Amorphous high-entropy alloy multilayer film and preparation method and application thereof

Abstract

The invention discloses a preparation method of an amorphous high-entropy alloy multilayer film, which comprises the following steps of: S1, coating a film on a substrate by adopting a TiVZrNb alloy target material through a magnetron sputtering method to form a TiVZrNb alloy film layer; s2, adopting a transition metal target material or a light metal target material to continuously coat the TiVZrNb alloy film layer through a magnetron sputtering method to form an interlayer metal film layer; s3, continuously coating a film on the interlayer metal film layer by adopting a TiVZrNb alloy target material through a magnetron sputtering method to form a TiVZrNb alloy film layer; s4, circularly repeating the step S2 and the step S3; and S5, after the step S4 is completed, the amorphous high-entropy alloy multilayer film is prepared. According to the preparation method, non-crystallization of the refractory high-entropy alloy is achieved through the magnetron sputtering technology, the TiVZrNb alloy multilayer film containing the transition metal interlayer or the light metal interlayer is prepared and has excellent hydrogen storage performance and good structural stability, and effective application of the refractory high-entropy alloy in the field of hydrogen storage materials is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen storage materials, and particularly relates to an amorphous high-entropy alloy multilayer film, a preparation method thereof, and an application thereof. Background Art

[0002] The storage of hydrogen energy is a key scientific issue for the large-scale commercial application of hydrogen energy. Due to the cocktail effect and lattice distortion effect, high-entropy alloys have a relatively high hydrogen storage capacity. However, the high thermodynamic stability and sluggish hydrogen absorption and desorption kinetic performance of traditional high-entropy hydrogen storage alloys with body-centered cubic and face-centered cubic structures greatly limit their practical applications. In particular, in order to improve the hydrogen storage capacity of the alloy by reducing the doping of hydrogen-repelling elements, the alloy has a high hydrogen storage capacity but it is difficult to desorb hydrogen.

[0003] Amorphous alloys have the characteristics of short-range order and long-range disorder in their microstructures. This disordered structure determines that amorphous alloys have very excellent physical, chemical, and mechanical properties and thus have broad application prospects. They also exhibit excellent performance in the field of hydrogen storage, such as high hydrogen storage capacity. At present, there are few reports on the research of amorphizing high-entropy alloys and applying them to hydrogen storage performance. In addition, due to the high melting point and poor liquid fluidity of refractory high-entropy alloys, it is difficult to amorphize them by ordinary methods, making it difficult to effectively apply refractory high-entropy alloys in the field of hydrogen storage materials.

[0004] On the other hand, the hydrogen storage reversibility of materials can be improved by thinning them into films. Previous researchers reported hydrogen storage materials in the form of films such as magnesium-based, zirconium-based, and vanadium-based ones, which can significantly improve the hydrogen storage cycling performance. However, the thickness of the hydrogen storage film will affect the hydrogen storage kinetics. An increase in the film thickness easily leads to a decrease in the diffusion rate during the hydrogenation process because the hydrogenated part hinders the diffusion of hydrogen. Therefore, further research is needed for the development of high-performance hydrogen storage thin film materials. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a preparation method for an amorphous high-entropy alloy multilayer film, which prepares an amorphous TiVZrNb alloy multilayer film containing a transition metal interlayer or a light metal interlayer. The film has excellent hydrogen storage performance, can absorb hydrogen at room temperature, has good dehydrogenation ability at 150 - 250 °C, and can still maintain an amorphous structure after cyclic hydrogen absorption and desorption, and has good structural stability.

[0006] The present invention is achieved through the following technical solutions:

[0007] A preparation method for an amorphous high-entropy alloy multilayer film, comprising the following steps:

[0008] S1. Using a titanium vanadium zirconium niobium (TiVZrNb) alloy target, coating a film on a substrate by magnetron sputtering to form a TiVZrNb alloy film layer;

[0009] S2. Continuously deposit a film on the TiVZrNb alloy film layer by magnetron sputtering using a transition metal target or a light metal target to form an interlayer metal film layer;

[0010] S3. Continuously deposit a film on the interlayer metal film layer by magnetron sputtering using a TiVZrNb alloy target to form a TiVZrNb alloy film layer;

[0011] S4. Repeat steps S2 and S3 cyclically;

[0012] S5. After step S4 is completed, an amorphous high-entropy alloy multilayer film is prepared.

