Antioxidant, application of antioxidant, anti-oxidation copper foil and preparation method of anti-oxidation copper foil

Abstract

The invention provides an antioxidant, application of the antioxidant, an anti-oxidation copper foil and a preparation method of the anti-oxidation copper foil. The antioxidant comprises the following components in parts by weight: 15-40 parts of plant polyphenol, 5-30 parts of rare earth elements and 3-8 parts of polydopamine modified graphene. According to the antioxidant provided by the invention, the duration of anti-oxidation treatment can be shortened, and a relatively good anti-oxidation effect is achieved.

Description

Technical Field

[0001] The present application relates to the field of antioxidant technology, and in particular to an antioxidant and its application, an antioxidant copper foil and its preparation method. Background Art

[0002] Copper foil, as the core material for the negative electrode current collector of lithium-ion batteries, affects the battery's energy density, safety, and manufacturing cost. Therefore, copper foil must not only have high mechanical properties and strong conductivity, but also good oxidation resistance.

[0003] The chromic anhydride-glucose anti-oxidation system currently used in the production process relies on hexavalent chromium to form a dense chromium oxide protective film, isolating the copper foil from the air and preventing oxidation. However, hexavalent chromium is strictly regulated by the World Health Organization and other organizations as a strong carcinogen, and its disposal costs are extremely high. For the sake of human health and environmental protection, countries are gradually strengthening their regulation of chromium use. Therefore, research on chromium-free, green anti-oxidation technologies for copper foil is a major trend. However, current chromium-free anti-oxidation systems for copper foil often suffer from problems such as prolonged anti-oxidation treatment time and poor anti-oxidation effectiveness. Summary of the Invention

[0004] Based on this, the present application provides an antioxidant and its application, an anti-oxidation copper foil and its preparation method, aiming to shorten the duration of the anti-oxidation treatment and achieve better anti-oxidation effect.

[0005] A first aspect of the present application provides an antioxidant comprising the following components in parts by weight: 15 to 40 parts of plant polyphenols, 5 to 30 parts of rare earth elements, and 3 to 8 parts of polydopamine-modified graphene.

[0006] In some embodiments of the present application, the antioxidant further comprises the following components in parts by weight: 2 to 10 parts of titanium phosphate nanotubes and 2 to 10 parts of nano-silicon dioxide.

[0007] In some embodiments of the present application, the following components are included in parts by weight: 20 to 34 parts of plant polyphenols, 10 to 18 parts of rare earth elements, 6 to 8 parts of titanium phosphate nanotubes, 4 to 6 parts of nano-silica, and 4 to 6 parts of polydopamine-modified graphene.

[0008] In some embodiments of the present application, the plant polyphenols include one or more of naringenin, naringenin-7-methyl ether, glycyrrhizin, hesperetin, silybin and dihydroquercetin.

[0009] In some embodiments of the present application, the plant polyphenol contains a catechol group;

[0010] Optionally, the plant polyphenols include one or more of hesperetin, silybin and dihydroquercetin.

[0011] In some embodiments of the present application, one or more of the following conditions are met:

[0012] (1) The ionic radius of the rare earth element is greater than or equal to 95 pm;

[0013] Optionally, the rare earth element includes one or more of lanthanum, cerium, indium, samarium and yttrium;

[0014] (2) The average particle size of the nano-silicon dioxide is 10 nm to 15 nm.

[0015] In some embodiments of the present application, one or more of the following conditions are met:

[0016] (1) The mass ratio of the plant polyphenols to the rare earth elements is (1.7-2.9):1;

[0017] (2) The mass ratio of the rare earth element to the polydopamine-modified graphene is (2.2-3.6):1.

[0018] The second aspect of the present application provides a use of the antioxidant as described in the first aspect of the present application in the anti-oxidation of copper foil.

