KR20140053285A - Rolled copper foil for secondary battery collector and production method therefor - Google Patents

Abstract

Provided is a rolled copper foil having a wide striped irregularity formed area and excellent uniformity of roughened plating and a method for producing the same. The rolled copper foil 20 made of copper or a copper alloy formed by rolling has an area ratio of 15% or less within 13 占 from the orientation of the RDW orientation {012} <100> in the crystal orientation of the surface.

Description

TECHNICAL FIELD [0001] The present invention relates to a rolled copper foil for a secondary battery current collector,

The present invention relates to a rolled copper foil applicable to a current collector for a secondary battery and a method of manufacturing the same. More particularly, the present invention relates to a rolled copper foil having improved roughening plating property for the purpose of improving adhesion with an active material, .

The rolled copper foil is used as an anode current collector of a secondary battery such as a lithium ion battery, and is usually coated with an active material.

Therefore, if the adhesion between the collector and the active material is poor, various problems arise. For example, the active material falls off due to external stress in the battery manufacturing process. In addition, peeling of the collector and active material occurs due to expansion and contraction of the active material due to charging and discharging during use of the battery.

Thus, the surface of the rolled copper foil is subjected to roughening treatment by wet plating to positively form a surface having large irregularities, thereby improving the adhesion between the current collector and the active material.

Since the uniformity of the unevenness of the surface after the roughening treatment is ensured by the uniformity of the unevenness of the surface of the copper foil after the rolling, the control of the surface irregularities in the production of the rolled copper foil for a battery is an important technical problem to be.

BACKGROUND ART [0002] Disclosure of an active material is a main cause of capacity reduction in view of a recent demand for a greater capacity of a battery. In addition, since the active material is expected to be applied to a large expansion / shrinkage active material such as a silicon (Si) type or a tin (Sn) type, its importance is increasing.

Typically, the striped irregularities of 60 to 120 DEG with respect to the rolling direction are formed on the surface after rolling. However, there is a problem that a striped irregular region is formed at a size of several tens of micrometers (占 퐉) in the width direction and 100 占 퐉 in the length direction with respect to the rolling direction.

If a large amount of roughness and roughness around the periphery is included in the surface of the rolled copper foil, roughness plating becomes a roughened surface including a small area of roughness There is a problem that the active material is partially peeled off.

Several methods have been proposed for controlling the unevenness of the surface of the rolled copper foil (see, for example, Patent Documents 1 to 3).

Patent Document 1 proposes a method of raising the average interval of irregularities by optimizing the rolling conditions and Patent Document 2 proposes to reduce the average interval of irregularities.

In Patent Document 3, the surface roughness (Ra) and the average spacing (S) between tops of local portions are shown in the optimum range.

Japanese Patent Laid-Open No. 2006-281249 Japanese Patent Application Laid-Open No. 2007-268596 International Publication No. WO2001 / 029912

In this patent document, only the interval of one-dimensional irregularities in a certain direction is controlled with an index, and area control is not performed. Furthermore, the glossiness, surface roughness (Ra), and (Rz) are indicators based on an average of a wide measurement range, and the nonuniformity thereof was not controlled.

Also, in the patent documents 1 and 2, the control method is suitable for rolling conditions, and is not a fundamental one for eliminating non-uniformity. Therefore, there have been cases in which the demand for the recent battery use is not satisfied.

It is an object of the present invention to provide a rolled copper foil for a secondary battery current collector having a wide striped irregularities and excellent uniformity of roughened plating and a method of manufacturing the same.

The present inventors have diligently studied the effect of the crystal orientation with regard to the non-uniform formation of the striped concavo-convex in each place. It is to be noted that the crystal orientation of the region where the striped concavities and convexities are not formed is mainly the RDW direction {012} < 100 >, and that the surface irregularities are made uniform by reducing this orientation of the rolled copper foil surface to realize adhesion with a good active material And reached the present invention.

Further, the RDW orientation in the rolled copper foil was strongly influenced by the final annealing structure in the manufacturing process and invented a process for controlling the RDW orientation.

According to the present invention, there is provided a rolled copper foil made of copper or a copper alloy formed by rolling, the rolled copper foil having an area ratio of 15% or less from the orientation of the RDW orientation {012} < 100 & do.

The rolled copper foil refers to a rolled foil of pure copper, but the present application means a rolled foil of a copper alloy widely.

Preferably, the area ratio of the stripe-shaped surface irregularities in the direction of 60 占 to 120 占 with respect to the rolling direction is 60% or more.

Preferably, the rolled copper foil is a Cu- (Cr, Zr) based copper alloy containing at least one of Cr and Zr as a main component, and contains 0.01 to 0.9 mass% of at least one of Cr and Zr as main components.

Also, the Cu- (Cr, Zr) based rolled copper foil may contain 0.01 to 0.45 mass% of at least one of Sn, Zn, Si, Mn, and Mg as additive components in total.

In addition, the Cu- (Cr, Zr) based rolled copper foil is formed by inevitable impurities (unavoidable impurities), with the remainder excluding the main component, or the remainder excluding the main component and the minor additive component.

Preferably, the rolled copper foil is a Cu-Ag-based copper alloy containing Ag as a main component and contains Ag in a total amount of 0.01 to 0.9 mass% as a main component.

In addition, the Cu-Ag-based rolled copper foil may contain 0.01 to 0.45% by mass of at least one of Sn, Zn, Si, Mn, and Mg as additive components in total.

In addition, the remainder of the Cu-Ag-based rolled copper foil except for the main component, or the remainder excluding the main component and the minor additive component, is formed by unavoidable impurities.

Preferably, the rolled copper foil is a Cu-Sn-based copper alloy containing Sn as a main component and contains 0.01 to 4.9 mass% of Sn as a main component in total.

In addition, the Cu-Sn-based rolled copper foil may contain 0.01 to 0.45% by mass of at least one of Zn, Si, P, and Mg as additive components in total.

In addition, the remainder of the Cu-Sn-based rolled copper foil, except for the main component, or the remainder excluding the main component and the minor additive component, is formed by unavoidable impurities.

Preferably, the rolled copper foil is a Cu-Ni-Si based copper alloy containing Ni and Si as main components and contains 1.4 to 4.8% by mass of Ni and 0.2 to 1.3% by mass of Si as main components.

Further, the Cu-Ni-Si-based rolled copper foil may contain 0.005 to 0.9 mass% in total of at least one of Sn, Zn, Si, Cr, Mn, Mg,

In addition, the remainder of the Cu-Ni-Si-based rolled copper foil excluding the main component, or the remainder excluding the main component and the minor additive component, is formed by unavoidable impurities.

Preferably, the rolled copper foil is a pure copper system containing oxygen and has an oxygen content of 2 to 200 ppm.

Further, the pure copper-based rolled copper foil is formed by unavoidable impurities.

According to the present invention, there is also provided a method of manufacturing a rolled copper foil for manufacturing any one of the rolled copper foils of the above-mentioned rolled copper foil, comprising: a hot rolling step of heating the rolled copper foil to a temperature not lower than a recrystallization temperature for hot rolled, At least two intermediate cold rolling steps for performing cold rolling under a temperature at which recrystallization does not occur and at least one intermediate annealing step for performing intermediate annealing at a temperature rising rate while heating at a predetermined temperature, And a final annealing step of performing a final annealing at a predetermined heating rate while a predetermined temperature is raised after the final intermediate cold rolling step, When the temperature raising rate does not give a time for the recrystallization bulb phenomenon Is set, there is provided a method for producing the ultimate temperature is set to a high temperature is obtained suppressing the movement of the first particles and a specific type recrystallized structure with randomized.

Preferably, in the intermediate annealing step performed before entering the final annealing step, the arrival temperature is a temperature higher than the upper limit of the recrystallization temperature of the copper alloy.

Preferably, in the intermediate annealing step performed before entering the final annealing step, the temperature raising rate is 2 ° C / second or more, and the arrived temperature is a high temperature of 800 ° C or more.

Preferably, the method further includes a first intermediate cold rolling step of performing cold rolling after the hot rolling step, a first intermediate annealing step of performing intermediate annealing subsequent to the first intermediate cold rolling step, A second intermediate cold rolling step of performing cold rolling after the first intermediate cold rolling step, a second intermediate annealing step of performing intermediate annealing after the second intermediate cold rolling step, and a second intermediate annealing step of performing cold rolling Wherein the final annealing step is performed after the third intermediate cold rolling step and before the second intermediate annealing step enters the final annealing step, The rate of temperature rise is set at a rate that does not give rise to the time of the recrystallization bulb phenomenon, and the arrival temperature suppresses the preferential movement of the specific grain system, Is set to a high temperature is a recrystallized structure is obtained.

Preferably, the method further includes a homogenizing heat treatment step of subjecting the pressurized strip material to a homogenization heat treatment before the step of hot rolling.

According to the present invention, it is possible to realize a rolled copper foil having a wide area where striped irregularities are formed and excellent uniformity of roughened plating, and the adhesion between the collector and the active material can be improved.

