Copper foil polishing agent and copper foil cleaning method

Abstract

The invention discloses a copper foil polishing agent and a copper foil cleaning method, the copper foil leveling polishing agent is prepared by mixing an inorganic acid, an inorganic salt, a nonionic surfactant and water, the proportion of the inorganic acid is 60-80%, the proportion of the inorganic salt is 0.1-1%, and the proportion of the nonionic surfactant is 0.1-1%. According to the copper foil polishing agent and the copper foil cleaning method, the polishing speed is moderate, good glossiness can be achieved, loss of copper metal can be reduced, the corrosion speed is consistent in all areas of the metal surface, the original shape of a circuit can be well kept, meanwhile, the corrosion inhibition performance is excellent, the occurrence probability of pitting corrosion can be effectively reduced, and the service life of the copper foil is prolonged. In addition, the maintenance method is simple and convenient, the use cost of a use unit is greatly reduced, the light emitting speed is high, the production efficiency can be improved, the polishing agent can be stored conveniently, and the polishing agent is prevented from being decomposed.

Description

Technical Field

[0001] The invention relates to the field of copper foil leveling polishing agent, in particular to a copper foil polishing agent and a copper foil cleaning method. Background Art

[0002] As the new energy industry develops rapidly, lithium batteries are widely used. Among them, copper foil is crucial as a key material for the positive electrode current collector. Polished copper foil, with its smooth surface and low roughness, can improve current collection efficiency, reduce battery internal resistance, and increase output power. Compared with rough copper foil, polished copper foil has better contact with the negative electrode active material, which can prevent the coating active material from falling off due to decreased adhesion, thereby ensuring the battery cycle life.

[0003] There are many disadvantages in the polishing cleaning agent in the prior art. In terms of ingredients, the polishing cleaning agent containing hexavalent chromium is not environmentally friendly and causes serious pollution to the environment. In terms of use effect, its corrosion rate on copper metal is too fast, resulting in excessive reduction in the thickness of the copper foil after polishing. In addition, due to the inconsistent corrosion rate on the copper surface, it lacks specificity. In order to make up for the environmental defects of the hexavalent chromium system polishing cleaning agent, a hydrogen peroxide system polishing agent has been launched on the market.

[0004] The above and prior art have the following defects: the hydrogen peroxide contained in the polishing agent of hydrogen peroxide system is easy to decompose, the effect of use is unstable, and it will cause harm to the human body if it accidentally contacts the skin. Summary of the invention

[0005] The main purpose of the present invention is to provide a copper foil polishing agent and a copper foil cleaning method, which can effectively solve the problems in the background technology.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A copper foil polishing agent is prepared by mixing inorganic acid, inorganic salt, nonionic surfactant and water, wherein the proportion of the inorganic acid is 60-80%, the proportion of the inorganic salt is 0.1-1%, the proportion of the nonionic surfactant is 0.1-1%, and the proportion of water is 15-30%.

[0008] Furthermore, the proportions of the components in the copper foil leveling and polishing agent are: 70% inorganic acid, 1% inorganic salt, 1% nonionic surfactant, and 28% water.

[0009] Furthermore, the proportions of the components in the copper foil leveling and polishing agent are: 80% inorganic acid, 0.5% inorganic salt, 0.5% nonionic surfactant, and 19% water.

[0010] Furthermore, the proportions of the components in the copper foil leveling and polishing agent are: 78% inorganic acid, 1% inorganic salt, 1% nonionic surfactant, and 20% water.

[0011] Furthermore, the proportions of the components in the copper foil leveling and polishing agent are: 79% inorganic acid, 0.2% inorganic salt, 0.8% nonionic surfactant, and 20% water.

[0012] Furthermore, the inorganic acid is formed by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion, the inorganic salt is formed by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion, and the nonionic surfactant is fatty alcohol polyoxyethylene ether.

