CN115874172A - Passivation solution, aluminum foil passivation treatment method, aluminum plastic film and lithium battery - Google Patents
Passivation solution, aluminum foil passivation treatment method, aluminum plastic film and lithium battery Download PDFInfo
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Abstract
The invention discloses a passivation solution, an aluminum foil passivation treatment method, an aluminum plastic film and a lithium battery. The passivation solution comprises trivalent chromium salt, a film forming promoter, a complexing agent, a thickening agent, nano-scale modified carbon black, a carbon black dispersing agent and water. The passivation solution is adopted to treat the aluminum foil to obtain a passivation layer with excellent blackness, stable color and high adhesive force, the aluminum foil passivated by the passivation solution can be used for preparing an aluminum-plastic film with excellent electrolyte resistance, good stability and strong aging resistance, the aluminum-plastic film can meet the color requirement of a mobile phone battery, and meanwhile, the passivation solution has the advantages of no cobalt, no silver, low toxicity, low cost and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of aluminum foil surface treatment, and particularly relates to a passivation solution, an aluminum foil passivation treatment method, an aluminum plastic film and a lithium battery.
Background
The passivation solution is a chemical agent which forms a layer of compact oxide film (passivation film) on the surface of the metal under certain conditions to enhance the corrosion resistance of the metal. In the passivation of metals, the surface passivation of the aluminum foil layer occupies a special position due to the large area and the strict requirement, and is increasingly concerned by the industry and the whole society. At present, the components and concentrations of the passivator at home and abroad are developing towards high quality, high stability, high corrosion resistance and low toxicity.
The passivating agent used in the current market has the common problems that the passivating agent used for the conventional aluminum foil is colorless after passivation and cannot endow the aluminum foil with a color effect; secondly, the existing black passivation solution is reactive, needs to react with zinc on the surface, is only suitable for the surface of a galvanized part or a zinc alloy, and lacks of the black passivation solution suitable for aluminum foil passivation; thirdly, the corrosion resistance effect of the passivation solution is poor; fourthly, in the traditional black passivation solution, a large amount of hexavalent chromium, silver salt and copper salt are used, which causes great damage and loss to the environment and resources and causes the problem of overhigh cost.
Therefore, the existing black passivation solution suitable for aluminum foil is to be developed.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide a passivation solution, an aluminum foil passivation treatment method, an aluminum plastic film and a lithium battery. The passivation solution has a good coloring effect by introducing the nano modified carbon black material, the black layer also has a good reflection heat radiation effect, and meanwhile, the introduction of the nano material can also be used as a novel sealant, so that the passivation effect and the corrosion resistance of the passivation layer are improved, and the addition amount of trivalent chromium can be reduced to a certain extent. The passivation solution is adopted to treat the aluminum foil to obtain a passivation layer with excellent blackness, stable color and high adhesive force, the aluminum foil passivated by the passivation solution can be used for preparing an aluminum-plastic film with excellent electrolyte resistance, good stability and strong aging resistance, the aluminum-plastic film can meet the color requirement of a mobile phone battery, and meanwhile, the passivation solution has the advantages of no cobalt, no silver, low toxicity, low cost and environmental friendliness.
In one aspect of the invention, a passivation solution is provided. According to an embodiment of the present invention, a passivation solution includes: trivalent chromium salt, a film forming promoter, a complexing agent, a thickening agent, nano-scale modified carbon black, a carbon black dispersing agent and water.
The passivation solution according to the embodiment of the invention comprises trivalent chromium salt, a film forming promoter, a complexing agent, a thickening agent, nanoscale modified carbon black, a carbon black dispersing agent and water. The passivation solution firstly performs acid etching on the surface of the aluminum foil, then combines the trivalent chromium serving as the center with a ligand to form a metal complex, and firmly bonds or adheres the trivalent chromium to the surface of the aluminum foil through mutual bonding among coordination bonds, so that a layer of corrosion-resistant compact protective film is formed on the surface of the aluminum foil; meanwhile, the nano-scale modified carbon black has better space stability in water and shows better coloring uniformity due to the advantages of hydrophilic groups on the surface and small particle size of the nano material, and is uniformly and compactly distributed in the passivation layer in the formation process of the passivation layer under the action of the carbon black dispersing agent, so that the passivation layer has uniform color, black and bright color and good blackness, can meet the color requirement of a mobile phone battery, and saves the existing black ink coating process. The nano-modified carbon black is uniformly dispersed in the passivation layer, so that the passivation layer can further protect the stable and continuous existence of color, and the modified nano material can be used as a novel passivation solution sealant, so that the corrosion resistance of the passivation layer is improved to a great extent. Therefore, the passivation layer with excellent blackness, stable color and high adhesive force can be obtained by processing the aluminum foil with the passivation solution, the aluminum foil passivated by the passivation solution can be used for preparing an aluminum-plastic film with excellent electrolyte resistance, good stability and strong aging resistance, the aluminum-plastic film can meet the color requirement of a mobile phone battery, and meanwhile, the passivation solution has the advantages of no cobalt or silver, low toxicity, low cost and environmental friendliness.
