Electrodeposition-based FeCoNiMnHf high-entropy film and preparation method thereof

Abstract

The invention relates to a FeCoNiMnHf high-entropy thin film based on electro-deposition and a preparation method of the FeCoNiMnHf high-entropy thin film. According to the technical scheme, the preparation method comprises the following steps: dissolving dried ferrous chloride tetrahydrate, dried nickel chloride hexahydrate, dried cobalt chloride hexahydrate and dried manganese chloride tetrahydrate in deionized water by adopting a constant potential electrodeposition method, then dissolving potassium chloride and hafnium chloride in the deionized water, and stirring to obtain a precursor; and ascorbic acid, trisodium citrate, saccharin sodium, lauryl sodium sulfate, boric acid and malonic acid are added and stirred, and the electrolyte is obtained. And performing electrochemical deposition by taking a graphite electrode as a counter electrode and indium tin oxide conductive glass as a working electrode to obtain the FeCoNiMnHf high-entropy film based on electro-deposition. The preparation method has the characteristics of being simple in process, low in energy consumption and environmentally friendly, and the prepared FeCoNiMnHf high-entropy thin film based on electro-deposition is high in metal glossiness, good in film integrity, free of impurity elements, good in uniformity and good in magnetic performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of high entropy thin films, and specifically relates to a FeCoNiMnHf high entropy thin film based on electrodeposition and a preparation method thereof. Background Art

[0002] Existing magnetic materials have poor impedance matching and effective absorption bandwidth due to insufficient soft magnetic properties and low resistivity. Magnetic high entropy films play a crucial role in performance by regulating the size and morphology of the second phase particles, especially in terms of soft magnetic properties. Similar to amorphous nanocrystals, the precipitation of fine spherical magnetic nanoparticles plays a key role in reducing coercivity. However, existing high entropy film preparation methods have some inevitable disadvantages. For example, the high entropy alloy prepared by arc melting has a low yield and cannot be mass-produced; although the induction melting method has high component purity, unpredictable element reactions may occur during feeding and heating, and the results cannot be fully controlled; high entropy alloys prepared by mechanical alloying are mostly blocky and cannot adapt to a variety of application environments; laser coating is a preparation process derived from the combination of disciplines, and its disadvantages are that the synthesis equipment has high requirements and is expensive. Therefore, the development of new high entropy films is of concern to those skilled in the art.

[0003] For example, the patented technology of "A high-strength Al-Co-Cr-Fe-Ni high-entropy alloy and its preparation method" (CN114990406B) uses arc welding to prepare Al-Co-Cr-Fe-Ni high-entropy alloy, and obtains high-strength Al-Co-Cr-Fe-Ni high-entropy alloy, but the process is cumbersome and complicated, and the prepared high-entropy material is prone to brittle cracking and easy to contain impurity elements.

[0004] The patented technology of "A method for preparing a directional array of ceramic phase reinforced high-entropy alloy wear-resistant coatings using plasma cladding" (CN112251749B) uses plasma cladding to prepare directional high-entropy alloy coatings. Refractory metal powders are selected and mixed with equal atomic mass ratios or near atomic mass ratios for ball milling, hot pressing sintering, and cladding to obtain high-entropy wear-resistant coatings. Like other existing methods, it has high energy consumption because refractory metals are difficult to synthesize and the target material needs to be replaced frequently.

[0005] The patented technology of "A high-entropy alloy film on the inner surface of a barrel and its preparation method" (CN114657514B) adopts a plasma sputtering method to prepare a WMoTaNbSi high-entropy film layer, and selects a WMoTaNb target material to deposit a WMoTaNb layer on the inner barrel substrate. Although the product obtained by this preparation method has a high melting point and high hardness, the WMoTaNb target material is a refractory metal target material, which is expensive and a lossy material that requires long-term ordering. In addition, the surface of the prepared high-entropy film has vacancies, is uneven, and has uneven colors. Summary of the invention

[0006] The present invention aims to overcome the defects of the prior art and aims to provide a preparation technology of a FeCoNiMnHf high entropy film based on electrodeposition which has simple process, low energy consumption and is green and environmentally friendly. The FeCoNiMnHf high entropy film based on electrodeposition prepared by the method has high metallic gloss, good film integrity, no impurity elements, good uniformity and good magnetic properties.