[0013] A copper foil cleaning method using a copper foil polishing agent comprises the following steps:

[0014] S1: Remove oil and oxide film;

[0015] S2: Wash;

[0016] S3: Drain the water;

[0017] S4: copper foil leveling polishing agent, polishing and cleaning;

[0018] S5: Wash;

[0019] S6: Dilute acid stripping;

[0020] S7: Cleaning - copper protection;

[0021] S8: Wash;

[0022] S9: Blowing water;

[0023] S10: Drying.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The polishing speed of the present invention is moderate (25-30°C, 0.95±0.1μm / min), which can achieve good glossiness and reduce the loss of copper metal. The corrosion speed is consistent in various areas of the metal surface, and the original shape of the circuit can be kept intact. At the same time, the corrosion inhibition is excellent, and the probability of pitting corrosion can be effectively reduced, thereby significantly improving the physical properties of the metal. In addition, the maintenance method is simple and convenient, which greatly reduces the use cost of the user unit. The light emission speed is fast, which helps to improve production efficiency, and it is also convenient to store the polishing agent to avoid decomposition of the polishing agent. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Embodiment 1:

[0028] A copper foil polishing agent is prepared by mixing inorganic acid, inorganic salt, non-ionic surfactant and water, wherein the proportion of inorganic acid is 60-80%, the proportion of inorganic salt is 0.1-1%, the proportion of non-ionic surfactant is 0.1-1%, and the proportion of water is 15-30%. The inorganic acid is prepared by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion, the inorganic salt is prepared by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion, and the non-ionic surfactant is fatty alcohol polyoxyethylene ether.

[0029] The cleaning method of copper foil leveling polishing agent includes the following steps:

[0030] S1: remove oil and oxide film; S2: clean; S3: drain water; S4: copper foil leveling polishing agent, polishing and cleaning; S5: clean; S6: dilute acid stripping; S7: clean - copper protection; S8: clean; S9: blow water; S10: dry.

[0031] The maintenance method of copper foil leveling polishing agent is to titrate copper ions with EDTA standard solution under the condition of PH=10, using PAN as indicator;

[0032] (1) Reagents include:

[0033] ① 0.2% PAN indicator: dissolve 0.2g PAN [1-(2-pyridyl azo)-2-naphthol] in 100ml anhydrous ethanol;

[0034] ②PH=10 buffer solution: weigh 54g ammonium chloride, dissolve it in about 400ml water, add 350ml concentrated ammonia water, dilute to 1000ml with water, and stir evenly;

[0035] ③0.1NEDTA standard solution;

[0036] (2) Analytical methods:

[0037] ① Use a glass pipette to draw V1 = 1 mL of the solution into a 250 mL conical flask; add 100 mL of pure water;

[0038] ②Add 10 ml of pH=10 buffer solution; add 5-6 drops of 0.2% PAN indicator (the solution turns blue-purple);

[0039] ③ Titrate with 0.1N EDTA standard solution until the solution changes from blue-purple to light yellow, and record the consumption of milliliters of EDTA standard solution V2;

[0040] (3) Calculation: Copper ion concentration C = 64 × N × V2 ÷ V1 (g / L)

[0041] In the formula

[0042] N—molar concentration of EDTA standard solution;

[0043] V1—the number of milliliters of plating solution absorbed, i.e. 1mL;

[0044] V2—the number of milliliters of EDTA standard solution consumed;

[0045] 64—Relative molecular mass of copper ion.

[0046] (4) Supplementation method:

[0047] ① The liquid level drop caused by carry-out can be compensated by adding the original solution of the medicine;

[0048] ②The reduction in polishing speed can be restored by adding additives; the addition formula is as follows:

[0049] Addition amount (g) = N × (C2-C1) × tank volume;

[0050] Wherein N=2-5; C1 refers to the copper ion concentration obtained in the previous test; C2 refers to the copper ion concentration obtained in the current test.

[0051] Embodiment 2:

[0052] A copper foil polishing agent is prepared by mixing inorganic acid, inorganic salt, non-ionic surfactant and water. The proportions of the components in the copper foil polishing agent are: 70% of inorganic acid, 1% of inorganic salt, 1% of non-ionic surfactant and 28% of water. The inorganic acid is prepared by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion. The inorganic salt is prepared by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion. The non-ionic surfactant is fatty alcohol polyoxyethylene ether.

