Copper foil, electrodes containing the same, a secondary battery containing the same, and a method for manufacturing the same.

Abstract

The present invention provides copper foil, an electrode containing the same, a secondary battery containing the same, and a method for manufacturing the same. [Solution] One embodiment of the present invention provides a copper foil comprising a copper film having a matte surface and a shiny surface, and a protective layer on the copper film, wherein the thermogravimetric coefficient is 1.1% or less. The thermogravimetric coefficient is measured using a thermogravimetric analyzer (TGA) in an oxygen atmosphere at a rate of 10°C / min from 25°C to 800°C.

Description

Technical Field

[0001] The present invention relates to a copper foil, an electrode containing the same, a secondary battery containing the same, and a method for manufacturing the same. Specifically, the present invention relates to a copper foil having excellent charge and discharge characteristics, an electrode containing the same, a secondary battery containing the same, and a method for manufacturing the same.

Background Art

[0002] A secondary battery is a type of energy conversion device that stores electrical energy by converting it into chemical energy and generates electricity by converting the chemical energy back into electrical energy when electricity is needed. It is used not only in portable household appliances such as mobile phones and notebook computers but also as an energy source for electric vehicles. A secondary battery is also referred to as a rechargeable battery because it can be recharged.

[0003] Examples of secondary batteries that have economic and environmental advantages compared to disposable primary batteries include lead-acid batteries, nickel-cadmium secondary batteries, nickel-metal hydride secondary batteries, and lithium secondary batteries.

[0004] In particular, lithium secondary batteries can store relatively more energy compared to other secondary batteries in terms of size and weight. Therefore, lithium secondary batteries are preferably used in the field of information and communication equipment where portability and mobility are important, and their application range is also expanding to energy storage devices for hybrid vehicles and electric vehicles.

[0005] Lithium secondary batteries are repeatedly used with one charge and discharge cycle. When operating any device with a fully charged lithium secondary battery, in order to increase the operating time of the device, the lithium-ion secondary battery must have a high charge and discharge capacity. Therefore, research is constantly required to meet the increasing expected values (needs) of consumers for the charge and discharge capacity of lithium secondary batteries.

[0006] Such secondary batteries include a negative electrode current collector made of copper foil, and among copper foils, electrolytic copper foil is widely used as the negative electrode current collector in secondary batteries. As the demand for secondary batteries increases, and as the demand for high-capacity, high-efficiency, and high-quality secondary batteries increases, there is a need for electrolytic copper foil that can improve the characteristics of secondary batteries. In particular, there is a need for electrolytic copper foil that can increase the capacity of secondary batteries and guarantee stable capacity retention and performance.

[0007] Furthermore, even if a secondary battery has a sufficiently high charge / discharge capacity, if its charge / discharge capacity decreases rapidly as the charge / discharge cycle is repeated (i.e., if the capacity retention rate is low or the lifespan is short), consumers will need to replace the secondary battery frequently, which will result in inconvenience for consumers and waste of resources. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Therefore, the present invention relates to copper foil, an electrode containing the same, a secondary battery containing the same, and a method for manufacturing the same, which can prevent problems arising from the limitations and drawbacks of the aforementioned related technologies.

[0009] One embodiment of the present invention aims to provide a copper foil having a thermogravimetric coefficient of 1.1% or less and excellent charge-discharge characteristics.

[0010] One embodiment of the present invention aims to provide a copper foil having a 1% weight change temperature of 340°C or higher and excellent charge-discharge characteristics.

[0011] One embodiment of the present invention aims to provide a copper foil having a 5% weight change temperature of 430°C or higher and excellent charge-discharge characteristics.

[0012] One embodiment of the present invention aims to provide a copper foil having a 10% weight change temperature of 500°C or higher and excellent charge-discharge characteristics.

[0013] Another embodiment of the present invention aims to provide an electrode for a secondary battery containing such copper foil, and a secondary battery containing such an electrode for a secondary battery.

[0014] Yet another embodiment of the present invention aims to provide a method for manufacturing copper foil having excellent charge-discharge characteristics.

[0015] In addition to the aspects of the present invention mentioned above, other features and advantages of the present invention are described below, or can be clearly understood from such description to a person with ordinary skill in the art to which the present invention pertains. [Means for solving the problem]

[0016] One embodiment of the present invention provides a copper foil comprising a copper film having a matte surface and a shiny surface, and a protective layer on the copper film, wherein the thermogravimetric coefficient is 1.1% or less. The thermogravimetric coefficient is measured using a thermogravimetric analyzer (TGA) in an oxygen atmosphere at a rate of 10°C / min from 25°C to 800°C.

[0017] Another embodiment of the present invention includes the steps of: producing an electrolyte containing copper ions; forming a copper film; and forming a protective layer on the copper film, wherein the step of forming the copper film includes the steps of: showering the surface of the rotating anode drum with a cleaning agent; and forming a copper film on the rotating anode drum by energizing the positive electrode plate and the rotating anode drum, which are arranged spaced apart from each other in the electrolyte in the electrolytic cell, wherein the electrolyte contains 70-150 g / L of copper ions; 80-130 g / L of sulfuric acid; 15 The present invention provides a method for producing copper foil, comprising approximately 25 ppm of chlorine (Cl) and an organic additive, wherein the organic additive comprises a brightener (component A), a moderator (component B), and a roughness modifier, the brightener (component A) comprises a sulfonic acid or a metal salt thereof with a concentration of 1 to 15 ppm, the moderator (component B) comprises a nonionic water-soluble polymer with a concentration of 0.1 to 15 ppm, and the roughness modifier (component C) comprises a nitrogen-containing heterocyclic quaternary ammonium salt or a derivative thereof with a concentration of 1 to 15 ppm. [Effects of the Invention]

[0018] According to one embodiment of the present invention, the copper foil can improve charge-discharge characteristics by having a thermal weight coefficient of 1.1% or less.