As a result, the active material is less likely to fall off the current collector due to the external force in the manufacturing process of the battery or the like, and the capacity of the secondary battery can be improved. Further, even when the active material such as tin (Sn) or silicon (Si) based materials having a large amount of expansion and shrinkage during charging and discharging is deformed, it is possible to prevent the separation of the active material and the current collector and to improve the charge- have.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing a schematic configuration of a lithium secondary battery to which a rolled copper foil according to an embodiment of the present invention is applied as an anode current collector. FIG.
2 is a schematic enlarged view of a rolled copper foil according to an embodiment of the present invention.
Fig. 3 is a view for explaining the manufacturing process of the rolled copper foil according to the embodiment of the present invention.
Fig. 4 is a view showing a low concavity and convexity region seen between the striped concavo-convex region and the striped concavo-convex region in the surface texture of the rolled copper foil.
Fig. 5 is a diagram showing a state in which the surface texture of the rolled copper foil according to the present embodiment is rich in stripe-shaped irregularities.
6 is a view showing the measurement result by EBSD.
Fig. 7 is a diagram showing an example of a bearing whose deviation angle from the RDW direction is within 13 占 Fig.
8 is a view showing a manufacturing method of a comparative example.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing a schematic configuration of a lithium secondary battery to which a rolled copper foil according to an embodiment of the present invention is applied as an anode current collector. FIG.

2 is a schematic enlarged view of a rolled copper foil according to an embodiment of the present invention.

The lithium secondary battery 10 of FIG. 1 includes a positive electrode 11, a negative electrode 12, a positive electrode collector 13, a negative electrode collector 14, a separator 15, a positive electrode side battery can 16, A can 17, and an insulating packing 18.

The positive electrode 11 and the negative electrode 12 are arranged to face each other with the separator 15 interposed therebetween. The positive electrode 11, the negative electrode 12 and the separator 15 are housed in a battery case formed by the positive electrode side battery can 16 and the negative electrode side battery can 17.

In this accommodated state, the anode 11 is connected to the anode-side battery can 16 via the cathode current collector 13, and the cathode 12 is connected to the cathode-side battery can 17 via the anode current collector 14. [ Respectively.

With this structure, the secondary battery 10 can be charged and discharged.

In the present embodiment, the rolled copper foil 20 as shown in Fig. 2 is applied as the negative electrode collector 14.

The rolled copper foil 20 according to the present embodiment is formed with the following characteristics, for example, the thickness d being set to 12 μm or less.

The rolled copper foil (20) has an area ratio of 60% or more in a region where stripe-shaped surface irregularities in the direction of 60 to 120 占 with respect to the rolling direction are visible.

The area of the rolled copper foil 20 within 13 DEG from the orientation {012} < 100 > in the RDW orientation in the surface crystal orientation is 15% or less.

As the crystal orientation, crystal orientation measurement by electron backscattering diffraction (EBSD method) is applicable.

The rolled copper foil 20 according to the present embodiment is formed as a copper alloy or a pure copper system as shown in the following (1) to (5).

(1): Cu- (Cr, Zr) based copper alloy

The rolled copper foil 20 is a Cu- (Cr, Zr) -based copper alloy containing at least one of Cr and Zr as a main component and is formed as a copper alloy containing at least one of Cr and Zr as a main component in a total amount of 0.01 to 0.9 mass% do. Also, the Cu- (Cr, Zr) based copper alloy is formed as a copper alloy containing at least one kind of Sn, Zn, Si, Mn, and Mg as total of 0.01 to 0.45 mass%

The Cu- (Cr, Zr) based copper alloy is formed by inevitable impurities (inevitable impurities) with the remainder excluding the main component, or the remainder excluding the main component and the additive component.

(2): Cu-Ag-based copper alloy

The rolled copper foil 20 is a Cu-Ag-based copper alloy containing Ag as a main component and is formed as a copper alloy containing Ag in a total amount of 0.01 to 0.9 mass% as a main component.

Further, the Cu-Ag-based copper alloy is formed as a copper alloy containing 0.01 to 0.45% by mass of at least one of Sn, Zn, Si, Mn, and Mg as auxiliary addition components, if necessary.

The Cu-Ag-based copper alloy is formed by inevitable impurities, with the remainder excluding the main component, or the remainder excluding the main component and the additive component.

(3): Cu-Sn-based copper alloy

The rolled copper foil 20 is a Cu-Sn-based copper alloy containing Sn as a main component and is formed as a copper alloy containing 0.01 to 4.9 mass% of Sn as a main component in total.

Further, the Cu-Sn-based copper alloy is formed as a copper alloy containing 0.01 to 0.45% by mass of at least one of Zn, Si, P, and Mg as auxiliary addition components, if necessary.

The rest of the Cu-Sn-based copper alloy except for the main component, or the remainder excluding the main component and the minor additive component, is formed by inevitable impurities.

(4): Cu-Ni-Si based copper alloy

The rolled copper foil 20 is a Cu-Ni-Si based copper alloy containing Ni and Si as main components and is formed as a copper alloy containing 1.4 to 4.8% by mass of Ni and 0.2 to 1.3% by mass of Si as main components.

Also, the Cu-Ni-Si based copper alloy is formed as a copper alloy containing 0.005 to 0.9 mass% in total of at least one of Sn, Zn, Si, Cr, Mn, Mg,

The remainder of the Cu-Ni-Si-based copper alloy except for the main component, or the remainder excluding the main component and the minor additive component, is formed by unavoidable impurities.

(5): pure oxygen system (TPC system)

The rolled copper foil 20 is a pure copper (TPC) copper material containing oxygen with an oxygen content of 2 to 200 ppm and the balance of unavoidable impurities.

Here, inevitable impurities are generally impurities which are present in raw materials in metal products or which are inevitably incorporated in the production process, although they are originally unnecessary, but are small amounts and do not affect the properties of metal products.

3 is a diagram for explaining a manufacturing process of the rolled copper foil 20 according to the present embodiment.

The rolled copper foil 20 is manufactured by using the first step (ST1) to the thirteenth step (ST13) as basic steps as shown in Fig.

The first step ST1 is a dissolving step for dissolving the raw material and the second step ST2 is a casting step for casting the molten raw material to form ingots under pressure. The third step (ST3) It is a homogenization heat treatment process that is a heat treatment to homogenize the casting structure of serial materials.

The fourth step (ST4) is a hot rolling step. Hot rolling refers to rolling performed by heating a metal to a recrystallization temperature or higher. The fifth step (ST5) is a water-cooling step, and the sixth step (ST6) is a cutting step for removing an oxide scale.

The seventh step (ST7) is a first (intermediate) cold rolling step, and the eighth step (ST8) is a first intermediate annealing step for performing intermediate annealing. Cold rolling refers to rolling performed at a temperature range in which recrystallization does not occur (for example, normal temperature).

The ninth step ST9 is a second intermediate cold rolling step, the tenth step ST10 is a second intermediate annealing step, and the eleventh step ST11 is a third intermediate cold rolling step.

The twelfth step ST12 is a final annealing step for final annealing, and the thirteenth step ST13 is a finish rolling step.

The characteristic processing for manufacturing the rolled copper foil 20 according to the present embodiment is the same as the first intermediate annealing step in the eighth step ST8 and the twelfth step ST12 in the second intermediate annealing step in the tenth step ST10 In the second intermediate annealing step performed before the final annealing step, the temperature raising rate and the reaching temperature are set as follows.

In this embodiment, in the second intermediate annealing step of the tenth step (ST10), the rate of temperature rise is set higher than the rate of temperature rise of ordinary intermediate annealing so as not to give time for the recrystallization bulb phenomenon, The temperature is set to be higher than the upper limit of the recrystallization temperature of the copper alloy so as to obtain a recrystallized structure in which the priority movement of the grain system is suppressed and randomized.

In the production of the rolled copper foil 20 according to the present embodiment, the temperature raising rate in the second intermediate annealing in the tenth step (ST10) is 2 deg. C / second or more and the arrival temperature is 800 deg. C or more.

As described above, in the production of the rolled copper foil 20 according to the present embodiment, the temperature is raised in steps of several degrees Celsius or every several tens of degrees Celsius for one second.

The feature points of the above-described surface structure, crystal orientation, crystal orientation of the rolled copper foil 20 according to the present embodiment, the manufacturing process for controlling the crystal orientation, alloy components, etc. will be described concretely, Examples of the copper alloy will be described in connection with the reference examples and comparative examples.

[Surface organization]

Fig. 4 is a view showing a low concavity and convexity region seen between the striped concavo-convex region and the striped concavo-convex region in the surface texture of the rolled copper foil.

In Fig. 4, 1H denotes a stripe-shaped uneven region and 1L denotes a low uneven region.

Fig. 5 is a diagram showing a state in which the surface texture of the rolled copper foil 20 according to the present embodiment is rich in striped irregularities.

In the present embodiment, the area of the stripe rugged area 1H shown in Fig. 4 is divided by the total area to obtain the area ratio.

An area ratio of 60% or more is necessary to ensure uniformity of roughened plating. , Preferably at least 70%, more preferably at least 80%.

The rolled copper foil 20 according to the present embodiment shown in Fig. 5 is in a state in which there are many stripe-shaped irregularities.

[Crystal orientation]

The smaller the RDW orientation in the rolled copper foil 20 is, the higher the area ratio of the stripe-shaped rugged area is, the better the roughened plating becomes possible, and the area ratio of the RDW orientation is 15% or less. , Preferably not more than 12%, more preferably not more than 8%.

6 is a view showing the measurement result by EBSD.

In Fig. 6, a grain boundary system in which the angle between the direction of the Brass orientation and the orientation of the S orientation and the RDW orientation and the adjacent measurement point is defined as 15 deg. Or more is shown.

The regions of Brass orientation and S orientation (RGN-BS) are divided into crystal grains having a size of about 10 mu m in the rolling direction (RD, left and right direction in the drawing), and their sizes and stripe-shaped irregularities correspond.