[0019] A third aspect of the present application provides a method for preparing an oxidation-resistant copper foil, comprising:

[0020] The antioxidant is mixed with water and the pH is adjusted to 4-6 to obtain a standby solution, wherein the mass concentration of the standby solution is 3.5%-7%, wherein the antioxidant comprises the following components in parts by weight: 15-40 parts of plant polyphenols, 5-30 parts of rare earth elements, and 3-8 parts of polydopamine-modified graphene;

[0021] After adjusting the temperature of the standby liquid, immersing the copper foil in the standby liquid for anti-oxidation treatment;

[0022] The copper foil after the anti-oxidation treatment is dried to obtain the anti-oxidation copper foil.

[0023] In some embodiments, the temperature of the standby solution is adjusted to 20°C to 40°C.

[0024] The fourth aspect of the present application provides an oxidation-resistant copper foil, which is prepared by the preparation method described in the third aspect of the present application.

[0025] The antioxidant provided in the present application can form a uniform organic-inorganic composite film, i.e., a passivation film, on the surface of the copper foil through the interaction between plant polyphenols, rare earth elements and polydopamine-modified graphene; the antioxidant can not only quickly passivate the surface of the copper foil and shorten the duration of the anti-oxidation treatment, but also improve the room temperature and high temperature oxidation resistance, wettability and conductivity of the copper foil, so that the copper foil has higher anti-oxidation stability and achieves better anti-oxidation effect. DETAILED DESCRIPTION

[0026] To facilitate understanding of the present application, the present application will be described in more detail below. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present application.

[0027] For simplicity, this application only explicitly discloses certain numerical ranges. However, any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. In addition, although not explicitly stated, each point or individual value between the endpoints of a range is included in the range. Thus, each point or individual value may serve as its own lower limit or upper limit and be combined with any other point or individual value, or with other lower limits or upper limits, to form an unspecified range.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. It should be noted that, unless otherwise stated, the term "and / or" used herein includes any and all combinations of one or more related listed items, "above" and "below" are inclusive of the number, and the meaning of "multiple" in "one or more" is more than two.

[0029] As used herein, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. "Numerical interval" allows for a broad range of numerical interval types including percentage intervals, ratio intervals, and ratio intervals.

[0030] In this document, if a method flow involves multiple steps, unless otherwise specified herein, there is no strict order restriction on the execution of these steps, and they can be performed in an order other than the order described. Moreover, any step can include multiple sub-steps or multiple stages, and these sub-steps or stages do not necessarily need to be completed at the same time, but can be performed at different times, and their execution order does not necessarily need to be sequential, but can be performed in rotation, alternation, or simultaneously with other steps or parts of sub-steps or stages of other steps.

[0031] The above disclosure of the present application is not intended to describe every disclosed embodiment or every implementation in the present application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided through a series of examples, which can be used in various combinations. In each example, the enumeration is intended only as a representative group and should not be construed as exhaustive.

[0032] In a first aspect, the present application provides an antioxidant comprising the following components in parts by weight:

[0033] 15 to 40 parts of plant polyphenols, 5 to 30 parts of rare earth elements, and 3 to 8 parts of polydopamine-modified graphene.

[0034] The antioxidant provided by the present application includes the above-mentioned content of plant polyphenols, rare earth elements and polydopamine-modified graphene. In the antioxidant, the phenolic hydroxyl groups contained in the plant polyphenols are highly hydrophilic and can be adsorbed on the surface of the copper foil to form an adsorption layer containing oxygen (oxygen particles). The oxygen-containing adsorption layer saturates the chemical affinity of the copper foil surface, reduces the activity of copper, and can reduce the removal of metal copper atoms from the lattice, passivating the copper foil surface and inhibiting the oxidation reaction on its surface. At the same time, the oxygen-containing adsorption layer occupies the active points such as the edges and corners of the copper grains on the surface of the copper foil, which is beneficial to hindering the dissolution of the copper foil surface and can also passivate the copper foil surface. In this way, plant polyphenols are beneficial to passivating the copper foil surface and inhibiting the oxidation reaction on the copper foil surface, thereby improving the anti-oxidation ability and anti-oxidation stability of the copper foil.

