Method for preparing palladium membrane and palladium membrane

Abstract

The invention relates to the technical field of hydrogen purification, and discloses a palladium membrane and a preparation method thereof.The method comprises the steps that irradiation treatment is conducted on a palladium-based membrane to obtain the palladium membrane, irradiation ions are adopted to conduct irradiation on at least one surface of the palladium-based membrane in the irradiation treatment, the ion implantation dosage is 1 * 10 < 17 > ions / cm < 2 >-8 * 10 < 17 > ions / cm < 2 >, and the energy of the irradiation ions is 15 keV-2 MeV. The palladium membrane provided by the invention has the advantages of high permeation flux, excellent isotope separation effect, short activation time and stable long-term operation stability.

Description

Technical Field

[0001] The present application relates to the technical field of hydrogen purification, and in particular to a method for preparing a palladium membrane and a palladium membrane. Background Art

[0002] The purification and separation of hydrogen isotopes is a critical step in the fuel cycle of fusion energy devices, involving the efficient recovery and purification of fusion fuels such as deuterium and tritium. Palladium (Pd) membranes exhibit differential permeability to different hydrogen isotopes (i.e., the hydrogen isotope effect), enabling the separation of hydrogen isotopes. They are selectively permeable to hydrogen and block the passage of gases other than hydrogen through the membrane layer. Therefore, Pd membranes are widely used in hydrogen isotope separation devices as hydrogen isotope purification membranes. For example, in fusion reactor fuel systems, Pd membranes can be used to extract hydrogen isotopes from hydrogen containing impurities (such as helium and residual gases), offering important applications in fusion reactor fuel cycles and tritium extraction systems.

[0003] In existing technologies, hydrogen isotopes possess unique solubility and diffusion properties in palladium metal, but their permeation rate is relatively slow due to the transition from gaseous to solid and back to gaseous states along the thickness of the palladium membrane. To improve the hydrogen permeability and selectivity of palladium membranes, researchers have attempted methods such as reducing the membrane thickness and fabricating ultrathin palladium membranes on substrates. Thinning the palladium membrane does improve the hydrogen permeation rate, but when the membrane thickness falls below a critical value (<10µm), the reaction of hydrogen isotopes on the membrane surface becomes the limiting factor for the permeation rate. This reduces the effectiveness of reducing the palladium membrane thickness on increasing the hydrogen permeation rate and also results in a decrease in the membrane's mechanical properties, making the membrane susceptible to rupture during repeated cycles. While fabricating ultrathin palladium membranes using polymer matrices or porous inorganic substrates can reduce the risk of perforation, these membranes often exhibit pinhole defects. Helium can pass through the membrane through these pinholes, affecting hydrogen-helium selectivity. In addition, existing technologies make it difficult to control the microstructure of palladium membranes and are unable to fundamentally break through the upper limit of the trade-off between hydrogen / helium selectivity, isotope separation effect, and permeation rate.

[0004] It should be noted that the above statements are only used to provide background technical information related to this application and do not necessarily constitute prior art. Summary of the Invention

[0005] In a first aspect of the present application, a method for preparing a palladium film is proposed, comprising: irradiating a palladium-based film to obtain a palladium film, wherein the irradiation treatment is to irradiate at least one surface of the palladium-based film with irradiating ions, and the ion implantation dose is 1×10 17 ions / cm 2 ~8×10 17 ions / cm 2, the energy of the irradiated ions is 15keV~2MeV.

[0006] In some embodiments, the irradiating ions include He + and at least one of other rare gas ions, wherein the other rare gas ions include Ar + .

[0007] In some embodiments, the He + The ion implantation dose of the irradiation treatment is 6×10 17 ions / cm 2 ~7×10 17 ions / cm 2 .

[0008] In some embodiments, the palladium-based film includes at least one of a palladium metal film and a palladium alloy film, wherein the palladium metal purity of the palladium metal film is 99.99%, and the palladium alloy film includes at least one of a Pd-Ag alloy film and a Pd-Cu alloy film.

[0009] In some embodiments, the palladium-based film has a thickness of 82 μm.