On the other hand, it can be seen that the region (RGN-R) in the RDW orientation has a direction gradient within the crystal grain but has no grain boundaries and is coarse and large in the direction of the RD, and corresponds to a region having no stripe- .

This is because the specificity of the RDW orientation originates from a small amount of crystal slip. There is Taylor's model of the effect of crystal orientation on the slip deformation of polycrystalline materials (see, for example, J. Inst. Metals, 62 (1938), 307-324), Taylor factor do.

The Taylor factor of the RDW orientation is 2.4 and the lowest of all the crystal orientations, while the Taylor factors in the rolling deformation of Brass orientation and S orientation are 3.3 and 3.5, respectively.

That is, under the condition that the thin rolling process with a high processing ratio is performed and the density of lattice defects such as dislocation and vacancies is remarkably high, crystal slip is hard to occur in Brass orientation or S orientation , Deformation is caused by formation of a shear band or grain boundary, and the crystal grains are divided, and as a result, pits are formed on the rolled surface.

On the other hand, since the RDW orientation is deformed by crystal slip, only one crystal grain elongates and a new grain boundary is not formed in the grain, resulting in a surface with fewer pits.

The method of displaying the crystal orientation in this specification is a method in which the rolling direction RD of the material is taken as an X axis, the width direction (TD) as a Y axis, and the rolling normal direction (ND) as a rectangular coordinate system of Z axis, (Hkl) [uvw] is calculated by using the exponent hkl of the crystal plane perpendicular to the Z axis (parallel to the rolled surface (XY plane)) and the index [uvw] of the crystal plane (parallel to the YZ plane) .

Equivalent orientations based on the cubic symmetry of the copper alloy, such as (120) [001] and (210) [001], are denoted by {hkl} <uvw> using the bracket symbols indicating the family.

The EBSD method is used for the analysis of the crystal orientation in the present embodiment. EBSD is an abbreviation of Electron Back Scatter Diffraction, which is a reflection electron Kikuchi ray diffraction (Kikuchi pattern) generated when a sample is irradiated with an electron beam in a Scanning Electron Microscope (SEM) Is a crystal orientation analysis technique using

In the present embodiment, the sample is scanned at a step of 0.2 占 퐉 with respect to a sample area of 50,000 square micrometers or more, and the orientation is analyzed.

The area ratio is calculated by dividing the area of the area where the deviation angle from the ideal direction is within 13 占 by the entire measuring area.

With respect to the deviation angle from the ideal direction, the rotation angle was calculated around the common rotation axis to obtain the deviation angle.

Fig. 7 is a diagram showing an example of a bearing whose deviation angle from the RDW direction is within 13 占 Fig.

In Fig. 7, the directions of (001), (101), and (111) are shown to be within 13 degrees with respect to the rotation axis, but the rotation angles with respect to all the rotation shafts are calculated. And the rotation axis can be expressed by the smallest deviation angle.

The information obtained in the orientation analysis by the EBSD contains azimuth information up to a depth of several tens of nanometers at which the electron beam penetrates the sample but is sufficiently small for the area to be measured and is described in the present specification as the area ratio. The orientation distribution was measured from the plate surface.

[Process for controlling crystal orientation]

The manufacturing process for controlling the crystal orientation in which the effectiveness is found in the embodiment of the present invention.

Further, as described above, the area ratio of the stripe-shaped surface irregularities in the direction of 60 to 120 占 with respect to the rolling direction is 60% or more, and the area ratio from the RDW orientation {012} <100> Is not more than 15%, it is not limited to the manufacturing process shown here.

As the manufacturing process of the rolled copper foil 20 for controlling the crystal orientation, the first step (ST1) to the thirteenth step (ST13) are the basic steps as shown in Fig.

That is, the present invention provides a method of manufacturing a steel sheet, which includes a melting step, a casting step, a homogenizing heat treatment step, a hot rolling step, a water cooling step, a surface cutting step, a first (intermediate) cold rolling step, a first intermediate annealing step, 3 The basic manufacturing process consists of intermediate cold process, final annealing process, and finish rolling process.

In general, the purpose of the intermediate annealing step is to soften and soften the structure of a material which is hardened by machining and is hard to further process, so that it can be processed.

The recrystallization temperature of the copper alloy is approximately 150 to 800 캜 (here, less than 800 캜) though it varies depending on the alloy.

In the embodiment of the present invention, the RDW orientation to be controlled low tends to remain in the non-rotated state even if it is the preferred growth orientation in the recrystallization and at the same time rolling.

Therefore, it is necessary to reduce the RDW orientation in the structure in the final annealing in the twelfth step (ST12).

According to the manufacturing method of the rolled copper foil 20 according to the present embodiment, by setting the temperature raising rate to 2 캜 / second or more and the arrival temperature to 800 캜 or more in the second intermediate annealing in the tenth step (ST10) It was possible.

The formation of the preferred orientation in the recrystallization process is thought to be influenced by the difference in the recovery speed for each crystal orientation. It is considered that the time for the recrystallization bulb phenomenon is not increased by raising the temperature increase rate, This is because a recrystallized structure in which the preferential movement of the system is suppressed and randomized is obtained.

A preferable range of the annealing speed is 5 占 폚 / second or more, and a more preferable range is 10 占 폚 / second or more. The upper limit is not specially set, but the maximum is 200 ° C / sec.

A preferable range of the reaching temperature is 870 DEG C or higher, and a more preferable range is 950 DEG C or higher. The upper limit is 1000 占 폚 at which the high temperature brittleness of the material is remarkable.

Further, if such a random recrystallization heat treatment is performed by the final annealing in the twelfth step (ST12), it is undesirable that the crystal grain is rough and large, which causes surface cracking and side cracking. Therefore, the grain diameter after final annealing is preferably 30 mu m or less.

[Alloy Ingredients]

The effect of the above-described crystal orientation control can be applied to various alloy systems.

The characteristics required for the copper foil are changed by the design of the whole battery, and an appropriate alloy system may be selected accordingly. The strength and the conductivity of the rolled foil are roughly in trade-off relation, and the characteristics of each alloy system are as shown in Table 1 below.

In Table 1, the tensile strength of the Cu- (Cr, Zr) based copper alloy according to the present embodiment is 400 to 700 MPa and the conductivity is 70 to 95% IACS (International Annealed Copper Standard) Respectively.

Here, 70% IACS indicates that the conductor has a conductivity of 70% when the electrical resistivity is 100% of the "standard annealing copper wire" referred to as IACS (International Annealing Wire Standard).

The Cu- (Cr, Zr) based copper alloy has a conductivity of 70 to 95% IACS and good electrical characteristics.

Similarly, the Cu-Ag based copper alloy according to the present embodiment shows a tensile strength of 350 to 550 MPa and a conductivity of 80 to 98% IACS.

Such a Cu-Ag-based copper alloy exhibits high electrical properties with an electrical conductivity of 80 to 98% IACS.

The Cu-Sn based copper alloy according to the present embodiment has a tensile strength of 400 to 750 MPa and a conductivity of 15 to 95% IACS.

Although such a Cu-Sn-based copper alloy has a conductivity of 15 to 95% and a large variation range, it can exhibit high electric (battery) characteristics by optimizing the amount of added components of the main component and the auxiliary addition component.

The Cu-Ni-Si based copper alloy according to the present embodiment has a tensile strength of 600 to 1000 MPa and a conductivity of 20 to 50% IACS.

Although such a Cu-Ni-Si based copper alloy has a slightly low conductivity of 20 to 50%, it can exhibit electric (battery) characteristics depending on the application by optimizing the addition amount of components of the main component and the auxiliary addition component.

The pure copper (TPC) copper material according to the present embodiment has a tensile strength of 350 to 550 MPa and a conductivity of 95 to 100% IACS.

Such pure copper based copper material exhibits high electrical properties with a conductivity of 95 to 100% IACS.

When the upper limit of the component specified by each of the copper alloys of (1) to (5) is added, it is possible to obtain a copper alloy having a large and submicron sized submicron order in the form of oxides, precipitates, It is dispersed as the second phase, and pinholes and plate breakage are caused at the time of rolling to a thickness of 12 탆 or less, which is not preferable. And the conductivity is remarkably lowered, which is not preferable.

Further, when it is added at less than the lower limit of the component specified by each of the copper alloys of (1) to (5), the effect of the addition is not sufficiently obtained. The amount of the component added is appropriately adjusted according to the use described above.

The total amount of the main components Cr and Zr contained in the Cu- (Cr, Zr) based alloy is preferably 0.15 to 0.43 mass%, more preferably 0.22 to 0.31 mass%.

The preferred range of Ag as the main component of the Cu-Ag system is 0.02 to 0.15 mass%, more preferably 0.03 to 0.05 mass%.

The preferable range of Sn of the main component of the Cu-Sn system is 0.1 to 2.3 mass%, more preferably 0.6 to 0.9 mass%.

The preferred range of the main component Ni of the Cu-Ni-Si system is 2.1 to 4.2 mass%, more preferably 3.4 to 3.9 mass%.

Addition of auxiliary additive elements such as Sn, Zn, Si, Mn, Mg and P is allowed for the purpose of improving strength, heat resistance and the like in addition to the above-mentioned main components.

Particularly, the problem that pinholes are generated by the second phase inherent in the rolling up to the thickness of 12 탆 or less can be solved by deoxidizing the molten metal by the addition of Si, Mg, P, It is effective to suppress the formation of sulfides and to inhibit the formation of sulfides by addition of Mn.

