Patent Application
20240204167
This application claims the benefit of the Korean Patent Applications No. 10-2022-0174874 filed on Dec. 14, 2022 and No. 10-2023-0132910 filed on Oct. 5, 2023, which are hereby incorporated by reference as if fully set forth herein.
The present disclosure relates to a copper foil capable of preventing defects of a tear or wrinkle thereof, an electrode including the same, a secondary battery including the same, and a method for manufacturing the same.
Secondary batteries are types of energy conversion devices that convert electrical energy into chemical energy, store the chemical energy therein, and then convert the chemical energy back to electrical energy when electricity is needed, thereby generating electricity. The secondary batteries are used as energy sources for electric vehicles as well as portable home appliances such as mobile phones, laptop computers, and the like. The secondary batteries are rechargeable and thus are also referred to as rechargeable batteries.
As secondary batteries that have economic and environmental advantages over disposable primary batteries, there are lead-acid batteries, nickel-cadmium secondary batteries, nickel-hydrogen secondary batteries, and lithium secondary batteries.
In particular, lithium secondary batteries may store a relatively large amount of energy relative to their size and weight compared with other secondary batteries. Accordingly, in the field of information communication devices in which portability and mobility are important, the lithium secondary batteries are preferred, and an application range thereof is also expanding to energy storage devices for hybrid vehicles and electric vehicles.
Lithium secondary batteries are repeatedly used through one cycle of charging and discharging. When a certain device is operated with a fully charged lithium secondary battery, the lithium secondary battery should have a high charge/discharge capacity in order to increase an operating time of the device. Accordingly, research to satisfy ever-increasing expectations (needs) of consumers regarding the charge/discharge capacity of a lithium secondary battery is continuously required.
Such a secondary battery includes an anode current collector made of a copper foil, and among copper foils, an electrolytic copper foil is widely used as an anode current collector of a secondary battery. Along with an increase in demand for secondary batteries, there is an increase in demand for secondary batteries with high capacity, high efficiency, and high quality, and thus, there is a need for copper foils capable of improving characteristics of secondary batteries. In particular, there is a need for copper foils that can ensure high capacity to secondary batteries and enable secondary batteries to stably maintain capacity and performance.
Meanwhile, as copper foils become smaller in thickness, the amount of active materials that can be included in the same space may be increased, and the number of current collectors may be increased, and thus, the capacity of secondary batteries can be increased. However, as the copper foils become smaller in thickness, curling occurs, and thus, when the copper foil is wound, defects such as tears or wrinkles of the copper foil occur due to curling of an edge, and accordingly, there is difficulty in manufacturing copper foils in the form of a very thin film. Accordingly, in order to manufacture a copper foil having a very thin thickness, the curling of the copper foil should be prevented.
Accordingly, the present disclosure relates to a copper foil capable of preventing the problems caused by the limitations and disadvantages of the related art described above, an electrode including the same, a secondary battery including the same, and a method for manufacturing the same.
According to one embodiment of the present disclosure, there is provided a copper foil that is not curled, wrinkled, or teared during a manufacturing process by allowing a copper film to have a room temperature loss factor of 0.05 or less.
According to another embodiment of the present disclosure, there is provided a copper foil that is not curled, wrinkled, or teared during a high-temperature manufacturing process by allowing a copper film to have a high-temperature loss factor of 0.2 or less.
According to still another embodiment of the present disclosure, there is provided an electrode for a secondary battery including the copper foil, and a secondary battery including the electrode for a secondary battery.
According to yet another embodiment of the present disclosure, there is provided a method for manufacturing a copper foil in which the occurrence of curls, wrinkles, or tears is prevented.
In addition to the aspects of the present disclosure described above, other features and advantages of the present disclosure will be described in the following detailed description, or may be clearly understood by those skilled in the art to which the present disclosure pertains from such description.
According to one embodiment of the present disclosure, there is provided a copper foil including a copper film including 99.9 wt % or more of copper, wherein the copper film has a room temperature loss factor of 0.05 or less, wherein the room temperature loss factor is calculated by Equation 1 below,
room temperature loss factor=room temperature loss modulus/room temperature storage modulus. [Equation 1]
According to another embodiment of the present disclosure, there is provided a method for manufacturing a copper foil, the method including preparing an electrolyte containing copper ions, forming a copper film, and forming a protective layer on the copper film, wherein the forming of the copper film includes forming the copper film on a rotating anode drum by electrically connecting a cathode plate and the rotating anode drum, which are disposed to be spaced apart from each other in an electrolyte in an electrolytic bath, wherein the electrolyte includes copper ions at a concentration of 70 g/L to 100 g/L, sulfuric acid at a concentration of 70 g/L to 150 g/L, chlorine (Cl) at a concentration of 15 ppm to 25 ppm, lead ions (Pb2+) at a concentration of 1 ppm to 100 ppm, hydrogen peroxide at a concentration of 1 ml/L to 10 ml/L, tungsten (W) at a concentration of 0.3 ppm to 5 ppm, and an organic additive, wherein the organic additive includes at least one of a polishing agent (component A), a moderator (component B), and a leveling agent (component C), wherein the polishing agent (component A) includes sulfonic acid or a metal salt thereof, the moderator (component B) includes a non-ionic water-soluble polymer, and the leveling agent (component C) includes at least one of nitrogen (N) and sulfur (S).
