron) in the catalyst methoxy(cyclooctadiene)iridium dimer is a1:b1:c1:d1, wherein a1 is 0.5-3, b1 is 0.1-0.8, c1 is 1-4, and d1 is 0.1-0.5. Preferably, a1:b1:c1:d1 is 1:0.2:1.7:0.1.

[0078] The reaction in S31 can be carried out using tetrahydrofuran as a solvent. After adding triptycene, raw material 1, raw material 2, and raw material 3 to the solvent, the mixture is stirred at 50° C. to 150° C. and reacted for 8 h to 24 h. For example, the mixture can be stirred at 80° C. and reacted for 10 h to obtain borated triptycene.

[0079] S32: The borated triptycene prepared in S31 is reacted with the raw material 4: brominated graphene under the action of the 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. The light type of the light can be visible light, the illumination time can be 0.3h~2h, and the illumination intensity can be 1000lux~5000lux. Preferably, the illumination time 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 the 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.

[0080] In S32, the molar ratio of triptycene borate, graphene bromide, and 1,1'-bis(diphenylphosphino)ferrocenepalladium 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.

[0081] The reaction in S32 can be carried out in 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 10 to 30 hours, for example, at 55°C for 20 hours, so that the graphene replaces the boric acid in the borated triptycene, and then the target product, three-dimensional graphene, is generated under the catalytic action of light and I2.

[0082] Based on the flexible isotope source prepared above ( 14 C and 3 H-generation polyolefin or 14 C and 3 The flexible isotope source obtained in S3 is calendered using the gap between multiple counter-rotating horizontal rollers at a pressure range of 400 to 800 N. During the calendering process, the flexible isotope source is subjected to both shear and tensile stresses, aligning along the calendering direction to form a flat, flexible isotope film with a thickness of approximately 0.01 mm to 0.5 mm. This flexible isotope film is then cut using a cutting machine (e.g., a PE film cutter) into the required dimensions for a flexible isotope battery, for example, 2 cm x 4 cm. The flexible transducer component of the beta-radiation voltaic cell is then attached and, after bonding and packaging, the flexible isotope battery is completed.

[0083] In order to more clearly illustrate the preparation steps of the flexible isotope source of the present invention, the carbon source is Ba. 14 C2. Tritium source is tritium gas 3 H2 or tritium chloride 3 Taking HCl as an example, and in combination with Examples 1 to 6 and a comparative example, the preparation steps of the flexible isotope source of the present invention and possible implementation methods of the flexible isotope film are specifically described.

[0084] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available.

[0085] Thermal stability: The thermal shrinkage of the flexible isotope film was tested according to the test method of 5.6.3 shrinkage rate in the national standard GB / T 13519-2016, and the thermal stability of the flexible isotope film was evaluated based on the thermal shrinkage rate.

[0086] Example 1:

[0087] Will 3 H2 and oxygen are mixed in a ratio of 1.8:1 and introduced into the reactor. Under the catalytic action of Pt catalyst, the reaction as shown in the above formula 1 is carried out at 200°C to produce tritiated water. 3 H2O.

[0088] 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.

[0089] Triptylene, 4,4'-di-tert-butylbipyridine, and bis(diboron) were added to tetrahydrofuran (THF), and a catalyst (methoxy(cyclooctadiene)iridium dimer) was added to the mixture. The mixture was stirred at 80°C to generate boronated triptycene. The molar ratio of triptycene, 4,4'-di-tert-butylbipyridine, bis(diboron), and methoxy(cyclooctadiene)iridium dimer was 1:0.2:1.7:0.1. The boronated triptycene and brominated graphene were then added to a mixture of water and THF. The catalyst, 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride, was added to the mixture, and the mixture was stirred at 55°C to generate the target product, three-dimensional graphene, by replacing the boric acid in the boronated triptycene. The reaction was then irradiated with visible light at an intensity of 2000 lux and catalyzed by I2. The ratio of triptycene borate, graphene bromide and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride is 1:3.1:0.1.

[0090] will be produced 14 C and 3 H-acetylene and tritium 3 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 above is fed into the reactor. The three-dimensional graphene fed into the reactor is reacted with 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.

[0091] After purging the gas-phase stirred bed reactor with argon, the obtained 14 C and 3 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 shown 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.

[0092] Prepared by the above method 14 C and 3 The yield of H-generation polyethylene was 94.4%. 14 C and 3 The flexible isotope film prepared from H-generation polyethylene has a service life of about 10 years. Compared with the flexible isotope film prepared from a flexible isotope source without the addition of three-dimensional graphene, the thermal shrinkage rate is reduced from 40% to 19.2%, and the thermal stability is increased by 52%.

[0093] Example 2:

[0094] 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-substituted acetylene is 1:3. 14 C and 3 The yield of H-generation polyethylene was 92%. 14 C and 3 The flexible isotope film prepared from H-generation polyethylene has a service life of about 13 years. Compared with the flexible isotope film prepared from a flexible isotope source without the addition of three-dimensional graphene, the thermal shrinkage rate is reduced from 40% to 18%, and the thermal stability is increased by 55%.