In addition, the passivation solution according to the above embodiment of the present invention may further have the following technical features:
in some embodiments of the invention, based on 1L of passivation solution, the addition amount of the trivalent chromium salt is 3g to 30g, the addition amount of the film forming accelerant is 1g to 10g, the addition amount of the complexing agent is 3g to 30g, the addition amount of the thickening agent is 1g to 4g, the addition amount of the nanoscale modified carbon black is 10g to 50g, the addition amount of the carbon black dispersing agent is 10g to 50g, and the balance is water. Therefore, the passivation layer with excellent blackness, stable color and high adhesive force can be obtained by treating the aluminum foil with the passivation solution.
In some embodiments of the invention, the passivation solution has a pH of 0.5 to 4.0. Therefore, the aluminum foil treated by the passivation solution can obtain a passivation layer with excellent corrosion resistance.
In some embodiments of the present invention, the nanoscale modified carbon black has a particle size of no greater than 100nm and a tinting strength of no less than 120%. Therefore, the passivation layer with excellent blackness and stable color can be obtained by treating the aluminum foil with the passivation solution.
In some embodiments of the invention, the nanoscale modified carbon black comprises at least one of a water-soluble carbon black powder, a pigment carbon black, and an aqueous ink.
In some embodiments of the present invention, the modifying group in the nanoscale modified carbon black comprises at least one of a carboxyl group, an ester group, a hydroxyl group, and a carbonyl group.
In some embodiments of the present invention, the carbon black dispersant includes at least one of an anionic wetting dispersant, a cationic wetting dispersant, a controlled radical hyperdispersant, a non-ionic wetting dispersant, and an amphoteric wetting dispersant.
In some embodiments of the invention, the anionic wetting dispersant comprises at least one of sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, and sodium dodecyl sulfate.
In some embodiments of the invention, the trivalent chromium salt comprises at least one of chromium nitrate, chromium sulfate, and chromium chloride.
In some embodiments of the invention, the film-forming promoting agent comprises at least one of potassium sulfate, sodium sulfate, potassium nitrate, phosphoric acid, sodium nitrate, fluotitanic acid, and polyacrylic acid.
In some embodiments of the invention, the complexing agent comprises at least one of a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, and butanetetracarboxylic acid.
In some embodiments of the invention, the monocarboxylic acid comprises at least one of formic acid, acetic acid, propionic acid, an amino acid, glycolic acid, acrylic acid, and methacrylic acid.
In some embodiments of the invention, the dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, tartaric acid, and malic acid.
In some embodiments of the invention, the triprotic acid comprises at least one of phosphoric acid and citric acid.
In some embodiments of the invention, the thickener comprises at least one of methyl cellulose and ethyl cellulose.
In a second aspect of the present invention, a method for passivating aluminum foil is provided. According to an embodiment of the invention, the method comprises: the above passivation solution was applied to at least one side of the aluminum foil and then dried, so that an aluminum foil having a black passivation layer was obtained. Therefore, the passivation layer with excellent blackness, stable color and high adhesive force can be formed on the surface of the aluminum foil by adopting the method to treat the aluminum foil, and the black aluminum-plastic film is prepared by using the passivated aluminum foil, so that the process is simple and the production efficiency is high.
In addition, the passivation treatment method for the aluminum foil according to the above embodiment of the present invention may further have the following technical features:
in some embodiments of the invention, the drying temperature is 120-240 ℃, and the drying time is 0.2-3 min.
In a third aspect of the present invention, an aluminum-plastic film is provided. According to the embodiment of the invention, the aluminum plastic film sequentially comprises a polyamide film layer, a first bonding layer, an aluminum foil layer, a second bonding layer and a polyolefin film layer; wherein the aluminum foil layer is prepared by the method. Therefore, the aluminum plastic film has excellent electrolyte resistance, good stability and strong aging resistance.
In addition, the aluminum plastic film according to the above embodiment of the present invention may further have the following technical features:
in some embodiments of the invention, the polyamide film layer has a thickness of 5 μm to 25 μm.