According to still another embodiment of the present disclosure, there is provided an electrode for a secondary battery, the electrode including a copper foil and an active material layer disposed on at least one surface of the copper foil.
According to yet another embodiment of the present disclosure, there is provided a secondary battery including a cathode configured to provide lithium ions during charging, and anode configured to provide electrons and lithium ions during discharge, an electrolyte disposed between the cathode and the anode to provide an environment in which the lithium ions are movable, and a separator configured to electrically insulate the anode and the cathode.
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this application, illustrate embodiments of the disclosure and together with the description serve to explain the principle of the disclosure. In the drawings:
Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. However, the embodiments described below are presented only for illustrative purposes to facilitate a clear understanding of the present disclosure and do not limit the scope of the present disclosure.
Shapes, sizes, ratios, angles, numbers, and the like disclosed in the drawings for describing the embodiments of the present disclosure are illustrative, and thus the present disclosure is not limited to the details illustrated in the drawings. Throughout the present specification, the same components may be referred to by the same reference numerals. In describing the present disclosure, detailed descriptions of related known technologies will be omitted when it is determined that they may unnecessarily obscure the gist of the present disclosure.
When terms “including,” “having,” “consisting of,” and the like described in the present specification are used, other parts may be added unless the term “only” is used herein. When a component is expressed in the singular form, the plural form is included unless otherwise specified. In addition, in interpreting a component, it is interpreted as including an error range even when not explicitly stated.
In describing a positional relationship, for example, when a positional relationship of two parts is described as being “on,” “above,” “below, “next to,” or the like, unless “immediately” or “directly” is not used, one or more other parts may be located between the two parts.
Spatially relative terms, such as “below,” “beneath,” “lower,” “above,” “upper” and the like, may be used herein for ease of description to describe one element or component's relationship to another element(s) or component(s) as illustrated in the drawings. It will be understood that the spatially relative terms are intended to include different orientations of the element in use or operation in addition to the orientation illustrated in the drawings. For example, when an element in the drawings is turned over, an element described as being “above” or “upper” relative to another element will then be “below” or “lower” relative to the other element. Thus, the exemplary term “below” may include both above and below orientations. Likewise, the exemplary terms “above” or “upper” may include both above and below orientations.
In describing a temporal relationship, for example, when a temporal predecessor relationship is described as being “after,” “subsequent,” “next to,” “prior to,” or the like, unless “immediately” or “directly” is used, cases that are not continuous may also be included.
In order to describe various components, terms such as “first,” “second,” and the like are used, but these components are not limited by these terms. These terms are only used to distinguish one component from another component. Therefore, a first component described below may be a second component within the technical spirit of the present disclosure.
The term “at least one” should be understood to include all possible combinations from one or more related items. For example, the meaning of “at least one of first, second, and third items” may mean all combinations of two or more items of the first, second, and third items as well as each of the first, second, and third items.
The features of various embodiments of the present disclosure may be partially or wholly coupled to or combined with each other, and may be various technically linked or operated, and each of the embodiments may be implemented independently of each other or may be implemented together in a related relationship.
Referring to
The copper film 111 may be formed on a rotating anode drum through electroplating, and has a shiny surface that is in direct contact with the rotating anode drum in the electroplating process and a matte surface opposite to the shiny surface.
The protective layer 112 is formed by electrodepositing an anticorrosion material on the copper film 111. The anticorrosion material may include at least one of a chromium compound, a silane compound, and a nitrogen compound. The protective layer 112 prevents oxidation and corrosion of the copper film 111 and improves heat resistance, thereby increasing a lifespan of a final product including the copper foil 110 as well as a lifespan of the copper foil 110 itself.
According to one embodiment of the present disclosure, the copper film 111 has a room temperature loss factor of 0.05 or less. The room temperature loss factor may be obtained through a calculation according to Equation 1 below.
Room temperature loss factor=room temperature loss modulus/room temperature storage modulus [Equation 1]
The room temperature storage modulus in Equation 1 refers to elastic energy stored in the copper film at room temperature, and the room temperature loss modulus in Equation 1 refers to elastic energy stored in the copper film, which is lost due to viscosity. Specifically, the room temperature refers to 25° C.
When the room temperature loss factor of the copper film 111 is greater than 0.05, the loss of the elastic energy stored in the copper film 111 is increased, so that the elastic energy stored in the copper film may not be sustained against an external impact. Accordingly, wrinkles or tears may occur during the manufacturing process of the copper foil 110, thereby reducing workability and increasing a defect rate of the secondary battery.
According to one embodiment of the present disclosure, the copper film 111 has a high-temperature loss factor of 0.2 or less. The high-temperature loss factor may be obtained through a calculation according to Equation 2 below.
High-temperature loss factor=high-temperature loss modulus/high-temperature storage modulus [Equation 2]
The high-temperature storage modulus in Equation 2 refers to elastic energy stored in the copper film after heat-treating at 350° C. for one hour, and the high-temperature loss modulus in Equation 2 refers to elastic energy stored in the copper film, which is lost due to viscosity after heat-treating at 350° C. for one hour.
