阅读说明：本技术 一种低温电沉积制备铝钒合金的方法 (Method for preparing aluminum-vanadium alloy by low-temperature electrodeposition ) 是由 汝娟坚 王道祥 杨克墙 华一新 王丁 于 2021-07-16 设计创作，主要内容包括：本发明提供了一种低温电沉积制备铝钒合金的方法,包括以下步骤：将三氯化铝与尿素混合,加热,得到呈路易斯酸性的三氯化铝-尿素离子液体；将五氧化二钒与三氯化铝-尿素离子液体混合,待五氧化二钒溶解,得到五氧化二钒-三氯化铝-尿素离子液体；以五氧化二钒-三氯化铝-尿素离子液体为电解液,在电压3.2V～3.4V,温度60℃～90℃的条件下电沉积至反应结束,收集阴极产物,得到铝钒合金。本发明的方法可以在低温条件下电化学制备铝钒合金,并且可以显著缩短铝钒合金的制备时间,降低生产所需的原料和反应温度,减少生产设备的损耗,能够实现铝钒的低污染生产。(The invention provides a method for preparing an aluminum-vanadium alloy by low-temperature electrodeposition, which comprises the following steps: mixing aluminum trichloride and urea, and heating to obtain a Lewis acidic aluminum trichloride-urea ionic liquid; mixing vanadium pentoxide with the aluminum trichloride-urea ionic liquid, and obtaining the vanadium pentoxide-aluminum trichloride-urea ionic liquid after the vanadium pentoxide is dissolved; taking vanadium pentoxide-aluminum trichloride-urea ionic liquid as electrolyte, carrying out electrodeposition under the conditions of voltage of 3.2V-3.4V and temperature of 60-90 ℃ until the reaction is finished, and collecting a cathode product to obtain the aluminum-vanadium alloy. The method can electrochemically prepare the aluminum-vanadium alloy at low temperature, can obviously shorten the preparation time of the aluminum-vanadium alloy, reduce the raw materials and reaction temperature required by production, reduce the loss of production equipment, and can realize low-pollution production of the aluminum-vanadium alloy.)

1. A method for preparing an aluminum-vanadium alloy by low-temperature electrodeposition is characterized by comprising the following steps:

controlling the mixing ratio of the aluminum trichloride and the urea, and heating to obtain the aluminum trichloride-urea ionic liquid with Lewis acidity;

mixing vanadium pentoxide with the aluminum trichloride-urea ionic liquid, and dissolving the vanadium pentoxide to obtain the vanadium pentoxide-aluminum trichloride-urea ionic liquid;

taking vanadium pentoxide-aluminum trichloride-urea ionic liquid as electrolyte, carrying out electrodeposition under the conditions of 3.2V-3.4V of voltage and 60-90 ℃ until the reaction is finished, and collecting a cathode product to obtain the aluminum-vanadium alloy.

2. The method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition according to claim 1, wherein the concentration of vanadium pentoxide in the vanadium pentoxide-aluminum trichloride-urea ionic liquid is 0.1mol/L to 0.5 mol/L.

3. The method for preparing the aluminum-vanadium alloy by the low-temperature electrodeposition according to claim 2, wherein the concentration of vanadium pentoxide is 0.1-0.2 mol/L.

4. The method for preparing the aluminum-vanadium alloy by the low-temperature electrodeposition according to claim 1, 2 or 3, wherein the voltage is 3.2V-3.4V and the temperature is 80 ℃ to 90 ℃.

5. The method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition according to claim 1, 2 or 3, wherein the electrodeposition time is 2 to 10 hours.

6. The method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition according to claim 5, wherein the electrodeposition time is 6-8 hours.

7. The method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition according to claim 1, 2, 3 or 6, wherein the molar ratio of aluminum trichloride to urea is (1.2-1.8): 1.