[0035] On this basis, the catechol groups contained in polydopamine can combine with rare earth elements and copper ions on the surface of copper foil to form a stable five-membered ring chelate. That is, through the chelation reaction of organic polymers and inorganic materials, it can be adsorbed on the surface of copper foil and form an organic-inorganic composite film layer, which can construct a dense passivation film on the surface of copper foil. This organic-inorganic composite film layer is stable and not easily soluble in a variety of solvents, has a good anti-corrosion protection effect, and is conducive to further improving the anti-oxidation ability and anti-oxidation stability of copper foil. Furthermore, while the catechol groups in polydopamine bond with rare earth ions and form a passivation film, they can also anchor graphene to the passivation film. In this way, the graphene sheet can form a penetrating conductive network on the surface of copper foil, reducing the surface resistivity of copper foil.

[0036] In summary, the antioxidant provided in this application forms a uniform organic-inorganic composite film on the surface of copper foil through the interaction between organic polymers, rare earth ions, and organic ligands. This antioxidant not only rapidly passivates the surface of the copper foil, quickly forming an anti-oxidation passivation film on the surface, which helps shorten the duration of the anti-oxidation treatment, but also provides the copper foil with high anti-oxidation ability and stability, achieving a good anti-oxidation effect. After treatment with the antioxidant, the copper foil can meet the parameter requirements of lithium battery copper foil, and the process is simple. The raw materials used are safe and environmentally friendly, making it a suitable alternative to traditional chromium salt anti-oxidation solutions.

[0037] It should be noted that the "polydopamine-modified graphene" mentioned in this application refers to a composite of polydopamine and graphene, in which polydopamine is adsorbed on the surface of graphene through hydrogen bonding, metal coordination, and the like.

[0038] It is understood that the antioxidant provided herein can be mixed with a solvent (e.g., water) before use to prepare an antioxidant solution, which can then be used for antioxidant treatment. The amount of solvent in the antioxidant solution can be adjusted based on actual needs and is not limited by this application.

[0039] As an example, in the antioxidant, the plant polyphenols can be 15 parts, 21 parts, 34 parts, 40 parts or within the range of any of the above values; the rare earth elements can be 5 parts, 13 parts, 26 parts, 30 parts or within the range of any of the above values; the polydopamine-modified graphene can be 3 parts, 5 parts, 8 parts or within the range of any of the above values.

[0040] In some embodiments, the antioxidant further comprises the following components in parts by weight: 2 to 10 parts of titanium phosphate nanotubes and 2 to 10 parts of nano-silicon dioxide.

[0041] When the antioxidant contains the above-mentioned content of titanium phosphate nanotubes and nano-silica, the titanium phosphate nanotubes can cover the surface of the copper foil, provide better active ion channels for the copper foil, and improve ion conduction; the silanol groups on the surface of the nano-silica can connect with plant polyphenol molecules through a hydrogen bond network to form a three-dimensional cross-linked structure, thereby enhancing the stability of the passivation film; and at the same time, it can enhance the stability of the antioxidant dispersion system.

[0042] As an example, in the antioxidant, the titanium phosphate nanotubes can be 2 parts, 5 parts, 8 parts, 10 parts, or any range thereof; the nano-silica can be 2 parts, 5 parts, 8 parts, 10 parts, or any range thereof.

[0043] In some embodiments, the average diameter of the titanium phosphate nanotubes is between 50 nm and 90 nm. For example, the average diameter can be 50 nm, 62 nm, 74 nm, 86 nm, 90 nm, or any range thereof. This arrangement facilitates better coverage on the copper foil surface, providing better active ion channels for the copper foil and further improving ion conduction.

[0044] In some embodiments, the antioxidant includes the following components, by weight: 20-34 parts plant polyphenols, 10-18 parts rare earth elements, 6-8 parts titanium phosphate nanotubes, 4-6 parts nano-silica, and 4-6 parts polydopamine-modified graphene. This configuration can enhance the copper foil's antioxidant capacity and stability, achieving better antioxidant effects.

[0045] In some embodiments, the plant polyphenols include one or more of naringenin, naringenin-7-methyl ether, liquiritigenin, hesperetin, silybin, and dihydroquercetin.