In some embodiments of the present invention, the first adhesive layer has a thickness of 3 μm to 5 μm.
In some embodiments of the invention, the passivation solution is applied to the side of the aluminum foil layer away from the second adhesive layer, and the thickness of the obtained passivation layer is 0.03 μm to 1 μm.
In some embodiments of the invention, the passivation solution is applied to the side of the aluminum foil layer away from the first adhesive layer, and the thickness of the obtained passivation layer is 0.03 μm to 1 μm.
In some embodiments of the invention, the passivation layer has a dry film amount of 0.01g/m 2 ～0.3g/m 2 . Therefore, a passivation layer which is bright in black and good in corrosion prevention effect can be obtained.
In some embodiments of the present invention, the aluminum foil layer has a thickness of 20 μm to 50 μm.
In some embodiments of the present invention, the second adhesive layer has a thickness of 2 μm to 10 μm.
In some embodiments of the present invention, the polyolefin film layer has a thickness of 20 μm to 40 μm.
In a fourth aspect of the present invention, a lithium battery is provided. According to the embodiment of the invention, the lithium battery adopts the aluminum plastic film. Thus, the lithium battery has excellent electrical properties and is low in production cost.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural diagram of an aluminum plastic film according to an embodiment of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the invention, a passivation solution is provided. According to an embodiment of the invention, the passivation solution comprises: trivalent chromium salt, a film forming promoter, a complexing agent, a thickening agent, nano-scale modified carbon black, a carbon black dispersing agent and water.
The passivation solution according to the embodiment of the invention comprises trivalent chromium salt, a film forming promoter, a complexing agent, a thickening agent, nanoscale modified carbon black, a carbon black dispersing agent and water. The passivation solution firstly performs acid etching on the surface of the aluminum foil, then combines the trivalent chromium serving as the center with a ligand to form a metal complex, and firmly bonds or adheres the trivalent chromium to the surface of the aluminum foil through mutual bonding among coordination bonds, so that a layer of corrosion-resistant compact protective film is formed on the surface of the aluminum foil; meanwhile, the nanoscale modified carbon black has the advantages of good space stability and good coloring uniformity in water due to the surface hydrophilic groups and small particle size of the nano material, and is uniformly and compactly distributed in the passivation layer forming process under the action of the carbon black dispersing agent, so that the passivation layer is uniform in color, black and bright and has good blackness, the color requirement of a mobile phone battery can be met, and the conventional black ink coating process is saved. The nano-modified carbon black is uniformly dispersed in the passivation layer, so that the passivation layer can further protect the stable and continuous existence of color, and the modified nano material can be used as a novel passivation solution sealant, so that the corrosion resistance of the passivation layer is improved to a great extent. Therefore, the passivation layer with excellent blackness, stable color and high adhesive force can be obtained by treating the aluminum foil with the passivation solution, the aluminum foil passivated by the passivation solution can be used for preparing an aluminum plastic film with excellent electrolyte resistance, good stability and strong aging resistance, the aluminum plastic film can meet the color requirement of a mobile phone battery, and meanwhile, the passivation solution has the advantages of no cobalt or silver, low toxicity, low cost and environmental friendliness.
It should be noted that the trivalent chromium salt, the film formation promoter, the complexing agent, the thickener, the nano-scale modified carbon black and the carbon black dispersant are conventional materials in the art, and may be selected by those skilled in the art according to the actual use, for example, the trivalent chromium salt includes at least one of chromium nitrate, chromium sulfate and chromium chloride; the film forming accelerant comprises at least one of potassium sulfate, sodium sulfate, potassium nitrate, phosphoric acid, sodium nitrate, fluotitanic acid and polyacrylic acid; the complexing agent comprises at least one of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and butanetetracarboxylic acid, the monocarboxylic acid comprises at least one of formic acid, acetic acid, propionic acid, amino acid, glycolic acid, acrylic acid and methacrylic acid, the dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, tartaric acid and malic acid, and the tricarboxylic acid comprises at least one of phosphoric acid and citric acid; the thickener comprises at least one of methyl cellulose and ethyl cellulose; the nano-scale modified carbon black includes at least one of water-soluble carbon black powder, pigment carbon black and aqueous ink, and further, the modifying group in the nano-scale modified carbon black includes at least one of a carboxyl group, an ester group, a hydroxyl group and a carbonyl group. The carbon black dispersant needs to have good compatibility with an aqueous base material to prevent flooding and bloom and stabilize various pigments (carbon black), so the carbon black dispersant includes at least one of an anionic wetting dispersant, a cationic wetting dispersant, a controlled radical type hyper-dispersant, a non-ionic wetting dispersant and an amphoteric wetting dispersant, and the anionic wetting dispersant includes at least one of sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium dodecyl sulfate.