[0053] The cleaning method of copper foil leveling polishing agent includes the following steps:

[0054] S1: remove oil and oxide film; S2: clean; S3: drain water; S4: copper foil leveling polishing agent, polishing and cleaning; S5: clean; S6: dilute acid stripping; S7: clean - copper protection; S8: clean; S9: blow water; S10: dry.

[0055] The maintenance method of copper foil leveling polishing agent is to titrate copper ions with EDTA standard solution under the condition of PH=10, using PAN as indicator;

[0056] (2) Reagents include:

[0057] ① 0.2% PAN indicator: dissolve 0.2g PAN [1-(2-pyridyl azo)-2-naphthol] in 100ml anhydrous ethanol;

[0058] ②PH=10 buffer solution: weigh 54g ammonium chloride, dissolve it in about 400ml water, add 350ml concentrated ammonia water, dilute to 1000ml with water, and stir evenly;

[0059] ③0.1NEDTA standard solution;

[0060] (2) Analytical methods:

[0061] ① Use a glass pipette to draw V1 = 1 mL of the solution into a 250 mL conical flask; add 100 mL of pure water;

[0062] ②Add 10 ml of pH=10 buffer solution; add 5-6 drops of 0.2% PAN indicator (the solution turns blue-purple);

[0063] ③ Titrate with 0.1N EDTA standard solution until the solution changes from blue-purple to light yellow, and record the consumption of milliliters of EDTA standard solution V2;

[0064] (3) Calculation: Copper ion concentration C = 64 × N × V2 ÷ V1 (g / L)

[0065] In the formula

[0066] N—molar concentration of EDTA standard solution;

[0067] V1—the number of milliliters of plating solution absorbed, i.e. 1mL;

[0068] V2—the number of milliliters of EDTA standard solution consumed;

[0069] 64—Relative molecular mass of copper ion.

[0070] (4) Supplementation method:

[0071] ① The liquid level drop caused by carry-out can be compensated by adding the original solution of the medicine;

[0072] ②The reduction in polishing speed can be restored by adding additives; the addition formula is as follows:

[0073] Addition amount (g) = N × (C2-C1) × tank volume;

[0074] Wherein N=2-5; C1 refers to the copper ion concentration obtained in the previous test; C2 refers to the copper ion concentration obtained in the current test.

[0075] Embodiment three:

[0076] A copper foil polishing agent is prepared by mixing inorganic acid, inorganic salt, non-ionic surfactant and water. The proportions of the components in the copper foil polishing agent are: 80% of inorganic acid, 0.5% of inorganic salt, 0.5% of non-ionic surfactant and 19% of water. The inorganic acid is prepared by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion. The inorganic salt is prepared by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion. The non-ionic surfactant is fatty alcohol polyoxyethylene ether.

[0077] The cleaning method of copper foil leveling polishing agent includes the following steps:

[0078] S1: remove oil and oxide film; S2: clean; S3: drain water; S4: copper foil leveling polishing agent, polishing and cleaning; S5: clean; S6: dilute acid stripping; S7: clean - copper protection; S8: clean; S9: blow water; S10: dry.

[0079] The maintenance method of copper foil leveling polishing agent is to titrate copper ions with EDTA standard solution under the condition of PH=10, using PAN as indicator;

[0080] (3) Reagents include:

[0081] ① 0.2% PAN indicator: dissolve 0.2g PAN [1-(2-pyridyl azo)-2-naphthol] in 100ml anhydrous ethanol;

[0082] ②PH=10 buffer solution: weigh 54g ammonium chloride, dissolve it in about 400ml water, add 350ml concentrated ammonia water, dilute to 1000ml with water, and stir evenly;

[0083] ③0.1NEDTA standard solution;

[0084] (2) Analytical methods:

[0085] ① Use a glass pipette to draw V1 = 1 mL of the solution into a 250 mL conical flask; add 100 mL of pure water;

[0086] ②Add 10 ml of pH=10 buffer solution; add 5-6 drops of 0.2% PAN indicator (the solution turns blue-purple);

[0087] ③ Titrate with 0.1N EDTA standard solution until the solution changes from blue-purple to light yellow, and record the consumption of milliliters of EDTA standard solution V2;

[0088] (3) Calculation: Copper ion concentration C = 64 × N × V2 ÷ V1 (g / L)

[0089] In the formula

[0090] N—molar concentration of EDTA standard solution;

[0091] V1—the number of milliliters of plating solution absorbed, i.e. 1mL;

[0092] V2—the number of milliliters of EDTA standard solution consumed;

[0093] 64—Relative molecular mass of copper ion.