[0046] In some embodiments, the plant polyphenols contain catechol groups. In addition to polydopamine, the catechol groups in the plant polyphenols can also combine with rare earth elements and copper ions on the surface of the copper foil to form stable five-membered ring chelates, thereby forming a dense passivation film on the copper foil surface, further enhancing the copper foil's antioxidant capacity and antioxidant stability.

[0047] In some embodiments, the plant polyphenols include one or more of hesperetin, silybin, and dihydroquercetin. These plant polyphenols all contain catechol groups and a relatively high number of phenolic hydroxyl groups, which are beneficial for further enhancing the anti-oxidation ability and anti-oxidation stability of the copper foil.

[0048] In some embodiments, the ionic radius of the rare earth element is greater than or equal to 95 μm. In this way, the rare earth ionic radius can match the copper lattice gap and fill the copper grain boundary defects, which is beneficial to further improve the anti-oxidation ability and anti-oxidation stability of the copper foil.

[0049] In some embodiments, the rare earth elements are derived from rare earth oxides and / or rare earth salts. Examples include lanthanum oxide, cerium oxide, indium oxide, samarium oxide, yttrium oxide, lanthanum chloride, and cerium bromide. Rare earth oxides have high thermal conductivity, which can improve the overall thermal conductivity of the passivation film and enhance its high-temperature tolerance.

[0050] In some embodiments, the rare earth element includes one or more of lanthanum, cerium, indium, samarium, and yttrium.

[0051] In some embodiments, the average particle size of the nano-silicon dioxide is 10 nm to 15 nm. For example, the average particle size of the nano-silicon dioxide can be 10 nm, 12 nm, 14 nm, 15 nm, or within a range consisting of any of the above values. When the average particle size of the nano-silicon dioxide is within this range, the nano-silicon dioxide is not easily precipitated or agglomerated in the antioxidant, and after the antioxidant treatment, there are almost no protrusions of silicon dioxide particles on the surface of the copper foil, which is beneficial to improving the density of the passivation film.

[0052] As a non-limiting example, the average particle size of nano-silica can be measured using dynamic light scattering (DLS).

[0053] In some embodiments, the mass ratio of the plant polyphenol to the rare earth element is (1.7-2.9):1. For example, the mass ratio can be 1.7:1, 2.1:1, 2.4:1, 2.7:1, 2.9:1, or any range thereof. This configuration further enhances the anti-oxidation capability and anti-oxidation stability of the copper foil.

[0054] In some embodiments, the mass ratio of the rare earth element to the polydopamine-modified graphene is (2.2-3.6):1. For example, the mass ratio can be 2.2:1, 2.5:1, 2.8:1, 3.3:1, 3.6:1, or any range thereof. This configuration further enhances the copper foil's anti-oxidation capability and stability, and further reduces its surface resistivity.

[0055] In a second aspect, the present application provides a use of the antioxidant as described in the first aspect of the present application in the anti-oxidation of copper foil.

[0056] In a third aspect, the present application provides a method for preparing an oxidation-resistant copper foil, which may include the following steps:

[0057] S1. Mixing an antioxidant with water and adjusting the pH to 4-6 to obtain a ready-to-use solution, wherein the mass concentration of the ready-to-use solution is 3.5%-7%, wherein the antioxidant comprises the following components in parts by weight: 15 parts to 40 parts of plant polyphenols and 5 parts to 30 parts of rare earth elements;

[0058] S2. After adjusting the temperature of the standby liquid, immersing the copper foil in the standby liquid for anti-oxidation treatment;

[0059] S3, drying the copper foil after the anti-oxidation treatment to obtain the anti-oxidation copper foil.

[0060] When the copper foil is treated with the antioxidant of the present application in the above steps, the antioxidant can effectively infiltrate the surface of the copper foil, which is beneficial for improving the roughness of the copper foil surface. At the same time, it can improve the appearance quality of the copper foil, reducing or even avoiding the occurrence of spoilage bacteria in the bath liquid and the organic scaling of the conductive rollers and squeeze rollers after a period of use, which can cause appearance problems such as streaking, color difference, embossing, and black spots on the copper foil surface, thereby improving the anti-oxidation stability of the copper foil. In addition, the anti-oxidation process for copper foil shown in the above steps is highly operable, does not require power supply or water washing, and does not generate additional cleaning wastewater, making it green, safe, and environmentally friendly.

