Method for preparing palladium film and palladium film

Abstract

The present application relates to the technical field of hydrogen purification, and discloses a palladium film and a preparation method thereof, wherein the method comprises: 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 15 keV to 2 MeV. The palladium membrane proposed in this application has a high permeation flux, a good isotope separation effect, a short activation time, and stability for long-term operation.

Description

Technical Field

[0001] This application relates to the field of hydrogen purification technology, specifically to a method for preparing palladium membranes and palladium membranes. Background Technology

[0002] The purification and separation of hydrogen isotopes is a crucial 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 different permeability to different hydrogen isotopes (i.e., the hydrogen isotope effect), enabling selective hydrogen permeability for hydrogen separation while blocking other gases from passing through the membrane. Therefore, palladium membranes are widely used in hydrogen isotope separation devices as hydrogen isotope purification membranes. For example, in fusion reactor fuel systems, palladium membranes can be used to extract hydrogen isotopes from hydrogen containing impurity gases (such as helium and residual gases), demonstrating significant application value in fusion reactor fuel cycles and tritium extraction systems.

[0003] In existing technologies, hydrogen isotopes possess unique dissolution and diffusion characteristics in palladium metal. However, the permeation rate of hydrogen isotope gas is relatively slow due to the gas-to-solid-to-gas transition of hydrogen isotopes along the thickness direction of the palladium film. To improve the hydrogen permeability and selectivity of palladium films, researchers have attempted methods such as reducing film thickness and preparing ultrathin palladium films on substrates. While thinning the palladium film does increase the hydrogen permeation rate, when the film thickness is less than a critical value (<10µm), the reaction process of hydrogen isotopes on the palladium film surface becomes a limiting factor for the permeation rate. This limits the effect of reducing the film thickness on improving the hydrogen permeation rate and causes a decrease in the mechanical properties of the palladium film, making it prone to rupture under repeated cycles. While using polymer or porous inorganic substrates to support the preparation of ultrathin palladium films can reduce perforation and rupture, these methods often result in pinhole defects. Helium gas can pass through these pinholes, affecting the hydrogen-helium selectivity. Furthermore, existing technologies struggle to control the microstructure of palladium films, making it impossible to fundamentally overcome 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 information related to this application and do not necessarily constitute prior art. Summary of the Invention

[0005] In a first aspect of this application, a method for preparing a palladium film is provided, comprising: irradiating a palladium-based film to obtain a palladium film, wherein the irradiation treatment is performed by irradiating at least one surface of the palladium-based film with irradiated ions, and the ion implantation dose is 1 × 10⁻⁶. 17 ions / cm 2 ~8×10 17 ions / cm 2The energy of the irradiated ions is 15 keV to 2 MeV.

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

[0007] In some embodiments, the He + The irradiation treatment is performed, wherein the ion implantation dose of the irradiation treatment is 6 × 10⁻⁶. 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 thickness of the palladium-based film is 82 μm.

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

[0011] In a second aspect, this application discloses a palladium film having a hydrogen isotope permeation rate of 3.2 × 10⁻⁶ within a temperature range of 573 K to 723 K. -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 this application, a method for separating hydrogen isotopes is proposed, using a palladium membrane proposed in this application, or a palladium membrane prepared using the method proposed in this application.

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

[0015] The beneficial effects of the technical solution proposed in this application include at least the following:

[0016] The method proposed in this application employs irradiation treatment with specific parameters of irradiated ions as a technical means to modify the surface of palladium membranes. The method is simple and controllable, and can prepare palladium membranes with high hydrogen isotope selectivity and permeability without altering the membrane material composition. It reduces the activation time required before stable operation of the palladium membrane, thereby improving the separation efficiency and stability of the palladium membrane. Attached Figure Description

[0017] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0018] 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));

[0019] Figure 2 The instantaneous permeation flux test results of the palladium membrane prepared in Example 2 of this application under different hydrogen isotope gases (H2, D2, H2+D2(1:1)) for permeation activation experiment;

[0020] Figure 3 The results of the instantaneous permeation flux test of the palladium-based membrane in Example 1 of this application after permeation activation experiment with different hydrogen isotope gases (H2, D2, H2+D2(1:1));

[0021] Figure 4 The H2 gas permeability was measured at 300℃~450℃ for the palladium membranes in Examples 1 and 2 of this application and the palladium-based membranes in the comparative examples.