[0095] Example 3:

[0096] 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-substituted acetylene is 1:9. 14 C and 3 The yield of H-generation polyethylene is 95%. 14 C and 3 The flexible isotope film prepared from H-generation polyethylene has a service life of about 8 years. Compared with the flexible isotope film prepared from a flexible isotope source without the addition of three-dimensional graphene, the heat shrinkage rate is reduced from 40% to 16%, and the thermal stability is increased by 60%.

[0097] Example 4:

[0098] 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.

[0099] Prepared by the above method 14 C and3 The yield of H-generation polyethylene is 95%. 14 C and 3 The flexible isotope film prepared from H-generation polyethylene has a service life of about 9 years. Compared with the flexible isotope film prepared from a flexible isotope source without the addition of three-dimensional graphene, the thermal shrinkage rate is reduced from 45% to 25%, and the thermal stability is increased by 44.4%.

[0100] Example 5:

[0101] 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.

[0102] Prepared by the above method 14 C and 3 The yield of H-generation polyethylene was 95.6%. 14 C and 3 The flexible isotope film prepared from H-generation polyethylene has a service life of about 8 years. Compared with the flexible isotope film prepared from a flexible isotope source without the addition of three-dimensional graphene, the thermal shrinkage rate is reduced from 47% to 26%, and the thermal stability is increased by 44.7%.

[0103] Example 6:

[0104] 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.

[0105] Then, per liter of tritium water 3 1.1m H2O was introduced into 3 Chlorine gas Cl2 to tritium water 3 Chlorine gas Cl2 is introduced into H2O to produce tritium chloride as shown in the above equations 7 and 8. 3 HCl.

[0106] will be produced 14 C and 3 H-acetylene and tritium chloride 3HCl was fed into the reactor at a molar ratio of 1:1, and 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.

[0107] 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 shown 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.

[0108] Prepared by the above method 14 C and 3 The yield of H-type polyvinyl chloride was 93%. 14 C and 3 The flexible isotope film prepared from H-generation polyethylene has a service life of about 12 years. Compared with the flexible isotope film prepared from a flexible isotope source without the addition of three-dimensional graphene, the thermal shrinkage rate is reduced from 62% to 28%, and the thermal stability is increased by 54.8%.

[0109] Comparative Example:

[0110] Will 3 H2 and oxygen are mixed in a ratio of 1.8:1 and introduced into the reactor. Under the catalytic action of Pt catalyst, the reaction as shown in the above formula 1 is carried out at 200°C to produce tritiated water. 3 H2O.

[0111] 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.

[0112] will be produced 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.

[0113] After purging the gas-phase stirred bed reactor with argon, the obtained 14 C and 3 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 shown 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.

[0114] Prepared by the above method 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.

[0115] It should be noted that, in the above embodiments, although the intermediate product is 14 C and 3 H-generation ethylene or 14 C and 3 H-generation vinyl chloride, flexible isotope source 14 C and 3 H-generation polyethylene or 14 C and 3 The 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 substitution 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.

[0116] Although the various steps in the above embodiment are described in the above-mentioned order, those skilled in the art will 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.

[0117] Thus far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it will be readily understood by those skilled in the art that the scope of protection of the present invention is obviously not limited to these specific embodiments. Without departing from the principles of the present invention, those skilled in the art may make equivalent changes or substitutions to the relevant technical features, and the technical solutions after such changes or substitutions will fall within the scope of protection of the present invention.

Claims

1. An isotope battery coupling carbon 14 and tritium radioactive sources, characterized in that: The isotope battery includes a flexible isotope film, which is prepared from a flexible isotope source. The flexible isotope source is prepared by the following steps: S1: Acquisition 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 polyhaloolefins.

2. The isotope battery coupled with carbon 14 and tritium radioactive sources according to claim 1, characterized in that: The tritium source is tritium gas 3 When H2 is used, the catalyst in S2 is a Lindela catalyst.

3. The isotope battery coupled with carbon 14 and tritium radioactive sources 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 isotope battery coupled with carbon 14 and tritium radioactive sources according to claim 2, characterized in that: The catalyst in S3 is a supported titanium catalyst or a supported Cr catalyst.

5. The isotope battery coupled with carbon 14 and tritium radioactive sources 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 isotope battery coupled with carbon 14 and tritium radioactive sources according to any one of claims 1 to 5, characterized in that: described 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 react to obtain tritium water 3 H2O; S12: the tritium water 3 H2O is mixed with the carbon source in a second ratio and reacts to obtain the 14 C and 3 H-substituted alkynes.

7. The isotope battery coupled with carbon 14 and tritium radioactive sources 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 isotope battery coupled with carbon 14 and tritium radioactive sources according to claim 7, characterized in that: The reaction in S11 is carried out under the catalysis of a Pt-based catalyst or a Pd-based catalyst.

9. The isotope battery coupled with carbon 14 and tritium radioactive sources according to claim 6, characterized in that: The steps also include: At the same time or after the reaction in S12 occurs, the tritiated water 3 Carbon dioxide CO2 is introduced into the mixture of H2O and the carbon source to recover the tritiated water. 3 H2O.

10. The isotope battery coupled with a carbon-14 and tritium radioactive source 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 isotope battery coupled with a carbon-14 and tritium radioactive source 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.

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