Brief Description of the Drawings

[0019] [Figure 1] It is a cross-sectional view of the copper foil according to one embodiment of the present invention. [Figure 2] It is a cross-sectional view of the copper foil according to another embodiment of the present invention. [Figure 3] It is a cross-sectional view of the electrode for a secondary battery according to another embodiment of the present invention. [Figure 4] It is a cross-sectional view of the electrode for a secondary battery according to still another embodiment of the present invention. [Figure 5] It is a schematic cross-sectional view of the secondary battery according to still another embodiment of the present invention. <​​​​​​​​​​​​​​​​Wherever "includes," "has," "consists of," etc., as used herein, other parts may be added unless the expression "only" is used. Wherever a component is expressed singularly, it includes multiple components unless otherwise explicitly stated. Furthermore, in the interpretation of a component, it shall be interpreted as including a margin of error, even without further explicit statement.

[0023] When describing spatial relationships, for example, when the relationship between two parts is described using phrases such as "on top," "above," "below," or "beside," one or more other parts may be located between the two parts, unless the expressions "immediately" or "directly" are used.

[0024] Spatially relative terms such as "below" or "beneath," "lower," "above," and "upper" can be used to easily describe the correlation between one element or component and another, as shown in the drawing. Spatially relative terms should be understood as terms that include different directions of elements in use or operation, in addition to the directions shown in the drawing. For example, if elements shown in the drawing are flipped over, an element described as "below" or "beneath" of another element may be positioned "above" of the other element. Thus, the exemplary term "below" may include both the downward and upward directions. Similarly, the exemplary terms "up" or "above" may include both the upward and downward directions.

[0025] When describing temporal relationships, for example, when a temporal sequence is described using phrases such as "after," "following," "next," or "before," it may include non-continuous events unless expressions like "immediately" or "directly" are used.

[0026] While terms such as "first," "second," etc., are used to describe various components, these components are not limited by these terms. These terms are simply used to distinguish one component from others. Therefore, the first component referred to below may be the second component within the technical concept of the present invention.

[0027] The term "at least one" should be understood to include all possible combinations of one or more related items. For example, "at least one of items 1, 2, and 3" could mean not just each of items 1, 2, or 3 individually, but all possible combinations of items that could be presented from two or more of items 1, 2, and 3.

[0028] Each of the various embodiments of the present invention is partially or entirely combinable or combined with one another, enabling a variety of technically diverse interlocking and driving processes. Each embodiment may be implemented independently of the others or together in relation to one another.

[0029] Figure 1 is a cross-sectional view of copper foil 110a according to one embodiment of the present invention. Referring to Figure 1, the copper foil 110a of the present invention includes a copper film 111 containing 99.9% by weight or more of copper. Referring to Figure 1, the copper foil 110a of the present invention includes the copper film 111 and a protective layer 112 on the copper film 111. Figure 1 shows a configuration in which the protective layer 112 is arranged on one surface of the copper film 111. However, the present invention is not limited thereto, and the protective layer 112 may be arranged on both surfaces of the copper film 111 (see Figure 2).

[0030] The copper film 111 may be formed on the rotating anode drum through electroplating, and may have a shiny surface that is in direct contact with the rotating anode drum during the electroplating process and a matte surface on the opposite side.

[0031] The protective layer 112 is formed by electrodepositing an anticorrosion material onto the copper film 111. The anticorrosion material may contain at least one of chromium compounds, silane compounds, and nitrogen compounds. The protective layer 112 prevents oxidation and corrosion of the copper film 111 and improves heat resistance, thereby extending the lifespan of the copper foil 110 itself, as well as the lifespan of the final product containing it.

[0032] The copper foil 110 described later can correspond to the copper foils 110a and 110b shown in Figures 1 and 2.

[0033] According to one embodiment of the present invention, the copper foil 110 may have a thermogravimetric coefficient of 1.1% or less. Specifically, when the thermogravimetric coefficient of the copper foil 110 is 1.1% or less, when the copper foil 110 is left outside for a long period of time, oxidation of the copper foil 110 and corrosion of the copper foil 110 due to the active material and air and oxygen flowing in from the outside can be prevented. As a result, the copper foil 110 can have an excellent capacity retention rate.

[0034] According to the present invention, the thermogravimetric coefficient is measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, it is measured at a rate of 10°C / min from 25°C to 800°C. According to the present invention, the thermogravimetric coefficient represents the ratio of the weight of copper foil 110 measured at 500°C to the weight of copper foil 110 measured at 25°C. The specific measurement conditions will be described later.

[0035] Generally, copper foil increases in weight when oxidized under oxygen conditions. Specifically, the reason for this weight increase is that the copper within the foil combines with oxygen to form copper oxide (CuO or Cu2O). When copper within a copper foil oxidizes in this way, its conductivity decreases, increasing its internal resistance. Furthermore, when the surface of the copper foil oxidizes, the adhesion between the copper foil and the active material weakens, which can cause the active material to separate during long-term charge-discharge cycles.

[0036] On the other hand, if the thermogravimetric coefficient of copper foil 110 is 1.1% or less, the capacity retention rate of a secondary battery manufactured using such copper foil can meet a certain level or higher (for example, 90% or more).

[0037] However, even if a secondary battery achieves a capacity retention rate of 90% or more, this does not necessarily mean that the thermogravimetric coefficient of the copper foil inside such a secondary battery will be 1.1% or less.

[0038] If the thermogravimetric coefficient of the copper foil 110 exceeds 1.1%, the copper foil 110 can be excessively oxidized by external oxygen. As a result, the stable capacity retention and performance of the secondary battery may deteriorate.

[0039] According to one embodiment of the present invention, the 1% weight change temperature may be 340°C or higher. Specifically, when the 1% weight change temperature is 340°C or higher, oxidation of the copper foil 110 and corrosion of the copper foil 110 can be prevented even in high-temperature environments. As a result, the copper foil 110 can have an excellent capacity retention rate.