[0094] (4) Supplementation method:

[0095] ① The liquid level drop caused by carry-out can be compensated by adding the original solution of the medicine;

[0096] ②The reduction in polishing speed can be restored by adding additives; the addition formula is as follows:

[0097] Addition amount (g) = N × (C2-C1) × tank volume;

[0098] Wherein N=2-5; C1 refers to the copper ion concentration obtained in the previous test; C2 refers to the copper ion concentration obtained in the current test.

[0099] Embodiment 4:

[0100] A copper foil polishing agent is prepared by mixing inorganic acid, inorganic salt, nonionic surfactant and water. The proportions of the components in the copper foil polishing agent are: 78% of inorganic acid, 1% of inorganic salt, 1% of nonionic surfactant and 20% of water. The inorganic acid is prepared by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion. The inorganic salt is prepared by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion. The nonionic surfactant is fatty alcohol polyoxyethylene ether.

[0101] The cleaning method of copper foil leveling polishing agent includes the following steps:

[0102] S1: remove oil and oxide film; S2: clean; S3: drain water; S4: copper foil leveling polishing agent, polishing and cleaning; S5: clean; S6: dilute acid stripping; S7: clean - copper protection; S8: clean; S9: blow water; S10: dry.

[0103] The maintenance method of copper foil leveling polishing agent is to titrate copper ions with EDTA standard solution under the condition of PH=10, using PAN as indicator;

[0104] (4) Reagents include:

[0105] ① 0.2% PAN indicator: dissolve 0.2g PAN [1-(2-pyridyl azo)-2-naphthol] in 100ml anhydrous ethanol;

[0106] ②PH=10 buffer solution: weigh 54g ammonium chloride, dissolve it in about 400ml water, add 350ml concentrated ammonia water, dilute to 1000ml with water, and stir evenly;

[0107] ③0.1NEDTA standard solution;

[0108] (2) Analytical methods:

[0109] ① Use a glass pipette to draw V1 = 1 mL of the solution into a 250 mL conical flask; add 100 mL of pure water;

[0110] ②Add 10 ml of pH=10 buffer solution; add 5-6 drops of 0.2% PAN indicator (the solution turns blue-purple);

[0111] ③ Titrate with 0.1N EDTA standard solution until the solution changes from blue-purple to light yellow, and record the consumption of milliliters of EDTA standard solution V2;

[0112] (3) Calculation: Copper ion concentration C = 64 × N × V2 ÷ V1 (g / L)

[0113] In the formula

[0114] N—molar concentration of EDTA standard solution;

[0115] V1—the number of milliliters of plating solution absorbed, i.e. 1mL;

[0116] V2—the number of milliliters of EDTA standard solution consumed;

[0117] 64—Relative molecular mass of copper ion.

[0118] (4) Supplementation method:

[0119] ① The liquid level drop caused by carry-out can be compensated by adding the original solution of the medicine;

[0120] ②The reduction in polishing speed can be restored by adding additives; the addition formula is as follows:

[0121] Addition amount (g) = N × (C2-C1) × tank volume;

[0122] Wherein N=2-5; C1 refers to the copper ion concentration obtained in the previous test; C2 refers to the copper ion concentration obtained in the current test.

[0123] Embodiment five:

[0124] A copper foil polishing agent is prepared by mixing inorganic acid, inorganic salt, non-ionic surfactant and water. The proportions of the components in the copper foil polishing agent are: 79% of inorganic acid, 0.2% of inorganic salt, 0.8% of non-ionic surfactant and 20% of water. The inorganic acid is prepared by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion. The inorganic salt is prepared by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion. The non-ionic surfactant is fatty alcohol polyoxyethylene ether.

[0125] The cleaning method of copper foil leveling polishing agent includes the following steps:

[0126] S1: remove oil and oxide film; S2: clean; S3: drain water; S4: copper foil leveling polishing agent, polishing and cleaning; S5: clean; S6: dilute acid stripping; S7: clean - copper protection; S8: clean; S9: blow water; S10: dry.