When the high-temperature loss factor of the copper film 111 is greater than 0.02, the loss of the elastic energy stored in the copper film 111 at high temperatures is increased, so that the elastic energy stored in the copper film may not be sustained against an external impact. In addition, due to the nature of the manufacturing process of the copper foil 110, which is conducted at high temperatures, softening may occur during the roll pressing process and/or the drying process, and deterioration of handleability due to wrinkles may occur.
According to one embodiment of the present disclosure, the copper film 111 may have a room temperature storage modulus in a range of 30 GPa to 80 GPa. The room temperature storage modulus refers to elastic energy stored in the copper film at room temperature.
When the room temperature storage modulus of the copper film 111 is less than 30 GPa, the elastic energy stored in the copper film 111 becomes so small that there is not enough elastic energy to withstand an external impact. Accordingly, wrinkles or tears may occur during the manufacturing process of the copper foil 110, thereby reducing workability and increasing a defect rate of the secondary battery.
When the room temperature storage modulus of the copper film 111 exceeds 80 GPa, it may not be able to respond to the expansion and contraction of an active material during the manufacturing process of an anode current collector of a secondary battery. As a result, the active material and copper foil 110 may be delaminated or the copper foil 110 may be broken, resulting in lower charge and discharge efficiency of the secondary battery.
According to one embodiment of the present disclosure, the copper film 111 has a room temperature loss modulus of 5 GPa or less. The room temperature loss modulus refers to elastic energy stored in the copper film, which is lost due to viscosity at room temperature.
When the room temperature loss modulus of the copper film 111 is greater than 5 GPa, the loss of the elastic energy stored in the copper film 111 is increased, so that the elastic energy stored in the copper film may not be sustained against an external impact. Accordingly, wrinkles or tears may occur during the manufacturing process of the copper foil 110, thereby reducing workability and increasing a defect rate of the secondary battery.
According to one embodiment of the present disclosure, the copper film 111 has a high-temperature storage modulus in a range of 20 GPa to 60 GPa. The high-temperature storage modulus refers to elastic energy stored in the copper film after heat-treating at 350° C. for one hour.
When the high-temperature storage modulus of the copper film 111 is less than 20 GPa, the elastic energy stored in the copper film 111 under high-temperature conditions is very small. Accordingly, in the nature of the manufacturing process of the copper foil 110, which is conducted at high temperatures, the copper foil 110 does not have sufficient elastic energy to withstand an external impact at high temperatures. Accordingly, wrinkles or tears may occur during the manufacturing process of the copper foil 110, thereby reducing workability and increasing a defect rate of the secondary battery.
In a case in which the high-temperature storage modulus of the copper film 111 is greater than 60 GPa, when the active material expands under high-temperature conditions, due to the nature of the manufacturing process of the copper foil 110, which is conducted at high temperatures, the active material and the copper foil 110 may bd delaminated or the copper foil 110 may be broken to lower the charge and discharge efficiency of the secondary battery.
According to one embodiment of the present disclosure, the copper film 111 has a high-temperature loss modulus of 10 GPa or less. The high-temperature loss modulus refers to elastic energy stored in the copper film, which is lost due to viscosity after heat treatment at 350° C. for one hour.
When the high-temperature loss modulus of the copper film 111 is greater than 10 GPa, the loss of the elastic energy stored in the copper film 111 at high temperatures is increased. Accordingly, due to the nature of the manufacturing process of the copper foil 110, which is conducted at high temperatures, in the copper foil 110 under high-temperature conditions, the elastic energy stored in the copper film may not be sustained against an external impact. In addition, due to the nature of the manufacturing process of the copper foil 110, which is conducted at high temperatures, softening may occur during the roll pressing process and/or the drying process, and deterioration of handleability due to wrinkles may occur.
According to one embodiment of the present disclosure, the copper foil 110 may have a coefficient of thermal expansion in a range of 5 ppm/° C. to 30 ppm/° C. Specifically, the copper foil 110 may have a coefficient of thermal expansion in a range of 10 ppm/° C. to 25 ppm/° C. More specifically, the copper foil 110 may have a coefficient of thermal expansion in a range of 15 ppm/° C. to 20 ppm/° C.
When the coefficient of thermal expansion of the copper foil 110 is less than 5 ppm/° C., wrinkling or tearing of the copper foil 110 may occur in a process of manufacturing the copper foil 110 through a roll-to-roll process.
On the other hand, when the coefficient of thermal expansion is greater than 30 ppm/° C., the copper foil 110 may be bent to a substantial degree in the process of manufacturing the copper foil 110 through the roll-to-roll process.
The copper foil 110 according to one embodiment of the present disclosure has a thickness of 4 μm to 35 μm. When the copper foil 110 is used as a current collector of an electrode in a secondary battery, as the thickness of the copper foil 110 becomes smaller, more current collectors can be accommodated in the same space, which is advantageous for high capacity of the secondary battery. However, the manufacture of a copper foil 110 having a thickness of less than 4 μm causes a decrease in workability.
On the other hand, when the secondary battery is manufactured with the copper foil 110 with a thickness exceeding 35 μm, it becomes difficult to achieve high capacity due to the thick copper foil 110.
The copper foil 110 according to one embodiment of the present disclosure may have a tensile strength of 45 kg/mm2 or more. In order to suppress wrinkling and tearing of the copper foil 110, the copper foil 110 of the present disclosure has a high tensile strength of 45 kg/mm2 or more. When the tensile strength of the copper foil 110 is less than 45 kg/mm2, during a roll-to-roll manufacturing process, folding of the copper foil 110 is caused between two adjacent rolls, or wrinkling of lateral end portions of the copper foil 110 is caused.