It has been confirmed that the RDW orientation tends to be formed as much as the alloy system containing a large amount of additive elements than the pure copper system. This is due to the fact that the rolling texture changes from a pure copper type to a brass type.

Therefore, the effect of the embodiment of the present invention becomes more remarkable as the alloy becomes a high concentration alloy. That is, in the application of the embodiment of the present invention, a preferable alloy system is a Cu-Ag system, and a more preferable alloy system is a Cu-Sn system, a Cu-Ni-Si system, and a Cu-Cr system.

The present embodiment is particularly applicable to a copper foil having a thickness of 12 탆 or less, but it can also be applied to a copper foil having a thickness of 12 탆 or more.

Example

Hereinafter, a specific embodiment of the present invention will be described.

The results of the examples are shown in Tables 2 to 6 below.

The evaluation results of the Cu- (Cr, Zr) -based examples are shown in Table 2, the evaluation results of the Cu-Ag-based examples are shown in Table 3, and the evaluation results of the Cu- Table 5 shows the evaluation results of the Cu-Ni-Si based samples, and Table 6 shows the evaluation results of the pure copper based samples.

Tables 2 to 6 show evaluation results of the copper alloy examples of (1) to (5) above in comparison with the reference examples and comparative examples.

Before describing the result evaluation of the examples of Tables 2 to 6, a method of manufacturing a rolled copper foil of this embodiment and a comparative example, a method of evaluating a rolled copper foil before roughening plating, a battery evaluation method, and the like will be described.

[Production method of rolled copper foil]

 An embodiment of a method for manufacturing a rolled copper foil according to the present embodiment will be described with reference to Fig.

 In the first step (ST1), the raw material was dissolved by a high-frequency melting furnace, and the dissolved raw material was cast at a cooling rate of 0.1 to 100 DEG C / sec in the second step (ST2) to obtain an ingot. The ingot contains the alloy components shown in Tables 2 to 6, and the remainder is formed of Cu and unavoidable impurities.

 In the third step (ST3), the ingot obtained in the second step (ST2) was subjected to a homogenizing heat treatment at a temperature of 800 to 1030 占 폚 for 5 minutes to 10 hours, and the hot rolling in the fourth step (ST4) .

 After hot working in the fourth step (ST4), water cooling was performed in the fifth step (ST5), and machining was performed in order to remove the oxide scale in the sixth step (ST6).

 Thereafter, the first (intermediate) cold rolling is performed in the seventh step (ST7), the first intermediate annealing is performed in the eighth step (ST8), and the second intermediate cold rolling is performed in the ninth step (ST9) . Further, the second intermediate annealing is performed in the tenth step (ST10), the third intermediate cold rolling is performed in the eleventh step (ST11), the final annealing is performed in the twelfth step (ST12), the thirteenth step ST13) to obtain a rolled foil having a thickness of 12 mu m or less.

 (Intermediate) cold rolling of the seventh step (ST7), the second intermediate cold rolling of the ninth step (ST9), the third intermediate cold rolling of the eleventh step (ST11) and the finishing rolling of the thirteenth step (ST13) Was carried out with a plate thickness reduction rate of 66 to 99%.

 Annealing heat treatment of the first intermediate annealing in the eighth step (ST8) and the final annealing in the twelfth step (ST12) was maintained at a temperature of 300 DEG C or more and less than 800 DEG C, which is a typical recrystallization temperature, for 3 seconds to 10 hours.

 However, the second intermediate annealing in the tenth step (ST10) was carried out under the conditions of a temperature raising rate of 2 DEG C / sec or more and an arrival temperature of 800 DEG C or more and 1000 DEG C or less.

 After each heat treatment or rolling, pickling or surface polishing was carried out depending on the oxidation or roughness of the material surface, and correction by tension leveler was performed depending on the shape.

 An example of the manufacturing method according to the present embodiment described above is referred to as step A.

 The comparative examples in Tables 2 to 6 were produced by any one of the following steps E to I shown in Fig.

[Process E]

 Step E is the same as Step A except that the temperature raising rate of the second intermediate annealing in the tenth step (ST10) is set to 0.2 to 1.8 占 폚 / second and the reaching temperature is set to 300 占 폚 to less than 800 占 폚.

[Step F]

 Step F is the same as Step A except that the temperature raising rate of the second intermediate annealing in the tenth step (ST10) is set to 0.2 to 1.8 占 폚 / sec and the reaching temperature is set to 800 to 1000 占 폚.

[Process G]

 Step G is the same as Step A except that the temperature raising rate of the second intermediate annealing in the tenth step (ST10) is 2 deg. C / sec or more and the reaching temperature is 300 deg. C or more and less than 800 deg.

[Process H] (a process described in Japanese Patent Laid-Open No. 2000-328159)

 Process H was melted in an atmosphere of charcoal in an atmosphere by an electric furnace, and a 50 mm x 80 mm x 180 mm ingot was melted and hot-rolled into a slab having a thickness of 15 mm and hot rolled at 820 캜 to form a slab having a thickness of 3.3 mm Followed by water-cooling.

 This plate was cold-rolled to a thickness of 1.2 mm, subjected to intermediate annealing at a furnace temperature of 750 占 폚 for 20 seconds, cold-rolled at a thickness of 0.4 mm, subjected to intermediate annealing at a furnace temperature of 700 占 폚 for 20 seconds, Followed by intermediate annealing at a furnace temperature of 650 占 폚 for 20 seconds, followed by cold rolling to produce a copper alloy foil having a thickness of 10 占 퐉.

 This process H is disclosed in Patent Document 4 (Japanese Patent Application Laid-Open No. 2000-328159).

[Process I] (a process described in Japanese Patent Laid-Open No. H11-310864)

 Step I is a step of subjecting the ingot to hot rolling at a finish temperature of 500 占 폚 after a soaking treatment and then subjecting each of the steps of cold rolling and final annealing to control the crystal orientation of the copper foil to a cold rolling rate of 10 to & 95%, a final annealing temperature of 400 占 폚 or higher, and a cold rolling rate after final annealing of 10 to 99%.

 This process I is disclosed in Patent Document 5 (Japanese Patent Application Laid-Open No. H11-310864).

 The rolled copper foil before the roughening plating was subjected to the following evaluation. The evaluation results are shown in Tables 2 to 6.

[Area ratio of striped unevenness area: AR1]

The area ratio AR1 of the striped concavo-convex area is obtained by blackening a region where stripe-like concavo-convex in the direction of 60 to 120 占 with respect to the rolling direction is confirmed in an optical microscope photograph, , And the black area was divided by the total area to obtain the area ratio. The area of the field of view was 200,000 sq. M., And the average of the measurements of the three fields of view was measured.

[RDW Bearing Area Ratio: AR2]

The RDW orientation area ratio AR2 was measured from the rolled surface by the above-mentioned EBSD method by the above-described method. When the pattern is not clear because the damaged layer on the rolled surface is thick, only the outermost layer is dissolved by chemical polishing and measured.

[Tensile strength (TS), elongation (EL)]

The tensile strength (TS) and the elongation percentage (EL) were measured according to JIS Z2241 by a tensile test in the rolling parallel direction.

[Conductivity (EC)]

The resistivity was measured by a four-terminal method in a thermostatic chamber maintained at 20 ° C (± 0.5 ° C) to calculate the conductivity. The distance between the terminals was set to 100 mm.

Thereafter, a battery was prepared by the following method, and the battery characteristics were evaluated.

[Coating method]

Fine roughened particles were prepared on the surface of the rolled copper foil under the following copper plating conditions.

<Plating bath composition>

Cu (as metal): 60 to 70 g / l

Sulfuric acid: 110 to 130 g / L

&Lt; Plating condition >

Temperature: 45 to 55 DEG C

Current density: 60 to 70 A / dm2

Processing time: 0.4 to 2.0 seconds

[Battery evaluation 1: Carbon type anode active material]

(i) an anode

A solution prepared by mixing 90% by weight of LiCoO 2 powder, 7% by weight of graphite powder and 3% by weight of polyvinylidene fluoride powder and dissolving N-methylpyrrolidone in ethanol was added and kneaded to prepare a positive electrode paste. This paste was uniformly applied to an aluminum foil, and then dried in a nitrogen atmosphere to volatilize ethanol, followed by roll rolling to obtain a sheet.

After cutting the sheet, a lead terminal of an aluminum foil was attached to one end thereof by ultrasonic welding to form a positive electrode.

(ii) cathode

90% by weight of natural graphite powder (average particle diameter 10 占 퐉) and 10% by weight of polyvinylidene fluoride powder were mixed and N-methylpyrrolidone dissolved in ethanol was added and kneaded to prepare a paste. Subsequently, this paste was applied to both surfaces of the rolled copper foil produced in Examples and Comparative Examples. The coated copper foil was dried in a nitrogen atmosphere, the solvent was volatilized, and then rolled to form a sheet.

After cutting the sheet, a lead of nickel foil was attached to one end thereof by ultrasonic welding to form a negative electrode.

(iii) assembly of the battery

A separator made of polypropylene having a thickness of 25 mu m was sandwiched between the positive electrode and the negative electrode manufactured as described above, and this was housed in a nickel-plated battery can on the mild steel surface, and the lead terminal of the negative electrode was spot welded to the bottom of the can. Subsequently, a top cover of an insulating material is provided, and a gasket is inserted. Then, the lead terminals of the positive electrode and the aluminum safety valve are ultrasonically welded to each other. A nonaqueous electrolyte solution composed of propylene carbonate, diethyl carbonate and ethylene carbonate is injected into the battery can , And a cover was attached to the safety valve to assemble a sealed lithium ion secondary battery.