[0013] Preferably, the TiVZrNb alloy target is selected from Ti x V y Zr z Nb k alloy targets, where x = 5 - 35 at%, y = 5 - 35 at%, z = 5 - 35 at%, k = 5 - 35 at%, and x + y + z + k = 100 at%, and at% is the atomic ratio; further preferably, the TiVZrNb alloy target is selected from Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 alloy target, including 33 at% of Ti, 28 at% of V, 11 at% of Zr, and 28 at% of Nb.

[0014] Preferably, the transition metal target is selected from any one of tantalum metal target, molybdenum metal target, platinum metal target, and palladium metal target; the light metal target is selected from magnesium metal target.

[0015] Preferably, the substrate is a polyimide flexible substrate.

[0016] Preferably, the coating parameters of the TiVZrNb alloy film layer are set as follows: the vacuum degree in the magnetron sputtering chamber is 5×10 -3 Pa, the sputtering power is 250 W, and the sputtering duration is 5500 s; the coating parameters of the interlayer metal layer are set as follows: the vacuum degree in the magnetron sputtering chamber is 5×10 -3 Pa, the sputtering power is 50 W, and the sputtering duration is 20 - 52 s.

[0017] Preferably, the single-layer thickness of the TiVZrNb alloy film layer of the amorphous high-entropy alloy multilayer film is 245 - 1250 nm, and the single-layer thickness of the interlayer metal film layer is 8 - 12 nm.

[0018] Preferably, the amorphous high-entropy alloy multilayer film comprises n TiVZrNb alloy film layers and n-1 interlayer metal film layers, where n is 2-10 (for example, n is 2, 3, 4, 5, 6, 7, 8, 9, 10).

[0019] More preferably, after step S4 is completed, a palladium metal target is used to continue coating on the surface TiVZrNb alloy film layer by magnetron sputtering to form an anti-oxidation protective layer, and the amorphous high-entropy alloy multilayer film is prepared. The coating parameters of the anti-oxidation protective layer are set as follows: the vacuum degree in the magnetron sputtering chamber is 5×10 -3 Pa, the sputtering power is 50 W, and the sputtering duration is 50 s; the thickness of the anti-oxidation protective layer of the amorphous high-entropy alloy multilayer film is 10 nm. The anti-oxidation protective layer plays a role in preventing oxidation and rapidly dissociating hydrogen.

[0020] As a preferred embodiment, the preparation method of the amorphous high-entropy alloy multilayer film comprises the following steps:

[0021] S1. Place each target in the magnetron sputtering instrument, place the substrate on the rotating tray, and turn on the mechanical pump and molecular pump of the magnetron sputtering instrument to evacuate; until the vacuum degree in the magnetron sputtering chamber reaches the preset vacuum degree;

[0022] S2. Sputter and coat the TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer on the substrate; let it stand for 5-10 minutes;

[0023] S3. Sputter and coat the transition metal target or light metal target on the TiVZrNb alloy film layer according to the set coating parameters to form an interlayer metal film layer; let it stand for 5-10 minutes;

[0024] S4. Sputter and coat the TiVZrNb alloy target on the interlayer metal film layer according to the set coating parameters to form a TiVZrNb alloy film layer; let it stand for 5-10 minutes;

[0025] S5. Repeat steps S3 and S4 in a cycle;

[0026] S6. After step S5 is completed, the amorphous high-entropy alloy multilayer film is prepared.

[0027] More preferably, each target is pre-sputtered for 2-5 minutes to remove the oxide layer and impurities on the target surface, and then layer-by-layer sputtering coating is carried out after the pre-sputtering is completed.

[0028] The present invention also provides an amorphous high-entropy alloy multilayer film prepared by the above preparation method.

