CN102888630B - A kind of ionic liquid/additive system Low-temperature electro-deposition prepares the method for nano aluminum or nano aluminum coating - Google Patents

Abstract

The present invention designs a method for preparing nano-aluminum or nano-aluminum coating by electrodeposition of ionic liquid/additive system, which is characterized in that ionic liquid is mixed with anhydrous aluminum trichloride to form low-temperature electrolyte, and suitable additives are added to prepare ionic liquid / additive system. The treated substrate is used as the deposition cathode, and nano-aluminum or nano-aluminum coating is prepared by direct current electrodeposition, and the size of aluminum particles can be adjusted as required. The method avoids the problems of high cost and low output of producing nano-aluminum in the existing process. The adopted ionic liquid is a conventional ionic liquid, which has wide sources, low price, high electrical conductivity, wide electrochemical window, non-volatile and environment-friendly. The use of suitable additives can achieve better quality nano-aluminum or nano-aluminum coating in a conventional ionic liquid system, and the obtained aluminum deposition layer is dense, smooth and smooth. The ionic liquid/additive system can obtain nanomaterials at a lower temperature, the reaction is easy to control, and the energy consumption is small. The obtained nano-aluminum has good quality and high current efficiency. The size of nano-aluminum can be effectively controlled by adjusting the amount and formula of additives. , the process is simple, the cost is low, and the application prospect is good.

Description

A method for preparing nano-aluminum or nano-aluminum coating by low-temperature electrodeposition of ionic liquid/additive system

technical field

The invention relates to a method for preparing nano-aluminum or nano-aluminum coating by electrodeposition of an ionic liquid/additive system. It belongs to the field of nonferrous metallurgy.

Background technique

The content of aluminum in the earth's crust is second only to oxygen and silicon, ranking third, and is the most abundant metal element in the earth's crust. Aluminum is the second largest metal material next to steel, accounting for half of the total output of ferrous metals. It has excellent physical and chemical properties and is extremely versatile. The correlation with the national economy is as high as 91%. It is a must for national economic development and national defense construction. Indispensable and important basic raw materials.

In daily life, various aluminum products have been widely used by people. As a new type of material, nano-aluminum has three main application fields, including rocket propellant, explosive additive and aluminum back field of solar panels. These three aspects are of great significance to the situation and economic development of the country. However, ordinary aluminum powder and micron-sized aluminum powder are limited in use due to long ignition delay and slow combustion dynamics. Condensation forms large "clumps" on the propellant burning surface, prolonging the burn time. At the same time, there may be defects such as incomplete combustion, increased infrared signature, loss of two-phase flow in the nozzle, and gas discharge that forms a plume. Compared with ordinary aluminum powder, nano-aluminum powder has the characteristics of faster burning and greater heat release. Compared with ordinary aluminum powder with the same content, the burning rate can be increased by 70%. The large-scale preparation and application research of nano-aluminum is related to the development of national defense construction and the development of high-tech products in our country. The methods for preparing nano-aluminum mainly include evaporation condensation method, line explosion method, mechanochemical method, pulse laser ablation method, arc discharge method and solution chemical method. Although nano-aluminum has very important value in application, the current preparation method is expensive and the output is small, which restricts the development of nano-aluminum in application. Therefore, it is of great significance to develop new low-cost, high-yield nano-aluminum preparation methods.

Ionic liquid is a new type of compound composed entirely of organic cations and inorganic or organic anions. It has low melting point (usually close to or even lower than room temperature), non-volatile, wide electrochemical window, good conductivity, wide liquid range, etc. Excellent properties. Based on the excellent physical and chemical properties of ionic liquids, especially the electrochemical properties, the electrodeposition of aluminum has been realized in a variety of ionic liquids. However, it is difficult to obtain nanometer-sized aluminum particles in common ionic liquids. Usually, the particle size of the deposited layer is on the micron scale, and the deposited layer is loose and rough. In addition, although nanoscale deposition layers can be obtained in some special ionic liquid systems (eg [BMP]NTf ₂ ), such ionic liquids are usually expensive and difficult to prepare, which greatly limits their application and promotion. Additives can be selectively adsorbed on the crystal growth point, inhibit the growth of crystals, and promote the formation of crystal nuclei. Therefore, adding appropriate additives to the conventional ionic liquid system can change the properties of the deposited layer, making the deposited layer dense, smooth, and flat, and finally get nano-aluminum. The ionic liquid/additive system can obtain nano-materials at a lower temperature, the reaction is easy to control, the energy consumption is small, and there is no side reaction. The obtained nano-aluminum has good quality and high current efficiency. By adjusting the amount and formula of additives, it can be better The size of nano-aluminum can be accurately controlled, the cost can be reduced, and the application prospect is broad.