[0010] In some embodiments, the irradiation treatment is performed at room temperature, which is 22°C to 28°C.

[0011] In the second aspect of the present application, a palladium membrane is proposed. In the temperature range of 573K~723K, the hydrogen isotope permeation rate of the palladium membrane is 3.2×10 -2 mol·m -2 ·s -1 ~7.7×10 -2 mol·m -2 ·s -1 .

[0012] In some embodiments, the palladium film is prepared using the method proposed in this application.

[0013] In a third aspect of the present application, the present application proposes a method for separating hydrogen isotopes, using the palladium membrane proposed in the present application, or a palladium membrane prepared by the method proposed in the present application.

[0014] In the fourth aspect of the present application, the present application proposes a hydrogen isotope, which is obtained using the method for separating hydrogen isotopes proposed in the present application.

[0015] The beneficial effects of the technical solution proposed in this application include at least: The method proposed in this application uses ion irradiation with specific parameters as a technical means to modify the surface of palladium membranes. This simple and controllable method can produce palladium membranes with high hydrogen isotope selectivity and permeability without changing the membrane material composition. This method also reduces the activation time required for stable operation of the palladium membrane, thereby improving the separation efficiency and stability of the palladium membrane. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which: Figure 1 The instantaneous permeation flux test results of the permeation activation experiment of the palladium-based membrane in this application with different hydrogen isotope gases (H2, D2, H2+D2 (1:1)); Figure 2 The instantaneous permeation flux test results of the permeation activation experiment of the palladium membrane prepared in Example 2 of the present application using different hydrogen isotope gases (H2, D2, H2+D2 (1:1)); Figure 3 The instantaneous permeation flux test results of the palladium membranes in Examples 1 and 2 of the present application and the palladium-based membrane in the comparative example after permeation activation experiments with different hydrogen isotope gases (H2, D2, H2+D2 (1:1)); Figure 4 The H2 gas permeability of the palladium membrane in Example 1 and Example 2 and the palladium-based membrane in the comparative example was measured at 300°C to 450°C; Figure 5 The D2 gas permeability of the palladium membrane in Example 1 and Example 2 and the palladium-based membrane in the comparative example was measured at 300°C to 450°C; Figure 6 The 1:1 H2+D2 gas permeability of the palladium membrane in Example 1 and Example 2 and the palladium-based membrane in the comparative example was measured at 300°C to 450°C. Figure 7 These are the measurement results of the hydrogen isotope separation factors of the palladium membranes in Examples 1 and 2 of the present application and the palladium-based membrane in the comparative example at 300°C~450°C. DETAILED DESCRIPTION

[0017] The following describes the embodiments of the present application in detail. Examples of the embodiments are shown in the accompanying drawings, but unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of substantially identical structures may be omitted. This is to avoid unnecessary lengthiness in the following description and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0018] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by technicians in the technical field to which this application belongs; the terms used in this application are only for the purpose of describing specific embodiments and are not intended to limit this application; unless otherwise specified, the numerical values ​​of the various parameters mentioned in this application can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of this application).

[0019] The terms "include" and "have" in the description and claims of this application and any variations thereof are open expressions, that is, including the contents specified in this application but not excluding other contents.

[0020] In the description of this application, all numbers disclosed herein are approximate, regardless of whether the word "about" or "approximately" is used. The value of each number may vary by less than 10% or by a reasonable difference considered by a person skilled in the art, such as 1%, 2%, 3%, 4% or 5%.

[0021] The "range" disclosed in this application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The range defined in this way can be inclusive or exclusive of end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, wherein a and b are both real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, stating that a parameter is an integer ≥ 2 is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0022] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0023] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0024] The method of the present application adopts the self-supporting metal palladium film rolled from metal raw materials. Compared with the palladium film composited with materials such as palladium and polymers, the self-supporting metal palladium film has extremely high screening properties for hydrogen and its isotopes in a mixed gas containing impurities such as helium, and the isotope separation effect is significant. However, in the hydrogen isotope separation process, the hydrogen / deuterium selectivity of the existing self-supporting palladium film is greatly affected by the surface state. When the surface state is poor, the separation coefficient of the palladium film is on the low side, and hydrogen isotopes cannot be efficiently purified. During the service process, the surface of the palladium film is easily adsorbed with impurities such as carbon and oxygen, resulting in a decrease in the initial permeability of the palladium film. It is necessary to increase high-temperature pretreatment or multiple cycles before achieving stable performance. Long-term pretreatment or activation treatment before stable operation not only reduces the working efficiency of the palladium film, but also increases operating costs.