[0007] To achieve the above purpose, the specific steps of the technical solution adopted by the present invention are:

[0008] Step 1: Grind ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate to a particle size of less than 100 μm, and then freeze-dry them in a freeze dryer.

[0009] Step 2: Dissolve the dried ferrous chloride tetrahydrate, the dried cobalt chloride hexahydrate, the dried nickel chloride hexahydrate and the dried manganese chloride tetrahydrate in deionized water.

[0010] Then, the concentration of potassium chloride is 0.005-4 mol / l, the concentration of hafnium chloride is 0.005-0.015 mol / l, the concentration of ascorbic acid is 0.005-0.02 mol / l, the concentration of trisodium citrate is 0.005-0.05 mol / l, the concentration of sodium saccharin is 0.005-0.025 mol / l, the concentration of sodium dodecyl sulfate is 0.0005-0.005 mol / l, the concentration of boric acid is 0.005-1 mol / l and the concentration of malonic acid is 0.005-0.01 mol / l, the hafnium chloride and the potassium chloride are dissolved in the deionized water, and then the ascorbic acid, the trisodium citrate, the sodium saccharin, the sodium dodecyl sulfate, the boric acid and the malonic acid are added, and stirred for 5-10 minutes to obtain an electrolyte.

[0011] Step 3: introducing nitrogen into the electrolyte at a flow rate of 1 to 2 l / min, and the time for introducing nitrogen per liter of electrolyte is 5 to 10 minutes.

[0012] Step 4: First, clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 5 to 10 minutes; then, clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 5 to 10 minutes.

[0013] Step 5: Place the indium tin oxide conductive glass cleaned with anhydrous ethanol as the working electrode and the graphite electrode as the counter electrode into an electrolytic cell, and connect to a DC power supply; perform electroplating for 30 to 90 minutes at an electrolytic cell temperature of 30 to 60° C. and a voltage of -10 to -5 V to obtain an electro-deposited FeCoNiMnHf high entropy film.

[0014] Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 10 to 20 seconds, and then dry it with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

[0015] The freeze-drying conditions are: freeze-drying at -60 to -40°C for 30 to 60 hours.

[0016] The purity of the ferrous chloride tetrahydrate, the cobaltous chloride hexahydrate, the nickel chloride hexahydrate, and the manganese chloride tetrahydrate are all above analytical grade.

[0017] The purity of the hafnium chloride and potassium chloride is analytical grade or above.

[0018] The purity of the ascorbic acid, trisodium citrate, sodium saccharin, sodium lauryl sulfate, boric acid and malonic acid is above analytical grade.

[0019] The plane of the indium tin oxide conductive glass is 20-1000×20-1000mm 2 .

[0020] The plane of the graphite electrode is 20-1000×20-1000mm 2 .

[0021] The inert gas is nitrogen or argon.

[0022] Due to the adoption of the above technical solution, the present invention has the following positive effects compared with the prior art:

[0023] 1. The present invention adopts an electrochemical deposition method to prepare an FeCoNiMnHf high entropy film based on electrodeposition. By passing an inert atmosphere during the electrodeposition process to reduce the oxygen content in the deposited layer, the electrodeposition time and the electrodeposition voltage can be freely adjusted to obtain a uniformly distributed FeCoNiMnHf high entropy film based on electrodeposition. In a multi-metal ion solution, a variety of metal ions can be co-deposited through their coordination structures. The high entropy film has a high saturation magnetization intensity and obvious magnetic anisotropy characteristics. The prepared FeCoNiMnHf high entropy film based on electrodeposition has good magnetic properties.

[0024] 2. The present invention uses a direct current power supply to achieve electrochemical deposition, does not require complex and expensive equipment, can use easily available raw materials, and is a low-cost method for synthesizing alloy films. This method has a simple process flow, is easy to operate, has a short production cycle, has low requirements for the substrate, and can be carried out at low processing temperatures and low energy consumption. By changing the electrodeposition parameters, it is easy to change the composition, morphology and crystal structure of the deposited layer, and then regulate the morphology and performance of the material. Secondly, the aqueous system is used as the electrolyte for electrodeposition, which is green, environmentally friendly, and low in cost, and is greener and safer than organic electrolytes.