[0022] Figure 5 The permeability of D2 gas in the palladium membranes of Examples 1 and 2 of this application and the palladium-based membranes in the comparative examples was measured at 300℃~450℃.

[0023] Figure 6 The H2+D2 gas permeability of the palladium membrane in Examples 1 and 2 of this application and the palladium-based membrane in the comparative example were measured at a 1:1 ratio at 300℃~450℃.

[0024] Figure 7 The results show the hydrogen isotope separation factor measurements of different palladium films at temperatures ranging from 300°C to 450°C in Examples 1 and 2 of this application and in the comparative example. Detailed Implementation

[0025] The embodiments of this application are described in detail below, with examples of these embodiments shown in the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0026] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used in this application is for the purpose of describing particular embodiments only and is not intended to limit this application; unless otherwise stated, the values ​​of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this application).

[0027] The terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are open-ended expressions, meaning they include what is specified in this application but do not exclude other aspects.

[0028] In the description of this application, all figures disclosed herein, whether or not the words "approximately" or "about" are used, are approximate values. Each figure may vary by less than 10% or by a difference that is considered reasonable by one of the art, such as 1%, 2%, 3%, 4%, or 5%.

[0029] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0030] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0031] 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.

[0032] The method in this application employs a self-supporting palladium membrane rolled from metallic raw materials. Compared to palladium membranes made by combining palladium with polymers and other materials, the self-supporting palladium membrane exhibits extremely high selectivity for hydrogen and its isotopes in mixed gases containing impurities such as helium, and the isotope separation effect is significant. However, in the hydrogen isotope separation process, the hydrogen / deuterium selectivity of existing self-supporting palladium membranes is greatly affected by the surface condition. Under poor surface conditions, the separation coefficient of the palladium membrane is low, and it cannot efficiently purify hydrogen isotopes. During service, the surface of the palladium membrane easily adsorbs impurities such as carbon and oxygen, leading to a decrease in the initial permeation performance of the palladium membrane. High-temperature pretreatment or multiple cycles are required to achieve stable operation. The long-term pretreatment or activation treatment before stable operation not only reduces the working efficiency of the palladium membrane but also increases operating costs.

[0033] The method proposed in this application prepares palladium membranes, which improve the selective separation performance of palladium membranes for hydrogen isotopes while maintaining a certain mechanical strength, and shorten the activation treatment time before the palladium membrane can operate stably.

[0034] In a first aspect of this application, a method for preparing a palladium film is provided, comprising: irradiating a palladium-based film to obtain a palladium film, wherein the irradiation treatment is performed by irradiating at least one surface of the palladium-based film with irradiated ions, and the ion implantation dose is 1 × 10⁻⁶. 17 ions / cm 2 ~8×10 17 ions / cm 2 The energy of the irradiated ions is 15 keV to 2 MeV.

[0035] The method for preparing palladium membranes proposed in this application involves subjecting the surface of a rolled palladium-based membrane to controlled-parameter ion irradiation treatment, thereby activating the surface of the palladium-based membrane efficiently. This alters the hydrogen isotope desorption / recombination coefficient at the gas-solid interface of the palladium-based membrane, increasing the gas-solid conversion rate of hydrogen isotopes at the gas-solid interface, and thus preparing a palladium membrane with significantly superior hydrogen isotope permeation and separation performance.

[0036] In some embodiments, the palladium-based film is a pure palladium sheet film. In this application, the terms "raw palladium film," "unirradiated palladium film," "raw film," and "untreated palladium film" all refer to palladium-based films that have not been treated by the palladium film preparation method of this application.