The copper foil 110 according to one embodiment of the present disclosure may have an elongation of 3% to 30%.
In a case in which the elongation of the copper foil 110 is less than 3%, when the copper foil 110 is used as a current collector of a secondary battery, there is a high risk that the copper foil 110 will be torn because it cannot be sufficiently stretched in response to a large expansion in volume of a high-capacity active material.
On the other hand, when the elongation of the copper foil 110 is greater than 30%, the copper foil 110 is easily stretched in a process of manufacturing an electrode for a secondary battery, thereby causing deformation in the electrode.
According to one embodiment of the present disclosure, the copper foil 110 may have an arithmetic mean roughness (Ra) of 0.2 μm to 0.3 μm.
As the secondary battery is repeatedly charged and discharged, an active material layer may alternately contract and expand, which leads to the separation of the active material layer from the copper foil 110, thus reducing the charge and discharge efficiency of the secondary battery. Accordingly, in order to secure a certain level or higher of capacity retention rate and lifespan of the secondary battery (that is, in order to suppress the deterioration of charge and discharge efficiency of the secondary battery), the bonding strength of the copper foil 110 and the active material layer should be high by allowing the copper foil 110 to have an excellent coatability on the active material.
Specifically, as the arithmetic mean roughness (Ra) of the copper foil 110 is smaller, the charge and discharge efficiency of the secondary battery including the copper foil 110 tends to be less poor. Thus, according to one embodiment of the present disclosure, the copper foil 110 has the arithmetic mean roughness (Ra) of 0.2 μm to 0.3 μm.
When the arithmetic mean roughness (Ra) of the copper foil 110 is less than 0.2 μm, the surface area of the copper foil 110 is relatively small so that the active material is easily delaminated from the copper foil 110, and as a result, rapid lifespan deterioration of the secondary battery due to a repetition of charging and discharging is caused.
On the other hand, when the arithmetic mean roughness (Ra) of the copper foil 110 is greater than 0.3 μm, a plurality of spaces exist between the copper foil 110 and the active material layer since contact uniformity between the copper foil 110 and the active material layer does not reach a predetermined level (i.e., the coating itself is partially performed), and as a result, rapid lifespan deterioration of the secondary battery due to a repetition of charging and discharging is caused.
Hereinafter, an electrode 100 including the copper foil 110 of the present disclosure and a secondary battery including the electrode 100 will be described in detail.
As illustrated in
Generally, in a lithium secondary battery, an aluminum foil is used as a cathode current collector combined with a cathode active material, and the copper foil 110 is used as an anode current collector combined with an anode active material.
According to one embodiment of the present disclosure, the electrode 100 for a secondary battery is an anode, the copper foil 110 is used as an anode current collector, and the active material layer 120 includes an anode active material.
In order to secure a high capacity of a secondary battery, the active material layer 120 of the present disclosure may be formed of a composite of carbon and metal. The metal may include, for example, at least one of silicon (Si), germanium (Ge), tin (Sn), lithium (Li), zinc (Zn), magnesium (Mg), cadmium (Cd), cerium (Ce), nickel (Ni), and iron (Fe), and preferably, may include Si and/or Sn.
Referring to
The cathode 370 includes a cathode current collector 371 and a cathode active material layer 372, and an aluminum foil may be used as the cathode current collector 371.
The anode 340 includes an anode current collector 341 and an anode active material layer 342, and the copper foil 110 may be used as the anode current collector 341.
According to one embodiment of the present disclosure, the copper foil 110 disclosed in
Hereinafter, a method for manufacturing the copper foil 110 of the present disclosure will be described in detail with reference to
The method for manufacturing the copper foil 110 of the present disclosure includes forming a copper film 111, and forming a protective layer 112 on the copper film 111.
The method of the present disclosure includes forming the copper film 111 on a rotating anode drum 40 by electrically connecting a cathode plate 30 and the rotating anode drum 40, which are disposed to be spaced apart from each other in an electrolyte 20 in an electrolytic bath 10.
As illustrated in
The forming of the copper film 111 may be performed by forming a seed layer through an electrical connection between the first cathode plate 31 and the rotating anode drum 40, and then growing a seed layer through an electrical connection between the second cathode plate 32 and the rotating anode drum 40.
A current density provided by each of the first and second cathode plates 31 and 32 may be 30 to 130 ASD (A/dm2).
When the current density provided by each of the first and second cathode plates 31 and 32 is less than 30 ASD, a surface roughness of the copper foil 110 is reduced, and thus the adhesion between the copper foil 110 and the active material layer 120 may not be sufficient.
On the other hand, when the current density provided by each of the first and second cathode plates 31 and 32 is greater than 130 ASD, a surface of the copper foil 110 may be rough, and thus the active material may not be smoothly coated.
The surface characteristics of the copper film 111 may be changed according to a buffing or polishing degree of a surface of the rotating anode drum 40. For example, the surface of the rotating anode drum 40 may be polished using a polishing brush having a grit of #800 to #3000.