[0040] According to the present invention, the 1% weight change temperature is measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, it is measured at 25°C at a rate of 10°C / min. According to the present invention, the 1% weight change temperature refers to the temperature at which the weight of copper foil 110, measured at 25°C, increases by 1%.

[0041] According to the present invention, a higher 1% weight change temperature may mean that the copper foil 110 will not oxidize or corrode in a high-temperature environment.

[0042] On the other hand, if the 1% weight change temperature of the copper foil 110 is 340°C or higher, the capacity retention rate of a secondary battery manufactured using such copper foil can meet a certain level or higher (for example, 90% or higher).

[0043] However, even if a secondary battery achieves a capacity retention rate of 90% or more, this does not necessarily mean that the temperature at which the 1% weight change of the copper foil inside the secondary battery occurs is 340°C or higher.

[0044] If the 1% weight change temperature of the copper foil 110 is less than 340°C, the copper foil 110 can be excessively oxidized at low temperatures before reaching high-temperature conditions. As a result, the stable capacity retention and performance of the secondary battery may deteriorate.

[0045] According to one embodiment of the present invention, the 5% weight change temperature may be 430°C or higher. Specifically, when the 5% weight change temperature is 430°C or higher, oxidation of the copper foil 110 and corrosion of the copper foil 110 can be prevented even in high-temperature environments. As a result, the copper foil 110 can have an excellent capacity retention rate.

[0046] According to the present invention, the 5% weight change temperature is measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, it is measured at 25°C at a rate of 10°C / min. According to the present invention, the 5% weight change temperature refers to the temperature at which the weight of copper foil 110, measured at 25°C, increases by 5%.

[0047] According to the present invention, a higher 5% weight change temperature may mean that the copper foil 110 will not oxidize or corrode in a high-temperature environment.

[0048] On the other hand, if the 5% weight change temperature of copper foil 110 is 430°C or higher, the capacity retention rate of a secondary battery manufactured using such copper foil can meet a certain level or higher (for example, 90% or higher).

[0049] However, even if a secondary battery achieves a capacity retention rate of 90% or more, this does not necessarily mean that the 5% weight change temperature of the copper foil inside the secondary battery will be 430°C or higher.

[0050] If the 5% weight change temperature of the copper foil 110 is less than 430°C, the copper foil 110 can be excessively oxidized at low temperatures before reaching high-temperature conditions. As a result, the stable capacity retention and performance of the secondary battery may deteriorate.

[0051] According to one embodiment of the present invention, the 10% weight change temperature may be 500°C or higher. Specifically, when the 10% weight change temperature is 500°C or higher, oxidation of the copper foil 110 and corrosion of the copper foil 110 can be prevented even in high-temperature environments. As a result, the copper foil 110 can have an excellent capacity retention rate.

[0052] According to the present invention, the 10% weight change temperature is measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, it is measured at 25°C at a rate of 10°C / min. According to the present invention, the 10% weight change temperature refers to the temperature at which the weight of copper foil 110, measured at 25°C, increases by 10%.

[0053] According to the present invention, a higher 10% weight change temperature may mean that the copper foil 110 will not oxidize or corrode in a high-temperature environment.

[0054] On the other hand, if the 10% weight change temperature of the copper foil 110 is 500°C or higher, the capacity retention rate of a secondary battery manufactured using such copper foil can meet a certain level or higher (for example, 90% or higher).

[0055] However, even if a secondary battery achieves a capacity retention rate of 90% or more, this does not necessarily mean that the 10% weight change temperature of the copper foil inside the secondary battery will be 500°C or higher.

[0056] If the 10% weight change temperature of the copper foil 110 is less than 500°C, the copper foil 110 can be excessively oxidized at low temperatures before reaching high-temperature conditions. As a result, the stable capacity retention and performance of the secondary battery may deteriorate.

[0057] A copper foil 110 according to one embodiment of the present invention has a thickness of 3 to 35 μm. When the copper foil 110 is used as a current collector for electrodes in a secondary battery, the thinner the copper foil 110, the more current collectors can be accommodated in the same space, which is advantageous for increasing the capacity of the secondary battery. However, manufacturing copper foil 110 with a thickness of less than 3 μm causes a decrease in workability.

[0058] On the other hand, when manufacturing secondary batteries with copper foil 110 exceeding 35 μm in thickness, the thick copper foil 110 makes it difficult to achieve high capacity.

[0059] The following will specifically describe the electrode 100 containing the copper foil 110 of the present invention and the secondary battery containing the electrode 100.

[0060] Figure 3 is a cross-sectional view of electrode 100a for a secondary battery according to one embodiment of the present invention. Figure 4 is a cross-sectional view of electrode 100b for a secondary battery according to another embodiment of the present invention.

[0061] As shown in Figure 3, an electrode 100a for a secondary battery according to one embodiment of the present invention includes one of the copper foils 110 and active material layer 120 from the embodiments of the present invention described above.

[0062] Figure 3 shows a configuration in which the active material layer 120 is formed on one surface of the copper foil 110. However, the present invention is not limited to this, and referring to Figure 4, the active material layer 120 can also be formed on both sides of the copper foil 110.

[0063] In lithium secondary batteries, aluminum foil is commonly used as the positive electrode current collector that bonds with the positive electrode active material, and copper foil 110 is commonly used as the negative electrode current collector that bonds with the negative electrode active material.

[0064] According to one embodiment of the present invention, the electrode 100 for the secondary battery is a negative electrode, the copper foil 110 is used as a negative electrode current collector, and the active material layer 120 contains a negative electrode active material.

[0065] To ensure the high capacity of the secondary battery, the active material layer 120 of the present invention may be formed of a carbon-metal composite. The metal may include, for example, at least one of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, and Fe, preferably Si and / or Sn.