[0025] The method proposed in this application is used to prepare a palladium membrane, so that the palladium membrane has a certain mechanical strength while improving the selective separation performance of the palladium membrane for hydrogen isotopes and shortening the activation treatment time before the palladium membrane stabilizes.

[0026] In a first aspect of the present application, a method for preparing a palladium film is proposed, comprising: irradiating a palladium-based film to obtain a palladium film, wherein the irradiation treatment is to irradiate at least one surface of the palladium-based film with irradiating ions, and the ion implantation dose is 1×10 17 ions / cm 2 ~8×10 17 ions / cm 2 , the energy of the irradiated ions is 15keV~2MeV.

[0027] The method for preparing a palladium membrane proposed in the present application performs ion irradiation treatment with controlled parameters on the surface of a rolled palladium-based membrane, so that the surface of the palladium-based membrane is efficiently activated, thereby changing the desorption / recombination coefficient of hydrogen isotopes at the gas-solid interface of the palladium-based membrane, and improving the gas-solid conversion rate of hydrogen isotopes at the gas-solid interface, so as to prepare a palladium membrane with significantly better hydrogen isotope permeation and separation performance.

[0028] In some embodiments, the palladium-based membrane is a pure palladium flat membrane. In this application, expressions such as original palladium membrane, unirradiated palladium membrane, original membrane, and untreated palladium membrane all refer to palladium-based membranes that have not been treated by the method for preparing a palladium membrane of this application.

[0029] As an example, the ion implantation dose is 1×10 17 ions / cm 2 , 1.5×10 17 ions / cm 2 , 2×10 17 ions / cm 2 , 2.5×10 17 ions / cm2 , 3×10 17 ions / cm 2 , 3.5×10 17 ions / cm 2 , 4×10 17 ions / cm 2 , 4.5×10 17 ions / cm 2 , 4×10 17 ions / cm 2 , 4.5×10 17 ions / cm 2 , 5×10 17 ions / cm 2 , 5.5×10 17 ions / cm 2 , 6×10 17 ions / cm 2 , 6.5×10 17 ions / cm 2 , 7×10 17 ions / cm 2 , 7.5×10 17 ions / cm 2 , 8×10 17 ions / cm 2 .

[0030] As an example, the energy of the irradiated ions is 15 keV, 50 keV, 100 keV, 200 keV, 300 keV, 400 keV, 500 keV, 600 keV, 700 keV, 800 keV, 900 keV, 1 MeV, 1.5 MeV, or 2 MeV.

[0031] As an example, a palladium-based membrane is placed in a vacuum ion irradiation apparatus. An ion accelerator is used to control the energy and total amount of irradiated ions. Irradiated ions within the aforementioned energy range are introduced in the form of an ion beam to uniformly irradiate at least one surface of the palladium-based membrane. Irradiation can be performed on either side of the palladium-based membrane first, followed by irradiation on the other side, thereby irradiating both sides of the membrane. During the irradiation process, when either side of the palladium-based membrane is bombarded by irradiated ions, collision displacement and electron excitation effects occur between the irradiated ions and the palladium metal in the palladium-based membrane, resulting in a certain density of dislocations and defects near the surface of the palladium-based membrane. This promotes a microstructure transition from a fully polycrystalline to a nanocrystalline / partially crystalline state within the palladium-based membrane. This change in crystal structure helps reduce the mass transfer resistance of hydrogen isotopes on the palladium membrane surface, making the process of hydrogen isotope separation through the palladium membrane more similar to a diffusion process. Furthermore, the bombardment and sputtering of the palladium membrane surface by irradiated ions can remove carbon and oxygen impurity layers on the membrane surface, achieving in-situ cleaning of the membrane. Thus, through a simple and controllable process, this method improves the initial permeability of the palladium membrane without changing the membrane material composition, reduces the activation time required for stable operation, and improves the separation efficiency and stability of the palladium membrane.