According to an embodiment of the invention, the pH of the passivating solution is between 0.5 and 4.0. The inventor finds that the pH of the passivation solution is lower than 0.5, the passivation solution is too strong in acidity, the reaction rate is too high, the compactness and the corrosion resistance of the passivation layer are poor, the pH of the passivation solution is higher than 4.0, the acidity of the passivation solution is lower, the reaction rate is too low, and the passivation effect is weakened. Therefore, the passivation layer with excellent corrosion resistance can be obtained by treating the aluminum foil with the passivation solution with the pH of 0.5-4.0.
According to the embodiment of the invention, based on 1L of passivation solution, the addition amount of trivalent chromium salt is 3-30 g, the addition amount of film forming accelerant is 1-10 g, the addition amount of complexing agent is 3-30 g, the addition amount of thickening agent is 1-4 g, the addition amount of nanoscale modified carbon black is 10-50 g, the addition amount of carbon black dispersing agent is 10-50 g, and the balance is water. The inventor finds that if the additive amount of the trivalent chromium salt is too large, the trivalent chromium of the passivation layer is excessive, the appearance of the passivation layer is poor, the surface of the passivation layer is rough, and if the additive amount of the trivalent chromium salt is too small, the adhesive force between the passivation layer and the aluminum foil is low, and the compactness and the corrosion resistance of the passivation layer are poor; if the addition amount of the film forming accelerant is too much, the film layer structure is not loose, and if the addition amount of the film forming accelerant is too little, the film forming speed is too slow, and the film layer is too thin; if the addition amount of the complexing agent is too much, the reaction rate is too high, the corrosion resistance of the passivation layer is not good, and if the addition amount of the complexing agent is too little, the reaction rate is too low, and the compactness of the passivation layer is not good; if the addition amount of the nano-scale modified carbon black is too large, the adhesion of a passivation layer is poor, and if the addition amount of the nano-scale modified carbon black is too small, the coloring effect is poor, the blackness of the passivation layer is not enough, and the passivation layer is grayed; the problem of agglomeration is easy to occur when the addition amount of the carbon black dispersing agent is too much, the carbon black dispersing effect is influenced when the addition amount of the carbon black dispersing agent is too little, and the system is unstable and is easy to settle and float. Therefore, the passivation layer with excellent blackness, stable color, high adhesion and corrosion resistance can be obtained by treating the aluminum foil with the passivation solution obtained by the formula of the addition amount of the components.
According to the embodiment of the invention, the nano-scale modified carbon black has a particle size of not more than 100nm and a tinting strength of not less than 120%. The inventor finds that if the particle size of the nano-scale modified carbon black is too large, the nano-scale modified carbon black is poor in dispersion and easy to settle; if the tinting strength is too low, the tinting effect is poor and the blackness of the passivation layer is insufficient. Therefore, the passivation layer with excellent blackness and stable color can be obtained by treating the aluminum foil with the passivation solution prepared from the nano-scale modified carbon black with the particle size of not more than 100nm and the tinting strength of not less than 120%.
In a second aspect of the present invention, a method for passivating aluminum foil is provided. According to an embodiment of the invention, the method comprises: the above passivation solution was applied to at least one side of the aluminum foil and then dried, so that an aluminum foil having a black passivation layer was obtained. Therefore, the passivation layer with excellent blackness, stable color and high adhesive force can be formed on the surface of the aluminum foil by adopting the method to treat the aluminum foil, and the black aluminum-plastic film is prepared by using the passivated aluminum foil, so that the process is simple and the production efficiency is high.
Further, the drying temperature is 120-250 ℃, and the drying time is 0.2-3 min. Meanwhile, the inventor finds that after the prepared passivation solution is aged for 3-10 days, the amount of free hydrogen ions is increased due to the coordination reaction in the passivation solution, so that the surface etching of the passivation solution on the aluminum foil can be well promoted, and the corrosion prevention effect of the passivation layer is enhanced. It should be noted that the features and advantages described above for the passivation solution are also applicable to the method for passivating aluminum foil, and are not described herein again.