[0025] 3. The present invention uses deionized water as the solvent of the electrolyte, introduces sodium dodecyl sulfate and sodium saccharin to make the electrodeposited film have better integrity and uniformity; and adds malonic acid as an electroplating polishing agent to make the electrodeposited metal film have a more metallic luster; secondly, boric acid, ascorbic acid and trisodium citrate are introduced to control the pH value of the solution to inhibit the electrolysis of water, prevent the appearance of oxides or other phases in the film, and significantly improve the purity of the product.

[0026] 4. The present invention can control the volume of the FeCoNiMnHf high-entropy film based on electrodeposition by changing the size of the electrolytic cell, thereby increasing the output for large-scale industrial production.

[0027] Therefore, the present invention has the characteristics of simple process, low energy consumption and green environmental protection. The prepared FeCoNiMnHf high entropy thin film based on electrodeposition has high metallic gloss, good film integrity, no impurity elements, good uniformity and good magnetic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 X-ray diffraction patterns of three FeCoNiMnHf high entropy films based on electrodeposition prepared by the present invention;

[0029] Figure 2 for Figure 1 The scanning electron microscope images of three FeCoNiMnHf high entropy films based on electrodeposition are shown;

[0030] Figure 3 for Figure 1 Magnetic anisotropy map of the second FeCoNiMnHf high-entropy film based on electrodeposition is shown. DETAILED DESCRIPTION

[0031] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments. This invention is not intended to limit the scope of protection of the present invention.

[0032] A FeCoNiMnHf high entropy film based on electrodeposition and a preparation method thereof. The steps of the specific method described in this specific embodiment are:

[0033] Step 1, grinding ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate respectively to a particle size of less than 100 μm; then placing the ground ferrous chloride tetrahydrate, the ground cobalt chloride hexahydrate, the ground manganese chloride tetrahydrate and the ground nickel chloride hexahydrate in a freeze dryer respectively, freeze-drying them at -60 to -40°C for 30 to 60 hours, and successively obtaining dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried manganese chloride tetrahydrate and dried nickel chloride hexahydrate.

[0034] Step 2: Dissolve the dried ferrous chloride tetrahydrate, the dried cobalt chloride hexahydrate, the dried nickel chloride hexahydrate and the dried manganese chloride tetrahydrate in deionized water.

[0035] Then, the concentration of potassium chloride is 0.005-4 mol / l, the concentration of hafnium chloride is 0.005-0.015 mol / l, the concentration of ascorbic acid is 0.005-0.02 mol / l, the concentration of trisodium citrate is 0.005-0.05 mol / l, the concentration of sodium saccharin is 0.005-0.025 mol / l, the concentration of sodium dodecyl sulfate is 0.0005-0.005 mol / l, the concentration of boric acid is 0.005-1 mol / l and the concentration of malonic acid is 0.005-0.01 mol / l, the hafnium chloride and the potassium chloride are dissolved in the deionized water, and then the ascorbic acid, the trisodium citrate, the sodium saccharin, the sodium dodecyl sulfate, the boric acid and the malonic acid are added, and stirred for 5-10 minutes to obtain an electrolyte.

[0036] Step 3: introducing nitrogen into the electrolyte at a flow rate of 1 to 2 l / min, and the time for introducing nitrogen per liter of electrolyte is 5 to 10 minutes.

[0037] Step 4: First, clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 5 to 10 minutes; then, clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 5 to 10 minutes.

[0038] Step 5: Place the indium tin oxide conductive glass cleaned with anhydrous ethanol as the working electrode and the graphite electrode as the counter electrode into an electrolytic cell, and connect to a DC power supply; perform electroplating for 30 to 90 minutes at an electrolytic cell temperature of 30 to 60° C. and a voltage of -10 to -5 V to obtain an electro-deposited FeCoNiMnHf high entropy film.

[0039] Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 10 to 20 seconds, and then dry it with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

[0040] The plane of the indium tin oxide conductive glass is 20-1000×20-1000mm 2 .

[0041] The plane of the graphite electrode is 20-1000×20-1000mm 2 .

[0042] The inert gas is nitrogen or argon.

[0043] In this specific implementation mode:

[0044] The purity of the ferrous chloride tetrahydrate, the cobalt chloride hexahydrate, the nickel chloride hexahydrate, and the manganese chloride tetrahydrate are all above analytical grade;

[0045] The purity of hafnium chloride and potassium chloride is analytical grade or above;

[0046] The purity of the ascorbic acid, trisodium citrate, sodium saccharin, sodium lauryl sulfate, boric acid and malonic acid is above analytical grade.