[0061] It can be understood that the “mass concentration of the standby liquid is 3.5% to 7%” mentioned in the present application means that the mass proportion of the antioxidant in the standby liquid is 3.5% to 7%.

[0062] In some embodiments, the mass concentration of the standby solution is 3.5% to 7%. For example, the mass concentration of the standby solution can be 3.5%, 4.7%, 5.9%, 6.6%, 7%, or any range thereof. This helps improve the dispersibility and passivation effects of the antioxidant. This not only helps increase the formation rate of the passivation film and reduces the number of antioxidant replenishments, facilitating continuous operation of the anti-oxidation treatment; it also helps improve the dispersibility and passivation effects of the antioxidant and helps control costs.

[0063] In some embodiments, the temperature of the standby solution is adjusted to 20°C to 40°C.

[0064] In some embodiments, the reagent used to adjust the pH in step S1 includes one or more of citric acid, tartaric acid, tannic acid, oxalic acid, and malic acid. A weakly acidic environment with a pH of 4 to 6 is conducive to accelerating the formation of the passivation layer.

[0065] In some embodiments, the time for immersing the copper foil in the standby liquid in step S2 is 3s to 5s.

[0066] In some embodiments, the drying temperature in step S3 is 70°C to 100°C.

[0067] In a fourth aspect, the present application provides an oxidation-resistant copper foil, which is prepared by the preparation method described in the third aspect of the present application.

[0068] The following are specific examples, which describe the present disclosure in more detail. These examples are intended for illustrative purposes only, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further processing. The instruments used in the examples are also commercially available.

[0069] Among them, polydopamine-modified graphene was purchased from Xi'an Ruixi Biotechnology Co., Ltd.; titanium phosphate nanotubes were purchased from Sinopharm Chemical.

[0070] Example 1

[0071] 1) Anti-oxidation liquid

[0072] Formula of anti-oxidation liquid: An anti-oxidation liquid, calculated by weight (the total weight of all raw materials is 100 parts), its raw materials include: 28 parts of plant polyphenols, 14 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silica, 4 parts of polydopamine-modified graphene, and the balance is water.

[0073] The plant polyphenol is naringenin.

[0074] The rare earth elements include lanthanum and cerium (derived from lanthanum oxide and cerium oxide, respectively), and the weight ratio between the two is 1:1.2.

[0075] The average particle size of the nano-silicon dioxide is 12 nm.

[0076] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0077] The mass ratio of the plant polyphenols to the rare earth elements is 2:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3.5:1.

[0078] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0079] 2) Anti-oxidation copper foil

[0080] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, the pH is adjusted to 5, and the solution to be used is obtained after being stirred evenly. The mass concentration of the solution to be used is 3.5%.

[0081] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0082] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0083] Example 2

[0084] 1) Anti-oxidation liquid

[0085] Formula of anti-oxidation liquid: An anti-oxidation liquid, calculated by weight (the total weight of all raw materials is 100 parts), its raw materials include: 22 parts of plant polyphenols, 16 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silicon dioxide, 4 parts of polydopamine-modified graphene, and the balance is water.

[0086] The plant polyphenol is naringenin.

[0087] The rare earth elements include lanthanum and cerium (derived from lanthanum oxide and cerium oxide, respectively), and the weight ratio between the two is 1:1.2.

[0088] The average particle size of the nano-silicon dioxide is 12 nm.

[0089] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0090] The mass ratio of the plant polyphenols to the rare earth elements is 1.375:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 4:1.

[0091] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0092] 2) Anti-oxidation copper foil

[0093] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, the pH is adjusted to 5, and the solution to be used is obtained after being stirred evenly. The mass concentration of the solution to be used is 3.5%.

[0094] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0095] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0096] Example 3

[0097] 1) Anti-oxidation liquid

[0098] Formula of anti-oxidation liquid: An anti-oxidation liquid, calculated by weight (the total weight of all raw materials is 100 parts), its raw materials include: 32 parts of plant polyphenols, 12 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silica, 4 parts of polydopamine-modified graphene, and the balance is water.