Contents of the invention

The purpose of the present invention is to overcome the problems of high cost and low output of the existing nano-aluminum preparation methods, and provide a method for preparing nano-aluminum by low-temperature electrodeposition of an ionic liquid/additive system. This method has low reaction temperature and low energy consumption, and the obtained nano-aluminum Aluminum has good quality and high current efficiency, which can better control the size of nano-aluminum and reduce costs.

The present invention adopts the method for preparing nano-aluminum by low-temperature electrodeposition of ionic liquid/additive system, and is characterized in that described method comprises the following steps:

(1) The ionic liquid is placed in a vacuum drying box equipped with phosphorus pentoxide, and is vacuum-dried at a constant temperature for 24 to 48 hours;

(2) In the glove box, under the protection of inert gas nitrogen or argon, slowly add aluminum trichloride to the ionic liquid under the stirring of a magnetic stirrer, and mix according to a certain proportion to form a low-temperature ionic liquid electrolyte. Stir evenly;

(3) Optionally add additives with a mass fraction of 0.01% to 50% as required, and stir evenly;

(4) The surface properties of the cathode base material directly affect the degree of bonding between the coating and the substrate and the compactness of the coating. Therefore, before the experiment, the substrate needs to be pretreated before plating. The method is as follows: sandpaper polishing→cleaning→chemical degreasing→water washing→pickling→water washing→acetone soaking→drying→activation treatment in mixed acid of concentrated hydrochloric acid and concentrated sulfuric acid after dilution → Deionized water cleaning → drying;

(5) The anode is made of aluminum, graphite, ceramics, glassy carbon, etc., and the distance between the anode and the cathode is 0.5-15cm;

(6) Add an appropriate amount of electrolyte in the electrolytic cell, under the protection of nitrogen or argon, the constant electrolysis temperature is 20 ℃ ~ 300 ℃, select the appropriate voltage and stirring speed, and the current density is 10 ~ 150A/m ² The nano-aluminum deposition layer was prepared by DC electrodeposition under certain conditions.

(7) Nano-aluminum powder can be obtained in the electrolytic cell under the operation condition of ultrasonic in the electrodeposition process. Clean the nano-aluminum powder with organic solvents such as acetonitrile and acetone in the glove box, and store it in an oil bath after drying.

The cations of the ionic liquid are quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazolium salt ions, pyridinium salt ions, etc., and the anions include halogen ions, tetrafluoroborate ions, hexafluorophosphate ions or other inorganic acid ions. Ionic liquids can be divided into imidazolium salts, pyridinium salts, quaternary ammonium salts and quaternary phosphonium salts, such as: 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methyl bromide Imidazole, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole trifluoromethyl acetate, 1-ethyl-3-methylimidazole bistrifluoro One or a mixed liquid of two or more of methanesulfonimide salt, 1-ethylpyridine chloride, ethylbutylpyrrole bistrifluoromethanesulfonimide salt, trimethylammonium chloride, etc.

The molar ratio of the anhydrous aluminum trichloride to the ionic liquid is 0.5-5:1.

The base material is steel (such as low carbon steel, stainless steel, etc.), metal (iron, aluminum, copper, nickel, etc.), alloy (aluminum alloy, magnesium alloy), carbon, graphite, resin, etc.

Described additive selects organic additive (such as benzene, toluene, xylene, cyclohexane, ammonium chloride, methanol, ethanol, formaldehyde, glyceraldehyde, anisaldehyde, choline chloride, glucose, nicotinic acid etc.), inorganic Additives (such as lanthanum chloride, sodium chloride, potassium chloride, lithium chloride, magnesium chloride, manganese chloride, cerium chloride, neodymium chloride, etc.), surfactants (such as Span-80, Tween-20, Span- 85, Span-40, Tween-20, CTAB, etc.), macromolecular polymers (PVPK-30, etc.), or a mixture of two or more.

During electroplating, the stirring speed of the ionic liquid electrolyte in the electrolytic tank is 0-1000 r/min.

The purity of the inert gas nitrogen or argon is greater than 99.99%.

