A ternary green cerium-manganese-zirconium anticorrosion passivation liquid for aluminum foil surface and preparation method thereof

Abstract

The invention discloses a ternary green anticorrosion passivation liquid of cerium-manganese-zirconium for aluminum foil surface and a preparation method thereof, including the following raw materials in parts by weight: 20-30 parts of cerium dioxide, 15-20 parts of manganese dioxide, 10-15 parts of zirconium nitrate, 3-4 parts of dispersant, 2-3 parts of surfactant, 20-70 parts of diluent monomer, and 1-6 parts of thiol compounds. The ternary green anticorrosion passivation liquid of cerium-manganese-zirconium of the present invention does not produce toxicity during use, has good corrosion resistance, is environmentally friendly and has less energy consumption. The ternary green anticorrosion passivation liquid of cerium-manganese-zirconium of the present invention can meet the wide range of use of coating amount, and there will be no color difference similar to that occurring due to the excessively high coating content of trivalent chromium passivation liquid, and the ternary green anticorrosion passivation liquid of cerium-manganese-zirconium has good stability and can be used for a long time.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of anticorrosion passivation liquid for aluminum foil surface, and particularly relates to a ternary green anticorrosion passivation liquid of cerium-manganese-zirconium for aluminum foil surface and a preparation method thereof. Background Art

[0002] With the rapid development of new energy vehicles, new energy batteries are also changing with each passing day. Among the three battery forms of cylindrical, square hard shell, and soft-pack laminated, soft-pack batteries have the characteristics of flexible design, light weight, small internal resistance, not easy to explode, and many cycles. The specific energy performance of the battery is also outstanding. Therefore, laminated soft-pack power lithium-ion batteries are currently a hot topic of research. The outer packaging material of the battery carries an arduous mission. It must not only meet the harsh conditions of high punch depth, electrolyte resistance, moisture and heat resistance, but also maintain a certain thickness. Considering all factors, aluminum-plastic film is the best outer packaging material.

[0003] Aluminum is a highly active metal. With the help of PP, it can protect aluminum foil to a great extent. However, if you want to extend the service life of aluminum foil, you need to treat the surface of the aluminum foil. Hexavalent chromium system passivation liquid is a good aluminum foil surface passivation liquid, but because of its strong toxicity, it cannot meet the current environmental protection requirements.

[0004] Currently, the trivalent chromium system passivation liquid is commonly used. Although its toxicity is only one millionth of the hexavalent chromium system passivation liquid, the trivalent chromium system passivation liquid still has certain toxicity and is harmful to the health of people who use it for a long time. Summary of the invention

[0005] The invention aims to provide a ternary green cerium-manganese-zirconium anticorrosion passivation liquid for aluminum foil surface and a preparation method thereof, which has the advantages of being non-toxic and pollution-free.

[0006] The above technical objectives of the present invention are achieved through the following technical solutions:

[0007] A ternary green cerium-manganese-zirconium anticorrosion passivation liquid for aluminum foil surface comprises the following raw materials in parts by weight: 20-30 parts of cerium dioxide, 15-20 parts of manganese dioxide, 10-15 parts of zirconium nitrate, 3-4 parts of dispersant, 2-3 parts of surfactant, 20-70 parts of diluent monomer and 1-6 parts of thiol compound.

[0008] More preferably, the weight parts of the raw materials are: 30 parts of cerium dioxide, 18 parts of manganese dioxide, 14 parts of zirconium nitrate, 3.6 parts of dispersant, 2.4 parts of surfactant, 50 parts of diluent monomer, and 3 parts of thiol compound.

[0009] More preferably, the surfactant includes sodium dodecahydrate benzene sulfonate and sodium linear alkyl benzene sulfonate.

[0010] More preferably, the ratio of sodium benzenesulfonate dodecahydrate to sodium linear alkylbenzenesulfonate is 1:1.

[0011] More preferably, the dispersant comprises aqueous ammonium acrylate and sodium lauryl sulfate.

[0012] More preferably, the ratio of aqueous ammonium acrylate to sodium lauryl sulfate is 3:1.