In the process of forming the copper film 111, the electrolyte 20 is maintained at a temperature of 48° C. to 60° C. More specifically, the temperature of the electrolyte 20 may be maintained at 50° C. or higher. At this time, the physical, chemical, and electrical characteristics of the copper film 111 may be controlled by adjusting a composition of the electrolyte 20.
According to one embodiment of the present disclosure, the electrolyte 20 includes copper ions at a concentration of 70 g/L to 100 g/L, sulfuric acid at a concentration of 70 g/L to 150 g/L, chlorine (Cl) at a concentration of 15 ppm to 25 ppm, lead ions (Pb2+) at a concentration of 1 ppm to 100 ppm, hydrogen peroxide (H2O2) at a concentration of 1 ml/L to 10 ml/L, tungsten (W) at a concentration of 0.3 ppm to 5 ppm, and an organic additive.
In order to facilitate the formation of the copper film 111 through copper electrodeposition, the concentration of copper ions and the concentration of sulfuric acid in the electrolyte 20 are adjusted in a range of 70 g/L to 100 g/L and a range of 70 g/L to 150 g/L, respectively.
In one embodiment of the present disclosure, the chlorine (Cl) includes all of chlorine ions (Cl−) and chlorine atoms present in a molecule. The chlorine (Cl) may, for example, be used to remove silver (Ag) ions input into the electrolyte 20 in a process of forming the copper film 111. Specifically, the chlorine (Cl) may precipitate silver (Ag) ions in the form of silver chloride (AgCl). The silver chloride (AgCl) may be removed through filtration.
When the concentration of chlorine (Cl) is less than 15 ppm, the silver (Ag) ions are not removed well. On the other hand, when the concentration of chlorine (Cl) exceeds 25 ppm, unnecessary reaction may occur due to the excessive amount of chlorine (Cl). Accordingly, the concentration of chlorine (Cl) in the electrolyte 20 is controlled in a range of 15 ppm to 25 ppm.
According to one embodiment of the present disclosure, the electrolyte 20 including an organic additive may further include lead ions (Pb2+). Specifically, the electrolyte 20 may include lead ions (Pb2+) at a concentration of 1 ppm to 100 ppm. When the lead ions (Pb2+) are maintained at the concentration of 1 ppm to 100 ppm, in the copper film 111 according to the present disclosure, the room temperature loss factor may be maintained to be 0.05 or less, and the high-temperature loss factor may be maintained to be 0.2 or less.
On the other hand, when the concentration of lead ions (Pb2+) is less than 1 ppm, a problem may occur where effectiveness is reduced in terms of maintaining of maintaining the physical properties of the present disclosure. As a result, rapid changes in values of the loss modulus and the storage modulus of the copper film 111 may occur, and thus the value of the room temperature loss factor exceeds 0.05, and the value of the high-temperature loss factor exceeds 0.2.
In addition, when the concentration of lead ions (Pb2+) is greater than 100 ppm, copper may be non-uniformly precipitated, which may cause rapid changes in the values of the loss modulus and the storage modulus of the copper film 111, and thus the value of the room temperature loss factor exceeds 0.05 and the high-temperature loss factor exceeds 0.2.
According to one embodiment of the present disclosure, the electrolyte 20 including an organic additive may further include hydrogen peroxide (H2O2). Due to the organic additive, organic impurities may be present in the electrolyte 20 that is continuously plated, and a content of carbon (C) in the copper foil may be appropriately adjusted by decomposing the organic impurities by treating the organic impurities with hydrogen peroxide (H2O2). As a concentration of total organic carbon (TOC) in the electrolyte 20 is increased, an amount of carbon (C) elements input into the copper film 111 is increased, which causes an increase in total amount of elements detached from the copper film 111 during heat treatment and thus causes a decrease in strength of the copper foil 110 after heat treatment.
The hydrogen peroxide (H2O2) is added in an amount of 1 ml to 10 ml per one L of the electrolyte. Specifically, the hydrogen peroxide (H2O2) may be added in an amount of 2 ml to 8 ml per one L of the electrolyte. When the amount of added hydrogen peroxide (H2O2) is less than 1 ml/L, it is meaningless because there is little effect on the decomposition of organic impurities. When the amount of added hydrogen peroxide (H2O2) exceeds 10 ml/L, the organic impurities are excessively decomposed, and thus, the effects of organic additives such as a polishing agent, a moderator, and a leveling agent, are also suppressed.
According to one embodiment of the present disclosure, the electrolyte 20 including an organic additive may further include tungsten (W). When the electrolyte 20 is treated with tungsten (W), the average size of the crystalline particles included in the copper film 111 may be reduced, and the strength of the copper foil 110 may be increased. The concentration of tungsten (W) in the electrolyte 20 may be in a range of 0.3 ppm to 5 ppm. Specifically, it is preferable that the tungsten (W) is added at a concentration of 1 ppm to 4 ppm.
On the other hand, when the concentration of tungsten (W) is less than 0.3 ppm, an average crystalline particle size of the copper film 111 is not constant, which may cause rapid changes in the values of the loss modulus and the storage modulus of the copper film 111, and thus the value of the room temperature loss factor exceeds 0.05 and the value of the high-temperature loss factor exceeds 0.2.
In addition, when the concentration of tungsten (W) is greater than 5 ppm, impurities are increased, which may cause rapid changes in the values of the loss modulus and storage modulus of the copper film 111, and thus the value of the room temperature loss factor exceeds 0.05 and the high-temperature loss factor exceeds 0.2.