[0032] In some embodiments, the irradiation treatment is performed at room temperature, which is 22°C to 28°C.

[0033] As an example, the room temperature is 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, or 28°C.

[0034] In some embodiments, the He + The ion implantation dose of the irradiation treatment is 6×10 17 ions / cm 2 ~7×10 17 ions / cm 2 Within the aforementioned irradiation treatment range, the helium ion implantation dose is controlled by an ion accelerator, ensuring relatively uniform irradiation of the palladium-based film and ensuring that the helium ions impact the palladium-based film at a specific depth. This results in a deep crystal structure change from the surface of the palladium film inward, facilitating the preparation of a palladium film with high stability.

[0035] As an example, the ion implantation dose of the irradiation treatment is 6×10 17 ions / cm 2 , 6.1×10 17 ions / cm 2 , 6.2×10 17 ions / cm 2 , 6.3×10 17 ions / cm2 , 6.4×10 17 ions / cm 2 , 6.5×10 17 ions / cm 2 , 6.6×10 17 ions / cm 2 , 6.7×10 17 ions / cm 2 , 6.8×10 17 ions / cm 2 , 6.9×10 17 ions / cm 2 , 7×10 17 ions / cm 2 .

[0036] In some embodiments, the irradiating ions include He + and at least one of other rare gas ions, wherein the other rare gas ions include Ar + The ion size of helium ions and argon ions is similar to that of hydrogen isotope gas. Therefore, the palladium membrane can be irradiated with the aforementioned irradiating ions, which can effectively activate the surface of the palladium-based membrane and optimize the permeation process of hydrogen isotope gas.

[0037] In some embodiments, the palladium-based membrane comprises at least one of a palladium metal membrane and a palladium alloy membrane, wherein the palladium metal purity of the palladium metal membrane is 99.99%. The palladium alloy membrane comprises at least one of a Pd-Ag alloy membrane and a Pd-Cu alloy membrane. Pd-Ag alloy membranes and Pd-Cu alloy membranes have good mechanical strength and anti-poisoning properties. The palladium-based membranes of the aforementioned compositions have excellent hydrogen isotope and surface anti-poisoning properties, thereby facilitating the preparation of palladium membranes with high separation efficiency and stability.

[0038] In some embodiments, the palladium-based membrane has a thickness of 82 μm. The palladium-based membrane comprises a self-supporting palladium membrane made from high-purity palladium metal through a rolling process, with a thickness within the aforementioned range. The palladium-based membrane has a certain hydrogen isotope selectivity and permeation flux, and the membrane structure has a certain mechanical strength, which is conducive to assembly and irradiation processing.

[0039] The surface of the palladium film treated with irradiation has been basically free of oxide and carbon contamination, and is in a clean metallic state.

[0040] In some embodiments, the method further comprises: cleaning the palladium-based film before the irradiation treatment.

[0041] As an example, the cleaning process includes ultrasonic cleaning for 2 minutes using an alcohol solvent (such as acetone (purity 99.99%)), followed by rinsing with clean water and drying.

[0042] In the second aspect of the present application, a palladium membrane is proposed. In the temperature range of 573K~723K, the hydrogen isotope permeation rate of the palladium membrane is 3.2×10 -2 mol·m -2 ·s -1 ~7.7×10 -2 mol·m -2 ·s -1 As a result, the palladium membrane proposed in this application can achieve a high hydrogen isotope permeation rate within a relatively low temperature range. The aforementioned palladium membrane can be used in service environments such as large-scale fusion projects and the hydrogen energy industry to purify hydrogen, achieving high hydrogen purification efficiency. Furthermore, the palladium membrane has low operating temperature requirements, which helps improve the stability of the hydrogen purification system.