In a third aspect of the present invention, an aluminum-plastic film is provided. According to an embodiment of the present invention, referring to fig. 1, the aluminum plastic film includes a polyamide film layer 10, a first adhesive layer 20, an aluminum foil layer 30, a second adhesive layer 40, and a polyolefin film layer 50 in this order; wherein, the aluminum foil layer 30 is prepared by the method. Therefore, the aluminum plastic film has excellent electrolyte resistance, good stability and strong aging resistance, and can meet the color requirement of the mobile phone battery.
The aluminum foil matte surface is treated by the passivation solution to obtain a black passivation layer, so that the aluminum-plastic film has black color, the black passivation layer can be prepared on the non-matte surface of the aluminum foil by the passivation solution, and the non-matte surface of the aluminum foil can be treated by the passivation solution to form a passivation layer. It should be noted that the features and advantages described above for the passivation solution and the passivation method for aluminum foil also apply to the aluminum-plastic film, and are not described herein again.
According to an embodiment of the present invention, referring to fig. 1, the polyamide film layer 10 has a thickness of 5 to 25 μm; the thickness of the first adhesive layer 20 is 3 μm to 5 μm; applying a passivation solution to one side of the aluminum foil layer 30 far away from the second adhesive layer 40, wherein the thickness of the obtained passivation layer 31 is 0.03-1 μm; applying a passivation solution to one side of the aluminum foil layer 30 far away from the first adhesive layer 20, wherein the thickness of the obtained passivation layer 32 is 0.03-1 μm; the thickness of the aluminum foil layer 30 is 20 μm to 50 μm; the thickness of the second adhesive layer 40 is 2 μm to 10 μm; the polyolefin film layer 50 has a thickness of 20 to 40 μm. Therefore, the aluminum plastic film has a good black effect and is resistant to electrolyte.
According to an embodiment of the present invention, the passivation layer has a dry film amount of 0.01g/m 2 ～0.3g/m 2 . The inventor finds that if the thickness of the passivation layer on one side of the aluminum foil is too thick, the passivation layer is loose in structure, and a good passivation effect cannot be achieved; if the thickness is too thin, the compactness of the passivation layer is not enough, the corrosion resistant effect is poor, and the blackness is low. Thus, the amount of dry film employed herein is 0.01g/m 2 ～0.3g/m 2 The aluminum-plastic film with bright black color and good corrosion resistance can be obtained by the passivation layer.
In a fourth aspect of the invention, a lithium battery is provided. According to the embodiment of the invention, the lithium battery adopts the aluminum plastic film. Thus, the lithium battery has excellent electrical properties and is low in production cost. It should be noted that the features and advantages described above for the aluminum plastic film are also applicable to the lithium battery, and are not described herein again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
The method for removing oil and activating the surface of the aluminum foil with the thickness of 40 mu m can refer to the cleaning method of Chinese patent CN100545308, and the specific proportion of the passivation solution is as follows: by taking 1L of passivation solution as a reference, 20g of chromic nitrate, 6g of polyacrylic acid, 20g of tartaric acid, 50g of pigment carbon black, 40g of sodium hexametaphosphate, 4g of methyl cellulose and the balance of pure water, wherein the particle size of the nanoscale modified carbon black is 60nm, the tinting strength is 136%, and the pH value of the passivation solution is 1.5.
Coating the passivation solution on two sides of the cleaned aluminum foil, and drying at 200 deg.C for 0.5min to obtain black and bright passivation layer with dry film amount of 0.2g/m 2 And coating an outer layer adhesive of 3 mu m on the passivated aluminum foil matte surface, then compounding a polyamide film of 25 mu m, coating an inner layer adhesive of 3 mu m on the aluminum foil bright surface, and then compounding a polypropylene film of 40 mu m to obtain the black aluminum-plastic film.
Example 2
The method for removing oil and activating the surface of the aluminum foil with the thickness of 35 μm can refer to the cleaning method of Chinese patent CN100545308, and the specific proportion of the passivation solution is as follows: based on 1L of passivation solution, 30g of chromium sulfate, 10g of sodium sulfate, 10g of citric acid, 20g of water-soluble carbon black powder, 50g of sodium pyrophosphate, 1g of ethyl cellulose and the balance of pure water, wherein the particle size of the nanoscale modified carbon black is 40nm, the tinting strength is 140%, and the pH value of the passivation solution is 2.8.
Coating the passivation solution on two side surfaces of the cleaned aluminum foil, and drying at 120 ℃ for 3min to obtain a black and bright passivation layer with a dry film amount of 0.08g/m 2 And coating an outer layer adhesive of 3 mu m on the passivated aluminum foil matte surface, then compounding a polyamide film of 15 mu m, coating an inner layer adhesive of 3 mu m on the aluminum foil bright surface, and then compounding a polypropylene film of 30 mu m to obtain the black aluminum-plastic film.