The organic additive included in the electrolyte 20 includes at least one of a polishing agent (component A), a moderator (component B), a leveling agent (component C). The organic additive in the electrolyte 20 has a concentration of 1 ppm to 100 ppm.
The organic additive may include two or more of the polishing agent (component A), the moderator (component B), and the leveling agent (component C), and may include all of the three components. In this case, the concentration of organic additive is 100 ppm or less. When the organic additive includes all of the polishing agent (component A), the moderator (component B), and the leveling agent (component C), the organic additive may have a concentration of 10 ppm to 100 ppm.
The polishing agent (component A) includes sulfonic acid or a metal salt thereof. The polishing agent (component A) may have a concentration of 1 ppm to 25 ppm in the electrolyte 20.
The polishing agent (component A) may increase an amount of electric charges of the electrolyte 20 to improve an electrodeposition speed of copper, may improve the curling characteristics of the copper foil, and may increase the gloss of the copper foil 110. When the concentration of polishing agent (component A) is less than 1 ppm, the gloss of the copper foil 110 is lowered, and when the concentration of polishing agent (component A) exceeds 25 ppm, the roughness of the copper foil 110 may be increased and the strength of the copper foil 110 may be lowered. As a result, wrinkles or tears may occur during the manufacturing process of the copper foil 110. In addition, rapid changes in values of the loss modulus and the storage modulus may occur, and thus the value of the room temperature loss factor exceeds 0.05, and the value of the high-temperature loss factor exceeds 0.2.
More specifically, the polishing agent (component A) may have a concentration of 5 ppm to 20 ppm in the electrolyte 20.
The polishing agent may include, for example, at least one selected from among a bis-(3-sulfopropyl)-disulfide disodium salt, a 3-mercapto-1-propanesulfonic acid, a 3-(N,N-dimethylthiocarbamoyl)-thiopropanesulfonate sodium salt, a 3-[(amino-iminomethyl)thio]-1-propanesulfonate sodium salt, an O-ethyldithiocarbonato-S-(3-sulfopropyl)-ester sodium salt, a 3-(benzothiazolyl-2-mercapto)-propyl-sulfonic acid sodium salt, and an ethylenedithiodipropylsulfonic acid sodium salt.
The moderator (component B) includes a non-ionic water-soluble polymer. The moderator (component B) may have a concentration of 1 ppm to 10 ppm in the electrolyte 20.
The moderator (component B) reduces the electrodeposition speed of copper to prevent a rapid increase in roughness and a decrease in strength of the copper foil 110. This moderator (component B) is referred to as an inhibitor or suppressor.
When the concentration of moderator (component B) is less than 1 ppm, the roughness of the copper foil 110 rapidly rises, and the strength of the copper foil 110 may be reduced. In addition, rapid changes in values of the loss modulus and the storage modulus may occur, and thus the value of the room temperature loss factor exceeds 0.05, and the value of the high-temperature loss factor exceeds 0.2. As a result, wrinkles or tears may occur during the manufacturing process of the copper foil 110. On the other hand, although the concentration of moderator (component B) exceeds 10 ppm, there is almost no change in physical properties such as the appearance, gloss, roughness, strength, and elongation of the copper foil 110. Accordingly, without increasing manufacturing costs and wasting raw materials due to an unnecessary increase in concentration of moderator (component B), the concentration of moderator (component B) may be adjusted in a range of 1 ppm to 10 ppm.
The moderator (component B) may include, for example, at least one non-ionic water-soluble polymer selected from among a polyethylene glycol (PEG), polypropylene glycol, a polyethylene polypropylene copolymer, polyglycerin, polyethylene glycol dimethyl ether, hydroxyethylene cellulose, polyvinyl alcohol, stearic acid polyglycol ether, and stearyl alcohol polyglycol ether. However, the type of the moderator is not limited thereto, and other non-ionic water-soluble polymers usable to manufacture the high strength copper foil 110 may be used as the moderator.
The leveling agent (component C) includes at least one of nitrogen (N) and sulfur (S). That is, the leveling agent (component C) may include one or more nitrogen atoms (N) or one or more sulfur atoms (S) in one molecule and may include one or more nitrogen atoms (N) and one or more sulfur atoms (S). For example, the leveling agent (component C) is an organic compound including at least one of nitrogen (N) and sulfur (S).
The leveling agent (component C) prevents excessively high peaks or excessively large protrusions from being generated in the copper film 111 to enable the copper film 111 to be macroscopically planarized. The leveling agent (component C) may have a concentration of 1 ppm to 10 ppm in the electrolyte 20.
When the concentration of leveling agent (component C) is less than 1 ppm, the strength of the copper foil 110 is reduced, and thus the copper foil 110 may be wrinkled or teared, and in addition, rapid changes in values of the loss modulus and the storage modulus may occur, and thus the value of the room temperature loss factor exceeds 0.05, and the value of the high-temperature loss factor exceeds 0.2. On the other hand, when the concentration of leveling agent (component C) exceeds 10 ppm, the surface roughness of the copper foil 110 may be excessively increased to decrease strength, and pinholes or curling may occur on a surface of the copper foil 110, which makes it difficult to separate the copper foil 110 from a winder WR after being manufactured. In addition, rapid changes in values of the loss modulus and the storage modulus may occur, and thus the value of the room temperature loss factor exceeds 0.05, and the value of the high-temperature loss factor exceeds 0.2.