[0013] Further preferably, the diluent monomer is one or a mixture of any several of monofunctional or difunctional or higher functional acrylate monomers; further preferably, the diluent monomer is one or a mixture of any several of tetrahydrofuran acrylate, isooctyl methacrylate, lauryl methacrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, and 1,4-butanediol diacrylate.

[0014] More preferably, the thiol compound is one of n-dodecyl mercaptan, tert-dodecyl mercaptan, trimethylolpropane tris(3-mercaptopropionate) or a mixture of any of them.

[0015] A method for preparing a ternary green cerium-manganese-zirconium anticorrosion passivation solution for an aluminum foil surface comprises at least the following steps:

[0016] S1: Weigh cerium dioxide, manganese dioxide, zirconium nitrate, and diluent monomer;

[0017] S2: adding the weighed raw materials into a blender in sequence, evacuating to a vacuum for the first time so that the excess oxygen in the air will not react with the zirconium nitrate to form a slightly soluble zirconium oxide precipitate during the following stirring process, and stirring evenly to obtain a basic passivation solution;

[0018] S3: Weigh the dispersant, surfactant, and thiol compound, and add them to the basic passivation solution in order, and evacuate to vacuum for the second time, which can more effectively prevent the added dispersant, surfactant, and thiol compound from reacting with oxygen in the air and the above raw materials during the stirring process, and can prevent the problem of uneven dispersion of the dispersant in the treatment agent caused by bubbles generated during the stirring process, and stir evenly to obtain a cerium-manganese-zirconium ternary green anticorrosion passivation solution;

[0019] S4: The obtained cerium-manganese-zirconium ternary green anti-corrosion passivation liquid is naturally cooled to room temperature and sealed and packaged for storage.

[0020] Further preferably, the first vacuuming parameter in S2 is a vacuum degree of -0.2 to -0.05 MPa; the second vacuuming parameter in S4 is a vacuum degree of -0.05 to -0.09 MPa, and the stirring parameters are a rotation speed of 600-1000 r / min and a time of 0.5-1 h. The first high vacuum degree can largely avoid the formation of slightly soluble zirconium oxide, and the second low vacuum degree is because the addition of dispersants and surfactants can well inhibit the reaction of zirconium nitrate and oxygen to form zirconium oxide, and an excessively high vacuum degree is no longer required.

[0021] In summary, the present invention has the following beneficial effects:

[0022] 1. The cerium-manganese-zirconium ternary green anti-corrosion passivation liquid of the present invention does not produce toxicity during use, has good corrosion resistance, is environmentally friendly and consumes less energy.

[0023] 2. The cerium-manganese-zirconium ternary green anticorrosion passivation liquid of the present invention can meet the use of a wide range of coating amounts, and will not have color differences similar to those caused by excessively high coating content of the trivalent chromium passivation liquid. At the same time, the cerium-manganese-zirconium ternary green anticorrosion passivation liquid has good stability and can be used for a long time.

[0024] 3. The cerium-manganese-zirconium ternary green anticorrosion passivation liquid of the present invention can be directly glued without complete drying, and can be put into the oven room for aging together with the adhesive, which greatly shortens the process cycle of the aluminum-plastic film, reduces the investment in manpower, time and energy consumption, and improves the production capacity of the aluminum-plastic film. DETAILED DESCRIPTION

[0025] The present invention is described in detail below in conjunction with preferred embodiments.

[0026] A method for preparing a ternary green cerium-manganese-zirconium anticorrosion passivation solution for an aluminum foil surface comprises at least the following steps:

[0027] S1: Weigh cerium dioxide, manganese dioxide, zirconium nitrate, and diluent monomer;

[0028] S2: Add the weighed raw materials into the mixer in sequence, evacuate to vacuum for the first time, and stir evenly to obtain a basic passivation solution;

[0029] S3: Weigh a dispersant, a surfactant, and a thiol compound, and add them to the basic passivation solution in order, evacuate to vacuum for the second time, stir evenly, and obtain a cerium-manganese-zirconium ternary green anticorrosion passivation solution;

[0030] S4: The obtained cerium-manganese-zirconium ternary green anti-corrosion passivation liquid is naturally cooled to room temperature and sealed and packaged for storage.

[0031] Coating amount: 0.5±0.1g / m2

[0032] Table 1 - Raw materials by weight

[0033]

[0034]

[0035] Table 2 - Preparation conditions parameters

[0036]

[0037] Comparative Example 1: Traditional trivalent chromium passivation solution.