[0066] Figure 5 is a schematic cross-sectional view of a secondary battery according to one embodiment of the present invention. Referring to Figure 5, the secondary battery includes a cathode 370, a negative electrode 340, an electrolyte 350 placed between the cathode 370 and the negative electrode 340 to provide an environment in which ions can move, and a separator 360 that electrically insulates the cathode 370 and the negative electrode 340. Here, the ions that move between the cathode 370 and the negative electrode 340 are, for example, lithium ions. The separator 360 separates the cathode 370 and the negative electrode 340 to prevent the charge generated at one electrode from being wasted by moving to the other electrode through the interior of the secondary battery. Referring to Figure 5, the separator 360 is placed within the electrolyte 350.

[0067] The positive electrode 370 includes a positive electrode current collector 371 and a positive electrode active material layer 372, and aluminum foil can be used as the positive electrode current collector 371.

[0068] The negative electrode 340 includes a negative electrode current collector 341 and a negative electrode active material layer 342, and copper foil 110 can be used as the negative electrode current collector 341.

[0069] According to one embodiment of the present invention, the copper foil 110 shown in Figures 1 and 2 can be used as the negative electrode current collector 341. In addition, the secondary battery electrodes 100a and 100b shown in Figure 3 or Figure 4 can be used as the negative electrode 340 of the secondary battery shown in Figure 5.

[0070] The method for manufacturing the copper foil 110 of the present invention will be specifically described below with reference to Figure 6. The present invention provides a method for manufacturing copper foil 110, which includes the steps of forming a copper film 111 and forming a protective layer 112 on the copper film 111.

[0071] The method of the present invention includes the step of forming a copper film 111 on a rotating negative electrode drum 40 by energizing a positive electrode plate 30 and a rotating negative electrode drum 40 that are arranged spaced apart from each other in an electrolyte 20 in an electrolytic cell 10.

[0072] As shown in Figure 6, the positive electrode plate 30 may include first and second positive electrode plates 31 and 32 that are electrically insulated from each other.

[0073] The copper film 111 formation step can be carried out by forming a seed layer by energizing the first positive electrode plate 31 and the rotating negative electrode drum 40, and subsequently growing the seed layer by energizing the second positive electrode plate 32 and the rotating negative electrode drum 40.

[0074] The current densities provided by the first and second positive plates 31 and 32, respectively, may be 40 to 130 ASD.

[0075] If the current densities provided by the first and second positive electrode plates 31 and 32, respectively, are less than 40 ASD, the surface roughness of the copper foil 110 may be low, and the adhesion between the copper foil 110 and the active material layer 120 may not be sufficient.

[0076] On the other hand, if the current densities provided by the first and second positive plates 31 and 32, respectively, exceed 130 ASD, the surface of the copper foil 110 may become rough, and the coating of the active material may not be carried out smoothly.

[0077] The surface properties of the copper film 111 can be changed by the degree of surface buffing or polishing of the rotating anode drum 40. For example, the surface of the rotating anode drum 40 can be polished with an abrasive brush having a grit size (Grit) of #800 to #3000.

[0078] During the formation of the copper film 111, the electrolyte 20 is maintained at a temperature of 40-65°C. More specifically, the temperature of the electrolyte 20 can be maintained at 45°C or higher. In this process, the physical, chemical, and electrical properties of the copper film 111 can be controlled by adjusting the composition of the electrolyte 20.

[0079] According to one embodiment of the present invention, the electrolyte 20 may contain copper ions, sulfuric acid, chlorine, and organic additives.

[0080] To facilitate the formation of the copper film 111 by copper electrodeposition, the concentrations of copper ions and sulfuric acid in the electrolyte 20 are adjusted to 70-150 g / L and 80-130 g / L, respectively.

[0081] In one embodiment of the present invention, chlorine (Cl) is a chloride ion (Cl - This includes all chlorine atoms present in the molecule. Chlorine (Cl) can be used, for example, to remove silver (Ag) ions that flow into the electrolyte 20 during the process of forming the copper film 111. Specifically, chlorine (Cl) can precipitate silver (Ag) ions in the form of silver chloride (AgCl). Such silver chloride (AgCl) can be removed by filtration.

[0082] If the chlorine (Cl) concentration is less than 15 ppm, the removal of silver (Ag) ions will not proceed smoothly. On the other hand, if the chlorine (Cl) concentration exceeds 25 ppm, unwanted reactions may occur due to an excess of chlorine (Cl). Therefore, the chlorine (Cl) concentration in the electrolyte 20 is controlled within the range of 15 to 25 ppm.

[0083] According to one embodiment of the present invention, the electrolyte 20 may contain organic additives. The organic additives contained in the electrolyte 20 include a brightener (component A), a moderator (component B), and a roughness modifier (component C).

[0084] The glossing agent (component A) contains sulfonic acid or a metal salt thereof. The glossing agent (component A) may have a concentration of 1 to 15 ppm in the electrolyte 20.

[0085] The brightener (component A) can increase the charge of the electrolyte 20, increase the electrodeposition rate of copper, improve the curl characteristics of the copper foil, and increase the gloss of the copper foil 110. If the concentration of the brightener (component A) is less than 1 ppm, the gloss of the copper foil 110 will decrease, and if it exceeds 15 ppm, problems such as changes in the weight or surface roughness of the copper foil 110 after immersion may occur.

[0086] The glossing agent may include, for example, at least one of the following: bis-(3-sulfopropyl)-disulfide disodium salt, 3-mercapto-1-propanesulfonic acid, 3-(N,N-dimethylthiocarbamoyl)-thiopropanesulfonate sodium salt, 3-[(amino-iminomethyl)thio]-1-propanesulfonate sodium salt, o-ethyldithiocarbonate-S-(3-sulfopropyl)-ester sodium salt, 3-(benzothiazolyl-2-mercapto)-propyl-sulfonate sodium salt, and ethylenedithiodipropylsulfonic acid sodium salt.