Example 3
The surface of a 35-micron aluminum foil is degreased and activated, which can be referred to the cleaning method of chinese patent CN100545308, and the specific ratio of the passivation solution is as follows: by taking 1L of passivation solution as a reference, 20g of chromium nitrate, 6g of polyacrylic acid, 20g of butane tetracarboxylic acid, 50g of pigment carbon black, 40g of sodium hexametaphosphate, 4g of methyl cellulose and the balance of pure water, wherein the particle size of the nanoscale modified carbon black is 80nm, the tinting strength is 126%, and the pH value of the passivation solution is 2.0.
Aluminum foil after cleaningCoating the passivation solution on two side surfaces, and drying at 160 deg.C for 2min to obtain black and bright passivation layer with single side passivation layer dry film amount of 0.15g/m 2 And coating an outer layer adhesive of 3 mu m on the passivated aluminum foil matte surface, then compounding a polyamide film of 15 mu m, coating an inner layer adhesive of 3 mu m on the polished aluminum foil surface, and then compounding a polypropylene film of 40 mu m to obtain the black aluminum-plastic film.
Comparative example 1
The method for removing oil and activating the surface of the aluminum foil with the thickness of 40 mu m can refer to the cleaning method of Chinese patent CN100545308, and the specific proportion of the passivation solution is as follows: by taking 1L of passivation solution as a reference, 20g of chromium sulfate, 6g of polyacrylic acid, 30g of maleic acid, 5g of water-soluble carbon black powder, 40g of sodium hexametaphosphate, 4g of ethyl cellulose and the balance of pure water, wherein the particle size of the nano-modified carbon black is 80nm, the tinting strength is 130%, and the pH value of the passivation solution is 2.4.
Coating passivation solution on two side surfaces of the cleaned aluminum foil, and drying at 180 ℃ for 1min to obtain a black passivation layer with a dry film amount of 0.15g/m 2 And coating an outer layer adhesive of 3 mu m on the passivated aluminum foil matte surface, then compounding a polyamide film of 25 mu m, coating an inner layer adhesive of 3 mu m on the polished aluminum foil surface, and then compounding a polypropylene film of 40 mu m to obtain the black aluminum-plastic film.
Comparative example 2
The method for removing oil and activating the surface of the aluminum foil with the thickness of 40 mu m can refer to the cleaning method of Chinese patent CN100545308, and the specific proportion of the passivation solution is as follows: 5g of chromium nitrate, 6g of sodium nitrate, 3g of phosphoric acid, 80g of pigment carbon black, 40g of sodium pyrophosphate, 4g of ethyl cellulose and the balance of pure water by taking 1L of passivation solution as a reference, wherein the particle size of the nano-scale modified carbon black is 60nm, the tinting strength is 132%, and the pH of the passivation solution is 3.0.
Coating passivation solution on two side surfaces of the cleaned aluminum foil, and drying at 180 ℃ for 0.5min to obtain a black passivation layer with a dry film amount of 0.06g/m 2 Coating an outer layer adhesive of 3 mu m on the passivated aluminum foil matte surface, compounding a polyamide film of 25 mu m, coating an inner layer adhesive of 3 mu m on the aluminum foil bright surface, and compounding40 μm polypropylene film to obtain a black aluminum plastic film.
Comparative example 3
Degreasing and activating the surface of a 40 μm aluminum foil by using a commercially available passivation solution according to the cleaning method of Chinese patent CN100545308, coating the commercially available passivation solution on both sides of the aluminum foil after cleaning, and drying at 180 deg.C for 1min to obtain a passivation layer with a dry film amount of 0.1g/m on one side 2 And coating an outer layer adhesive of 3 mu m on the passivated aluminum foil matte surface, then compounding a polyamide film of 25 mu m, coating an inner layer adhesive of 3 mu m on the aluminum foil bright surface, and then compounding a polypropylene film of 40 mu m to obtain the aluminum-plastic film.
The properties of the passivation layers prepared in examples 1 to 3 and comparative examples 1 to 3 were measured by the following specific methods:
(1) Apparent color of the aluminum foil passivation layer.
(2) And (3) copper sulfate dripping test: the prepared copper sulfate component is 40g/LCuSO 4 ·5H 2 O,30g/L NaCl,18ml/L30% HCl. And (3) dripping the copper sulfate solution on the surface of the passivation layer by using a syringe at room temperature, observing the color change of the copper sulfate, recording the time for changing the color from blue to black by using a stopwatch, and measuring three points of each sample and then taking an average value.