[0099] The plant polyphenol is naringenin.

[0100] The rare earth elements include lanthanum and cerium (derived from lanthanum oxide and cerium oxide, respectively), and the weight ratio between the two is 1:1.2.

[0101] The average particle size of the nano-silicon dioxide is 12 nm.

[0102] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0103] The mass ratio of the plant polyphenols to the rare earth elements is 2.67:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3:1.

[0104] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0105] 2) Anti-oxidation copper foil

[0106] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, the pH is adjusted to 5, and the solution to be used is obtained after being stirred evenly. The mass concentration of the solution to be used is 3.5%.

[0107] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0108] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0109] Example 4

[0110] 1) Anti-oxidation liquid

[0111] Formula of anti-oxidation liquid: An anti-oxidation liquid, calculated by weight (the total weight of all raw materials is 100 parts), its raw materials include: 28 parts of plant polyphenols, 14 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silica, 4 parts of polydopamine-modified graphene, and the balance is water.

[0112] The plant polyphenol is naringenin.

[0113] The rare earth elements include lanthanum and cerium (derived from lanthanum oxide and cerium oxide, respectively), and the weight ratio between the two is 1:1.2.

[0114] The average particle size of the nano-silicon dioxide is 12 nm.

[0115] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0116] The mass ratio of the plant polyphenols to the rare earth elements is 2:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3.5:1.

[0117] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0118] 2) Anti-oxidation copper foil

[0119] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, and the pH is adjusted to 4.5. After stirring evenly, a standby solution is obtained, and the mass concentration of the standby solution is 3.5%.

[0120] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0121] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0122] Example 5

[0123] 1) Anti-oxidation liquid

[0124] Formula of anti-oxidation liquid: An anti-oxidation liquid, calculated by weight (the total weight of all raw materials is 100 parts), its raw materials include: 28 parts of plant polyphenols, 14 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silica, 4 parts of polydopamine-modified graphene, and the balance is water.

[0125] The plant polyphenol is naringenin.

[0126] The rare earth elements include lanthanum and cerium (derived from lanthanum oxide and cerium oxide, respectively), and the weight ratio between the two is 1:1.2.

[0127] The average particle size of the nano-silicon dioxide is 12 nm.

[0128] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0129] The mass ratio of the plant polyphenols to the rare earth elements is 2:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3.5:1.

[0130] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0131] 2) Anti-oxidation copper foil

[0132] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, and the pH is adjusted to 5.5. After stirring evenly, a standby solution is obtained, and the mass concentration of the standby solution is 3.5%.

[0133] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0134] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0135] Example 6

[0136] 1) Anti-oxidation liquid

[0137] Formula of anti-oxidation liquid: An anti-oxidation liquid, calculated by weight (the total weight of all raw materials is 100 parts), its raw materials include: 50 parts of plant polyphenols, 5 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 4 parts of polydopamine-modified graphene, and the balance is water.

[0138] The plant polyphenol is naringenin.

[0139] The rare earth elements include lanthanum and cerium (derived from lanthanum oxide and cerium oxide, respectively), and the weight ratio between the two is 1:1.2.

[0140] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0141] The mass ratio of the plant polyphenols to the rare earth elements is 25:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 1.25:1.

[0142] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0143] 2) Anti-oxidation copper foil

[0144] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, the pH is adjusted to 5, and the solution to be used is obtained after being stirred evenly. The mass concentration of the solution to be used is 3.5%.

[0145] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0146] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0147] Example 7

[0148] The preparation process is similar to that of Example 1, with the main difference being that in the antioxidant solution in step 1), the plant polyphenol is hesperetin.

[0149] Comparative Example 1

[0150] 1) Anti-oxidation liquid

[0151] Formula of anti-oxidation liquid: An anti-oxidation liquid, whose raw materials include, by weight: 28 parts of plant polyphenols, 14 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silicon dioxide, 4 parts of graphene, and the balance is water.

[0152] The plant polyphenol is naringenin.