[0087] The moderator (component B) contains a nonionic water-soluble polymer. The moderator (component B) may have a concentration of 0.1 to 15 ppm in the electrolyte 20.

[0088] The moderator (component B) reduces the electrodeposition rate of copper, preventing a rapid increase in the roughness and decrease in strength of the copper foil 110. Such a moderator (component B) is also called an inhibitor or suppressor.

[0089] If the concentration of the moderator (component B) is less than 0.1 ppm, the roughness of the copper foil 110 increases rapidly, and a problem may arise where the surface condition of the copper foil 110 changes. On the other hand, even if the concentration of the moderator (component B) exceeds 15 ppm, there is almost no change in the physical properties of the copper foil 110, such as appearance, gloss, roughness, strength, and elongation. Therefore, the concentration of the moderator (component B) can be adjusted within the range of 0.1 to 15 ppm without unnecessarily increasing the concentration of the moderator (component B), thereby increasing manufacturing costs and wasting raw materials.

[0090] The moderator (component B) may include, for example, at least one nonionic water-soluble polymer selected from polyethylene glycol (PEG), polypropylene glycol, polyethylene polypropylene copolymer, polyglycerin, polyethylene glycol dimethyl ether, hydroxyethylene cellulose, polyvinyl alcohol, polyglycol stearate ether, and stearyl alcohol polyglycol ether. However, the type of moderator is not limited to these, and other nonionic water-soluble polymers that can be used in the production of high-strength copper foil 110 can be used as moderators.

[0091] The roughness modifier (component C) includes nitrogen-containing heterocyclic quaternary ammonium salts or their derivatives. The roughness modifier (component C) improves the glossiness and flatness of the copper foil 110. The roughness modifier (component C) may have a concentration of 1 to 15 ppm in the electrolyte 20.

[0092] If the concentration of the roughness modifier (component C) is less than 1 ppm, a problem occurs where the improvement in gloss and flatness of the copper foil 110 does not occur. On the other hand, if the concentration of the roughness modifier (component C) exceeds 15 ppm, a problem occurs where the surface gloss of the copper foil 110 becomes uneven and the surface roughness increases rapidly.

[0093] The roughness modifier (component C) may contain at least one of the compounds represented by the following chemical formulas 1 to 5.

[0094] [Chemical formula 1] [ka]

[0095] [Chemical formula 2] [ka]

[0096] [Chemical formula 3] [ka]

[0097] [Chemical formula 4] [ka]

[0098] [Chemical formula 5] [ka]

[0099] In chemical formulas 1-5, l1-l4, m1-m4, and n1-n5 each represent repeating units, are integers greater than or equal to 1, and may be the same or different from one another.

[0100] According to one embodiment of the present invention, the compounds represented by chemical formulas 1 to 5 each have a number average molecular weight of 500 to 12,000.

[0101] If the number-average molecular weight of the compounds represented by chemical formulas 1-5 used as roughness modifiers is less than 500, the monomer ratio is high, resulting in high surface roughness of the copper foil 110. If the roughness modifier content is low, the surface roughness of the copper film 111 increases, and its gloss and flatness may decrease.

[0102] When the number-average molecular weight of the compounds represented by chemical formulas 1-5 exceeds 12,000, the deviation in the surface roughness of the copper foil 110 increases. In this case, even by adjusting the concentrations of other additives, it is difficult to suppress the increase in the deviation in the surface roughness of the copper foil 110.

[0103] Compounds represented by chemical formulas 1 to 5 can be prepared, for example, by polymerization or copolymerization using DDAC (Diallyl dimethyl ammonium chloride).

[0104] Examples of compounds represented by chemical formula 1 include PAS-2451 (Mw 30,000, Nittobo).

[0105] Examples of compounds represented by chemical formula 2 include PAS-84 (Mw20,000, Nittobo).

[0106] Examples of compounds represented by chemical formula 3 include PAS-2351 (Mw 25,000, Nittobo).

[0107] Examples of compounds represented by chemical formula 4 include PAS-A-1 (Mw 5,000, Nittobo) and PAS-A-5 (Mw 4,000, Nittobo).

[0108] Examples of compounds represented by chemical formula 5 include PAS-J-81 (Mw 180,000, Nittobo).

[0109] When the copper film 111 is formed, the flow rate of the electrolyte 20 supplied into the electrolytic cell 10 is 41-45 m / s. 3 / hour is also acceptable.

[0110] According to one embodiment of the present invention, before immersing the rotating anode drum 40 in the electrolyte 20 manufactured as described above to form a copper film 111 on the rotating anode drum 40, the surface of the rotating anode drum 40 can be showered or washed with a cleaning agent.

[0111] According to the present invention, the cleaning agent is an aqueous solution containing 8% (w / w) to 12% (w / w) sulfuric acid and a glossing agent (component A) in the range of 0.1% (w / w) to 0.3% (w / w). In this case, the glossing agent (component A) may contain any one of the types of glossing agents (component A) described above.

[0112] According to the present invention, when the surface of the rotating anode drum 40 is showered with a cleaning agent, the sulfuric acid in the cleaning agent reacts with oxides present on the surface of the rotating anode drum 40, which is effective in dissolving or removing the oxides.

[0113] Furthermore, titanium (Ti) may be present on the surface of the rotating anode drum 40 from which the oxides have been removed. If the titanium (Ti) present on the surface of the rotating anode drum 40 is exposed to air, an oxide film may form on the surface of the rotating anode drum 40. Since such a titanium oxide film has insulating properties, it can obstruct the flow of current, which can make it difficult to achieve a uniform current distribution in the electroplating process. Also, if the titanium oxide film becomes thick, the surface of the rotating anode drum 40 becomes irregular, and the desired thickness and flatness may not be maintained during the plating process.

[0114] In this case, the brightener (component A) in the cleaning agent can coat the surface of the rotating anode drum 40 before the titanium (Ti) present on the surface of the rotating anode drum 40 is exposed to the air. As a result, it is possible to prevent the formation of a titanium oxide film on the surface of the rotating anode drum 40.