[0037] As an example, the ion implantation dose is 1×10⁻⁶. 17 ions / cm 2 1.5×10 17 ions / cm 2 2×10 17 ions / cm 2 2.5×10 17 ions / cm 2 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 17ions / cm 2 7×10 17 ions / cm 2 7.5×10 17 ions / cm 2 8×10 17 ions / cm 2 .

[0038] As an example, the irradiated ions have energies of 15keV, 50keV, 100keV, 200keV, 300keV, 400keV, 500keV, 600keV, 700keV, 800keV, 900keV, 1MeV, 1.5MeV, and 2MeV.

[0039] As an example, a palladium-based film is placed in a vacuum ion irradiation device. Using an ion accelerator, the energy and total amount of irradiated ions are controlled, introducing irradiated ions with the aforementioned energy range in the form of an ion beam to uniformly irradiate at least one surface of the palladium-based film. One side of the palladium-based film can be irradiated first, followed by the other side, to irradiate both sides of the film. During the irradiation process where either side of the palladium-based film is bombarded by irradiated ions, collision displacement and electronic excitation effects occur between the irradiated ions and the palladium metal in the film. This results in a certain density of dislocations and defects near the surface of the palladium-based film, promoting a transformation of the microstructure from fully polycrystalline to nanocrystalline / partially crystallized states. This change in crystal structure helps reduce the mass transfer resistance of hydrogen isotopes on the surface of the palladium film, making the isotope separation process through the palladium film more similar to a diffusion process. Furthermore, irradiated ions bombarding and sputtering the surface of the palladium-based membrane can remove the carbon and oxygen impurity layer on the surface, achieving in-situ cleaning of the palladium-based membrane. Therefore, this method, through a simple and controllable process, improves the initial permeation performance of the palladium membrane without altering the membrane material composition, reduces the activation time before stable operation, and enhances the separation efficiency and stability of the palladium membrane.

[0040] In some embodiments, the irradiation treatment is performed at room temperature, which is 22°C to 28°C.

[0041] As an example, the room temperature is 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, or 28℃.

[0042] In some embodiments, the He + The irradiation treatment is performed, wherein the ion implantation dose of the irradiation treatment is 6 × 10⁻⁶. 17 ions / cm 2 ~7×10 17 ions / cm 2Within the aforementioned irradiation treatment range, the helium ion implantation dose is controlled using an ion accelerator to ensure relatively uniform irradiation of the palladium-based film and to achieve a certain depth of incident collision between helium ions and the palladium-based film. This allows for the formation of a certain depth of crystal structure variation from the surface of the palladium film inwards, which is beneficial for preparing palladium films with high stability.

[0043] As an example, the ion implantation dose for the irradiation treatment is 6 × 10⁻⁶. 17 ions / cm 2 6.1×10 17 ions / cm 2 6.2×10 17 ions / cm 2 6.3×10 17 ions / cm 2 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 .

[0044] In some embodiments, the irradiated ions include He + At least one of other rare gas ions, wherein the other rare gas ions include Ar. + The ion sizes of helium and argon ions are similar to those of hydrogen isotope gases. Therefore, irradiating the palladium film with the aforementioned irradiated ions can efficiently activate the surface of the palladium-based film and optimize the permeation process of hydrogen isotope gases.

[0045] 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%, and 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 possess good mechanical strength and resistance to poisoning, while the aforementioned palladium-based membranes exhibit superior hydrogen isotope and surface anti-poisoning properties. Therefore, this facilitates the preparation of palladium membranes with high separation efficiency and stability.

[0046] In some embodiments, the thickness of the palladium-based membrane is 82 μm. The palladium-based membrane comprises a self-supporting palladium membrane obtained by rolling high-purity palladium metal, 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 beneficial for assembly and irradiation treatment.

[0047] The surface of the palladium film after irradiation treatment has been largely free of oxides and carbon contaminants, and is in a clean metallic state.

[0048] In some embodiments, the method further includes cleaning the palladium-based film prior to irradiation treatment.