(iv) Measurement of cell characteristics

A charging / discharging cycle test was performed in which the prepared battery was charged up to 4.2 V at a charging current of 50 mA and discharged at 50 mA until it became 2.5 V. The battery capacity at the time of the first charging is shown in Tables 2 to 6.

[Battery evaluation 2: Silicon-based anode active material]

(i) an anode

Using Li2CO3 and CoCO3 as starting materials, they were weighed so that the atomic ratio of Li: Co was 1: 1 and mixed in a mortar. The mixture was press-molded by a die and then calcined in air at 800 DEG C for 24 hours, A sintered body of LiCoO2 was obtained. This was pulverized in a mortar to prepare an average particle size of 20 mu m.

90 parts by weight of the obtained LiCoO 2 powder and 5 parts by weight of an artificial graphite powder as a conductive agent were mixed in a 5 wt% N-methylpyrrolidone solution containing 5 parts by weight of polyvinylidene fluoride as a binder, did.

The positive electrode mixture slurry was coated on an aluminum foil as a collector, dried and then rolled. The obtained product was cut out to obtain a positive electrode.

(ii) cathode

80.2 parts by weight of silicon powder (purity 99.9%) having an average particle diameter of 3 μm as an active material was mixed with 8.6% by weight of N-methylpyrrolidone solution containing 19.8 parts by weight of polyamic acid (binder α1) as a binder to obtain an anode mixture slurry.

The negative electrode mixture slurry was applied to the rolled copper foil prepared in Examples and Comparative Examples, dried and then rolled. This was heat-treated at 400 ° C for 30 hours in an argon atmosphere and sintered to obtain a negative electrode.

(iii) assembly of the battery

LiPF6 was dissolved in an amount of 1 mol / liter in an equal volume of a mixed solvent of ethylene carbonate and diethylene carbonate as an electrolytic solution. A lithium secondary battery was fabricated by using the positive electrode, the negative electrode, and the electrolytic solution.

The positive electrode and the negative electrode are opposed to each other via a separator.

(iv) Evaluation of battery characteristics

The charge-discharge cycle characteristics of the battery were evaluated. Each battery was charged to 4.2 V at a current value of 1 mA at 25 캜, and then discharged to 2.75 V at a current value of 1 mA. This was charged and discharged in one cycle. The discharge capacity after 50 cycles with respect to the discharge capacity in the first cycle was measured as the discharge capacity retention rate.

The evaluation results are shown in Tables 2 to 6.

As shown in the evaluation results of each of the tables below, the area ratio (AR1) of the stripe-shaped concavo-convex area in which the stripe-shaped surface irregularities in the direction of 60 DEG to 120 DEG with respect to the rolling direction specified in the embodiment of the present invention is 60% And the RDW orientation area ratio (AR2) within 13 DEG from the RDW orientation {012} < 100 > orientation in the surface crystal orientation was 15% or less, the characteristics in evaluation of the battery were satisfactory . On the other hand, the comparative examples prepared in the production steps E to I did not satisfy the area ratio (AR1) and the RDW orientation area ratio (AR2) of the striped concavo-convex area and the battery evaluation result was inferior.

Compared to the pure copper system shown in Table 6, the alloy system of Tables 2 to 5 exhibited good battery characteristics.

Table 2 shows the evaluation results of Cu- (Cr, Zr) based copper alloy.

Examples 1-1 to 1-8 produced by the manufacturing process A, Reference Example 1-11 manufactured by the manufacturing process A, and manufacturing processes E, F, G, and H (manufactured in the present example) , And Comparative Examples 1-21 to 1-25 prepared in I were evaluated.

Examples 1-1 to 1-7 and Comparative Examples 1-21 to 1-25 satisfy the condition that the total of the main components Cr and Zr is 0.01 to 0.9 mass% and the auxiliary addition components Sn, Zn, Si, Mn , And when Mg is contained, the total amount is 0.01 to 0.45 mass%.

However, in Examples 1-6, the total amount of the auxiliary addition components was 0.52% by mass, slightly exceeding the condition that the total amount of the auxiliary addition components was 0.01 to 0.45% by mass.

Also, Reference Example 1-11 does not satisfy the condition that the total of the main components Cr and Zr is 0.01 to 0.9 mass%.

In Examples 1-1 to 1-8, the area ratio AR1 of the striped irregularity area is 60% or more.

In Examples 1-1 to 1-8, the condition that the RDW orientation area ratio (AR2) is 15% or less is satisfied.

As can be seen from the values of the initial charge capacity as the battery evaluation 1 and the retention ratios as the battery evaluation 2, the characteristics of the battery evaluation in Examples 1-1 to 1-8 were good.

As described above, in Examples 1-6, the total content of auxiliary addition components was 0.52% by mass and slightly exceeded the condition of 0.01 to 0.45% by mass of the total amount of auxiliary addition components. However, It is presumed that whether or not the content of the main component is within the range specified in the present embodiment largely affects the electrical characteristics.

Examples 1-4 and 1-7 do not contain an additive, but the battery evaluation is satisfactory.

As described above, Reference Example 1-11 does not satisfy the condition of containing 0.93% by mass of Cr in the main components Cr and Zr and containing 0.01 to 0.9% by mass of the total of the main components.

In Reference Example 1-11, the production was stopped because there were many pinholes.

It is also presumed from the results of this Reference Example 1-11 that whether or not the content of the main component is within the range specified in this embodiment greatly affects the electrical characteristics.

In Comparative Example 1-21, the area ratio AR1 of the striped irregularity area is 45%, which is 60% or more. In Comparative Example 1-21, the RDW azimuthal area ratio (AR2) was 22% and the condition of 15% or less was not satisfied.

In Comparative Example 1-21, the initial charge capacity as the battery evaluation 1 is low as 342 mAh as compared with 481 mAh in Example 1-1, and the retention rate as the battery evaluation 2 is also 16% which is less than half of 36% in Example 1-1.

As described above, in Comparative Example 1-21, the characteristics in evaluating the cell are inferior to those in Examples.

This is due to the fact that it was manufactured by the manufacturing process E in which the temperature raising rate of the second intermediate annealing in the tenth step (ST10) was set to 0.2 to 1.8 占 폚 / sec and the reaching temperature was set to 300 占 폚 or more and less than 800 占 폚 instead of the manufacturing process A It is estimated that it is doing.

That is, in order to obtain a recrystallized structure in which the rate of temperature rise of the second intermediate annealing, which is a feature of the present production method, is not set at a heating rate which does not give a time for recrystallization bulb development, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 because the temperature reached is not higher than the upper limit of the recrystallization temperature of the copper alloy and that the cell characteristics are lowered do.

In Comparative Example 1-22, the area ratio AR1 of the striped irregularity area is 57%, which is 60% or more. In Comparative Example 1-22, the condition that the RDW bearing areal area ratio (AR2) was 16% and 15% or less was not satisfied.

In Comparative Example 1-22, the initial charge capacity as the battery evaluation 1 is low as 385 mAh as compared with 481 mAh in Example 1-1, and the retention rate as the battery evaluation 2 is 13% which is less than half of 36% in Example 1-1.

As described above, in Comparative Example 1-22, the characteristics in the evaluation of the cell are inferior to those in this example.

This is attributable to the fact that, in the second intermediate annealing in the tenth step (ST10), which is a feature of the present production method (step A), the temperature raising rate is set at 0.2 to 1.8 DEG C / sec without increasing the time for recrystallization bulb development .

That is, in the second intermediate annealing, which is a feature of the present manufacturing method (Step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized The conditions of the stripe rugged area ratios AR1 and RDW bearing area ratios AR2 can not be satisfied because the rate of temperature rise of the second intermediate annealing is not increased to 0.2 to 1.8 DEG C / Is estimated to be lowered.

In Comparative Example 1-23, the area ratio AR1 of the striped irregularity area is 52%, which is 60% or more. In Comparative Example 1-23, the condition that the RDW orientation area ratio (AR2) was 17% and 15% or less was not satisfied.

In Comparative Example 1-23, the initial charge capacity as the battery evaluation 1 is low as 372 mAh as compared with 481 mAh in Example 1-1, and the retention rate as the battery evaluation 2 is also 16% which is less than half of 36% in Example 1-1.

As described above, in Comparative Example 1-23, the characteristics in evaluating the cell are inferior to those in Examples.

This is not the manufacturing step A but the second intermediate annealing in the tenth step (ST10), which is a feature of the present production method (step A), in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized, Is set to be not higher than the upper limit of the recrystallization temperature of the copper alloy, but is set to a normal temperature of 300 deg. C or more and less than 800 deg.

That is, even in the second intermediate annealing, which is a feature of the present manufacturing method (step A), even if the heating rate is increased so as not to give rise to the time for the recrystallization bulb phenomenon, the recrystallized structure, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in terms of the fact that the temperature for reaching the critical temperature is not made higher than the upper limit of the recrystallization temperature of the copper alloy, It is presumed.

In Comparative Example 1-24, the area ratio AR1 of the striped irregularity area is 51%, which is 60% or more. In Comparative Example 1-24, the condition that the RDW bearing areal area ratio (AR2) was 18% and 15% or less was not satisfied.

In Comparative Example 1-24, the first charge capacity as the battery evaluation 1 is low as 362 mAh as compared with 481 mAh in Example 1-1, and the retention rate as the battery evaluation 2 is also 17% which is less than half of 36% in Example 1-1.