[0043] As an example, the hydrogen isotope permeation rate of the palladium membrane is 3.2×10 -2 mol·m -2 ·s -1 , 3.7×10 - 2 mol·m -2 ·s -1 , 4.2×10 -2 mol·m -2 ·s -1 , 4.7×10 -2 mol·m -2 ·s -1 , 5.2×10 -2 mol·m -2 ·s -1 , 5.7×10 -2 mol·m -2 ·s -1 , 6.2×10 -2 mol·m -2 ·s -1 , 6.7×10 -2 mol·m -2 ·s -1 , 7.2×10 -2 mol·m -2 ·s -1 , 7.7×10 -2 mol·m -2 ·s -1 .

[0044] In some embodiments, the palladium membrane is prepared using the method proposed in this application. Compared to conventional unmodified palladium membranes, the membrane retains its original mechanical strength while significantly improving hydrogen isotope permeation rate and separation performance, while also reducing activation time for engineering applications.

[0045] In a third aspect of the present application, the present application proposes a method for separating hydrogen isotopes, using the palladium membrane proposed in the present application, or a palladium membrane prepared by the method proposed in the present application.

[0046] In the fourth aspect of the present application, the present application proposes a hydrogen isotope, which is obtained using the method for separating hydrogen isotopes proposed in the present application.

[0047] The present invention will be described below by way of specific examples. It should be noted that the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. Where specific techniques or conditions are not specified in the examples, they are determined according to the techniques or conditions described in the literature in this area or according to the product specifications. Reagents or instruments not specified by manufacturer are all commercially available conventional products.

[0048] Example 1 A palladium-based film with a thickness of about 82µm and a purity of 99.99% was placed in a vacuum chamber of an ion irradiation treatment device. + Ion beam irradiation. + The ions were generated by an ion accelerator with an energy of 2 MeV. The acceleration current and irradiation time were controlled to achieve a total injection dose of approximately 6.4 × 10 17 ions / cm 2 .

[0049] Example 2 A palladium-based film with a thickness of about 82µm and a purity of 99.99% was placed in a vacuum chamber of an ion irradiation treatment device. + It is irradiated by ion beam. + The ions were generated by an ion accelerator with an energy of 15 keV. The acceleration current and irradiation time were controlled to achieve a total injection dose of about 1 × 10 17 ions / cm 2 .

[0050] Comparative Example It uses 82µm pure palladium flat membrane with a purity of 99.99%.

[0051] Test method: 1. Hydrogen isotope flux test Multiple permeation experiments were carried out on the unirradiated original palladium membrane and the He ion irradiated palladium membrane at 723K and a front-end permeation pressure of 300kPa using H2, D2, and H2+D2 (1:1) mixed gas, and the back-end permeation flux-time variation curve of each activation process was recorded. When the difference between the permeation flux-time variation curves obtained from two adjacent permeation experiments was less than 5%, the activation was considered successful and the palladium membrane reached a stable permeation state. The number of repeated experiments required from the initial permeation to the stable permeation was the number of activations.

[0052] 2. Separation performance test of hydrogen-deuterium mixture The hydrogen isotope separation coefficients of the palladium membranes prepared in the comparative example and Example 1 were compared using mass spectrometry. The changes in gas composition before and after the mixed hydrogen isotope gas passed through the palladium membrane were quantitatively calculated. The permeation separation coefficient α of the palladium membrane was defined as the ratio of the light to heavy isotope abundance ratio at the back end of the permeation to the light to heavy isotope abundance ratio at the front end of the permeation. The following relationship can be obtained, where C 轻 is the abundance of light isotopes, C 重 is the heavy isotope abundance:

[0053] Test results: The hydrogen isotope permeation flux test results are shown in Table 1.

[0054] Table 1 Comparison of permeation flux changes

[0055] refer to Figure 1 、 2 , 3 and Table 1, He + The hydrogen flux of the irradiated palladium membrane is increased by about 35% compared with the unirradiated palladium membrane, the deuterium flux is increased by about 50%, and the total permeation of the equal ratio hydrogen / deuterium mixture is increased by about 52%.