[0047] This will not be described in detail in the embodiments.

[0048] Example 1

[0049] A FeCoNiMnHf high entropy film based on electrodeposition and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0050] Step 1, grinding ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate respectively to a particle size of less than 100 μm; then placing the ground ferrous chloride tetrahydrate, the ground cobalt chloride hexahydrate, the ground manganese chloride tetrahydrate and the ground nickel chloride hexahydrate in a freeze dryer respectively, and freeze-drying them at -60°C for 30 hours, to obtain dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried manganese chloride tetrahydrate and dried nickel chloride hexahydrate in turn.

[0051] Step 2: Prepare ingredients with a concentration of 0.005 mol / l of dried ferrous chloride tetrahydrate, 0.005 mol / l of dried cobalt chloride hexahydrate, 0.005 mol / l of dried nickel chloride hexahydrate and 0.005 mol / l of dried manganese chloride tetrahydrate, and dissolve the dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried nickel chloride hexahydrate and dried manganese chloride tetrahydrate in deionized water.

[0052] Then, the concentrations of potassium chloride, hafnium chloride, ascorbic acid, trisodium citrate, sodium saccharin, sodium dodecyl sulfate, boric acid and malonic acid are prepared to be 0.005 mol / l, the hafnium chloride and potassium chloride are dissolved in the deionized water, and then the ascorbic acid, trisodium citrate, sodium saccharin, sodium dodecyl sulfate, boric acid and malonic acid are added, and stirred for 5 minutes to obtain an electrolyte.

[0053] Step 3: nitrogen is introduced into the electrolyte at a flow rate of 1 l / min, and the time for introducing nitrogen is 5 min per liter of electrolyte.

[0054] Step 4: Clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 5 minutes; and then clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 5 minutes.

[0055] Step 5: Place the indium tin oxide conductive glass cleaned with anhydrous ethanol as the working electrode and the graphite electrode as the counter electrode into an electrolytic cell, and connect to a DC power supply; perform electroplating for 30 minutes at an electrolytic cell temperature of 30° C. and a voltage of -10 V to obtain an electro-deposited FeCoNiMnHf high entropy film.

[0056] Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 10 seconds, and then blow dry with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

[0057] The plane of the indium tin oxide conductive glass is 20×20 mm 2 .

[0058] The plane of the graphite electrode is 20×20 mm 2 .

[0059] The inert gas is nitrogen.

[0060] Example 2

[0061] A FeCoNiMnHf high entropy film based on electrodeposition and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0062] Step 1, grinding ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate respectively to a particle size of less than 100 μm; then placing the ground ferrous chloride tetrahydrate, the ground cobalt chloride hexahydrate, the ground manganese chloride tetrahydrate and the ground nickel chloride hexahydrate in a freeze dryer respectively, and freeze-drying them at -55°C for 40 hours, to obtain dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried manganese chloride tetrahydrate and dried nickel chloride hexahydrate in turn.

[0063] Step 2: Prepare ingredients with a concentration of 0.01 mol / l of dried ferrous chloride tetrahydrate, 0.01 mol / l of dried cobalt chloride hexahydrate, 0.01 mol / l of dried nickel chloride hexahydrate and 0.01 mol / l of dried manganese chloride tetrahydrate, and dissolve the dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried nickel chloride hexahydrate and dried manganese chloride tetrahydrate in deionized water.

[0064] Then, the concentrations of potassium chloride, hafnium chloride, ascorbic acid, trisodium citrate, sodium saccharin, sodium dodecyl sulfate, boric acid and malonic acid are prepared to be 0.1 mol / l, 0.01 mol / l, 0.01 mol / l, 0.01 mol / l, 0.001 mol / l, 0.01 mol / l and 0.007 mol / l, and the hafnium chloride and potassium chloride are dissolved in the deionized water, and then the ascorbic acid, trisodium citrate, sodium saccharin, sodium dodecyl sulfate, boric acid and malonic acid are added, and stirred for 7 minutes to obtain an electrolyte.

[0065] Step 3: nitrogen is introduced into the electrolyte at a flow rate of 1.3 l / min, and the time for introducing nitrogen per liter of electrolyte is 7 minutes.