8. The method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition according to claim 1, 2, 3 or 6, wherein the step of controlling the mixing ratio of aluminum trichloride and urea and heating to obtain the aluminum trichloride-urea ionic liquid with Lewis acidity comprises the following steps:

under the protection of inert atmosphere, mixing and dissolving aluminum trichloride and urea, and heating the mixture for 1 to 3 hours at 60 to 80 ℃ in a shift mode at the rotating speed of 500 to 700r/min to obtain aluminum trichloride-urea ionic liquid;

adding vanadium pentoxide into the aluminum trichloride-urea ionic liquid, and stirring at the rotating speed of 500 r/min-700 r/min at the temperature of 60-80 ℃ until the vanadium pentoxide is dissolved to obtain the vanadium pentoxide-aluminum trichloride-urea ionic liquid.

9. The method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition according to claim 1, 2, 3 or 6, wherein the electrodeposition takes an aluminum sheet as an anode and a copper sheet as a cathode.

Technical Field

The invention relates to the technical field of aluminum-vanadium alloy preparation, in particular to a method for preparing an aluminum-vanadium alloy by low-temperature electrodeposition.

Background

The aluminum-vanadium alloy is a high-grade alloy material widely used in the field of aerospace, has high hardness and elasticity, is seawater-resistant, is light in weight, and can be used for manufacturing seaplanes, water gliders and the like.

At present, the preparation method of the aluminum vanadium alloy mainly comprises an aluminothermic reduction method and a powder metallurgy method. The aluminothermic reduction method generally adopts vanadium pentoxide, aluminum powder and a slag former as raw materials, and produces the aluminum-vanadium alloy according to the principle of metallothermic reduction. The aluminothermic method for producing the aluminum-vanadium alloy has the advantages of simple process and quick response, but has the defects of poor product quality uniformity and high impurity element content. The powder metallurgy method generally prepares a billet by the processes of powder making, compaction, degassing, sintering, hot pressing and the like, and then prepares the aluminum-vanadium alloy by a plastic deformation processing method. Although the powder metallurgy method has high utilization rate of materials, the method has the defects of high impurity content of products, difficult determination and nonuniformity of alloy component ratio, low mechanical property and the like.

Disclosure of Invention

In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, one of the purposes of the invention is to provide a preparation method of an aluminum-vanadium alloy with low operation temperature and controllable alloy component ratio.

The invention provides a method for preparing an aluminum-vanadium alloy by low-temperature electrodeposition, which comprises the following steps: controlling the mixing ratio of the aluminum trichloride and the urea, and heating to obtain the aluminum trichloride-urea ionic liquid with Lewis acidity; mixing vanadium pentoxide with the aluminum trichloride-urea ionic liquid, and obtaining the vanadium pentoxide-aluminum trichloride-urea ionic liquid after the vanadium pentoxide is dissolved; taking vanadium pentoxide-aluminum trichloride-urea ionic liquid as electrolyte, carrying out electrodeposition under the conditions of 3.2V-3.4V of voltage and 50-90 ℃ until the reaction is finished, and collecting a cathode product to obtain the aluminum-vanadium alloy.

The preparation method of the invention controls the proportion of the aluminum trichloride and the urea to ensure that the formed aluminum trichloride-urea ionic liquid is in Lewis acidity, and the aluminum trichloride-urea ionic liquid in Lewis acidity can dissolve a large amount of vanadium pentoxide powder. By applying a voltage, aluminum element and vanadium element contained in the electrolyte can be deposited on the cathode to form the aluminum-vanadium alloy. And the ratio of aluminum to vanadium in the product alloy can be controlled by controlling the content of vanadium pentoxide in the electrolyte.

Compared with the prior art, the beneficial effects of the invention at least comprise at least one of the following:

(1) the method can electrochemically prepare the aluminum-vanadium alloy at low temperature, can obviously shorten the preparation time of the aluminum-vanadium alloy, reduce the raw materials and reaction temperature required by production, reduce the loss of production equipment, and can realize low-pollution production of the aluminum-vanadium alloy.

(2) The method can control the component ratio in the aluminum-vanadium alloy by controlling the raw material ratio.