The invention uses the ionic liquid/additive system as the electrolyte, has low electrolysis temperature, high current efficiency, and low energy consumption, and overcomes the problems of high cost, complicated process, high cost, difficult particle size control and the like in the existing process. The material of the electrolysis device requires anti-corrosion and low cost, and glass, quartz, polytetrafluoroethylene, etc. are usually used. The size of the nano-aluminum can be controlled by changing the type, amount and formula of the additive, and the nano-aluminum with a purity higher than 99.9% can be obtained. The process of the invention is simple and easy, clean and green, has low requirements on the material of the equipment, wide sources of ionic liquid and additives, no pollution and low cost.

Description of drawings

Figure 1 is the morphology of nano-aluminum prepared by low-temperature electrodeposition of ionic liquid/additive system.

Detailed ways

The present invention is illustrated by the following examples, but the present invention is not limited to the following examples, and all implementation methods that meet the purpose described before and after are within the technical scope of the present invention.

Example 1

The ionic liquid 1-butyl-3-methylimidazole chloride was vacuum-dried at 50°C for 24 hours, and in the glove box, under the protection of inert gas argon, the 1-butyl-3-methylimidazole chloride was filled with imidazole and a jacketed electrolytic cell with a thermometer installed on a magnetic stirrer to keep the temperature constant, and gradually add anhydrous aluminum trichloride to the electrolyte to change the composition of the system until aluminum trichloride and 1-butyl chloride - The molar ratio of 3-methylimidazole is 2:1. After reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2 to 3 hours. Add lanthanum chloride and cyclohexane with a mass fraction of 0.1% of the ionic liquid and a molar ratio of 1:1, and continue stirring to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After polishing and polishing the copper sheet of the base electrode with sandpaper, it is used as a deposition cathode after degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying; the anode is polished, ultrasonic cleaning, and dried aluminum sheet. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1 cm, and the reaction temperature was kept at 50°C. The aluminum sheet is used as the anode, the copper sheet is used as the cathode, the current density is controlled at 10A/m ² , the stirring speed during the electrodeposition process is 200r/min, and the specimen is taken out after 30 minutes of electrodeposition. After taking out the test piece, wash it with acetone, ethanol, and deionized water in sequence, and dry it to obtain the nano-aluminum coating. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles in the deposited layer is 69.6nm, and the current efficiency is greater than 96%.

Example 2

The ionic liquid 1-ethyl-3-methylimidazole chloride was vacuum-dried at 50°C for 24 hours. In the glove box, under the protection of inert gas argon, the 1-ethyl-3-methylimidazole chloride was filled with imidazole and a jacketed electrolytic cell equipped with a thermometer is placed on a magnetic stirrer to keep the temperature constant, and anhydrous aluminum trichloride is gradually added to the electrolyte to change the system composition until aluminum trichloride and 1-ethyl chloride - The molar ratio of 3-methylimidazole is 1.1:1. After reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2 to 3 hours. Lithium chloride with a mass fraction of 0.01% of the ionic liquid is added, and stirring is continued to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After the base electrode stainless steel is polished with sandpaper, it is degreased, acid soaked, washed with water, acetone ultrasonically cleaned, and dried as the deposition cathode; the anode is polished, ultrasonically cleaned, and dried. Aluminum sheet. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 0.5 cm, and the reaction temperature was kept at 80°C. The aluminum sheet is used as the anode, the stainless steel is used as the cathode, the current density is controlled at 50A/m ² , the stirring speed during the electrodeposition process is 300r/min, and the specimen is taken out after 30 minutes of electrodeposition. After taking out the test piece, wash it with acetone, ethanol, and deionized water in sequence, and dry it to obtain the nano-aluminum coating. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles in the deposited layer is 33.4nm, and the current efficiency is greater than 98%.

Example 3

The ionic liquid 1-propyl-3-methylimidazole chloride was vacuum-dried at 50°C for 24 hours. In the glove box, under the protection of inert gas argon, the 1-propyl-3-methylimidazole chloride was filled with imidazole and a jacketed electrolytic cell with a thermometer installed on a magnetic stirrer, keeping the temperature constant, adding anhydrous aluminum trichloride to the electrolyte solution to change the system composition until aluminum trichloride and 1-propyl chloride - The molar ratio of 3-methylimidazole is 3:1. After reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2 to 3 hours. Add benzene with a mass fraction of 10% of the ionic liquid, and continue stirring to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After the base electrode low-carbon steel is polished with sandpaper, it is degreased, acid soaked, washed with water, acetone ultrasonically cleaned, and dried as the deposition cathode; the anode is polished, ultrasonically cleaned, and dried. Aluminum sheet. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1.5 cm, and the reaction temperature was kept at 50°C. The aluminum sheet is used as the anode, the low-carbon steel is used as the cathode, the current density is controlled at 100A/m ² , the stirring speed during the electrodeposition process is 500r/min, and the specimen is taken out after 30 minutes of electrodeposition. After taking out the test piece, wash it with acetone, ethanol, and deionized water in sequence, and dry it to obtain the nano-aluminum coating. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles in the deposited layer is 74.5nm, and the current efficiency is greater than 95%.