[0029] The surface of the amorphous high-entropy alloy multilayer film of the present invention has an island-like structure with an average particle size of 66-101 nm. During the film preparation process, due to the competitive growth interface of deposited atoms and the layer-by-layer stacking of deposited atoms, a columnar structure is formed in the cross-section of the alloy film. The growth structure of the surface layer film replicating the bottom alloy film makes the surface of the alloy multilayer film exhibit island-like characteristics.

[0030] The present invention also provides the application of the amorphous high-entropy alloy multilayer film as a solid-state hydrogen storage material.

[0031] The present invention has the following beneficial effects:

[0032] The present invention realizes the amorphization of refractory high-entropy alloys through magnetron sputtering technology. By using a layered sputtering method, a TiVZrNb alloy multilayer film containing a transition metal interlayer or a light metal interlayer is prepared. It has excellent hydrogen storage performance, can absorb hydrogen at room temperature, has good dehydrogenation ability at 150-250 °C, and can still maintain an amorphous structure after cyclic hydrogen absorption and desorption, with good structural stability. It realizes the effective application of refractory high-entropy alloy titanium vanadium zirconium niobium in the field of hydrogen storage materials.

[0033] By adding a transition metal interlayer or a light metal interlayer to the TiVZrNb alloy film in the present invention, it can play a role in shortening the hydrogen diffusion path, can serve as a rapid hydrogen diffusion channel, and effectively improve the hydrogen storage kinetics of the thin film material.

[0034] The preparation process of the present invention is simple, with high yield and stability, and is suitable for large-scale industrial production. Description of the Drawings

[0035] Figure 1 XRD patterns of the amorphous TiVZrNb / M (M = Pt, Mo, Ta, Mg) alloy multilayer films prepared in Examples 1-4;

[0036] Figure 2 SEM images of the amorphous TiVZrNb / M (M = Pt, Mo, Ta, Mg) alloy multilayer films prepared in Examples 1-4 and the average island-like particle size on the surface of the alloy film;

[0037] Figure 3 TEM image of the amorphous TiVZrNb / Ta alloy multilayer film prepared in Example 1;

[0038] Figure 4 Energy spectrum diagram of the amorphous TiVZrNb / Ta alloy multilayer film prepared in Example 1;

[0039] Figure 5 Hydrogen absorption and dehydrogenation kinetic curves of the amorphous TiVZrNb / Ta alloy multilayer film prepared in Example 1;

[0040] Figure 6 TEM image of the amorphous TiVZrNb / Mo alloy multilayer film prepared in Example 2;

[0041] Figure 7 EDS spectrum of the amorphous TiVZrNb / Mo alloy multilayer film prepared in Example 2;

[0042] Figure 8 Hydrogen absorption and desorption kinetic curves of the amorphous TiVZrNb / Mo alloy multilayer film prepared in Example 2;

[0043] Figure 9 TEM image of the amorphous TiVZrNb / Pt alloy multilayer film prepared in Example 3;

[0044] Figure 10 EDS spectrum of the amorphous TiVZrNb / Pt alloy multilayer film prepared in Example 3;

[0045] Figure 11 Hydrogen absorption and desorption kinetic curves of the amorphous TiVZrNb / Pt alloy multilayer film prepared in Example 3;

[0046] Figure 12 TEM image of the amorphous TiVZrNb / Mg alloy multilayer film prepared in Example 4;

[0047] Figure 13 EDS spectrum of the amorphous TiVZrNb / Mg alloy multilayer film prepared in Example 4;

[0048] Figure 14 Hydrogen absorption and desorption kinetic curves of the amorphous TiVZrNb / Mg alloy multilayer film prepared in Example 4;

[0049] Figure 15 XRD pattern of the TiVZrNb / Pd alloy multilayer film prepared in Example 5;

[0050] Figure 16 Cross-sectional SEM image of the TiVZrNb / Pd alloy multilayer film prepared in Example 5;

[0051] Figure 17 EDS spectrum of the TiVZrNb / Pd alloy multilayer film prepared in Example 5;

[0052] Figure 18 Desorption kinetic curve of the TiVZrNb / Pd alloy multilayer film prepared in Example 5. Detailed implementation manners

[0053] To elaborate on the technical content, achieved objectives, and effects of the present invention in detail, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments and with reference to the accompanying drawings. However, the described embodiments are only a part of the embodiments of the present invention, and the implementation and protection of the present invention are not limited thereto. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention. It should be noted that for the processes not specifically described in detail below, those skilled in the art can implement or understand them with reference to the prior art. For reagents or instruments without indicating the manufacturer, they are regarded as conventional products that can be obtained through commercial purchase.