(3) And (4) testing adhesive force, namely drawing grids on the surface layer of the passivation layer by using a grid knife, sticking the grid position by using a 3M adhesive tape, pressing and squeezing out air bubbles in the middle of the adhesive tape, keeping for 1min, then rapidly tearing the adhesive tape, and observing whether the passivation layer falls off or not.
The apparent colors of the passivation layers prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in table 1.
TABLE 1
| Apparent color | |
| Is not dullAluminum foil | Silver color |
| Example 1 | Black color (black) |
| Example 2 | Black color |
| Example 3 | Black color |
| Comparative example 1 | Light grey |
| Comparative example 2 | Black color (black) |
| Comparative example 3 | Silver color |
As can be seen from table 1, the passivation layers prepared using examples 1 to 3 were all black, and comparative example 1 used less carbon black, so the color of the passivation layer was light gray.
The results of adhesion and corrosion resistance tests on the passivation layers prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in table 2.
TABLE 2
| Adhesion test | Copper sulfate test(s) | |
| Example 1 | Without falling off | 50 |
| Example 2 | Without falling off | 66 |
| Example 3 | Without falling off | 58 |
| Comparative example 1 | Without falling off | 63 |
| Comparative example 2 | Falling off | / |
| Comparative example 3 | Without falling off | 45 |
| Non-passivated aluminium foil | / | 2 |
As can be seen from the data of the copper sulfate dropping test in the table 2, the color of the copper sulfate solution changes when the copper sulfate is dropped for 2s for the aluminum foil without passivation, but the color of the aluminum foil passivated by the passivation solution changes when the copper sulfate is dropped for more than 50s for the aluminum foil passivated by the passivation solution of the present application, while the color of the aluminum foil passivated by the copper sulfate changes when the copper sulfate is dropped for 63s in the comparative example 1, the passivation layer prepared in the comparative example 1 is light gray, and the adhesion of the passivation layer is poor due to excessive addition of the carbon black in the comparative example 2. As can be seen from the adhesion test results in Table 2, the passivation layer of the aluminum foil has good adhesion and does not fall off.
The performance of the aluminum plastic films prepared in examples 1 to 3 and comparative example 3 was measured by the following specific method:
(1) Electrolyte resistance performance test: the prepared aluminum-plastic film is cut into a sample strip with the width of 15mm, the sample strip is subjected to a mechanical property test to obtain the initial tension of the aluminum foil CPP film, the obtained aluminum-plastic film sample strip is placed in an electrolyte (containing 1000ppm of water) at the temperature of 85 ℃, and the peel strength test is carried out every 1 day.
(2) Boiling resistance test: after the aluminum plastic film sample is washed, the aluminum plastic film sample is placed in water at 70 ℃ to be boiled for 1 day, the apparent change of the sample piece before and after the water boiling is observed, the defects of layering, white lines, color change and the like are confirmed, and three parallel samples are placed for comparison in each sample test.
(3) And (3) heat resistance test: and (3) punching the aluminum-plastic film sample, standing at the high temperature of 85 ℃ for 1 day, taking out, observing the apparent change of the sample wafer before and after observation, confirming whether the defects such as layering, white lines, color change and the like exist, and simultaneously placing three parallel samples for comparison in each sample test.
(4) Moisture and heat resistance test: after punching the shell of the aluminum plastic film sample, placing the aluminum plastic film sample for 3 days under the condition of 60 ℃/90 percent RH, observing the apparent change of the sample piece before and after the humidity and heat resistance, confirming whether the defects of layering, white lines, discoloration and the like exist, and simultaneously placing three parallel samples for comparison in each sample test.
The electrolyte resistance test results of the aluminum plastic films prepared in examples 1 to 3 and comparative example 3 are shown in table 3.
TABLE 3
As can be seen from the results in table 3, the aluminum films prepared in examples 1 to 3 of the present application all had high initial peel force and little change in the bubble electrolyte post-peel force, while the commercially available aluminum film of comparative example 3 had a small initial peel force and a large change in the bubble electrolyte post-peel force, indicating that the aluminum film of the present application has excellent electrolyte resistance.
The results of the aging resistance tests on examples 1 to 3 are shown in Table 4.