Drawings

The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

FIG. 1 shows the cyclic voltammogram of the reduction of vanadium pentoxide in an aluminum trichloride-urea ionic liquid in inventive example 1.

Figure 2 shows the XRD pattern of the cathode product obtained in example 1 of the present invention.

Fig. 3 shows SEM-EDS of the cathode product obtained in example 1 of the present invention, wherein (a) is an SEM image and (b) is a spectrum at a point in the region.

Detailed Description

Hereinafter, a method for preparing an aluminum vanadium alloy by low temperature electrodeposition according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.

The invention provides a method for preparing an aluminum-vanadium alloy by low-temperature electrodeposition, which can comprise the following steps in one exemplary embodiment of the method for preparing the aluminum-vanadium alloy by low-temperature electrodeposition of the invention:

and S01, controlling the mixing ratio of the aluminum trichloride and the urea, and heating to obtain the aluminum trichloride-urea ionic liquid with Lewis acidity.

S02, mixing vanadium pentoxide with the aluminum trichloride-urea ionic liquid, and obtaining the vanadium pentoxide-aluminum trichloride-urea ionic liquid after the vanadium pentoxide is dissolved

And S03, taking the vanadium pentoxide-aluminum trichloride-urea ionic liquid as electrolyte, carrying out electrodeposition under the conditions of voltage of 3.2V-3.4V and temperature of 60-90 ℃ until the reaction is finished, and collecting a cathode product to obtain the aluminum-vanadium alloy.

Further, on the one hand, in order to dissolve vanadium pentoxide in the aluminum trichloride-urea ionic liquid, the aluminum trichloride-urea ionic liquid is required to be in lewis acidity, and the aluminum trichloride-urea in lewis acidity can dissolve vanadium pentoxide, so that lewis basic aluminum trichloride-urea cannot dissolve vanadium pentoxide. In order to make the aluminum trichloride-urea solution have Lewis acidity, the ratio of the aluminum trichloride to the urea can be controlled. On the other hand, the proper ratio of aluminum trichloride to urea can deposit the metallic aluminum. The molar ratio of the aluminum trichloride to the urea can be (1.2-1.8): 1. At the above proportion, the formed aluminum trichloride-urea ionic liquid can be made to be Lewis acidic, and aluminum can be electrodeposited on a cathode. For example, the molar ratio of aluminum trichloride to urea may be 1.6: 1. Preferably, the molar ratio of aluminum trichloride to urea may be 1.5: 1.

Further, in the vanadium pentoxide-aluminum trichloride-urea ionic liquid, the concentration of the vanadium pentoxide can be controlled to be 0.1 mol/L-0.5 mol/L. If the concentration of vanadium pentoxide in the electrolyte is lower than 0.1mol/L, no aluminum-vanadium alloy is generated on the cathode after electrodeposition is finished; if the concentration of vanadium pentoxide in the electrolyte is higher than 0.5mol/L, a large amount of foam can be generated in the electrodeposition process, and no deposit is generated on the cathode. Preferably, the concentration of vanadium pentoxide in the electrolyte can be controlled between 0.1mol/L and 0.2mol/L, where the amount of aluminium vanadium alloy obtained on the cathode is greater than that prepared by applying other voltages. More preferably, the concentration of vanadium pentoxide may be 0.2mol/L, under which conditions the maximum aluminium vanadium alloy product is obtained on the cathode.

Further, the voltage applied during the electrodeposition process may be controlled to be 3.2V to 3.4V. If the voltage is less than 3.2V, no aluminum-vanadium alloy is generated on the cathode; if the voltage is more than 3.4V, the vanadium pentoxide-aluminum trichloride-urea ionic liquid can be decomposed, and therefore, the voltage of the electrodeposition is controlled to be 3.2V-3.4V. Preferably, the voltage can be 3.2V, and the maximum amount of the cathode aluminum vanadium alloy can be obtained under the voltage condition of 3.2V.