[0153] The rare earth elements include lanthanum and cerium, and the weight ratio between the two is 1:1.2.

[0154] The average particle size of the nano-silicon dioxide is 25 nm.

[0155] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0156] The mass ratio of the plant polyphenols to the rare earth elements is 2:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3.5:1.

[0157] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0158] 2) Anti-oxidation copper foil

[0159] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water, the pH is adjusted to 5, and the solution to be used is obtained after being stirred evenly. The mass concentration of the solution to be used is 3.5%.

[0160] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0161] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0162] Comparative Example 2

[0163] 1) Anti-oxidation liquid

[0164] Formula of anti-oxidation liquid: An anti-oxidation liquid, whose raw materials include, by weight: 28 parts of plant polyphenols, 14 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silicon dioxide, 4 parts of polydopamine-modified graphene, and the balance is water.

[0165] The plant polyphenol is naringenin.

[0166] The rare earth elements include lanthanum and cerium, and the weight ratio between the two is 1:1.2.

[0167] The average particle size of the nano-silicon dioxide is 12 nm.

[0168] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0169] The mass ratio of the plant polyphenols to the rare earth elements is 2:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3.5:1.

[0170] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0171] 2) Anti-oxidation copper foil

[0172] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water and stirred evenly to obtain a standby solution, wherein the mass concentration of the standby solution is 3.5%.

[0173] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0174] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0175] Comparative Example 3

[0176] 1) Anti-oxidation liquid

[0177] Formula of anti-oxidation liquid: An anti-oxidation liquid, whose raw materials include, by weight: 28 parts of plant polyphenols, 14 parts of rare earth elements, 7 parts of titanium phosphate nanotubes, 5 parts of nano-silicon dioxide, 4 parts of polydopamine-modified graphene, and the balance is water.

[0178] The plant polyphenol is naringenin.

[0179] The rare earth elements include lanthanum and cerium, and the weight ratio between the two is 1:1.2.

[0180] The average particle size of the nano-silicon dioxide is 12 nm.

[0181] The average diameter of the titanium phosphate nanotubes is 50 nm to 90 nm.

[0182] The mass ratio of the plant polyphenols to the rare earth elements is 2:1, and the mass ratio of the rare earth elements to the polydopamine-modified graphene is 3.5:1.

[0183] Preparation of the anti-oxidation liquid: plant polyphenols, rare earth elements, titanium phosphate nanotubes, nano-silica, and polydopamine-modified graphene are added into a reaction kettle according to weight parts, stirred at a speed of 200 rpm / min, and stirred for 1.5 hours to obtain the anti-oxidation liquid.

[0184] 2) Anti-oxidation copper foil

[0185] The surface of the copper foil to be treated is cleaned, and the anti-oxidation liquid is dissolved in pure water. The pH is adjusted to 2 with sulfuric acid, and the mixture is stirred evenly to obtain a standby solution having a mass concentration of 3.5%.

[0186] The standby liquid is introduced into the anti-oxidation treatment tank and the temperature is controlled at 25° C. The cleaned copper foil is immersed in the anti-oxidation treatment tank through a guide roller and the copper foil is immersed in the standby liquid for 5 seconds before being taken out.

[0187] After taking out the copper foil, squeeze it to remove the residual liquid on the surface, and then dry it with hot air (temperature is 70℃) to obtain the anti-oxidation copper foil.

[0188] Comparative Example 4

[0189] The preparation process is similar to that of Example 1, with the main difference being that in step 1), an equal amount of rare earth elements is used to replace the plant polyphenol naringenin in the anti-oxidation solution (i.e., no plant polyphenol is added).

[0190] Comparative Example 5

[0191] The preparation process is similar to that of Example 1, with the main difference being that in step 1), an equal amount of plant polyphenol naringenin is used to replace rare earth elements in the anti-oxidation solution (ie, no rare earth elements are added).

[0192] The oxidation-resistant copper foils prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were subjected to relevant performance tests, and the test results are shown in Table 1 below.