TABLE 4
| Resistance to boiling | Heat resistance | Moisture and heat resistance | |
| Example 1 | Without change | Without change | Without change |
| Example 2 | Without change | Without change | Without change |
| Example 3 | Without change | Without change | Without change |
As can be seen from the results in table 4, the aluminum-plastic films of the present application are resistant to boiling, indicating that the stability of the aluminum-plastic films is good; the aluminum-plastic film disclosed by the application is heat-resistant and damp-heat resistant, so that the aluminum-plastic film has good aging resistance.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A passivation solution, comprising: trivalent chromium salt, a film forming promoter, a complexing agent, a thickening agent, nano-scale modified carbon black, a carbon black dispersing agent and water.
2. The passivation solution of claim 1, wherein based on 1L of passivation solution, the trivalent chromium salt is added in an amount of 3g to 30g, the film formation promoter is added in an amount of 1g to 10g, the complexing agent is added in an amount of 3g to 30g, the thickener is added in an amount of 1g to 4g, the nanoscale modified carbon black is added in an amount of 10g to 50g, the carbon black dispersant is added in an amount of 10g to 50g, and the balance is water;
optionally, the pH of the passivation solution is 0.5-4.0.
3. The passivation solution of claim 1 or 2, characterized in that the nanoscale modified carbon black has a particle size of not more than 100nm and a tinting strength of not less than 120%;
optionally, the nanoscale modified carbon black comprises at least one of a water-soluble carbon black powder, a pigment carbon black, and an aqueous ink;
optionally, the modifying group in the nanoscale modified carbon black comprises at least one of a carboxyl group, an ester group, a hydroxyl group, and a carbonyl group.
4. The passivation solution of claim 1 or 2, characterized in that the carbon black dispersant comprises at least one of an anionic wetting dispersant, a cationic wetting dispersant, a controlled radical hyperdispersant, a non-ionic wetting dispersant, and an amphoteric wetting dispersant;
optionally, the anionic wetting dispersant comprises at least one of sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, and sodium dodecyl sulfate.
5. The passivation solution of claim 1 or 2, characterized in that the trivalent chromium salt comprises at least one of chromium nitrate, chromium sulfate and chromium chloride;
optionally, the film forming promoter comprises at least one of potassium sulfate, sodium sulfate, potassium nitrate, phosphoric acid, sodium nitrate, fluotitanic acid, and polyacrylic acid;
optionally, the complexing agent comprises at least one of a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, and butanetetracarboxylic acid;
optionally, the monocarboxylic acid comprises at least one of formic acid, acetic acid, propionic acid, an amino acid, glycolic acid, acrylic acid, and methacrylic acid;
optionally, the dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, tartaric acid, and malic acid;
optionally, the triprotic acid comprises at least one of phosphoric acid and citric acid;
optionally, the thickener comprises at least one of methyl cellulose and ethyl cellulose.
6. A passivation treatment method for aluminum foil is characterized by comprising the following steps:
applying the passivation solution of any one of claims 1 to 5 on at least one side of an aluminum foil, followed by drying, so as to obtain an aluminum foil with a black passivation layer.
7. The method according to claim 6, wherein the drying temperature is 120-250 ℃ and the drying time is 0.2-3 min.
8. An aluminum-plastic film is characterized by sequentially comprising a polyamide film layer, a first bonding layer, an aluminum foil layer, a second bonding layer and a polyolefin film layer;
wherein the aluminum foil layer is prepared by the method of claim 6 or 7.
9. The aluminum-plastic composite film of claim 8, wherein the polyamide film layer has a thickness of 5 μm to 25 μm;
optionally, the first bonding layer has a thickness of 3 to 5 μm;
optionally, applying the passivation solution to one side of the aluminum foil layer away from the second adhesive layer, wherein the thickness of the obtained passivation layer is 0.03-1 μm;
optionally, the passivation solution is applied to one side of the aluminum foil layer away from the first bonding layer, and the thickness of the obtained passivation layer is 0.03-1 μm;
optionally, the passivation layer has a dry film amount of 0.01g/m 2 ～0.3g/m 2 ；
Optionally, the thickness of the aluminum foil layer is 20-50 μm;
optionally, the second adhesive layer has a thickness of 2 μm to 10 μm;
optionally, the polyolefin film layer has a thickness of 20 to 40 μm.
10. A lithium battery characterized in that the aluminum plastic film according to claim 8 or 9 is used.
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| CN202211701261.7A CN115874172A (en) | 2022-12-28 | 2022-12-28 | Passivation solution, aluminum foil passivation treatment method, aluminum plastic film and lithium battery |
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| CN202211701261.7A CN115874172A (en) | 2022-12-28 | 2022-12-28 | Passivation solution, aluminum foil passivation treatment method, aluminum plastic film and lithium battery |
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