[0049] As an example, the cleaning process includes ultrasonic cleaning for 2 minutes with an alcohol solvent (such as acetone (99.99% purity)), followed by rinsing with water and drying.

[0050] In a second aspect, this application discloses a palladium film having a hydrogen isotope permeation rate of 3.2 × 10⁻⁶ within a temperature range of 573 K to 723 K. -2 mol·m -2 ·s -1 ~7.7×10 -2 mol·m -2 ·s -1 Therefore, 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 applied in service environments such as large-scale fusion projects and the hydrogen energy industry to purify hydrogen, exhibiting high hydrogen purification efficiency. Furthermore, this palladium membrane has low requirements for the operating temperature, which is beneficial to improving the stability of the hydrogen purification system.

[0051] As an example, the hydrogen isotope permeation rate of the palladium membrane is 3.2 × 10⁻⁶. -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 -2mol·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 .

[0052] In some embodiments, the palladium membrane is prepared using the method proposed in this application. Compared with conventional unmodified palladium membranes, this membrane significantly improves the hydrogen isotope permeation rate and separation performance while retaining its original mechanical strength, and reduces the activation time for engineering applications.

[0053] In a third aspect of this application, a method for separating hydrogen isotopes is proposed, using a palladium membrane proposed in this application, or a palladium membrane prepared using the method proposed in this application.

[0054] In a fourth aspect of this application, a hydrogen isotope is proposed, which is obtained using the method for separating hydrogen isotopes proposed in this application.

[0055] The following specific embodiments illustrate the solution of this application. It should be noted that these embodiments are for illustrative purposes only and should not be considered as limiting the scope of this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0056] Example 1

[0057] A palladium-based film with a thickness of approximately 82 µm and a purity of 99.99% was used. The palladium film was placed in the vacuum chamber of an ion irradiation treatment apparatus and subjected to He... + It was irradiated with an ion beam. + Ions were generated by an ion accelerator with an energy set to 2 MeV. The total injected dose was controlled by the accelerating current and irradiation time to reach approximately 6.4 × 10⁻⁶. 17 ions / cm 2 .

[0058] Example 2

[0059] A palladium-based film with a thickness of approximately 82 µm and a purity of 99.99% was used. The palladium film was placed in the vacuum chamber of an ion irradiation treatment device and subjected to Ar... + It was irradiated with an ion beam. Ar +Ions are generated by an ion accelerator with an energy set at 15 keV. The total injected dose is controlled by the accelerating current and irradiation time to reach approximately 1 × 10⁻⁶. 17 ions / cm 2 .

[0060] Comparative Example

[0061] A pure palladium sheet membrane with a purity of 99.99% and a diameter of 82µm was used.

[0062] Test method:

[0063] 1. Hydrogen isotope transmission flux measurement

[0064] Multiple permeation experiments were conducted on unirradiated original palladium membranes and palladium membranes irradiated with He ions at a front-end permeation pressure of 723 K and 300 kPa, respectively, using H2, D2, and H2+D2 (1:1) mixed gases. The back-end permeation flux-time change curves were recorded for each activation process. Activation was considered successful when the difference between the permeation flux-time change curves obtained from two adjacent permeation experiments was less than 5%, and the palladium membrane reached a stable permeation state. The number of repeated experiments required from initial permeation to stable permeation was the activation number.

[0065] 2. Separation performance test of hydrogen-deuterium mixture

[0066] 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 permeated 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 downstream end of permeation to that at the upstream end of permeation, yielding the following relationship, where C... 轻 For light isotope abundance, C 重 Heavy isotope abundance:

[0067]

[0068] Test results:

[0069] The results of hydrogen isotope permeation flux tests are shown in Table 1.

[0070] Table 1 Comparison of changes in permeation flux

[0071]

[0072] refer to Figure 1 , 2 3 and Table 1, He + The irradiated palladium membrane has a hydrogen flux that is about 35% higher than that of the unirradiated palladium membrane, a deuterium flux that is about 50% higher, and a total permeation of the equivalent hydrogen / deuterium mixture that is about 52% higher.