[0066] Step 4: First, clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 7 minutes; then, clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 7 minutes.

[0067] Step 5: Place the indium tin oxide conductive glass cleaned with anhydrous ethanol as the working electrode and the graphite electrode as the counter electrode into an electrolytic cell and connect to a DC power supply; perform electroplating for 45 minutes at an electrolytic cell temperature of 40° C. and a voltage of -8 V to obtain an electro-deposited FeCoNiMnHf high entropy film.

[0068] Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 12 seconds, and then blow dry with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

[0069] The plane of the indium tin oxide conductive glass is 100×100 mm 2 .

[0070] The plane of the graphite electrode is 100×100 mm 2 .

[0071] The inert gas is argon.

[0072] Example 3

[0073] A FeCoNiMnHf high entropy film based on electrodeposition and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0074] Step 1, grinding ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate respectively to a particle size of less than 100 μm; then placing the ground ferrous chloride tetrahydrate, the ground cobalt chloride hexahydrate, the ground manganese chloride tetrahydrate and the ground nickel chloride hexahydrate in a freeze dryer respectively, freeze-drying them at -50°C for 50 hours, and successively obtaining dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried manganese chloride tetrahydrate and dried nickel chloride hexahydrate.

[0075] Step 2: Dissolve the dried ferrous chloride tetrahydrate, the dried cobalt chloride hexahydrate, the dried nickel chloride hexahydrate and the dried manganese chloride tetrahydrate in deionized water.

[0076] Then, the concentration of potassium chloride is 1 mol / l, the concentration of hafnium chloride is 0.015 mol / l, the concentration of ascorbic acid is 0.015 mol / l, the concentration of trisodium citrate is 0.025 mol / l, the concentration of sodium saccharin is 0.02 mol / l, the concentration of sodium dodecyl sulfate is 0.0025 mol / l, the concentration of boric acid is 0.5 mol / l and the concentration of malonic acid is 0.009 mol / l, the hafnium chloride and the potassium chloride are dissolved in the deionized water, and then the ascorbic acid, the trisodium citrate, the sodium saccharin, the sodium dodecyl sulfate, the boric acid and the malonic acid are added, and stirred for 9 minutes to obtain an electrolyte.

[0077] Step 3: nitrogen is introduced into the electrolyte at a flow rate of 1.6 l / min, and the time for introducing nitrogen per liter of electrolyte is 9 minutes.

[0078] Step 4: First, clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 9 minutes; then, clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 9 minutes.

[0079] Step 5: Place the indium tin oxide conductive glass cleaned with anhydrous ethanol as the working electrode and the graphite electrode as the counter electrode into an electrolytic cell and connect to a DC power supply; perform electroplating for 60 minutes at an electrolytic cell temperature of 50° C. and a voltage of -7 V to obtain an electro-deposited FeCoNiMnHf high entropy film.

[0080] Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 15 seconds, and then blow dry with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

[0081] The plane of the indium tin oxide conductive glass is 500×500 mm 2 .

[0082] The plane of the graphite electrode is 500×2500mm 2 .

[0083] The inert gas is nitrogen.

[0084] Example 4

[0085] A FeCoNiMnHf high entropy film based on electrodeposition and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0086] Step 1, grinding ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate respectively to a particle size of less than 100 μm; then placing the ground ferrous chloride tetrahydrate, the ground cobalt chloride hexahydrate, the ground manganese chloride tetrahydrate and the ground nickel chloride hexahydrate in a freeze dryer respectively, freeze-drying them at -40°C for 60 hours, and successively obtaining dried ferrous chloride tetrahydrate, dried cobalt chloride hexahydrate, dried manganese chloride tetrahydrate and dried nickel chloride hexahydrate.

[0087] Step 2: Dissolve the dried ferrous chloride tetrahydrate, the dried cobalt chloride hexahydrate, the dried nickel chloride hexahydrate and the dried manganese chloride tetrahydrate in deionized water.