Example 4

The ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate was vacuum-dried at 50°C for 24 hours. In the glove box, under the protection of inert gas argon, the 1-ethyl-3- Methylimidazolium tetrafluoroborate and the jacketed electrolytic cell with a thermometer installed are placed on a magnetic stirrer, and the temperature is kept constant. Anhydrous aluminum trichloride is gradually added to the electrolyte to change the system composition until the aluminum trichloride and The molar ratio of 1-ethyl-3-methylimidazolium tetrafluoroborate is 4:1. After reaching thermal equilibrium and mixing uniformly, stir at 50° C. for 2 to 3 hours. Add choline chloride and ammonium chloride with a mass fraction of 0.5% ionic liquid and a molar ratio of 1:1, and continue to stir to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After polishing and polishing the zinc sheet of the base electrode with sandpaper, it is used as a deposition cathode after degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying; the anode is polished, ultrasonic cleaning, and dried aluminum sheet. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1 cm, and the reaction temperature was kept at 50°C. With the aluminum sheet as the anode and the zinc sheet as the cathode, the current density is controlled at 80A/m ² , and the stirring speed during the electrodeposition process is 1000r/min. Under the operating conditions accompanied by ultrasound, nano-aluminum is obtained in the electrolytic cell after electrodeposition for 30 minutes. pink. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles in the deposited layer is 63.3nm, and the current efficiency is greater than 98.5%.

Example 5

The ionic liquid 1-ethyl-3-methylimidazole bromide was vacuum-dried at 50°C for 48 hours, and in the glove box, under the protection of inert gas argon, the 1-ethyl-3-methylimidazole bromide was filled with imidazole and a jacketed electrolytic cell with a thermometer installed on a magnetic stirrer to keep the temperature constant, and gradually add anhydrous aluminum trichloride to the electrolyte to change the composition of the system until aluminum trichloride and 1-ethyl bromide - The molar ratio of 3-methylimidazole is 0.5:1. After reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2 to 3 hours. Add potassium chloride and butadiene with a mass fraction of 5% ionic liquid and a molar ratio of 1:4, and continue stirring to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After polishing and polishing the nickel sheet of the base electrode with sandpaper, it is used as the deposition cathode after degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying; the anode is an aluminum sheet after polishing, ultrasonic cleaning, and drying. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1 cm, and the reaction temperature was kept at 50°C. The aluminum sheet is used as the anode, the nickel sheet is used as the cathode, and the current density is controlled at 30A/m ² . Under the operating condition accompanied by ultrasound, nano-aluminum powder is obtained in the electrolytic cell after electrodeposition for 30 minutes. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles is 66.3nm, and the current efficiency is greater than 92%.

Example 6

The ionic liquid 1-ethyl-3-methylimidazolium trifluoromethyl acetate was vacuum-dried at 50°C for 48 hours. In the glove box, under the protection of inert gas argon, the 1-ethyl- 3-Methylimidazole trifluoromethyl acetate and the jacketed electrolytic cell with a thermometer installed on a magnetic stirrer, keeping the temperature constant, adding anhydrous aluminum trichloride to the electrolyte solution to change the system composition until three The molar ratio of aluminum chloride to 1-ethyl-3-methylimidazolium trifluoromethyl acetate is 2:1. After reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2-3 hours. Add Span-85 with a mass fraction of 0.8% of the ionic liquid, and continue to stir to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After polishing and polishing the aluminum-zinc alloy of the base electrode with sandpaper, it is used as a deposition cathode after degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying; the anode is polished, ultrasonic cleaning, and dried aluminum sheet. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 3 cm, and the reaction temperature was kept at 50°C. Using aluminum sheet as the anode and aluminum-zinc alloy as the cathode, the current density is controlled at 150A/m ² , and the nano-aluminum powder is obtained in the electrolytic cell after electrodeposition for 30 minutes under the operation condition of ultrasonic. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles is 29.9nm, and the current efficiency is greater than 93%.