[0054] The raw materials and instruments used in the embodiments of the present invention are described as follows, but are not limited thereto:

[0055] TiVZrNb alloy target: Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 Alloy target, including 33 at% of Ti, 28 at% of V, 11 at% of Zr, 28 at% of Nb, Zhongnuo New Materials (Ti213494.35);

[0056] Tantalum metal target: Zhongnuo New Materials (Ta11435);

[0057] Molybdenum metal target: Zhongnuo New Materials (Mo11335);

[0058] Platinum metal target: Zhongnuo New Materials (Pt11432);

[0059] Magnesium metal target: Zhongnuo New Materials (Mg11435);

[0060] Palladium metal target: Zhongnuo New Materials (Pd11436);

[0061] Magnetron sputtering instrument: Shenzhen Supu Instruments Co., Ltd. (DSC 300Plus).

[0062] Example 1

[0063] S1. Install the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 alloy target, tantalum metal target, and palladium metal target in the magnetron sputtering instrument. Place the polyimide flexible substrate in the rotating tray, and set the vacuum degree in the cavity of the magnetron sputtering instrument to 5×10 - 3For the TiVZrNb alloy target, the sputtering power is 250 W and the sputtering time is 5500 s; for the tantalum metal target, the sputtering power is 50 W and the sputtering time is 45 s; for the palladium metal target, the sputtering power is 50 W and the sputtering time is 50 s.

[0064] Turn on the mechanical pump and molecular pump of the magnetron sputtering instrument to evacuate until the vacuum degree in the cavity of the magnetron sputtering instrument reaches 5×10 -3 Pa.

[0065] S2. Sputter coat the TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer on the substrate; let it stand for 10 minutes.

[0066] S3. Sputter coat the tantalum metal target on the TiVZrNb alloy film layer according to the set coating parameters to form an interlayer metal film layer; let it stand for 10 minutes.

[0067] S4. Sputter coat the TiVZrNb alloy target on the interlayer metal film layer according to the set coating parameters to form a TiVZrNb alloy film layer; let it stand for 10 minutes.

[0068] S5. Repeat steps S3 and S4 cyclically.

[0069] S6. After step S5 is completed, sputter coat the palladium metal target on the surface TiVZrNb alloy film layer according to the set coating parameters to form an anti-oxidation protective layer, and prepare an amorphous Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Ta alloy multilayer film. (Each target is pre-sputtered for 3 min to remove the oxide layer and impurities on the target surface, and then layer-by-layer sputter coating is carried out after the pre-sputtering is completed.)

[0070] From Figure 1 the X-ray diffraction pattern, it can be seen that a broad peak appears at 32° - 42°, indicating that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Ta alloy multilayer film is an amorphous structure. The alloy film still maintains an amorphous structure after hydrogen absorption and desorption, and has good structural stability.

[0071] From Figure 2 the SEM image, it can be seen that the surface of the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Ta alloy multilayer film is an island-like structure, and the average size of the island-like structure is 80.63 nm.

[0072] FromFigure 3 From the TEM image, it can be seen that for the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Ta alloy multilayer film, the total thickness is about 2.5 μm, and its structure is a multilayer structure composed of 10 layers of TiVZrNb alloy film layers with a thickness of 248.6 nm, 9 layers of interlayer metal film layers with a thickness of 10.5 nm, and 1 layer of 10 nm thick palladium anti-oxidation protective layer.

[0073] From Figure 4 the energy spectrum image, it can be seen that there is tantalum metal interlayer in the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Ta alloy multilayer film.

[0074] From Figure 5 the data in the hydrogen absorption and dehydrogenation kinetic curve graph, it can be seen that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Ta alloy multilayer film can absorb 0.6 wt% hydrogen at room temperature and 3 MPa hydrogen pressure, and can dehydrogenate 0.4 wt% at 250 °C and 0.05 atm.