Further, the temperature applied during electrodeposition may be 60 ℃ to 90 ℃. The aluminum vanadium alloy obtained on the cathode can be increased along with the increase of the temperature, and the higher the temperature is, the more the aluminum vanadium alloy is obtained. If the temperature is lower than 60 ℃, no aluminum-vanadium alloy is generated on the cathode; if the temperature is too high, the electrolyte may decompose. Therefore, the temperature at which electrodeposition is applied is controlled to 60 ℃ to 90 ℃. Preferably, the temperature may be 80 ℃ to 90 ℃.

Further, the time of electrodeposition may be 2 to 10 hours. If the electrodeposition time is less than 2 hours, no aluminum-vanadium alloy is generated on the cathode; if the time of the electrodeposition is longer than 10 hours, a large amount of aluminum-vanadium alloy deposited on the cathode falls off, and the recovery rate of the product aluminum-vanadium alloy is low. Within the range of 2-10 hours of electrodeposition time, the amount of the aluminum-vanadium alloy obtained on the cathode tends to decrease after increasing with the increase of the electrodeposition time. Preferably, the electrodeposition time may be 6 hours to 8 hours, at which more aluminum vanadium alloy is obtained than other electrodeposition times. More preferably, the time of electrodeposition is 8 hours.

Further, in order to obtain as much aluminum vanadium alloy as possible on the cathode, the conditions applied during the preparation may be: the concentration of vanadium pentoxide in the electrolyte is 0.2mol/L, the electrodeposition voltage is 3.2V, the temperature is 90 ℃, and the deposition time is 8 hours. By the mutual matching of the concentration of vanadium pentoxide, the electrodeposition voltage, the temperature and the deposition time, the aluminum-vanadium alloy can be obtained on the cathode to the maximum extent.

Further, the obtaining of the vanadium pentoxide-aluminum trichloride-urea ionic liquid may include the following steps:

s100, under the protection of inert atmosphere, dissolving aluminum trichloride in urea, and uniformly mixing to obtain the aluminum trichloride-urea ionic liquid. The inert gas may be under an argon atmosphere or under a nitrogen atmosphere. For example, aluminum trichloride can be slowly added into a urea solution under an argon atmosphere, and stirring is continuously carried out during the adding process to obtain the aluminum trichloride-urea ionic liquid. The dissolving process can be carried out under the condition of 60-80 ℃ and the constant temperature of 500-700 r/min for heating and magnetic stirring for 1-3 h. Of course, the stirring time in the present invention is not limited thereto, and aluminum trichloride and urea may be mixed uniformly. For example, stirring is carried out at a temperature of 70 ℃ and a speed of 600 r/min. The aluminum trichloride-urea ionic liquid obtained after stirring can be a reddish brown transparent solution. The aluminum trichloride used can be aluminum trichloride which is dried in vacuum. The temperature of vacuum drying is 60-80 ℃, and the drying time can be 20-28 h. For example, the drying temperature is 70 ℃ and the drying time is 24 hours.

S200, adding vanadium pentoxide into the aluminum trichloride-urea ionic liquid until the vanadium pentoxide is completely dissolved to obtain the vanadium pentoxide-aluminum trichloride-urea ionic liquid. After the aluminum trichloride-urea ionic liquid is obtained, adding vanadium pentoxide into the aluminum trichloride-urea ionic liquid, and heating and stirring until the vanadium pentoxide is completely dissolved to obtain the vanadium pentoxide-aluminum trichloride-urea ionic liquid. The heating and stirring can be constant temperature heating at 60-80 ℃ and the rotating speed of 500-700 r/min, and magnetic stirring is carried out until the vanadium pentoxide is dissolved. For example, stirring is carried out at a temperature of 70 ℃ and a speed of 600r/min for 4 h. Of course, the stirring time is not limited to this, and it may be sufficient to stir until all the vanadium pentoxide is dissolved.

In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.