[0115] In other words, if the surface of the rotating anode drum 40 is not showered or washed with a cleaning agent before immersing the rotating anode drum 40 in the electrolyte 20 to form a copper film 111 on the rotating anode drum 40, the surface of the manufactured copper foil may become irregular, and the surface area of ​​the copper foil may increase. As a result, the contact area with the outside air increases, and the copper foil may have a thermogravimetric coefficient of more than 1.1%.

[0116] Therefore, in order for the copper foil 110 to have a thermogravimetric coefficient of 1.1% or less, it is necessary to shower or wash the surface of the rotating anode drum 40 with a cleaning agent before immersing the rotating anode drum 40 in the electrolyte 20 to form a copper film 111 on the rotating anode drum 40.

[0117] According to the present invention, the glossing agent (component A) in the cleaning agent needs to be maintained at a concentration in the range of 0.1% (w / w) to 0.3% (w / w).

[0118] If the concentration of the polishing agent (component A) in the cleaning agent is less than 0.1% (w / w), the amount of polishing agent (component A) in the cleaning agent may be insufficient, and the pretreatment effect of the rotating negative electrode drum 40 may not be adequate.

[0119] Furthermore, if the concentration of the brightener (component A) in the cleaning agent exceeds 0.3% (w / w), the brightener (component A) can be excessively adsorbed onto the rotating anode drum 40. When a large amount of brightener (component A) is adsorbed onto the rotating anode drum 40 in this way, it occupies sites on the rotating anode drum 40 where other organic additives are adsorbed, thus reducing the opportunity for other organic additives to be adsorbed onto the rotating anode drum 40. If an appropriate adsorption balance is maintained among the organic additives, the physical properties of the copper foil 110 according to the present invention can be obtained. However, if the brightener (component A) is excessively adsorbed onto the rotating anode drum 40, this balance may be disrupted. That is, the gloss of the copper foil may become even better, but the decelerator (component B) and roughness modifier (component C), which improve the surface properties of the copper foil, may not be sufficiently adsorbed onto the rotating anode drum 40, which may lead to a problem where the surface properties of the copper foil deteriorate.

[0120] According to the present invention, the sulfuric acid in the detergent needs to be maintained at a concentration in the range of 8% (w / w) to 12% (w / w).

[0121] If the concentration of sulfuric acid in the cleaning agent is less than 8% (w / w), it may react with oxides present on the surface of the rotating negative electrode drum 40, potentially resulting in insufficient dissolution or removal of the oxides.

[0122] Furthermore, if the concentration of sulfuric acid in the cleaning agent exceeds 12% (w / w), a high concentration of sulfuric acid is present on the surface of the rotating negative electrode drum 40, which excessively increases the current density and makes it difficult to obtain copper foil of the desired quality. In addition, if the concentration of sulfuric acid in the cleaning agent is excessive, it may cause uneven defects on the surface of the copper foil, making it difficult to obtain the physical properties of the copper foil 110 according to the present invention.

[0123] According to the present invention, even if the surface of the rotating negative electrode drum 40 is showered with a cleaning agent, the brightener (component A) in the electrolyte 20 may have a concentration of 1 to 15 ppm, and the sulfuric acid may have a concentration of 70 to 150 g / L.

[0124] To ensure the cleanliness of the electrolyte 20, the copper wire (Cu wire) that is the raw material for the electrolyte 20 can be washed.

[0125] According to one embodiment of the present invention, the steps for producing the electrolyte 20 may include a step of heat-treating a copper wire, a step of pickling the heat-treated copper wire, a step of washing the pickled copper wire with water, and a step of putting the washed copper wire into sulfuric acid for the electrolyte.

[0126] More specifically, in order to maintain the cleanliness of the electrolyte 20, copper for the production of the electrolyte 20 can be produced by sequentially following the steps of: heat-treating high-purity (99.9% or higher) copper wire (Cu wire) in an electric furnace at 750°C to 850°C to burn off various organic impurities attached to the copper wire; pickling the copper wire that has been heat-treated with a 10% sulfuric acid solution for 10 to 20 minutes; and rinsing the pickled copper wire with distilled water. The rinsed copper wire can then be added to sulfuric acid for the electrolyte to produce the electrolyte 20.

[0127] The copper film 111 manufactured in this manner can be washed in a washing tank. For example, acid cleaning can be performed sequentially to remove impurities on the surface of the copper film 111, such as resin components or natural oxide films, followed by water cleaning to remove the acidic solution used in acid cleaning. The cleaning step may be omitted.

[0128] Next, a protective layer 112 is formed on the copper film 111. Referring to Figure 6, the step may further include immersing the copper film 111 in an anticorrosion solution 60. When the copper film 111 is immersed in the anticorrosion solution 60, it may be guided by a guide roll placed in the anticorrosion solution 60.

[0129] As mentioned above, the rust-preventive liquid 60 may contain at least one of a chromium compound, a silane compound, and a nitrogen compound. For example, the copper film 111 can be immersed in a 1-10 g / L potassium dichromate solution at room temperature for 1-30 seconds.

[0130] Furthermore, the protective layer 112 may contain silane compounds obtained by silane treatment, or nitrogen compounds obtained by nitrogen treatment. The copper foil 110 is produced by forming such a protective layer 112.

[0131] The electrode for a secondary battery (i.e., a negative electrode) of the present invention can be manufactured by coating one or more negative electrode active materials selected from the group consisting of carbon; metal (Me) of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; alloys containing the metal (Me); oxides (MeOx) of the metal (Me); and composites of the metal (Me) and carbon onto one or both sides of the copper foil 110 of the present invention manufactured by the method described above.