[0127] The maintenance method of copper foil leveling polishing agent is to titrate copper ions with EDTA standard solution under the condition of PH=10, using PAN as indicator;

[0128] (5) Reagents include:

[0129] ① 0.2% PAN indicator: dissolve 0.2g PAN [1-(2-pyridyl azo)-2-naphthol] in 100ml anhydrous ethanol;

[0130] ②PH=10 buffer solution: weigh 54g ammonium chloride, dissolve it in about 400ml water, add 350ml concentrated ammonia water, dilute to 1000ml with water, and stir evenly;

[0131] ③0.1NEDTA standard solution;

[0132] (2) Analytical methods:

[0133] ① Use a glass pipette to draw V1 = 1 mL of the solution into a 250 mL conical flask; add 100 mL of pure water;

[0134] ②Add 10 ml of pH=10 buffer solution; add 5-6 drops of 0.2% PAN indicator (the solution turns blue-purple);

[0135] ③ Titrate with 0.1N EDTA standard solution until the solution changes from blue-purple to light yellow, and record the consumption of milliliters of EDTA standard solution V2;

[0136] (3) Calculation: Copper ion concentration C = 64 × N × V2 ÷ V1 (g / L)

[0137] In the formula

[0138] N—molar concentration of EDTA standard solution;

[0139] V1—the number of milliliters of plating solution absorbed, i.e. 1mL;

[0140] V2—the number of milliliters of EDTA standard solution consumed;

[0141] 64—Relative molecular mass of copper ion.

[0142] (4) Supplementation method:

[0143] ① The liquid level drop caused by carry-out can be compensated by adding the original solution of the medicine;

[0144] ②The reduction in polishing speed can be restored by adding additives; the addition formula is as follows:

[0145] Addition amount (g) = N × (C2-C1) × tank volume;

[0146] Wherein N=2-5; C1 refers to the copper ion concentration obtained in the previous test; C2 refers to the copper ion concentration obtained in the current test.

[0147] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A copper foil polishing agent, characterized in that: The copper foil leveling polishing agent is prepared by mixing inorganic acid, inorganic salt, nonionic surfactant and water, wherein the proportion of the inorganic acid is 60-80%, the proportion of the inorganic salt is 0.1-1%, the proportion of the nonionic surfactant is 0.1-1%, and the proportion of water is 15-30%.

2. A copper foil polishing agent according to claim 1, characterized in that: The proportions of the components in the copper foil leveling and polishing agent are: 70% of inorganic acid, 1% of inorganic salt, 1% of nonionic surfactant and 28% of water.

3. A copper foil polishing agent according to claim 1, characterized in that: The proportions of the components in the copper foil leveling and polishing agent are: 80% of inorganic acid, 0.5% of inorganic salt, 0.5% of nonionic surfactant and 19% of water.

4. A copper foil polishing agent according to claim 1, characterized in that: The proportions of the components in the copper foil leveling and polishing agent are: 78% of inorganic acid, 1% of inorganic salt, 1% of nonionic surfactant and 20% of water.

5. The copper foil polishing agent according to claim 1, characterized in that: The proportions of the components in the copper foil leveling and polishing agent are: 79% of inorganic acid, 0.2% of inorganic salt, 0.8% of nonionic surfactant and 20% of water.

6. A copper foil polishing agent according to any one of claims 1 to 5, characterized in that: The inorganic acid is formed by mixing two or three of sulfuric acid, phosphoric acid and acetic acid in any proportion; the inorganic salt is formed by mixing two or three of potassium chloride, sodium chloride and calcium magnesium nitrate in any proportion; and the nonionic surfactant is fatty alcohol polyoxyethylene ether.

7. A method for cleaning copper foil using the copper foil polishing agent according to any one of claims 1 to 6, characterized in that: The steps include: S1: Remove oil and oxide film; S2: Wash; S3: Drain the water; S4: copper foil leveling polishing agent, polishing and cleaning; S5: Wash; S6: Dilute acid stripping; S7: Cleaning - copper protection; S8: Wash; S9: Blowing water; S10: Drying.