[0038] Comparative Example 2: Chromium-free cerium system passivation solution.

[0039] Performance test

[0040] Test aluminum-plastic film structure: nylon film 25μm, aluminum foil 40μm, CPP film 40μm.

[0041] 1. Electrolyte resistance test

[0042] The aluminum foil treated with different passivation solutions was made into aluminum-plastic film using the same nylon film, CPP film and adhesive, and cut into dumbbell shapes. They were placed in the electrolyte and immersed at 85°C for different times, and then the peel strength of the inner layer was tested.

[0043] Sample shape: dumbbell shape (stretching area width 15mm)

[0044] Stretching speed: 100mm / min

[0045] Table 3 - Electrolyte resistance performance test results

[0046]

[0047] In combination with Table 1, Table 2 and Table 3, and in combination with Examples 1-5, it can be seen that when the raw materials weight parts of the cerium-manganese-zirconium ternary green anti-corrosion passivation liquid are 30 parts of cerium dioxide, 18 parts of manganese dioxide, 14 parts of zirconium nitrate, 3.6 parts of dispersant, 2.4 parts of surfactant, 50 parts of diluent monomer, and 3 parts of thiol compound, and the preparation condition parameters are the first vacuum degree -0.07MPa, the first vacuum degree -0.09MPa, the rotation speed is 900r / min, and the stirring time is 0.9h, the aluminum-plastic film has the best electrolyte resistance performance.

[0048] Combining Example 5 and Comparative Examples 1-2, it can be seen that the cerium-manganese-zirconium ternary green anti-corrosion passivation solution has the best corrosion resistance, followed by the chromium-free cerium system passivation solution, while the traditional trivalent chromium passivation solution has the worst electrolyte resistance.

[0049] 2. Moisture and heat resistance test

[0050] The aluminum-plastic film coated with aluminum foil of different passivation liquids was subjected to a deep-drawing test under a deep-drawing machine. 50 samples were drawn for each sample and placed in a constant temperature and humidity chamber. After a period of time, it was observed whether the outer layer had any debonding.

[0051] Mould model: 105050

[0052] Punching depth: 6mm

[0053] Test conditions: temperature 60°C, humidity 90%

[0054] Table 4 - Test results of moisture and heat resistance

[0055]

[0056] Combining Table 1, Table 2 and Table 4, and combining Examples 1-5, it can be seen that when the weight of the raw materials of the cerium-manganese-zirconium ternary green anticorrosion passivation liquid is 30 parts of cerium dioxide, 18 parts of manganese dioxide, 14 parts of zirconium nitrate, 3.6 parts of dispersant, 2.4 parts of surfactant, 50 parts of diluent monomer, and 3 parts of thiol compounds, and the preparation condition parameters are the first vacuum degree -0.07MPa, the first vacuum degree -0.09MPa, the speed is 900r / min, and the stirring time is 0.9h, the aluminum plastic film has the best wet heat resistance. During the stirring process, the speed determines the dispersion degree of the dispersant and the surfactant in the treatment agent, because the lower speed during the stirring process will cause the dispersant to agglomerate before it has time to disperse, and it is not easy to separate after agglomeration, and a higher speed can solve the problem of agglomeration well, but the higher the speed, the higher the probability of generating large bubbles, and large bubbles will cause the agglomeration of the dispersant and the surfactant, therefore, by adjusting the speed within a certain range, it is possible to solve the agglomeration problem without generating large bubbles.