[0132] For example, 100 parts by weight of carbon for the negative electrode active material is mixed with 1 to 3 parts by weight of styrene-butadiene rubber (SBR) and 1 to 3 parts by weight of carboxymethylcellulose (CMC), and then a slurry is prepared using distilled water as a solvent. Next, the slurry is applied to the copper foil 110 to a thickness of 20 to 60 μm using a doctor blade, and heated at 110 to 130°C for 0.5 to 1.5 ton / cm². 2 Press with this pressure.

[0133] A secondary battery can be manufactured using the electrode (negative electrode) for the secondary battery of the present invention, manufactured by the method described above, along with a conventional positive electrode, electrolyte, and separator membrane.

[0134] The present invention will be described in detail below with reference to examples and comparative examples. However, the following examples are provided to aid in understanding the present invention, and the scope of the present invention is not limited to these examples.

[0135] Examples 1-4 Copper foil was manufactured using a foil-making machine that included an electrolytic cell 10, a rotating negative electrode drum 40 positioned in the electrolytic cell 10, and a positive electrode plate 30 positioned away from the rotating negative electrode drum 40. The electrolyte 20 was a copper sulfate solution. The concentration of copper ions in the electrolyte 20 was set to 87 g / L, the concentration of sulfuric acid to 110 g / L, the temperature of the electrolyte to 55°C, and the current density to 60 ASD.

[0136] Furthermore, the concentration of chlorine (Cl) in the electrolyte solution 20 was maintained at 20 ppm, and the concentrations of the organic additives were as shown in Table 1 below.

[0137] Among the organic additives, bis-(3-sulfopropyl)-disulfide disodium salt (SPS) is used as the brightener (component A), polyethylene glycol (PEG) is used as the moderator (component B), and diallylmethylethylammonium ethyl sulfate maleic acid copolymer (PAS-2451) is used as the roughness modifier (component C). TM Nittobo (MW30,000) was used.

[0138] Before immersing the rotating anode drum 40 in the electrolyte solution 20, the surface of the rotating anode drum 40 was cleaned using a cleaning agent. The cleaning agent used was an aqueous solution containing sulfuric acid and a polishing agent (component A). Bis-(3-sulfopropyl)-disulfide disodium salt (SPS) was used as the polishing agent (component A) in the cleaning agent. The concentrations of sulfuric acid and polishing agent (component A) in the cleaning agent are shown in Table 1 below.

[0139] A copper film 111 was manufactured by applying a current at a current density of 60 ASD between the rotating negative electrode drum 40 and the positive electrode plate 30. Next, copper foil was manufactured by immersing the copper film 111 in a rust-preventive solution for about 2 seconds and applying a chromate treatment to both sides of the copper film 111 to form a protective layer 112. A rust-preventive solution mainly composed of chromic acid was used, and the concentration of chromic acid was 5 g / L.

[0140] As a result, copper foils of Examples 1 to 4 were manufactured. The thickness of the manufactured copper foil was 8 μm.

[0141] Comparative Examples 1-2 The concentrations of organic additives, whether or not drum cleaning was performed, and the concentrations of polishing agents in the cleaning agent are as shown in Table 1 below.

[0142] Comparative Examples 1 and 2 were manufactured using the same method as in Examples 1 to 4. In this case, the thickness of the manufactured copper foil was 8 μm.

[0143] Comparative Examples 3-4 The concentration of organic additives and whether or not drum cleaning was performed are as shown in Table 1 below. The copper foil was manufactured in the same manner as in Examples 1 to 4, except that the surface of the rotating anode drum 40 was showered with a cleaning agent before immersing the rotating anode drum 40 in the electrolyte 20 to form a copper film 111 on the rotating anode drum 40. In this case, the thickness of the manufactured copper foil was 8 μm.

[0144] [Table 1]

[0145] [Table 2]

[0146] [Table 3]

[0147] For the copper foils of Examples 1-4 and Comparative Examples 1-4 manufactured in this manner, (i) the weight of the sample at 25°C, (ii) the weight of the sample at 500°C, (iii) the temperature at which weight changed by 1%, (iv) the temperature at which weight changed by 5%, (v) the temperature at which weight changed by 10%, (vi) the thermogravimetric coefficient, and (vii) the volume retention rate were confirmed. The copper foil was cut to obtain a sample.

[0148] (i) Weight of the sample at 25°C The weight of the manufactured copper foil samples was measured at room temperature (25°C).

[0149] (ii) Weight of the sample at 500°C The weight of manufactured copper foil samples was measured at 500°C using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, measurements were taken at a rate of 10°C / min from 25°C to 800°C. An air atmosphere refers to atmospheric conditions.

[0150] The specific conditions for the thermogravimetric analyzer (TGA) according to the present invention are as follows: -Model name: STA7300 -Manufacturer: HITACHI -Balance Type:Horizontal Differential Type -Gas Control:Integrated Mass Flow Controller -Gas Purity: Air 99.999%

[0151] (iii) 1% weight change temperature The manufactured copper foil samples were measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, measurements were taken at a rate of 10°C / min from 25°C to 800°C. The 1% weight change temperature refers to the temperature at which the weight of the sample measured at 25°C increases by 1%.

[0152] (iv) 5% weight change temperature The manufactured copper foil samples were measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, measurements were taken at a rate of 10°C / min from 25°C to 800°C. The 5% weight change temperature refers to the temperature at which the weight of the sample measured at 25°C increases by 5%.

[0153] (v) 10% weight change temperature The manufactured copper foil samples were measured using a thermogravimetric analyzer (TGA) in an air atmosphere. Specifically, measurements were taken at a rate of 10°C / min from 25°C to 800°C. The 10% weight change temperature refers to the temperature at which the weight of the sample measured at 25°C increases by 10%.

[0154] (vi) thermogravimetric coefficient The thermogravimetric coefficient is the ratio of the weight of copper foil 110 measured at 500°C to the weight of copper foil 110 measured at 25°C. Specifically, according to Examples 1-5 and Comparative Examples 1-5, this refers to the ratio of the weight of copper foil 110 measured at 500°C to the weight of the sample measured at 25°C.