[0075] Example 2

[0076] S1. Install the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 alloy target, molybdenum metal target and palladium metal target in the magnetron sputtering instrument. Place the polyimide flexible substrate in the rotating tray, and set the vacuum degree in the magnetron sputtering instrument cavity to 5×10 - 3 Pa. The sputtering power of the TiVZrNb alloy target is 250 w, the sputtering time is 5500 s, the sputtering power of the molybdenum metal target is 50 w, the sputtering time is 52 s, and the sputtering power of the palladium metal target is 50 w, the sputtering time is 50 s;

[0077] Turn on the mechanical pump and molecular pump of the magnetron sputtering instrument to pump vacuum until the vacuum degree in the magnetron sputtering instrument cavity reaches 5×10 -3 Pa;

[0078] S2. Sputter and coat the TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer on the substrate; let it stand for 10 minutes;

[0079] S3. Continuously perform sputtering coating on the TiVZrNb alloy film layer with a molybdenum metal target according to the set coating parameters to form an interlayer metal film layer; let it stand for 10 minutes;

[0080] S4. Continuously coat on the interlayer metal film layer with a TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer; let it stand for 10 minutes;

[0081] S5. Repeat steps S3 and S4 cyclically;

[0082] S6. After step S5 is completed, continuously coat on the surface TiVZrNb alloy film layer with a palladium metal target according to the set coating parameters to form an anti-oxidation protection layer, and prepare an amorphous Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mo alloy multilayer film. (Each target is pre-sputtered for 3 minutes to remove the oxide layer and impurities on the target surface, and then layer-by-layer sputtering coating is carried out after the pre-sputtering is completed.)

[0083] From Figure 1 the X-ray diffraction pattern, it can be seen that a broad peak appears at 32° - 42°, indicating that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mo alloy multilayer film of the present invention is an amorphous structure. The alloy film still maintains an amorphous structure after hydrogen absorption and desorption, and has good structural stability.

[0084] From Figure 2 the SEM image, it can be seen that the surface of the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mo alloy multilayer film is an island-like structure, and the average size of the island-like structure is 84.72 nm.

[0085] From Figure 6 the TEM image, it can be seen that the total thickness of the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mo alloy multilayer film of the present invention is about 2.5 μm, and its structure is a multilayer structure composed of 10 layers of TiVZrNb alloy film layers with a thickness of 247.7 nm, 9 layers of interlayer metal film layers with a thickness of 9.8 nm, and 1 layer of palladium anti-oxidation protection layer with a thickness of 10 nm.

[0086] From Figure 7 the energy spectrum diagram, it can be seen that the Ti 0.33 V 0.28 Zr 0.11 Nb0.28 The existence of a molybdenum metal interlayer in the TiVZrNb / Mo alloy multi-layer film.

[0087] From Figure 8 the data in the hydrogen absorption and dehydrogenation kinetic curve graphs, it can be seen that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mo alloy multi-layer film can absorb 0.41 wt% of hydrogen at room temperature and a hydrogen pressure of 3 MPa. It can dehydrogenate 0.28 wt% at 250 °C and 0.05 atm.

[0088] Example 3

[0089] S1. Install a Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 alloy target, a platinum metal target, and a palladium metal target in a magnetron sputtering instrument. Place the polyimide flexible substrate in the rotating tray, and set the vacuum degree in the magnetron sputtering instrument cavity to 5×10 - 3 Pa. The sputtering power of the TiVZrNb alloy target is 250 w, the sputtering time is 5500 s, the sputtering power of the platinum metal target is 50 w, the sputtering time is 47 s, and the sputtering power of the palladium metal target is 50 w, the sputtering time is 50 s;

[0090] Turn on the mechanical pump and molecular pump of the magnetron sputtering instrument to pump vacuum until the vacuum degree in the magnetron sputtering instrument cavity reaches 5×10 -3 Pa;

[0091] S2. Sputter and coat the TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer on the substrate; let it stand for 10 minutes;

[0092] S3. Sputter and coat the platinum metal target on the TiVZrNb alloy film layer according to the set coating parameters to form an interlayer metal film layer; let it stand for 10 minutes;