[0073] refer to Figure 1 , 2 As shown in Tables 3 and 1, after the reaction of He ions and Ar... + Irradiated palladium membranes exhibit significantly higher permeation fluxes during both initial and steady-state permeation compared to unirradiated membranes. + The corresponding test results for the irradiated palladium membrane. The irradiated palladium membrane exhibited more stable and reliable performance during long-term operation. In contrast, the unmodified palladium membrane showed a gradual increase in permeation performance during the initial few runs. Irradiation removes surface factors that lead to membrane instability, making the membrane permeation process more controllable.

[0074] He ion irradiation of palladium membranes significantly shortens the activation process before commissioning. Irradiation-modified palladium membranes reach stable permeation flux after only a few initial runs, eliminating the need for lengthy pretreatment. Table 2 details the specific number of activation cycles required for different palladium membranes to reach stability under various test gases. He ion irradiation enables palladium membranes to reach steady-state permeation more quickly, improving the system's immediate availability and operational efficiency.

[0075] Table 2. Number of activations required for palladium films to reach stability under different test gases.

[0076]

[0077] refer to Figure 4-Figure 6 In Examples 1 and 2, the permeability of the palladium films obtained after irradiation treatment was higher than that of the untreated palladium-based films measured under different hydrogen isotope gases and operating temperatures.

[0078] Results of the separation performance test of hydrogen-deuterium mixture:

[0079] refer to Figure 7 The separation coefficients of the palladium membrane irradiated with He ions were higher than those of the unirradiated palladium membrane in the temperature range of 573K to 723K, indicating that the separation efficiency of hydrogen and deuterium was improved after He ion modification. The palladium membrane treated with He ion irradiation can achieve higher hydrogen isotope separation efficiency than the traditional palladium membrane at temperatures of 673K ​​to 723K, which helps to improve the purification effect of hydrogen isotopes.

[0080] In the description of this application, "A and / or B" can include any of the cases of A alone, B alone, or A and B, where A and B are merely examples and can be any technical feature connected by "and / or" in this application.

[0081] In this application, the order in which the steps are written does not imply a strict execution order and does not limit 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 in this application can be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0082] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method for preparing a palladium film, characterized in that, include: A palladium-based film is irradiated to obtain a palladium film, wherein, The irradiation treatment involves irradiating at least one surface of the palladium-based film with irradiated ions, wherein the ion implantation dose is 1 × 10⁻⁶. 17 ions / cm 2 ~8×10 17 ions / cm 2 The irradiated ions have an energy of 15 keV to 2 MeV; the irradiated ions include He. + At least one of other rare gas ions, wherein the other rare gas ions include Ar. + .

2. The method according to claim 1, characterized in that, Using the He + The irradiation treatment is performed, wherein the ion implantation dose of the irradiation treatment is 6 × 10⁻⁶. 17 ions / cm 2 ~7×10 17 ions / cm 2 .

3. The method according to claim 1, characterized in that, The palladium-based film includes a palladium-containing metal film, wherein the palladium-containing metal film includes at least one of a palladium film with a palladium metal purity of 99.99%, a Pd-Ag alloy film, and a Pd-Cu alloy film.

4. The method according to claim 3, characterized in that, The thickness of the palladium-based film is 82 μm.

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

6. A palladium film, characterized in that, The palladium film is prepared by the method described in any one of claims 1 to 5; the hydrogen isotope permeation rate of the palladium film is 3.2 × 10⁻⁶ within a temperature range of 573 K to 723 K. -2 mol·m -2 ·s -1 ~7.7×10 - 2 mol·m -2 ·s -1 .

7. A method for separating hydrogen isotopes, characterized in that, The palladium film as described in claim 6, or the palladium film prepared by the method described in any one of claims 1 to 5.

8. A hydrogen isotope, characterized in that, It is obtained by separation using the method described in claim 7.

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