As described above, in Comparative Example 1-24, the characteristics in evaluation of the cell are inferior to those in Examples.

This is not the manufacturing process A. In the final second intermediate annealing, which is a feature of the present manufacturing method (process A), in order to suppress the preferential movement of a specific grain system and obtain a randomized recrystallized structure, The temperature is not higher than the upper limit of the temperature.

That is, in the final intermediate annealing, which is a feature of the present manufacturing method (step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized It is not possible to satisfy the conditions of the stripe-shaped uneven area area ratio AR1 and the RDW azimuth area ratio AR2, and it is conjectured that the battery characteristics are lowered.

In Comparative Example 1-25, the area ratio AR1 of the striped irregularity area is 48%, which is 60% or more. In Comparative Example 1-25, the condition that the RDW orientation area ratio (AR2) is 19% and 15% or less is not satisfied.

In Comparative Example 1-25, the first charge capacity as the battery evaluation 1 is low as 362 mAh as compared with 481 mAh in Example 1-1, and the retention rate as the battery evaluation 2 is also 21%, which is lower than 36% in Example 1-1.

In Comparative Example 1-25, the characteristics in evaluating the cell are inferior to those in Examples.

This is because, before the final annealing, which is a feature of the present manufacturing method (step A), the temperature raising rate is increased so as not to give time for the recrystallization bulb phenomenon, which is a characteristic of the present manufacturing method (step A) It is presumed that the second intermediate annealing is not performed in order to obtain a recrystallized structure by setting the arrival temperature to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy.

That is, before the final annealing, which is a feature of the present manufacturing method, the rate of temperature rise is raised so as not to give time for the recrystallization bulb phenomenon, which is a characteristic of the present manufacturing method (step A) It is not possible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in that the second intermediate annealing is not performed so that the reaching temperature is higher than the upper limit of the recrystallization temperature of the copper alloy , And further, the battery characteristics are lowered.

Table 3 shows the evaluation results of the Cu-Ag-based copper alloy.

Examples 2-1 to 2-5 produced by the manufacturing process A, Reference Example 2-11 produced by the manufacturing process A, and manufactured by the manufacturing processes G, H, and I, respectively, as the rolled copper foil (present example) Comparative Examples 2-21 to 2-23 were evaluated.

In Examples 2-1 to 2-5 and Comparative Examples 2-21 to 2-23, the additive components Sn, Zn, Si, Mn, and Mg were mixed so that the total content of the main components Ag was 0.01 to 0.9 mass% , The total amount thereof is 0.01 to 0.45 mass%.

However, Reference Example 2-11 does not satisfy the condition that the total amount of the main component Ag is 0.01 to 0.9 mass%.

Examples 2-1 to 2-5 satisfied the condition that the area ratio AR1 of the striped concave-convex area was 60% or more.

In Examples 2-1 to 2-5, the condition that the RDW orientation area ratio AR2 is 15% or less is satisfied.

As can be seen from the values of the first charging capacity as the battery evaluation 1 and the retention ratios as the battery evaluation 2, the performance in the battery evaluation was good in Examples 2-1 to 2-5.

In Reference Example 2-11, as described above, 0.95 mass% of the main component Ag is contained, and the condition that the total of the main components is 0.01 to 0.9 mass% is not satisfied.

In Reference Example 2-11, the production was stopped because there were many pinholes.

It is presumed also from the results of this Reference Example 2-11 that whether or not the content of the main component is within the range specified in this embodiment greatly affects the electrical characteristics.

In Comparative Example 2-21, the area ratio AR1 of the striped irregularity area is 51%, which is 60% or more. In Comparative Example 2-21, the RDW azimuthal area ratio (AR2) was 20%, which was 15% or less.

In Comparative Example 2-21, the initial charge capacity as the battery evaluation 1 is 355 mAh as compared with 432 mAh in Example 2-2, and the retention rate as the battery evaluation 2 is 15% which is less than half of 31% of Example 2-2.

As described above, in Comparative Example 2-21, the characteristics in the evaluation of the battery are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-23 produced in the manufacturing process G shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, even in the second intermediate annealing, which is a feature of the present manufacturing method (step A), even if the heating rate is increased so as not to give rise to the time for the recrystallization bulb phenomenon, the recrystallized structure, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in terms of the fact that the temperature for reaching the critical temperature is not made higher than the upper limit of the recrystallization temperature of the copper alloy, It is presumed.

In Comparative Example 2-22, the area ratio AR1 of the striped irregularity area is 53%, which is 60% or more. In Comparative Example 2-22, the condition that the RDW bearing areal area ratio (AR2) is 18% and 15% or less is not satisfied.

In Comparative Example 2-22, the first charge capacity as the battery evaluation 1 was as low as 361 mAh as compared with 432 mAh of Example 2-2 of the present example, and the retention rate as the battery evaluation 2 was 13%, which is less than half of 31% to be.

As described above, in Comparative Example 2-22, the characteristics in the evaluation of the cell are inferior to those in this example.

This is presumed to be the same reason as that of Comparative Example 1-24 made in the manufacturing process H shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, in the final intermediate annealing, which is a feature of the present manufacturing method (step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized It is not possible to satisfy the conditions of the stripe-shaped uneven area area ratio AR1 and the RDW azimuth area ratio AR2, and it is conjectured that the battery characteristics are lowered.

In Comparative Example 2-23, the area ratio AR1 of the striped irregularity area is 45%, which is 60% or more. In Comparative Example 2-23, the condition that the RDW bearing areal area ratio (AR2) was 20% and 15% or less was not satisfied.

In Comparative Example 2-23, the first charge capacity as the battery evaluation 1 is low as 355 mAh as compared with 432 mAh in Example 2-2, and the retention rate as the battery evaluation 2 is 11% which is less than half of 31% of Example 2-2.

As described above, in Comparative Example 2-23, the characteristics in the evaluation of the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-25 produced in the manufacturing process I shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy in Table 2. [

That is, before the final annealing, which is a feature of the present manufacturing method, the rate of temperature rise is raised so as not to give time for the recrystallization bulb phenomenon, which is a characteristic of the present manufacturing method (step A) It is not possible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in that the second intermediate annealing is not performed so that the reaching temperature is higher than the upper limit of the recrystallization temperature of the copper alloy , And further, the battery characteristics are lowered.

Table 4 shows the evaluation results of the Cu-Sn-based copper alloy.

Examples 3-1 to 3-6 produced by the manufacturing process A, Reference Example 3-11 produced by the manufacturing process A, and manufactured by the manufacturing processes G, H, and I, respectively, as the rolled copper foil (present example) Comparative Examples 3-21 to 3-23 were evaluated.

In Examples 3-1 to 3-6 and Comparative Examples 3-21 to 3-23, the condition that the total of the main component Sn was 0.01 to 4.9 mass% was satisfied, and one of the additive components Zn, Si, P, and Mg , The total amount thereof is 0.01 to 0.45 mass%.

However, Reference Example 3-11 does not satisfy the condition that the total of the main component Sn is 0.01 to 4.9 mass%.

Examples 3-1 to 3-6 satisfied the condition that the area ratio AR1 of the striped concave-convex area was 60% or more.

In Examples 3-1 to 3-6, the conditions that the RDW orientation area ratio AR2 is 15% or less are satisfied.

As can be seen from the values of the first charge capacity as the battery evaluation 1 and the retention ratios as the battery evaluation 2, the characteristics in the battery evaluation were good in Examples 3-1 to 3-6.

Reference Example 3-11 contains 5.12 mass% of the main component Sn and does not satisfy the condition of 0.01 to 4.9 mass% of the main component.

In Reference Example 3-11, the production was stopped because there were many pinholes.

It is also presumed from the results of Reference Example 3-11 that whether or not the content of the main component is within the range specified in this embodiment greatly affects the electrical characteristics.

In the comparative example 3-21, the area ratio AR1 of the striped irregularity area is 57%, which is 60% or more. In Comparative Example 3-21, the condition that the RDW bearing areal area ratio (AR2) was 18% and 15% or less was not satisfied.

In Comparative Example 3-21, the first charge capacity as the battery evaluation 1 is as low as 375 mAh as compared with 441 mAh in Example 3-1, and the retention rate as the battery evaluation 2 is 15% which is less than half of 31% in Example 3-1.

As described above, in Comparative Example 3-21, the characteristics in the evaluation of the battery are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-23 produced in the manufacturing process G shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, even in the second intermediate annealing, which is a feature of the present manufacturing method (step A), even if the heating rate is increased so as not to give rise to the time for the recrystallization bulb phenomenon, the recrystallized structure, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in terms of the fact that the temperature for reaching the critical temperature is not made higher than the upper limit of the recrystallization temperature of the copper alloy, It is presumed.

In Comparative Example 3-22, the area ratio AR1 of the striped irregularities is 51%, which is 60% or more. In Comparative Example 3-22, the condition that the RDW bearing areal area ratio (AR2) was 22% and 15% or less was not satisfied.

In Comparative Example 3-22, the first charge capacity as the battery evaluation 1 is as low as 375 mAh as compared with 441 mAh in Example 3-1, and the retention rate as the battery evaluation 2 is 13% which is less than half of 31% in Example 3-1.

As described above, in Comparative Example 3-22, the characteristics in the evaluation of the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-24 produced in the manufacturing process H shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, in the final intermediate annealing, which is a feature of the present manufacturing method (step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized It is not possible to satisfy the conditions of the stripe-shaped uneven area area ratio AR1 and the RDW azimuth area ratio AR2, and it is conjectured that the battery characteristics are lowered.