[0093] S4. Sputter and coat the TiVZrNb alloy target on the interlayer metal film layer according to the set coating parameters to form a TiVZrNb alloy film layer; let it stand for 10 minutes;

[0094] S5. Repeat step S3 and step S4 in a cycle;

[0095] S6. After step S5 is completed, sputter and coat the palladium metal target on the surface TiVZrNb alloy film layer according to the set coating parameters to form an anti-oxidation protection layer, and prepare an amorphous Ti 0.33 V 0.28 Zr 0.11 Nb0.28 TiVZrNb / Pt alloy multilayer film. (Each target was pre-sputtered for 3 min to remove the oxide layer and impurities on the target surface, and then layer-by-layer sputtering coating was carried out after the pre-sputtering was completed.)

[0096] From Figure 1 the X-ray diffraction pattern, it can be seen that a broad peak appears at 32° - 42°, indicating that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pt alloy multilayer film is an amorphous structure. The alloy film still maintains an amorphous structure after hydrogen absorption and desorption, and has good structural stability.

[0097] From Figure 2 the SEM image, it can be seen that the surface of the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pt alloy multilayer film is an island-like structure, and the average size of the island-like structure is 100.07 nm.

[0098] From Figure 9 the TEM image, it can be seen that the total thickness of the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pt alloy multilayer film of the present invention is about 2.5 μm, and its structure is a multilayer structure composed of 10 layers of TiVZrNb alloy film layers with a thickness of 252 nm, 9 layers of interlayer metal film layers with a thickness of 11.4 nm, and 1 layer of 10 nm thick palladium anti-oxidation protection layer.

[0099] From Figure 10 the energy spectrum diagram, it can be seen the presence of platinum metal interlayer in the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pt alloy multilayer film of the present invention.

[0100] From Figure 11 the hydrogen absorption and desorption kinetic curve graph data, it can be seen that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pt alloy multilayer film of the present invention can absorb 0.31 wt% of hydrogen at room temperature and 3 MPa hydrogen pressure. It can desorb 0.30 wt% of hydrogen at 250 °C and 0.05 atm.

[0101] Example 4

[0102] S1. Install Ti 0.33 V 0.28 Zr 0.11Nb 0.28 TiVZrNb alloy target, magnesium metal target and palladium metal target. Place the polyimide flexible substrate in the rotating tray, and set the vacuum degree in the cavity of the magnetron sputtering instrument to 5×10 - 3 Pa. The sputtering power of the TiVZrNb alloy target is 250 w, and the sputtering time is 5500 s. The sputtering power of the magnesium metal target is 50 w, and the sputtering time is 20 s. The sputtering power of the palladium metal target is 50 w, and the sputtering time is 50 s;

[0103] Turn on the mechanical pump and molecular pump of the magnetron sputtering instrument to evacuate until the vacuum degree in the cavity of the magnetron sputtering instrument reaches 5×10 -3 Pa;

[0104] S2. Sputter and coat the TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer on the substrate; let it stand for 10 minutes;

[0105] S3. Sputter and coat the magnesium metal target on the TiVZrNb alloy film layer according to the set coating parameters to form an interlayer metal film layer; let it stand for 10 minutes;

[0106] S4. Sputter and coat the TiVZrNb alloy target on the interlayer metal film layer according to the set coating parameters to form a TiVZrNb alloy film layer; let it stand for 10 minutes;

[0107] S5. Repeat step S3 and step S4 in a cycle;

[0108] S6. After step S5 is completed, sputter and coat the palladium metal target on the surface TiVZrNb alloy film layer according to the set coating parameters to form an anti-oxidation protective layer, and prepare an amorphous Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mg alloy multilayer film. (Each target is pre-sputtered for 3 min to remove the oxide layer and impurities on the target surface, and then layer-by-layer sputter coating is carried out after the pre-sputtering is completed.)

[0109] From Figure 1 the X-ray diffraction pattern, it can be seen that a broad peak appears at 32°-42°, indicating that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mg alloy multilayer film is an amorphous structure. The alloy film still maintains an amorphous structure after hydrogen absorption and desorption, and has good structural stability.