The leveling agent (component C) may include, for example, at least one selected from among diethylthiourea, ethylenethiourea, acetylenethiourea, dipropylthiourea, dibutylthiourea, N-trifluoroacetylthiourea, N-ethylthiourea, N-cyanoacetylthiourea, N-allylthiourea, o-tolylthiourea, N,N′-butylenethiourea, thiazolidinethiol, 4-thiazolinethiol, 4-methyl-2-pyrimidinethiol, 2-thiouracil, a 3-(benzotriazole-2-mercapto)-pyrosulfuric acid, 2-mercaptopyridine, 3-(5-mercapto-1H-tetrazole)benzenesulfonate, 2-mercaptobenzothiazole, dimethylpyridine, 2,2′-bipyridine, 4,4′-bipyridine, pyrimidine, pyridazine, pyrinoline, oxazole, thiazole, 1-methylimidazole, 1-benzylimidazole, 1-methyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-ethyl-4-methylimidazole, 1-ethyl-2-ethyl-4-methylol, N-methylpyrrole, N-ethylpyrrole, N-butylpyrrole, N-methylpyrroline, N-ethylpyrroline, N-butylpyrroline, purine, quinoline, isoquinoline, N-methylcarbazole, N-ethylcarbazole, and N-butylcarbazole.
When the copper film 111 is formed, a flow rate of the electrolyte 20 supplied into the electrolytic bath 10 may be 41 m3/hour to 45 m3/hour.
The forming of the copper film 111 may include at least one of filtering the electrolyte 20 using activated carbon, filtering the electrolyte 20 using diatomaceous earth, and treating the electrolyte 20 with ozone (O3).
Specifically, in order to filter the electrolyte 20, the electrolyte 20 may be circulated at a flow rate of 35 m3/hour to 45 m3/hour. That is, in order to remove solid impurities present in the electrolyte 20 while electroplating to form the copper film 111, filtering may be performed at a flow rate of 35 m3/hour to 45 m3/hour. In this case, activated carbon or diatomaceous earth may be used.
In order to maintain the cleanliness of the electrolyte 20, the electrolyte 20 may be treated with ozone (O3).
In addition, in order to maintain the cleanliness of the electrolyte 20, a copper (Cu) wire used as a raw material for the electrolyte 20 may be cleaned.
According to one embodiment of the present disclosure, preparing the electrolyte 20 may include heat-treating a Cu wire, acid-cleaning the heat-treated Cu wire, water-cleaning the acid-cleaned Cu wire, and inputting the water-cleaned Cu wire into sulfuric acid for an electrolyte.
More specifically, in order to maintain the cleanliness of the electrolyte 20, a Cu wire with a high purity (99.9% or more) is heat-treated in an electric furnace at a temperature of 750° C. to 850° C. to burn various organic impurities attached to the Cu wire, the heat-treated Cu wire is acid-cleaned using a 10% sulfuric acid solution for 10 to 20 minutes, and the acid-cleaned Cu wire is then water-cleaned using distilled water, thereby preparing copper for manufacturing the electrolyte 20. The water-cleaned Cu wire may be input into sulfuric acid for an electrolyte to prepare the electrolyte 20.
According to one embodiment of the present disclosure, in order to satisfy the characteristics of the copper foil 110, a concentration of TOC in the electrolyte 20 is controlled to be 50 ppm or less. That is, the electrolyte 20 may have a TOC concentration of 50 ppm or less.
The copper film 111 thus prepared may be cleaned in a cleaning bath.
For example, an acid cleaning process for removing impurities on a surface of the copper film 111, for example, resin components or natural oxides, and a water cleaning process for removing acidic solutions used for the acid cleaning may be sequentially performed. The cleaning process may be omitted.
Next, the protective layer 112 is formed on the copper film 111.
Referring to
As described above, the anticorrosion solution 60 may include at least one of a chromium compound, a silane compound, and a nitrogen compound. For example, the copper film 111 may be immersed in a 1 g/L to 10 g/L potassium dichromate solution at room temperature for 1 to 30 seconds.
Meanwhile, the protective layer 112 may include a silane compound by silane treatment or a nitrogen compound by nitrogen treatment.
The copper foil 110 is formed by forming the protective layer 112.
At least one anode active material selected from the group consisting of carbon, a metal (Me) of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe, an alloy including the metal (Me), an oxide (MeOx) of the metal (Me), and a composite of the metal (Me) and carbon is coated on one surface or both surfaces the copper foil 110 of the present disclosure prepared through the method as described above to manufacture an electrode (i.e., anode) for a secondary battery of the present disclosure.
For example, 100 parts by weight of carbon for an anode active material, 1 to 3 parts by weight of styrene butadiene rubber (SBR), and 1 to 3 parts by weight of carboxymethyl cellulose (CMC) are mixed and prepared as a slurry using a distilled water as a solvent. Subsequently, the slurry is applied on the copper foil 110 to a thickness of 20 μm to 60 μm using a doctor blade and pressed at a pressure of 0.5 to 1.5 ton/cm2 at 110° C. to 130° C.