[0056] refer to Figure 1 、 2 , 3 and Table 1 show that after He ions and Ar + The permeation flux of the irradiated palladium membrane in the initial permeation and steady-state permeation is much higher than that of the unirradiated palladium membrane. + Corresponding test results for irradiated palladium membranes. Irradiated palladium membranes exhibit more stable and reliable performance over long-term operation. In contrast, unirradiated palladium membranes exhibited gradual fluctuations in permeability during the initial few runs. Irradiation removes surface factors that can cause membrane instability, making the membrane's permeability process more controllable.

[0057] He ion-irradiated palladium membranes significantly shorten the activation process before commissioning. The irradiated palladium membranes achieve stable permeation flux after just a few runs, eliminating the need for lengthy preconditioning. Table 2 compares the number of activation cycles required for different palladium membranes to achieve stability under different test gases. He ion-irradiated palladium membranes achieve a more rapid steady-state permeation, improving system availability and operational efficiency.

[0058] Table 2 The number of activation times required for the palladium membrane to reach stability under different test gases

[0059] refer to Figure 4-Figure 6 The permeabilities of the palladium membranes obtained by irradiation treatment in Example 1 and Example 2 measured under different hydrogen isotope gases and operating temperatures are higher than those of the untreated palladium-based membranes.

[0060] Separation performance test results of hydrogen-deuterium mixture: refer to Figure 7 The separation coefficient of the He ion-irradiated palladium membrane in the temperature range of 573K to 723K is higher than that of the unirradiated palladium membrane, indicating that the membrane's hydrogen-deuterium separation efficiency is improved after He ion modification. The palladium membrane treated with He ions can achieve higher hydrogen isotope separation efficiency than traditional palladium membranes at temperatures of 673K ​​to 723K, which helps improve the effectiveness of hydrogen isotope purification.

[0061] In the description of this application, "A and / or B" may include the case of A alone, the case of B alone, or any of the cases of A and B, where A and B are only used for example, and may be any technical feature connected by "and / or" in this application.

[0062] In this application, the writing order of each step does not mean a strict execution order and does not constitute any limitation on the implementation process. The specific execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of this application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or steps (b) and (a) performed sequentially. For example, it is mentioned that the method may also include step (c), indicating that step (c) can be added to the method in any order. For example, the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0063] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A method for preparing a palladium film, characterized in that: include: The palladium-based film is irradiated to obtain a palladium film, wherein: The irradiation treatment is to irradiate at least one surface of the palladium-based film with irradiated ions, and the ion implantation dose is 1×10 17 ions / cm 2 ~8×10 17 ions / cm 2 , the energy of the irradiated ions is 15keV~2MeV.

2. The method according to claim 1, characterized in that The irradiating ions include He + and at least one of other rare gas ions, wherein the other rare gas ions include Ar + .

3. The method according to claim 2, characterized in that Using the He + The ion implantation dose of the irradiation treatment is 6×10 17 ions / cm 2 ~7×10 17 ions / cm 2 .

4. The method according to claim 1, wherein The palladium-based film includes at least one of a palladium metal film and a palladium alloy film, wherein the palladium metal purity of the palladium metal film is 99.99%, and the palladium alloy film includes at least one of a Pd-Ag alloy film and a Pd-Cu alloy film.

5. The method according to claim 4, characterized in that The thickness of the palladium-based film is 82 μm.

6. The method according to claim 1, characterized in that The irradiation treatment is performed at room temperature, which is 22° C. to 28° C.

7. A palladium membrane, characterized in that In the temperature range of 573K~723K, the hydrogen isotope permeation rate of the palladium membrane is 3.2×10 -2 mol·m -2 ·s -1 ~7.7×10 -2 mol·m -2 ·s -1 .

8. The palladium membrane according to claim 7, characterized in that The palladium film is prepared by the method according to any one of claims 1 to 6.

9. A method for separating hydrogen isotopes, characterized in that: A palladium membrane according to claim 7 or 8, or a palladium membrane prepared by the method according to any one of claims 1 to 6.

10. A hydrogen isotope, characterized in that The method according to claim 9 is used to separate the obtained product.

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