[0110] From Figure 2 the SEM image, it can be seen that Ti 0.33 V 0.28 Zr0.11 Nb 0.28 The surface of the Nb / Mg alloy multilayer film is an island-like structure, and the average size of the island-like structure is 66.97 nm.

[0111] From Figure 12 the TEM image, it can be seen that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mg alloy multilayer film has a total thickness of about 2.5 μm. Its structure is a multilayer structure composed of 10 layers of TiVZrNb alloy film layers with a thickness of 246.5 nm, 9 layers of interlayer metal film layers with a thickness of 8.7 nm, and 1 layer of 10 nm thick palladium anti-oxidation protective layer.

[0112] From Figure 13 the energy spectrum diagram, it can be seen that there is a magnesium metal interlayer in the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mg alloy multilayer film.

[0113] From Figure 14 the data in the hydrogen absorption and dehydrogenation kinetic curve diagram, it can be seen that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Mg alloy multilayer film can absorb 0.26 wt% of hydrogen at room temperature and a hydrogen pressure of 3 MPa. It can dehydrogenate 0.25 wt% at 250 °C and 0.05 atm.

[0114] Example 5

[0115] S1. Install the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 alloy target and palladium metal target in the magnetron sputtering instrument. Place the polyimide flexible substrate in the rotating tray, and set the vacuum degree in the magnetron sputtering instrument cavity to 5×10 -3 Pa. The sputtering power of the TiVZrNb alloy target is 250 w, the sputtering time is 5500 s, the sputtering power of the palladium metal target is 50 w, and the sputtering time is 50 s;

[0116] Turn on the mechanical pump and molecular pump of the magnetron sputtering instrument to evacuate until the vacuum degree in the magnetron sputtering instrument cavity reaches 5×10 -3 Pa;

[0117] S2. Sputter and coat the TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer on the substrate; let it stand for 10 minutes;

[0118] S3. Continuously perform sputtering coating on the TiVZrNb alloy film layer with a palladium metal target according to the set coating parameters to form an interlayer metal film layer; let it stand for 10 minutes;

[0119] S4. Continuously coat the interlayer metal film layer with a TiVZrNb alloy target according to the set coating parameters to form a TiVZrNb alloy film layer; let it stand for 10 minutes;

[0120] S5. Repeat steps S3 and S4 in a cycle;

[0121] S6. After step S5 is completed, continuously coat the TiVZrNb alloy film layer on the surface with a palladium metal target according to the set coating parameters to form an anti-oxidation protection layer, and prepare an amorphous Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pd alloy multilayer film (each target is pre-sputtered for 2 minutes to remove the oxide layer and impurities on the target surface, and then layer-by-layer sputtering coating is carried out after the pre-sputtering). By controlling the number of cycles of repeated sputtering coating, amorphous Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pd alloy multilayer films (named F2, F5, and F10 respectively) are prepared.

[0122] From Figure 15 the X-ray diffraction pattern, it can be seen that a broad peak appears at 32° - 42° for F2, F5, and F10, indicating that the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pd alloy multilayer film of the present invention is an amorphous structure.

[0123] From Figure 16 the SEM image, it can be seen that the structure of the F2 film is a multilayer structure composed of 2 layers of TiVZrNb alloy film layers with a thickness of about 1250 nm, 1 layer of interlayer metal film layer with a thickness of about 10 nm, and 1 layer of palladium anti-oxidation protection layer with a thickness of about 10 nm; the structure of the F5 film is a multilayer structure composed of 5 layers of TiVZrNb alloy film layers with a thickness of about 500 nm, 4 layers of interlayer metal film layers with a thickness of about 10 nm, and 1 layer of palladium anti-oxidation protection layer with a thickness of about 10 nm; the structure of the F5 film is a multilayer structure composed of 10 layers of TiVZrNb alloy film layers with a thickness of about 250 nm, 9 layers of interlayer metal film layers with a thickness of about 10 nm, and 1 layer of palladium anti-oxidation protection layer with a thickness of about 10 nm.