A secondary battery may be manufactured using the electrode (anode) for a secondary battery of the present disclosure manufactured through the method as described above, together with a conventional cathode, electrolyte, and separator.
Hereinafter, the present disclosure will be described in detail with reference to examples and comparative examples. However, the examples described below are only intended to aid the understanding of the present disclosure, and the scope of the present disclosure is not limited to these examples.
A copper foil was prepared using a foil maker including an electrolytic bath 10, a rotating anode drum 40 disposed in the electrolytic bath 10, and a cathode plate 30 disposed to be spaced apart from the rotating anode drum 40. An electrolyte 20 was a copper sulfate solution. A concentration of copper ions in the electrolyte 20 was set to 87 g/L, a concentration of sulfuric acid was set to 110 g/L, a temperature of the electrolyte was set to 55° C., and a current density was set to 60 ASD.
In addition, concentrations of chlorine (Cl), lead (Pb), hydrogen peroxide (H2O2), and tungsten (W), which are contained in the electrolyte 20, and a concentration of an organic additive were as shown in Table 1 below.
In the organic additive, a bis-(3-sulfopropyl)-disulfide disodium salt (SPS) was used as a polishing agent (component A), PEG was used as a moderator (component B), and ethylene thiourea (ETU) was used as a leveling agent (component C).
A current at a current density of 60 ASD was applied between the rotating anode drum 40 and the cathode plate 30 to prepare a copper film 111. Thereafter, the copper film 111 was immersed in an anticorrosion solution for about two seconds to treat a surface of the copper film 111 with chromium to form a protective layer 112, thereby preparing a copper foil 110. An anticorrosion solution containing chromic acid as a main component was used as the anticorrosion solution, and a concentration of chromic acid was 5 g/L.
As a result, copper foils of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared.
For the copper foils manufactured according to Examples 1 to 6 and Comparative Examples 1 to 4 as described above, i) room temperature storage modulus (E′), ii) room temperature loss modulus (E″), iii) room temperature loss factor, iv) high-temperature storage modulus (E′), v) high-temperature loss modulus (E″), vi) high-temperature loss factor, and vii) occurrence of wrinkles/tears were checked.
The copper foil 110 was cooled to 20° C. and then heated to 500° C. at a heating rate of 5° C./min, and the viscoelasticity thereof was measured using Seiko Exstar 6000 (DMA/SS6100) from Seiko at a vibration frequency of 1 Hz.
The room temperature storage modulus (E′) and the room temperature loss modulus (E″) at 25° C. were calculated from the obtained viscoelastic curve.
iii) Calculation of Room Temperature Loss Factor (E″/E′)
The room temperature loss factor (E″/E′) may be obtained by calculating values of the measured i) room temperature storage modulus (E″) and ii) room temperature loss modulus (E′) according to Equation 1 below.
The high-temperature storage modulus (E′) and the high-temperature loss modulus (E″) were measured in the same manner as the room temperature storage modulus (E′) and the room temperature loss modulus (E′), except that the high-temperature storage modulus (E′) and the high-temperature loss modulus (E″) were measured after heating the copper foil 110 at 350° C. for one hour.
The high-temperature loss factor (E″/E′) may be obtained by calculating values of the measured i) high-temperature storage modulus (E″) and ii) high-temperature loss modulus (E′) according to Equation 2 below.
vii) Occurrence of Wrinkle/Tear
After 100 charge and discharge cycles, the secondary battery was disassembled to observe whether a wrinkle or a tear occurred on the copper foil. When the copper foil was wrinkled or torn, the copper foil was labeled as “occurrence,” and when the copper foil was not wrinkled or tom, the copper foil was labeled as “no.”
Referring to Tables 1 and 2, the following results may be confirmed.
A tear/wrinkle occurred in the copper foil of Comparative Example 1 prepared using an electrolyte including a polishing agent (component A) in an excessive amount, and lead and tungsten in small amounts.
A tear/wrinkle occurred in the copper foil of Comparative Example 2 prepared using an electrolyte including a moderator (component B) and lead in excessive amounts, and tungsten in a small amount.
A tear/wrinkle occurred in the copper foil of Comparative Example 3 prepared using an electrolyte including a leveling agent (component C), lead, and tungsten in excessive amounts.
A tear/wrinkle occurred in the copper foil of Comparative Example 4 prepared using an electrolyte including a leveling agent (component C) and hydrogen peroxide in excessive amounts.
On the other hand, all the copper foils of Examples 1 to 6 according to the present disclosure satisfied values within the above standard ranges, resulting in no tears/wrinkles occurred in the copper foil.
According to the present disclosure, by preventing the occurrence of wrinkles or tears in a copper foil during a manufacturing process and using the copper foil to manufacture intermediate parts and final products, such as flexible printed circuit boards (FPCBs) and secondary batteries, productivity of the intermediate parts as well as the final products can be improved.
It will be apparent to those skilled in the art that the present disclosure described above is not limited by the above-described embodiments and the accompanying drawings and that various substitutions, modifications, and variations can be made in the present disclosure without departing from the spirit and scope of the present disclosure.
Accordingly, the scope of the present disclosure is defined by the accompanying claims, and it is intended that all variations and modifications derived from the meaning, scope, and equivalent concept of the claims fall within the scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0174874 | Dec 2022 | KR | national |
| 10-2023-0132910 | Oct 2023 | KR | national |