Example 1

Step 1, weighing aluminum trichloride (AlCl) after vacuum drying (T70 ℃, T24 h)₃) And urea (molar ratio ═ 1.5: 1). Mixing ureaPlacing the mixture in a beaker, and then placing AlCl in an argon atmosphere₃Slowly adding the mixture and continuously stirring the mixture by using a glass rod until AlCl is obtained₃Gradually dissolving with urea, heating at 70 deg.C and 600r/min, magnetically stirring for 2 hr to obtain red brown transparent aluminum trichloride-urea ionic liquid (AlCl)₃-urea ionic liquid).

Step 2, weighing V after vacuum drying (T70 ℃, T24 h)₂O₅Adding the powder into the prepared AlCl₃The concentration of vanadium pentoxide in the urea ionic liquid is 0.1mol/L, and the mixture is heated at the constant temperature of 70 ℃ and 600r/min and stirred magnetically for 4h to V₂O₅Completely dissolving to obtain yellow brown vanadium pentoxide-aluminum trichloride-urea ionic liquid (V)₂O₅-AlCl₃-urea ionic liquid).

Step 3, adopting a stabilized voltage power supply to supply power with V₂O₅-AlCl₃And (3) taking the urea ionic liquid as an electrolyte, taking an aluminum sheet (2cm multiplied by 3cm) as an anode and a copper sheet (2cm multiplied by 3cm) as a cathode, and electrodepositing for 6h at 80 ℃ and 3.2V. And after the electrodeposition is finished, taking out the cathode, putting the cathode into absolute ethyl alcohol for ultrasonic treatment, collecting the deposit, then ultrasonically cleaning the deposit for multiple times by adopting the absolute ethyl alcohol, finally drying the deposit in vacuum at the temperature of 70 ℃ for 2 hours, and sealing the deposit.

Fig. 1 shows the cyclic voltammetry curve of the reduction of vanadium pentoxide in an aluminum trichloride-urea ionic liquid. In the vanadium pentoxide-aluminum trichloride-urea ionic liquid, the first reduction peak appearing in negative scanning is as follows: al (iii) is reduced to metallic aluminum, and the second reduction peak appearing thereafter is presumed to be: v (V) is reduced to vanadium metal. Fig. 2 is the corresponding XRD pattern of the collected cathode product. As can be seen from FIG. 2, an aluminum vanadium alloy (Al) was prepared by the above method₁₁V and Al₃V). FIG. 3 is an SEM-EDS diagram of the obtained cathode product, wherein (a) is an SEM diagram, and (b) is an energy spectrum diagram of a point in the region, and the atomic percentage (At%) in (b): o was 52.4, Al was 36.5, Cl was 7.6, and V was 3.5. The obtained aluminum vanadium alloy is in the form of porous particles as shown in figure (a).

Example 2

In comparison with example 1, the voltage of only electrodeposition becomes 3.4V, and other conditions are the same.

Comparative example 1

In comparison with example 1, the voltage of only electrodeposition becomes 2.6V, and the other conditions are the same.

Comparative example 2

In comparison with example 1, the voltage of only electrodeposition becomes 2.8V, and the other conditions are the same.

Comparative example 3

In comparison with example 1, the voltage of only electrodeposition becomes 3.0V, and the other conditions are the same.

Example 3

In comparison with example 1, only the concentration of vanadium pentoxide became 0.2mol/L, and the other conditions were the same.

Example 4

In comparison with example 1, only the concentration of vanadium pentoxide became 0.5mol/L, and the other conditions were the same.

Comparative example 4

In comparison with example 1, only the concentration of vanadium pentoxide became 0.02mol/L, and the other conditions were the same.

Comparative example 5

In comparison with example 1, only the concentration of vanadium pentoxide became 0.05mol/L, and the other conditions were the same.

Comparative example 6

In comparison with example 1, only the concentration of vanadium pentoxide became 1.0mol/L, and the other conditions were the same.

Example 5

In comparison with example 1, only the electrodeposition temperature was changed to 60 ℃, and the other conditions were the same.

Example 6

In comparison with example 1, only the electrodeposition temperature was changed to 70 ℃, and the other conditions were the same.