[0124] From Figure 17 the energy spectrum diagram, it can be seen that the Ti of the present invention0.33 V 0.28 Zr 0.11 Nb 0.28 The presence of a palladium metal interlayer in the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pd alloy multilayer film is proved by the increasing Pd atomic ratio in F2, F5, and F10. The increase in the number of Pd interlayers in the Ti

[0125] From Figure 18 the data in the dehydrogenation kinetic curve graph, it can be seen that for the Ti 0.33 V 0.28 Zr 0.11 Nb 0.28 / Pd alloy two-layer, five-layer, and ten-layer films, the dehydrogenation amount increases with the increase in the number of interlayers, which are 0.29 wt%, 0.34 wt%, and 0.35 wt% respectively.

[0126] The above are only embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in the relevant technical fields, shall be equally included in the patent protection scope of the present invention.

Claims

1. A method for preparing an amorphous high entropy alloy multilayer film, characterized in that: The following steps are involved: S1. coating a TiVZrNb alloy target on a substrate by magnetron sputtering to form a TiVZrNb alloy film layer; S2. Using a transition metal target or a light metal target to continue coating on the TiVZrNb alloy film layer by magnetron sputtering to form an interlayer metal film layer; S3. Using a TiVZrNb alloy target material to continue coating on the interlayer metal film layer by magnetron sputtering to form a TiVZrNb alloy film layer; S4. Repeat steps S2 and S3 in a loop; S5. After step S4 is completed, an amorphous high entropy alloy multilayer film is prepared.

2. The method for preparing an amorphous high entropy alloy multilayer film according to claim 1, characterized in that: The TiVZrNb alloy target is selected from Ti x V y Zr z Nb k Alloy target, wherein x=5-35at%, y=5-35at%, z=5-35at%, k=5-35at%, x+y+z+k=100at%, at% is atomic ratio; the transition metal target is selected from any one of tantalum metal target, molybdenum metal target, platinum metal target and palladium metal target; the light metal target is selected from magnesium metal target; the substrate is a polyimide flexible substrate.

3. The method for preparing an amorphous high entropy alloy multilayer film according to claim 1, characterized in that: The coating parameters of the TiVZrNb alloy film layer are set as follows: the vacuum degree in the magnetron sputtering chamber is 5×10 -3 Pa, sputtering power 150-250W, sputtering time 5500-8000s; the coating parameters of the interlayer metal layer are set as follows: the vacuum degree in the magnetron sputtering chamber is 5×10 -3 Pa, sputtering power 50W, sputtering time 20-52s.

4. The method for preparing an amorphous high entropy alloy multilayer film according to claim 1, characterized in that: The thickness of a single layer of the TiVZrNb alloy film layer of the amorphous high entropy alloy multilayer film is 245-1250 nm, and the thickness of a single layer of the interlayer metal film layer is 8-12 nm.

5. The method for preparing an amorphous high entropy alloy multilayer film according to claim 1, characterized in that: The amorphous high entropy alloy multilayer film comprises n TiVZrNb alloy film layers and n-1 interlayer metal film layers, where n is 2-10.

6. The method for preparing an amorphous high entropy alloy multilayer film according to claim 1, characterized in that: After step S4 is completed, a palladium metal target is used to continue coating on the surface TiVZrNb alloy film layer through magnetron sputtering to form an anti-oxidation protective layer, thereby preparing an amorphous high entropy alloy multilayer film.

7. The method for preparing an amorphous high entropy alloy multilayer film according to claim 6, characterized in that: The coating parameters of the anti-oxidation protective layer are set as follows: the vacuum degree in the magnetron sputtering chamber is 5×10 -3 Pa, sputtering power 50W, sputtering time 50s; the thickness of the anti-oxidation protection layer of the amorphous high entropy alloy multilayer film is 10nm.

8. An amorphous high entropy alloy multilayer film, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 7.

9. The amorphous high entropy alloy multilayer film according to claim 8, characterized in that: The surface of the amorphous high entropy alloy multilayer film has an island-like structure with an average particle size of 66-101 nm.

10. Use of the amorphous high entropy alloy multilayer film prepared by the preparation method according to any one of claims 1 to 7 as a solid-state hydrogen storage material.

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