[0057] Combining Example 5 and Comparative Examples 1-2, it can be seen that the bonding performance of the cerium-manganese-zirconium ternary green anti-corrosion passivation liquid to the outer layer adhesive of the aluminum foil is better than that of the chromium-free cerium system passivation liquid and the traditional trivalent chromium passivation liquid. The aluminum-plastic film prepared with the cerium salt passivation layer has better moisture and heat resistance than the aluminum-plastic film prepared with the trivalent chromium salt passivation layer. The reason may be that the cerium salt passivation layer eventually forms a cerium dioxide coating on the surface of the aluminum foil, in which part of the Ce 4+ React with the aluminum foil surface to form Ce 3+ The passivation film skeleton eventually forms a dense passivation film, which can largely prevent oxygen in the air from entering the surface of the aluminum foil and prevent the aluminum foil from corroding. Once the passivation film is damaged, Ce that has not been reduced by the aluminum foil will 4+ It will migrate to the metal surface, oxidize the exposed aluminum foil, and generate Ce 3+Repair the passivation film and restore its protective properties. Therefore, the cerium salt passivation layer has self-repairing properties, just like the hexavalent chromium passivation layer, but the trivalent chromium passivation layer does not have self-repairing properties. Therefore, the aluminum-plastic film with the cerium salt passivation layer has better moisture and heat resistance than the trivalent chromium passivation layer. And manganese and zirconium elements can promote this process.

[0058] The above-mentioned implementation mode is only an explanation of the present invention, and it is not a limitation of the present invention. After reading this specification, those skilled in the art can make non-creative modifications to the present implementation mode as needed, but as long as it is within the scope of the claims of the present invention, it is protected by the patent law.

Claims

1. A ternary green cerium-manganese-zirconium anticorrosion passivation solution for aluminum foil surface, characterized in that: The method is composed of the following raw materials in parts by weight: 20-30 parts of cerium dioxide, 15-20 parts of manganese dioxide, 10-15 parts of zirconium nitrate, 3-4 parts of dispersant, 2-3 parts of surfactant, 20-70 parts of diluent monomer, and 1-6 parts of thiol compound; The surfactant includes sodium benzene sulfonate dodecahydrate and sodium linear alkyl benzene sulfonate; The diluent monomer is one or a mixture of any of monofunctional, difunctional or higher functional acrylate monomers; The thiol compound is one of n-dodecyl mercaptan, tert-dodecyl mercaptan, trimethylolpropane tris(3-mercaptopropionic acid) ester or a mixture of any of them.

2. The cerium-manganese-zirconium ternary green anti-corrosion passivation solution for aluminum foil surface according to claim 1, characterized in that: The weight parts of the raw materials are as follows: 30 parts of cerium dioxide, 18 parts of manganese dioxide, 14 parts of zirconium nitrate, 3.6 parts of dispersant, 2.4 parts of surfactant, 50 parts of diluent monomer, and 3 parts of thiol compound.

3. The cerium-manganese-zirconium ternary green anticorrosion passivation solution for aluminum foil surface according to claim 1, characterized in that: The ratio of sodium benzenesulfonate dodecahydrate to sodium linear alkylbenzenesulfonate is 1:

1.

4. The cerium-manganese-zirconium ternary green anticorrosion passivation solution for aluminum foil surface according to claim 1, characterized in that: The dispersant comprises aqueous ammonium acrylate and sodium lauryl sulfate.

5. The cerium-manganese-zirconium ternary green anticorrosion passivation solution for aluminum foil surface according to claim 4, characterized in that: The ratio of the aqueous ammonium acrylate to sodium lauryl sulfate is 3:

1.

6. The method for preparing the cerium-manganese-zirconium ternary green anticorrosion passivation solution for aluminum foil surface according to any one of claims 1 to 5, characterized in that: At least the following steps are included: S1: Weigh cerium dioxide, manganese dioxide, zirconium nitrate, and diluent monomer; S2: Add the weighed raw materials into the mixer in sequence, evacuate to vacuum for the first time, and stir evenly to obtain a basic passivation solution; S3: Weigh a dispersant, a surfactant, and a thiol compound, and add them to the basic passivation solution in order, evacuate to vacuum for the second time, stir evenly, and obtain a cerium-manganese-zirconium ternary green anticorrosion passivation solution; S4: The obtained cerium-manganese-zirconium ternary green anti-corrosion passivation liquid is naturally cooled to room temperature and sealed and packaged for storage.

7. The method for preparing the cerium-manganese-zirconium ternary green anticorrosion passivation solution for the surface of aluminum foil according to claim 6, characterized in that: The parameters for the first vacuum pumping described in S2 are a vacuum degree of -0.2 to -0.05 MPa; the parameters for the second vacuum pumping described in S4 are a vacuum degree of -0.05 to -0.09 MPa, and the stirring parameters are a rotation speed of 600-1000 r / min and a time of 0.5-1 h.

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