Example 7

In comparison with example 1, only the electrodeposition temperature was changed to 90 ℃, and the other conditions were the same.

Comparative example 7

In comparison with example 1, only the electrodeposition temperature was changed to 50 ℃, and the other conditions were the same.

Example 8

Compared to example 1, only the electrodeposition time becomes 2h, and the other conditions are the same.

Example 9

Compared to example 1, only the electrodeposition time becomes 4h, and the other conditions are the same.

Example 10

Compared to example 1, only the electrodeposition time becomes 8h, and the other conditions are the same.

Example 11

Compared to example 1, only the electrodeposition time becomes 10h, and the other conditions are the same.

By comparing examples 1, 2 and comparative examples 1 to 3, the amounts of cathode products obtained at different voltage depositions were counted, as shown in table 1.

Comparative example 8

In contrast to example 1, only aluminum trichloride (AlCl)₃) The molar ratio of urea to urea was 1.1:1, and the other conditions were the same.

Comparative example 9

In contrast to example 1, only aluminum trichloride (AlCl)₃) The molar ratio of urea to urea was 1.9:1, and the other conditions were the same.

TABLE 1 comparison of the Effect of deposition Voltage on the amount of AlV alloy produced

As can be seen from Table 1, when the applied voltage is 3.2V to 3.4V, an aluminum vanadium alloy can be obtained on the cathode. When the voltage is less than 3.2V, no aluminum-vanadium alloy product is generated on the cathode. The product obtained on the cathode does not correspondingly increase with the increase of the voltage, and the product aluminum-vanadium alloy is generated in the largest amount at the voltage of 3.2V.

Through comparative examples 1, 3, 4 and comparative examples 4 to 6, statistics on different electrolytes V are provided₂O₅The results of the amounts of the obtained cathode products at the concentrations are shown in table 2.

TABLE 2V₂O₅Comparison table of influence of concentration on amount of aluminum-vanadium alloy product

As can be seen from Table 2, when the vanadium pentoxide concentration in the electrolyte is less than 0.02mol/L, no Al-V alloy is formed on the cathode, indicating that too low a vanadium pentoxide concentration cannot produce Al-V alloy on the cathode. When the concentration of vanadium pentoxide reaches 0.1mol/L, aluminum-vanadium alloy begins to be generated on the cathode, and the amount of the product is increased along with the increase of the concentration; when the concentration reached 0.2mol/L, the amount of the cathode produced reached the maximum, which was the optimum concentration. When the concentration reached 0.5mol/L, the amount of product began to decrease significantly and a small amount of scum occurred during the deposition. After the concentration is increased to 1.0mol/L, no product aluminum-vanadium alloy is generated on the cathode, and a large amount of froth is generated in the deposition process.

The effect on the amount of the obtained cathode product at different electrodeposition temperatures was counted by comparing example 1, examples 5 to 7, and comparative example 7, and the statistics thereof are shown in table 3.

TABLE 3 influence of temperature on the amount of AlV alloy product

As can be seen from table 3, when the temperature during electrodeposition was less than 60 ℃, the cathode was not produced with deposits. As the temperature increased, after reaching 60 ℃, very little deposition began to appear on the cathode, indicating that the formation of the aluminum vanadium alloy began. The product aluminum vanadium alloy produced on the cathode gradually increases with increasing temperature.

By comparing example 1 with examples 8 to 11, the amounts of cathode products obtained at different electrodeposition times were counted, and the statistics are shown in Table 4:

TABLE 4 comparison of the Effect of electrodeposition time on the amount of AlV alloy produced

As can be seen from table 4, the amount of the produced cathode product tends to increase and decrease with the increase of the deposition time, and when the deposition time is 8 hours, the amount of the aluminum vanadium alloy obtained on the cathode is the largest, but there may be a small amount of the deposit falling off.

The cathodes of comparative examples 1, 8-9, 8 and 9 have no black precipitate, which shows that the ratio of aluminum trichloride and urea cannot be too high or too low, and neither too high nor too low can obtain the aluminum-vanadium alloy.

Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.