Example 7

The ionic liquid 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt was vacuum-dried at 50°C for 48 hours. In a glove box, under the protection of inert gas argon, the 1-ethyl Base-3-methylimidazole bistrifluoromethanesulfonylimide salt and a jacketed electrolytic cell with a thermometer installed on a magnetic stirrer, keeping the temperature constant, adding anhydrous aluminum trichloride to the electrolyte one by one to change the system Composition, until the molar ratio of aluminum trichloride and 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt is 1.5:1, after reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2 to 3 Hour. Add magnesium chloride and TX-100 with a mass fraction of 0.2% ionic liquid and a molar ratio of 1:1, and continue to stir to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. The base electrode magnesium alloy is polished and polished with sandpaper, followed by degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying as the deposition cathode; the anode is polished, ultrasonic cleaning, and dried aluminum sheet. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 0.8 cm, and the reaction temperature was kept at 50°C. The aluminum sheet is used as the anode, the magnesium alloy is used as the cathode, the current density is controlled at 60A/m ² , and the nano-aluminum powder is obtained in the electrolytic cell after electrodeposition for 30 minutes under the operating condition accompanied by ultrasound. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles is 40.9nm, and the current efficiency is greater than 96%.

Example 8

The ionic liquid 1-ethyl-3-methylimidazole bromide was vacuum-dried at 50°C for 48 hours, and in the glove box, under the protection of inert gas argon, the 1-ethyl-3-methylimidazole bromide was filled with imidazole and a jacketed electrolytic cell with a thermometer installed on a magnetic stirrer to keep the temperature constant, and gradually add anhydrous aluminum trichloride to the electrolyte to change the composition of the system until aluminum trichloride and 1-ethyl bromide - The molar ratio of 3-methylimidazole is 2.5:1. After reaching thermal equilibrium and mixing uniformly, stir at 50°C for 2 to 3 hours. Add cerium chloride and methanol with a mass fraction of 5% ionic liquid and a molar ratio of 1:10, and continue stirring to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After polishing and polishing the nickel sheet of the base electrode with sandpaper, it is used as the deposition cathode after degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying; the anode is an aluminum sheet after polishing, ultrasonic cleaning, and drying. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1 cm, and the reaction temperature was kept at 20°C. The aluminum sheet is used as the anode, the nickel sheet is used as the cathode, the current density is controlled at 30A/m ² , and the nano-aluminum powder is obtained in the electrolytic cell after electrodeposition for 30 minutes under the operating condition accompanied by ultrasound. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles is 66.3nm, and the current efficiency is greater than 84%.

Example 9

The ionic liquid 1-ethylpyridine chloride was vacuum-dried at 50°C for 48 hours. In the glove box, under the protection of inert gas argon, the jacket filled with 1-ethylpyridine chloride and equipped with a thermometer was electrolyzed. Place the cell on a magnetic stirrer, keep the temperature constant, and gradually add anhydrous aluminum trichloride to the electrolyte to change the composition of the system until the molar ratio of aluminum trichloride to 1-ethylpyridine chloride is 5:1, reaching thermal equilibrium After mixing evenly, stir at 50°C for 2 to 3 hours. Add toluene whose mass fraction is 50% of the ionic liquid, and continue to stir to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After polishing and polishing the copper sheet of the base electrode with sandpaper, it is used as a deposition cathode after degreasing, acid soaking, water washing, acetone ultrasonic cleaning, and drying; the anode is made of glassy carbon. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1 cm, and the reaction temperature was kept at 200°C. Using glassy carbon as the anode and copper sheet as the cathode, the current density is controlled at 600A/m ² , and the nano-aluminum powder is obtained in the electrolytic cell after electrodeposition for 30 minutes under the operation condition of ultrasonic. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles is 72.6nm, and the current efficiency is greater than 99%.