[0155] (vii) Capacity retention rate For the negative electrode active material, 100 parts by weight of commercially available carbon was mixed with 2 parts by weight of SBR (styrene-butadiene rubber) and 2 parts by weight of CMC (carboxymethylcellulose). Next, distilled water was added to this mixture as a solvent to produce a slurry. Using a doctor blade, the slurry was applied to the surface of electrolytic copper foil (width: 10 cm) to a thickness of approximately 60 μm, dried at 120°C for 10 minutes, and then subjected to a pressing process (pressure: 1 ton / cm²). 2 The negative electrode was manufactured by performing the following procedure.

[0156] Lithium manganese oxide (Li 1.1 Mn 1.85 Al 0.05 A positive electrode active material was prepared by mixing O4 and orthorhombic lithium manganese oxide (o-LiMnO2) in a weight ratio of 90:10. A slurry was prepared by mixing the positive electrode active material, carbon black, and polyvinylidene fluoride (PVDF) with NMP as an organic solvent in a weight ratio of 85:10:5. The positive electrode was prepared by coating both sides of a 20 μm thick aluminum foil with the slurry and then drying it.

[0157] Furthermore, a basic electrolyte was prepared by dissolving 1 M of LiPF6 as a solute in a non-aqueous organic solvent, which was a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a 1:2 weight ratio. This basic electrolyte was then mixed with 0.5% by weight of succinic anhydride to produce another electrolyte.

[0158] A secondary battery was manufactured using the negative electrode, positive electrode, and electrolyte produced in this manner. Next, the capacity per g of the positive electrode was measured for the secondary batteries manufactured in this manner at a charging operating voltage of 4.3V and a discharging operating voltage of 3.4V. A charge-discharge experiment was performed 50 times at a charge-discharge rate of 0.2C at 50°C, and the capacity retention rate of the secondary batteries was calculated using Equation 1 below.

[0159] [Formula 1] Capacity retention rate (%) = (Discharge capacity at 50th discharge / Discharge capacity at 1st discharge) × 100

[0160] Referring to Tables 1 to 3, the copper foils used in Examples 1 to 4 met the requirement of a thermogravimetric coefficient of 1.1% or less and a secondary battery capacity retention rate of 90% or more. However, the copper foils used in Comparative Examples 1 to 4 did not meet the requirement of a thermogravimetric coefficient of 1.1% or less and a secondary battery capacity retention rate of 90% required by the industry.

[0161] The present invention, as described above, is not limited by the embodiments and examples and accompanying drawings, and it will be apparent to those with ordinary skill in the art to which the present invention pertains that various substitutions, modifications, and alterations are possible without departing from the technical matters of the present invention. Accordingly, the scope of the present invention is expressed by the claims described below, and it should be understood that all modified or altered forms derived from the meaning, scope, and equivalent concepts of the claims are included within the scope of the present invention. [Explanation of Symbols]

[0162] 100 Electrodes for secondary batteries 110, 110a, 110b copper foil 111 Copper film 112 Protective layer 120 Active material layer 10 Electrolytic cell 20 Electrolyte

Claims

1. A copper film having a matte surface and a shiny surface, The protective layer on the copper film includes, Copper foil with a thermogravimetric coefficient of 1.1% or less: The aforementioned thermogravimetric coefficient is measured in an oxygen atmosphere using a thermogravimetric analyzer (TGA) at a rate of 10°C / min from 25°C to 800°C.

2. The copper foil according to claim 1, wherein the 1% weight change temperature is 340°C or higher: The aforementioned 1% weight change temperature is measured using a thermogravimetric analyzer (TGA) in an oxygen atmosphere and refers to the temperature at which the weight increases by 1% compared to the initial weight.

3. The copper foil according to claim 1, wherein the 5% weight change temperature is 430°C or higher: The aforementioned 5% weight change temperature is measured using a thermogravimetric analyzer (TGA) in an oxygen atmosphere and refers to the temperature at which the weight increases by 5% compared to the initial weight.

4. The copper foil according to claim 1, wherein the 10% weight change temperature is 500°C or higher: The aforementioned 10% weight change temperature is measured using a thermogravimetric analyzer (TGA) in an oxygen atmosphere and refers to the temperature at which the weight increases by 10% compared to the initial weight.

5. The copper foil according to claim 1, wherein the protective layer comprises at least one of a chromium compound, a silane compound, and a nitrogen compound.

6. The steps of manufacturing an electrolyte containing copper ions, The step of forming a copper film, The step includes forming a protective layer on the copper film, The step of forming the copper film is: The step of showering the surface of the rotating negative electrode drum with a cleaning agent, The step includes forming a copper film on the rotating negative electrode drum by energizing the positive electrode plates and the rotating negative electrode drum, which are arranged in the electrolyte in the electrolytic cell so as to be spaced apart from each other, The aforementioned electrolyte is 70-150 g / L of copper ions; 80-130 g / L sulfuric acid; 15-25 ppm chlorine (Cl); and Contains organic additives; The aforementioned organic additive comprises a brightener (component A), a moderator (component B), and a roughness modifier (component C). The glossing agent (component A) comprises sulfonic acid or a metal salt thereof and has a concentration of 1 to 15 ppm. The aforementioned moderator (component B) contains a nonionic water-soluble polymer and has a concentration of 0.1 to 15 ppm. The roughness modifier (component C) comprises a nitrogen-containing heterocyclic quaternary ammonium salt or a derivative thereof, and has a concentration of 1 to 15 ppm. A method for manufacturing copper foil.

7. The cleaning agent comprises 8% (w / w) to 12% (w / w) sulfuric acid and a glossing agent (component A) in the range of 0.1% (w / w) to 0.3% (w / w), The method for producing copper foil according to claim 6, wherein the glossing agent (component A) in the cleaning agent comprises sulfonic acid or a metal salt thereof.

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