In Comparative Example 3-23, the area ratio AR1 of the striped irregularities is 40%, which is 60% or more. In Comparative Example 3-23, the condition that the RDW orientation area ratio (AR2) is 23% and 15% or less is not satisfied.

In Comparative Example 3-23, the initial charge capacity as the battery evaluation 1 is low as 340 mAh as compared with 441 mAh in Example 3-1, and the retention rate as the battery evaluation 2 is 11% which is less than half of 31% in Example 3-1.

As described above, in Comparative Example 3-23, the characteristics in the evaluation of the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-25 produced in the manufacturing process I shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy in Table 2. [

That is, before the final annealing, which is a feature of the present manufacturing method, the rate of temperature rise is raised so as not to give time for the recrystallization bulb phenomenon, which is a characteristic of the present manufacturing method (step A) It is not possible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in that the second intermediate annealing is not performed so that the reaching temperature is higher than the upper limit of the recrystallization temperature of the copper alloy , And further, the battery characteristics are lowered.

Table 5 shows the evaluation results of Cu-Ni-Si based copper alloy.

Examples 4-1 to 4-8 prepared by the manufacturing process A, Reference Example 4-11 produced by the manufacturing process A, and manufactured by the manufacturing processes G, F and I were used as the rolled copper foil (this example) Comparative Examples 4-21 to 4-23 were evaluated.

Examples 4-1 to 4-8 and Comparative Examples 4-21 to 4-23 satisfied the condition of containing 1.4 to 4.8% by mass of Ni as the main component and satisfied the condition of 0.2 to 1.3% by mass of the main component Si, And the total content of the additive components Sn, Zn, Si, Cr, Mn, Mg, and Co is 0.005 to 0.9 mass%.

However, Reference Example 4-11 does not satisfy the condition of containing 1.4 to 4.8% by mass of the main component Ni.

Examples 4-1 to 4-8 satisfied the condition that the area ratio AR1 of the striped concave-convex area is 60% or more.

In Examples 4-1 to 4-8, the conditions that the RDW bearing areal area ratio (AR2) is 15% or less are satisfied.

As can be seen from the values of the first charge capacity as the battery evaluation 1 and the retention ratios as the battery evaluation 2 in Examples 4-1 to 4-8, the characteristics in the battery evaluation were good.

Reference Example 4-11 does not satisfy the condition of containing 4.92% by mass of Ni in the main component Ni and Si and containing 1.4 to 4.8% by mass of the main component Ni.

It is also presumed from the results of Reference Example 4-11 that whether or not the content of the main component is within the range specified in this embodiment greatly influences the electrical characteristics.

In Comparative Example 4-21, the area ratio AR1 of the striped irregularity area is 54%, which is 60% or more. In Comparative Example 4-21, the RDW azimuthal area ratio (AR2) was 17%, which was 15% or less.

In Comparative Example 4-21, the initial charge capacity as the battery evaluation 1 is 381 mAh as compared with 441 mAh in Example 4-1, and the retention rate as the battery evaluation 2 is 14% which is less than half of 32% in Example 4-1.

As described above, in Comparative Example 4-21, the characteristics in the evaluation of the battery are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-23 produced in the manufacturing process G shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, even in the second intermediate annealing, which is a feature of the present manufacturing method (step A), even if the heating rate is increased so as not to give rise to the time for the recrystallization bulb phenomenon, the recrystallized structure, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in terms of the fact that the temperature for reaching the critical temperature is not made higher than the upper limit of the recrystallization temperature of the copper alloy, It is presumed.

In Comparative Example 4-22, the area ratio AR1 of the striped irregularity area is 49%, which is 60% or more. In Comparative Example 4-22, the condition that the RDW bearing areal area ratio (AR2) is 21% and 15% or less is not satisfied.

In Comparative Example 4-22, the initial charge capacity as the battery evaluation 1 was 351 mAh as compared with 441 mAh in Example 4-1 of this example, and the maintenance rate as the battery evaluation 2 was 13%, which is less than half of 32% to be.

As described above, in Comparative Example 4-22, the characteristics in the evaluation of the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-22 shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, in the second intermediate annealing, which is a feature of the present manufacturing method (Step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized The conditions of the stripe rugged area ratios AR1 and RDW bearing area ratios AR2 can not be satisfied because the rate of temperature rise of the second intermediate annealing is not increased to 0.2 to 1.8 DEG C / Is estimated to be lowered.

In Comparative Example 4-23, the area ratio AR1 of the striped irregularity area is 43%, which is 60% or more. In Comparative Example 4-23, the condition that the RDW bearing areal area ratio (AR2) is 24% and 15% or less is not satisfied.

In Comparative Example 4-23, the first charge capacity as the battery evaluation 1 was low as 326 mAh as compared with 441 mAh in Example 4-1 of this example, and the retention rate as the battery evaluation 2 was 11%, which is less than half of 32% to be.

As described above, in Comparative Example 4-23, the characteristics in evaluating the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-25 produced in the manufacturing process I shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy in Table 2. [

That is, before the final annealing, which is a feature of the present manufacturing method, the rate of temperature rise is raised so as not to give time for the recrystallization bulb phenomenon, which is a characteristic of the present manufacturing method (step A) It is not possible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in that the second intermediate annealing is not performed so that the reaching temperature is higher than the upper limit of the recrystallization temperature of the copper alloy , And further, the battery characteristics are lowered.

Table 6 shows the evaluation results of the pure copper system.

Examples 5-1 to 5-2 prepared by the manufacturing process A and Comparative Examples 5-21 to 5 (manufactured by the production process E, F, G, H, I) prepared as the rolled copper foil -25.

In Example 5-1 and Comparative Examples 5-21 to 5-25, the oxygen amount was 180 ppm and the oxygen amount condition was 2 to 200 ppm.

In Example 5-2, the oxygen amount is 6 ppm and the oxygen amount condition is 2 to 200 ppm.

In Examples 5-1 and 5-2, the stripe-shaped unevenness area ratio AR1 is at least 60%.

In Examples 5-1 and 5-2 of this example, the condition that the RDW orientation area ratio AR2 is 15% or less is satisfied.

As can be seen from the values of the first charge capacity as the battery evaluation 1 and the retention ratios as the battery evaluation 2 in Examples 5-1 and 5-2, the characteristics in the battery evaluation were good.

In Comparative Example 5-21, the area ratio AR1 of the striped irregularity area is 51%, which does not satisfy the condition of 60% or more. In Comparative Example 5-21, the RDW azimuthal area ratio (AR2) was 16%, which was 15% or less.

In Comparative Example 5-21, the initial charge capacity as the battery evaluation 1 was low as 385 mAh as compared with 451 mAh in Example 5-1, and the retention rate as the battery evaluation 2 was 9%, which is 1/3 of 27% to be.

As described above, in Comparative Example 5-21, the characteristics in the evaluation of the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-21 produced in the manufacturing process E shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, in order to obtain a recrystallized structure in which the rate of temperature rise of the second intermediate annealing, which is a feature of the present production method, is not set at a heating rate which does not give a time for recrystallization bulb development, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 because the temperature reached is not higher than the upper limit of the recrystallization temperature of the copper alloy and that the cell characteristics are lowered do.

In Comparative Example 5-22, the area ratio AR1 of the striped irregularity area is 57%, which is 60% or more. In Comparative Example 5-22, the condition that the RDW orientation area ratio (AR2) is 17% and 15% or less is not satisfied.

In Comparative Example 5-22, the initial charge capacity as the battery evaluation 1 was as low as 375 mAh as compared with 451 mAh in Example 5-1, and the retention rate as the battery evaluation 2 was 8% or less, which is 1/3 or less of 27% to be.

As described above, in Comparative Example 5-22, the characteristics in the evaluation of the cell are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-22 produced in the manufacturing process F shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy in Table 2. [

That is, in the second intermediate annealing, which is a feature of the present manufacturing method (Step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized The conditions of the stripe rugged area ratios AR1 and RDW bearing area ratios AR2 can not be satisfied because the rate of temperature rise of the second intermediate annealing is not increased to 0.2 to 1.8 DEG C / Is estimated to be lowered.

In Comparative Example 5-23, the area ratio AR1 of the striped irregularity area is 43%, which is 60% or more. In Comparative Example 5-23, the RDW azimuthal area ratio (AR2) was 24% and the condition of 15% or less was not satisfied.

In Comparative Example 5-23, the initial charge capacity as the battery evaluation 1 was low as 355 mAh as compared with 451 mAh in Example 5-1, and the retention ratio as the battery evaluation 2 was 6%, which is 1/4 or less of 27% to be.

As described above, in Comparative Example 5-23, the characteristics in the evaluation of the battery are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-23 produced in the manufacturing process G shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, even in the second intermediate annealing, which is a feature of the present manufacturing method (step A), even if the heating rate is increased so as not to give rise to the time for the recrystallization bulb phenomenon, the recrystallized structure, It is impossible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in terms of the fact that the temperature for reaching the critical temperature is not made higher than the upper limit of the recrystallization temperature of the copper alloy, It is presumed.

In Comparative Example 5-24, the area ratio AR1 of the striped irregularity area is 55%, which is 60% or more. In Comparative Example 5-24, the condition that the RDW bearing areal area ratio (AR2) was 19% and 15% or less was not satisfied.