Example 10

The ionic liquid trimethylammonium chloride was vacuum-dried at 50°C for 48 hours. In the glove box, under the protection of inert gas argon, the jacketed electrolytic cell filled with trimethylammonium chloride and equipped with a thermometer was placed in On a magnetic stirrer, keep the temperature constant, and gradually add anhydrous aluminum trichloride to the electrolyte to change the composition of the system until the molar ratio of aluminum trichloride to trimethylammonium chloride is 4:1, after reaching thermal equilibrium and mixing uniformly , and stirred at 50°C for 2 to 3 hours. Add lanthanum chloride, ammonium chloride, and cyclohexane with a mass fraction of 1% ionic liquid and a molar ratio of 1:1:5, and continue stirring to ensure that the electrolyte is evenly mixed to obtain an ionic liquid/additive electrolyte system. After the base electrode stainless steel was polished with sandpaper, it was degreased, acid bubbled, washed with water, cleaned with acetone ultrasonically, and dried as a deposition cathode; the anode was made of graphite after ultrasonic cleaning. The ionic liquid was added into the electrolytic cell, the distance between the anode and the cathode was controlled at 1 cm, and the reaction temperature was kept at 150°C. Using graphite as the anode and stainless steel as the cathode, the current density is controlled at 500A/m ² , under the operating conditions accompanied by ultrasound, the nano-aluminum powder is obtained in the electrolytic cell after electrodeposition for 30 minutes. Clean the nano-aluminum powder with acetonitrile in the glove box, dry it and store it in an oil tank. By combining scanning electron microscopy and X-ray dispersion (SEM/EDX) to analyze the base, it is determined that the average particle size of aluminum particles is 50.1nm, and the current efficiency is greater than 98%.

Claims (9)

1. A method for preparing nano-aluminum or nano-aluminum coating by electrodeposition of ionic liquid/additive system, characterized in that described method comprises the following steps: (1) The ionic liquid is placed in a vacuum drying box equipped with phosphorus pentoxide, and is vacuum-dried at a constant temperature for 24 to 48 hours; (2) In the glove box, under the protection of inert gas nitrogen or argon, slowly add anhydrous aluminum trichloride to the ionic liquid under the stirring of a magnetic stirrer, mix to form a low-temperature ionic liquid electrolyte, and stir at a constant temperature Uniform; (3) Add additives with a mass fraction of 0.01% to 50%, and stir evenly; (4) Perform pre-plating pretreatment on the cathode substrate, the method is as follows: sandpaper polishing→cleaning→chemical degreasing→water washing→pickling→water washing→acetone soaking→drying→activation treatment in mixed acid of diluted concentrated hydrochloric acid and concentrated sulfuric acid→ Cleaning with deionized water→drying; (5) The anode is made of aluminum, graphite, ceramics, glassy carbon, and the distance between the anode and the cathode is 0.5-15cm; (6) Add an appropriate amount of electrolyte in the electrolytic cell, under the condition of nitrogen or argon protection, the constant electrolysis temperature is 20 ℃ ~ 300 ℃, and the DC electrodeposition is carried out under the condition of the current density of 10 ~ 150A/m ² to prepare nano aluminum; (7) Under the operating conditions accompanied by ultrasound during the electrodeposition process, nano-aluminum powder was obtained in the electrolytic cell after 30 minutes of electrodeposition; the nano-aluminum powder was cleaned with acetonitrile in the glove box, dried and stored in an oil bath . 2. The method according to claim 1, wherein the ionic liquid cation is a quaternary ammonium salt ion, a quaternary phosphonium salt ion, an imidazolium salt ion or a pyridinium salt ion, and the anion is a halogen ion, tetrafluoroborate ion, hexafluoroborate ion, Fluorophosphate ions or other inorganic acid ions. 3. The method according to claim 1, wherein the ionic liquid is 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole bromide, 1-ethyl- 3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethyl acetate, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide, chlorine One or a mixed liquid of 1-ethylpyridine, ethylbutylpyrrole bistrifluoromethanesulfonimide, trimethylammonium chloride. 4. The method according to claim 1, characterized in that the molar ratio of the anhydrous aluminum trichloride to the ionic liquid is 0.5-5:1. 5. The method according to claim 1, characterized in that the base material is metal, alloy, carbon or resin. 6. The method according to claim 1, characterized in that the base material is low carbon steel, stainless steel, iron, aluminum, copper, nickel, aluminum alloy, magnesium alloy, carbon, graphite, glassy carbon, ceramics. 7. The method according to claim 1, characterized in that the additive is selected from one or more mixtures of organic additives, inorganic additives, surfactants and macromolecular polymers. 8. The method according to claim 1, wherein said additive is benzene, toluene, xylene, cyclohexane, butadiene, styrene, ethylenediamine, ammonium chloride, methyl alcohol, ethanol, formaldehyde , glyceraldehyde, anisaldehyde, choline chloride, glucose, niacin, sodium chloride, potassium chloride, lithium chloride, manganese chloride, magnesium chloride, lanthanum chloride, cerium chloride, neodymium chloride, Span- 80, Span-85, Span-40, Tween-20, CTAB, PVPK-30. 9. The method according to claim 1, characterized in that the stirring speed of the ionic liquid electrolyte in the electrolytic tank is 0 to 1000 r/min during the electroplating.