[0193] Among them, the test conditions or test standards for each performance test item are as follows:

[0194] (1) Passivation film appearance inspection

[0195] Place the anti-oxidation copper foil in a blast drying oven at a baking temperature of 60°C~100°C (such as 80°C) for 20~30 hours (such as 24 hours). After baking, the anti-oxidation copper foil must not change color, be sticky, or have any odor.

[0196] (2) High temperature oxidation resistance test

[0197] Place the A4-sized anti-oxidation copper foil in an oven, set the temperature to 140°C, and let it stand for 15 minutes. The surface of the copper foil sample must not change color, and there must be no oxidation points or corrosion points.

[0198] (3) Corrosion resistance test in salt spray environment

[0199] Place the anti-oxidation copper foil sample in a salt spray test chamber, and use a salt spray tester to spray sodium chloride solution in a mist form onto the copper foil surface. The salt spray concentration is 5%~10% (such as 10%), the test chamber temperature is 30~50℃ (such as 40℃), and the test time is 72 hours. After the test is completed, take out the anti-oxidation copper foil for observation. There must be no discoloration, oxidation points, and corrosion points on its surface.

[0200] Table 1

[0201]

[0202] From Table 1 above, it can be seen from the comparison of Examples 1 to 7 with Comparative Examples 1 to 5 that the surface of the copper foil treated with the anti-oxidation solution provided by the present application has high stability, the passivation film formed can be stable at high temperatures, has good corrosion resistance, and is not easy to change color when placed at room temperature.

[0203] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0204] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art could make various modifications and improvements without departing from the spirit of the present application, all of which fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. An antioxidant, characterized in that The invention comprises the following components in parts by weight: 15 to 40 parts of plant polyphenols, 5 to 30 parts of rare earth elements and 3 to 8 parts of polydopamine-modified graphene.

2. The antioxidant according to claim 1, characterized in that The antioxidant further comprises the following components in parts by weight: 2 to 10 parts of titanium phosphate nanotubes and 2 to 10 parts of nano-silicon dioxide.

3. The antioxidant according to claim 1 or 2, characterized in that The invention comprises the following components in parts by weight: 20 to 34 parts of plant polyphenols, 10 to 18 parts of rare earth elements, 6 to 8 parts of titanium phosphate nanotubes, 4 to 6 parts of nano-silicon dioxide and 4 to 6 parts of polydopamine-modified graphene.

4. The antioxidant according to claim 1 or 2, characterized in that The plant polyphenols include one or more of naringenin, naringenin-7-methyl ether, glycyrrhizin, hesperetin, silybin and dihydroquercetin.

5. The antioxidant according to claim 1 or 2, characterized in that One or more of the following conditions are met: (1) The plant polyphenols contain catechol groups; Optionally, the plant polyphenols include one or more of hesperetin, silybin and dihydroquercetin; (2) The ionic radius of the rare earth element is greater than or equal to 95 pm; Optionally, the rare earth element includes one or more of lanthanum, cerium, indium, samarium and yttrium.

6. The antioxidant according to claim 2, characterized in that The average particle size of the nano-silicon dioxide is 10nm~15nm.

7. The antioxidant according to claim 1 or 2, characterized in that One or more of the following conditions are met: (1) The mass ratio of the plant polyphenols to the rare earth elements is (1.7-2.9):1; (2) The mass ratio of the rare earth element to the polydopamine-modified graphene is (2.2-3.6):

1.

8. Use of the antioxidant according to any one of claims 1 to 7 in anti-oxidation of copper foil.

9. A method for preparing an oxidation-resistant copper foil, characterized in that: include: The antioxidant is mixed with water and the pH is adjusted to 4-6 to obtain a standby solution, wherein the mass concentration of the standby solution is 3.5%-7%, wherein the antioxidant comprises the following components in parts by weight: 15-40 parts of plant polyphenols, 5-30 parts of rare earth elements, and 3-8 parts of polydopamine-modified graphene; After adjusting the temperature of the standby liquid, immersing the copper foil in the standby liquid for anti-oxidation treatment; The copper foil after the anti-oxidation treatment is dried to obtain the anti-oxidation copper foil.

10. An anti-oxidation copper foil, characterized in that: It is prepared by the preparation method according to claim 9.

Images