[0088] Then, the concentration of potassium chloride is 4 mol / l, the concentration of hafnium chloride is 0.012 mol / l, the concentration of ascorbic acid is 0.02 mol / l, the concentration of trisodium citrate is 0.05 mol / l, the concentration of sodium saccharin is 0.025 mol / l, the concentration of sodium dodecyl sulfate is 0.005 mol / l, the concentration of boric acid is 1 mol / l and the concentration of malonic acid is 0.01 mol / l, the hafnium chloride and the potassium chloride are dissolved in the deionized water, and then the ascorbic acid, the trisodium citrate, the sodium saccharin, the sodium dodecyl sulfate, the boric acid and the malonic acid are added, and stirred for 10 minutes to obtain an electrolyte.

[0089] Step 3: nitrogen is introduced into the electrolyte at a flow rate of 2 l / min, and the time for introducing nitrogen per liter of electrolyte is 10 min.

[0090] Step 4: Clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 10 minutes; and then clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 10 minutes.

[0091] Step 5: Place the indium tin oxide conductive glass cleaned with anhydrous ethanol as the working electrode and the graphite electrode as the counter electrode into an electrolytic cell, and connect to a DC power supply; perform electroplating for 90 minutes at an electrolytic cell temperature of 60° C. and a voltage of -5 V to obtain an electro-deposited FeCoNiMnHf high entropy film.

[0092] Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 20 seconds, and then blow dry with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

[0093] The plane of the indium tin oxide conductive glass is 1000×1000mm 2 .

[0094] The plane of the graphite electrode is 1000×1000mm 2 .

[0095] The inert gas is argon.

[0096] Compared with the prior art, this specific implementation has the following positive effects:

[0097] 1. This specific embodiment adopts an electrochemical deposition method to prepare an FeCoNiMnHf high entropy film based on electrodeposition. By passing an inert atmosphere during the electrodeposition process to reduce the oxygen content in the deposited layer, the electrodeposition time and electrodeposition voltage can be freely adjusted to obtain a uniformly distributed FeCoNiMnHf high entropy film based on electrodeposition. In a multi-metal ion solution, multiple metal ions can be co-deposited through their coordination structure. The high entropy film has a high saturation magnetization and obvious magnetic anisotropy. The prepared FeCoNiMnHf high entropy film based on electrodeposition is shown in the attached figure. Figure 1 X-ray diffraction patterns of three FeCoNiMnHf high entropy films based on electrodeposition prepared in Example 1, Example 2 and Example 3; Figure 2 for Figure 1 The scanning electron microscope images of three FeCoNiMnHf high entropy films based on electrodeposition are shown; Figure 3 for Figure 1 The magnetic anisotropy diagram of the second FeCoNiMnHf high entropy film based on electrodeposition is shown. Figure 1 It can be seen that the FeCoNiMnHf high entropy film based on electrodeposition has a uniform XRD phase; Figure 2 It can be seen that the FeCoNiMnHf high entropy thin film based on electrodeposition has similar particle size, uniform distribution and good film forming effect; Figure 3 It can be seen that the relationship between the magnetic anisotropy and the magnetic field angle of the electrodeposited FeCoNiMnHf high entropy film rotated 360° within the magnetic field range shows that the change in the angle between the film and the magnetic field will cause the magnetic properties of the film to change, indicating that the film has obvious magnetic anisotropy and good magnetic properties.

[0098] 2. This specific implementation method uses a direct current power supply to achieve electrochemical deposition. It does not require complex and expensive equipment and can use easily available raw materials. It is a low-cost method for synthesizing alloy films. This method has a simple process flow, is easy to operate, has a short production cycle, has low requirements for the substrate, and can be carried out at low processing temperatures and low energy consumption. By changing the electrodeposition parameters, it is easy to change the composition, morphology and crystal structure of the deposited layer, and then regulate the morphology and performance of the material. Secondly, the aqueous system is used as the electrolyte for electrodeposition, which is green, environmentally friendly, and low in cost, and is greener and safer than organic electrolytes.

[0099] 3. This specific implementation method uses deionized water as the solvent of the electrolyte, and introduces sodium dodecyl sulfate and sodium saccharin to make the electrodeposited film have better integrity and uniformity; and the addition of malonic acid as an electroplating polishing agent makes the electrodeposited metal film have a more metallic luster; secondly, boric acid, ascorbic acid and trisodium citrate are introduced to control the pH value of the solution to inhibit the electrolysis of water, prevent the appearance of oxides or other phases in the film, and significantly improve the purity of the product.

[0100] 4. This specific embodiment can control the volume of the FeCoNiMnHf high-entropy thin film based on electrodeposition by changing the size of the electrolytic cell, thereby increasing the yield for large-scale industrial production.