In Comparative Example 5-24, the first charge capacity as the battery evaluation 1 was as low as 365 mAh as compared with 451 mAh in Example 5-1, and the retention ratios as the battery evaluation 2 were 9%, which is 1/3 of 27% to be.

As described above, in Comparative Example 5-24, the characteristics in the evaluation of the battery are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-24 produced in the manufacturing process H shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy of Table 2. [

That is, in the final intermediate annealing, which is a feature of the present manufacturing method (step A), the arrival temperature is set to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to suppress the preferential movement of the specific grain system and obtain a recrystallized structure randomized It is not possible to satisfy the conditions of the stripe-shaped uneven area area ratio AR1 and the RDW azimuth area ratio AR2, and it is conjectured that the battery characteristics are lowered.

In Comparative Example 5-25, the area ratio AR1 of the striped irregularity area is 46%, which is 60% or more. In Comparative Example 5-25, the RDW azimuthal area ratio (AR2) was 17%, which was 15% or less.

In Comparative Example 5-25, the initial charge capacity as the battery evaluation 1 was as low as 370 mAh as compared with 451 mAh in Example 5-1, and the retention ratio as the battery evaluation 2 was 6%, which is 1/4 or less of that in Example 5-1. to be.

As described above, in Comparative Example 5-25, the characteristics in the evaluation of the battery are inferior to those in Examples.

This is presumed to be the same reason as that of Comparative Example 1-25 produced in the manufacturing process I shown in the evaluation results of the Cu- (Cr, Zr) based copper alloy in Table 2. [

That is, before the final annealing, which is a feature of the present manufacturing method, the rate of temperature rise is raised so as not to give time for the recrystallization bulb phenomenon, which is a characteristic of the present manufacturing method (step A) It is not possible to satisfy the conditions of the stripe rugged area ratios AR1 and RDW azimuth area ratios AR2 in that the second intermediate annealing is not performed so that the reaching temperature is higher than the upper limit of the recrystallization temperature of the copper alloy , And further, the battery characteristics are lowered.

As described above, the area ratio (AR1) of the striped concavo-convex area having stripe-like surface irregularities in the 60 占 to 120 占 direction with respect to the rolling direction defined by the embodiment of the present invention is 60% , The RDW orientation area ratio (AR2) within 13 DEG from the RDW orientation {012} < 100 > orientation in the cell was satisfactory by 15% or less.

Further, in the second intermediate annealing in the manufacturing method (the manufacturing step A) of the rolled copper foil according to the present embodiment, the rate of temperature rise is raised so as not to give time for recrystallization bulb development, The area ratio AR1 of the stripe rugged area and the RDW bearing area ratio AR2 satisfy the stipulated conditions by setting the arrival temperature to a temperature higher than the upper limit of the recrystallization temperature of the copper alloy in order to obtain the recrystallized structure having the The characteristics were good.

On the other hand, in the comparative examples manufactured in the manufacturing processes E to I, the area ratio (AR1) of the stripe-shaped unevenness area and the RDW bearing area ratio (AR2) did not satisfy the specified conditions, and the battery evaluation result was inferior.

It can be said that the alloy system of Tables 2 to 5 exhibits good battery characteristics as compared with the pure copper system shown in Table 6.

According to the present embodiment, roughened plated surfaces having uniform irregularities are formed, and the adhesion between the current collector and the active material is improved. Therefore, in the manufacturing process of the battery and the like, . Further, it is possible to improve the initial discharge capacity of the battery, prevent the discharge capacity from decreasing after repeating the charging and discharging cycles, and realize the high performance of the secondary battery.

The present invention is not limited to the alloys shown in the present embodiment, but may be applied to copper alloys of all the alloys such as Cu-Fe, Cu-Ti, Cu-Be, Cu-Zn, Cu- Applicable.

The present invention is also applicable to an anode current collector of a battery made of a variety of active materials such as a tin (Sn) system, a system obtained by combining them, as well as the carbon-based or silicon (Si) Is not limited to the configuration of the battery shown in Fig.

The rolled copper foil of the embodiment of the present invention can be used for a flexible substrate (FPC), a tape carrier package (TCP, TAB), and a chip on flex (COF).

10 ... Secondary battery
11 ... anode
12 ... cathode
13 ... Anode collector
14 ... Cathode collector
15 ... Separator
16 ... Anode-side battery cans
17 ... Cathode-side battery can
18 ... Insulation packing
20 ... Rolled copper foil

Claims (17)

1. A rolled copper foil made of copper or a copper alloy formed by rolling,
Wherein the area ratio within 13 占 from the orientation of the RDW orientation {012} <100> in the crystal orientation of the surface is 15% or less. The rolled copper foil for a secondary battery current collector according to claim 1, wherein an area ratio of an area in which stripe-shaped surface irregularities in a direction of 60 to 120 占 with respect to the rolling direction is visible is 60% or more. A Cu- (Cr, Zr) based copper alloy containing at least one of Cr and Zr as a main component and containing 0.01 to 0.9 mass% of at least one of Cr and Zr as main components, doing
Rolled copper foil for secondary battery collectors. 4. The positive electrode active material according to claim 3, wherein 0.01 to 0.45% by mass of at least one of Sn, Zn, Si, Mn, and Mg,
Rolled copper foil for secondary battery collectors. The Cu-Ag based copper alloy according to any one of claims 1 to 3, which contains Ag as a main component and contains 0.01 to 0.9 mass% of Ag as a main component in total
Rolled copper foil for secondary battery collectors. The positive electrode active material according to claim 5, wherein 0.01 to 0.45% by mass of at least one of Sn, Zn, Si, Mn, and Mg,
Rolled copper foil for secondary battery collectors. 3. The Cu-Sn based copper alloy according to claim 1 or 2, wherein the Cu-Sn based copper alloy containing Sn as a main component contains 0.01 to 4.9 mass% of Sn as a main component in total
Rolled copper foil for secondary battery collectors. The positive electrode active material according to claim 7, which contains 0.01 to 0.45% by mass of at least one of Zn, Si, P, and Mg as auxiliary addition components
Rolled copper foil for secondary battery collectors. The Cu-Ni-Si-based copper alloy according to any one of claims 1 to 3, which contains Ni and Si as main components and contains 1.4 to 4.8% by mass of Ni and 0.2 to 1.3% by mass of Si,
Rolled copper foil for secondary battery collectors. The positive electrode active material according to claim 9, which contains at least 0.005 to 0.9 mass% of at least one of Sn, Zn, Si, Cr, Mn, Mg,
Rolled copper foil for secondary battery collectors. The pure copper system according to any one of claims 1 to 3, wherein the oxygen content is in the range of 2 to 200 ppm
Rolled copper foil for secondary battery collectors. 12. The method according to any one of claims 3 to 11, wherein the remainder excluding the main component, or the remainder excluding the main component and the auxiliary addition component, is formed of an unavoidable impurity (inevitable impurity)
Rolled copper foil for secondary battery collectors. A process for producing a rolled copper foil for a secondary battery current collector according to any one of claims 1 to 12,
A hot rolling step in which the hot rolled steel sheet is heated at a temperature not lower than the recrystallization temperature for hot rolled steel sheet,
At least two intermediate cold rolling steps for performing cold rolling under a temperature at which recrystallization does not occur after the hot rolling step,
At least one intermediate annealing step for performing intermediate annealing at a heating rate while heating at a predetermined temperature during the intermediate cold rolling step,
And a final annealing step of performing final annealing at a predetermined heating rate with a predetermined temperature high after the last intermediate cold rolling step,
In the intermediate annealing step performed before entering the final annealing step,
The rate of temperature rise is set at a rate that does not give a time for recrystallization bulb phenomenon,
The arrival temperature is set to a high temperature at which a recrystallized structure in which the preferential movement of a specific grain system is suppressed and randomized
(Method for manufacturing rolled copper foil for secondary battery current collector). 14. The method according to claim 13, wherein in the intermediate annealing step performed before entering the final annealing step,
The temperature reaches a temperature higher than the upper limit of the recrystallization temperature of the copper alloy
(Method for manufacturing rolled copper foil for secondary battery current collector). 15. The method according to claim 13 or 14, wherein in the intermediate annealing step performed before entering the final annealing step,
Wherein the temperature raising rate is not less than 2 DEG C /
When the arrival temperature is 800 ° C or higher
(Method for manufacturing rolled copper foil for secondary battery current collector). 16. The method according to any one of claims 13 to 15, further comprising: a first intermediate cold rolling step of performing cold rolling after the hot rolling step;
A first intermediate annealing step of performing an intermediate annealing subsequent to the first intermediate cold rolling step,
A second intermediate cold rolling step of performing cold rolling after the first intermediate annealing step,
A second intermediate annealing step of performing intermediate annealing subsequent to the second intermediate cold rolling step,
And a third intermediate cold rolling step of performing cold rolling after the second intermediate annealing step,
In the final annealing step,
A third intermediate cold rolling step,
Wherein the second intermediate annealing step comprises:
In the intermediate annealing step performed before entering the final annealing step,
The rate of temperature rise is set at a rate that does not give a time for recrystallization bulb phenomenon,
The arrival temperature is set to a high temperature at which a recrystallized structure in which the preferential movement of a specific grain system is suppressed and randomized
(Method for manufacturing rolled copper foil for secondary battery current collector). 17. The method according to any one of claims 13 to 16, wherein before the hot rolling step,
And a homogenization heat treatment step of performing homogenization heat treatment on the pressured sheet
(Method for manufacturing rolled copper foil for secondary battery current collector).

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