[0101] Therefore, this specific implementation has the characteristics of simple process, low energy consumption, and green environmental protection. The prepared FeCoNiMnHf high-entropy thin film based on electrodeposition has high metallic gloss, good film integrity, no impurity elements, good uniformity and good magnetic properties.

Claims

1. A method for preparing a FeCoNiMnHf high entropy film based on electrodeposition, characterized in that: The steps of the preparation method are as follows: Step 1, grinding ferrous chloride tetrahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate and nickel chloride hexahydrate respectively to a particle size of less than 100 μm, and then placing them in a freeze dryer for freeze drying; Step 2, preparing ingredients with a concentration of 0.005-0.015 mol / l of dried ferrous chloride tetrahydrate, a concentration of 0.005-0.015 mol / l of dried cobalt chloride hexahydrate, a concentration of 0.005-0.015 mol / l of dried nickel chloride hexahydrate and a concentration of 0.005-0.015 mol / l of dried manganese chloride tetrahydrate, and dissolving the dried ferrous chloride tetrahydrate, the dried cobalt chloride hexahydrate, the dried nickel chloride hexahydrate and the dried manganese chloride tetrahydrate in deionized water; Then, the concentration of potassium chloride is 0.005-4 mol / l, the concentration of hafnium chloride is 0.005-0.015 mol / l, the concentration of ascorbic acid is 0.005-0.02 mol / l, the concentration of trisodium citrate is 0.005-0.05 mol / l, the concentration of sodium saccharin is 0.005-0.025 mol / l, the concentration of sodium dodecyl sulfate is 0.0005-0.005 mol / l, the concentration of boric acid is 0.005-1 mol / l and the concentration of malonic acid is 0.005-0.01 mol / l, the hafnium chloride and the potassium chloride are dissolved in the deionized water, and then the ascorbic acid, the trisodium citrate, the sodium saccharin, the sodium dodecyl sulfate, the boric acid and the malonic acid are added, and stirred for 5-10 minutes to obtain an electrolyte; Step 3, introducing nitrogen into the electrolyte at a flow rate of 1 to 2 l / min, and the time for introducing nitrogen per liter of electrolyte is 5 to 10 min; Step 4, first clean the indium tin oxide conductive glass used in the electrolytic cell with acetone for 5 to 10 minutes; then clean the cleaned indium tin oxide conductive glass with anhydrous ethanol for 5 to 10 minutes; Step 5, the indium tin oxide conductive glass cleaned with anhydrous ethanol is used as a working electrode and the graphite electrode is used as a counter electrode in an electrolytic cell, and a DC power supply is connected; the electrolytic cell temperature is 30 to 60° C. and the voltage is -10 to -5 V. The electrolytic deposition is performed for 30 to 90 minutes to obtain an electro-deposited FeCoNiMnHf high entropy film; Step 6: Rinse the electrodeposited FeCoNiMnHf high entropy film with anhydrous ethanol for 10 to 20 seconds, and then dry it with an inert gas to obtain a FeCoNiMnHf high entropy film based on electrodeposition.

2. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The freeze-drying conditions are: freeze-drying at -60 to -40°C for 30 to 60 hours.

3. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The purity of the ferrous chloride tetrahydrate, the cobaltous chloride hexahydrate, the nickel chloride hexahydrate, and the manganese chloride tetrahydrate are all above analytical grade.

4. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The purities of the hafnium chloride and potassium chloride are both above analytical grade.

5. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The purity of the ascorbic acid, trisodium citrate, sodium saccharin, sodium lauryl sulfate, boric acid and malonic acid is above analytical grade.

6. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The plane of the indium tin oxide conductive glass is 20-1000×20-1000mm 2 .

7. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The plane of the graphite electrode is 20-1000×20-1000mm 2 .

8. The method for preparing a FeCoNiMnHf high entropy thin film based on electrodeposition according to claim 1, characterized in that: The inert gas is nitrogen or argon.

9. A FeCoNiMnHf high entropy film based on electrodeposition, characterized in that The FeCoNiMnHf high entropy film based on electrodeposition is a FeCoNiMnHf high entropy film based on electrodeposition prepared by the method for preparing a FeCoNiMnHf high entropy film based on electrodeposition according to any one of claims 1 to 7.

Images