JP5822928B2 - Electrolytic copper foil having high strength and low warpage and method for producing the same - Google Patents

Description

  The present invention relates to an electrolytic copper foil having high strength and little warpage and a method for producing the same, and more particularly to an electrolytic copper foil useful for a secondary battery negative electrode current collector.

  Electrolytic copper foil produced by electroplating greatly contributes to the development of electrical and electronic industries, and is indispensable as a printed circuit material and a secondary battery negative electrode current collector. The manufacturing history of the electrolytic copper foil is old (see Patent Document 1 and Patent Document 2), but recently its usefulness as a secondary battery negative electrode current collector has been reconfirmed.

An example of production of electrolytic copper foil is as follows. For example, in an electrolytic cell, a titanium or stainless steel rotating drum having a diameter of about 3000 mm and a width of about 2500 mm and an electrode distance of about 5 mm around the drum are arranged. Deploy.
Copper, sulfuric acid, and glue are introduced into this electrolytic cell to form an electrolytic solution. Then, the linear velocity, the electrolyte solution temperature, and the current density are adjusted, copper is deposited on the surface of the rotating drum, the copper deposited on the surface of the rotating drum is peeled off, and a copper foil is continuously produced.

  This electrolytic copper foil manufacturing method can reduce the manufacturing cost, and can manufacture from a very thin layer thickness of about several μ to a thick copper foil of about 70 μm, and one side of the electrolytic copper foil is moderate. Therefore, it has many advantages such as high adhesive strength with the resin.

  In recent years, an electrolytic copper foil has been used as a copper foil for a battery negative electrode material for vehicles, and the strength of the electrolytic copper foil is required as its characteristics. Conventionally manufactured electrolytic copper foils have characteristics that can meet this heat resistance requirement, but there is a problem that when the copper foil is drawn from a roll, the foil warps.

  This is considered to be caused by the structure generated in the manufacturing process of the electrolytic copper foil. In the process of manufacturing the battery negative electrode material using the electrolytic copper foil, the warpage of the electrolytic copper foil is not preferable, and therefore it is necessary to reduce it as much as possible or not to occur at all. Here, as an evaluation method of the warpage amount, an electrolytic copper foil is punched out into a 100 mm square sheet with a press and defined as an average value of the four-corner lift amount when left at room temperature for 30 minutes, and the subsequent examination is to be advanced .

JP-A-7-188969 JP 2004-107786 A

  The present invention relates to an electrolytic copper foil having high strength and little warpage, and a method for producing the same, and an object of the present invention is to provide an electrolytic copper foil that is particularly useful for a secondary battery negative electrode current collector.

The present application provides the following invention.
(1) Tensile strength in a normal state (hereinafter referred to as “normal tensile strength”) is 45 kgf / mm ^{2 to} 55 kgf / mm ² , and an average value of lifting heights at four corners of 100 mm square is 2 mm or less. An electrolytic copper foil characterized by that.
(3) The crystal grain of the cross section of the electrolytic copper foil is composed of fine particles having an aspect ratio of less than 2.0 and columnar particles having an aspect ratio of 2.0 or more. Electrolytic copper foil of description.
(4) The electrolytic copper foil according to any one of (1) to (3) above, wherein the total area of the columnar particles is 5% to 30%, and the remainder is fine particles.

The present application also provides the following invention.
(5) The electrolytic copper foil according to any one of (1) to (4) above, wherein an average particle diameter of fine particles having an aspect ratio of less than 2.0 is 0.2 μm or less.
(6) The electrolytic copper foil as described in any one of (1) to (5) above, which is a copper foil for a secondary battery negative electrode current collector.
(7) In a method for producing an electrolytic copper foil by an electrolytic method using a sulfuric acid-based copper electrolytic solution, electrolysis is performed at an electrolytic solution temperature of 60 to 65 ° C. and a current density of 60 to 120 A / dm ^2. A method for producing electrolytic copper foil.
(8) In a method for producing an electrolytic copper foil by an electrolytic method using a sulfuric acid-based copper electrolytic solution, electrolysis is performed at an electrolytic solution temperature of 60 to 65 ° C. and a current density of 60 to 120 A / dm ^2. The manufacturing method of the electrolytic copper foil characterized by manufacturing the electrolytic copper foil as described in any one of (1)-(6).

  The present invention relates to an electrolytic copper foil having high strength and less warpage and a method for producing the same, and particularly has an excellent effect of providing an electrolytic copper foil useful for a secondary battery negative electrode current collector.

2 is a photomicrograph showing the shape of particles in the cross section of the electrolytic copper foil of Example 1. FIG. 4 is a photomicrograph showing the shape of a cross-sectional particle of the electrolytic copper foil of Comparative Example 1.

The present invention provides an electrolytic copper foil in which columnar particles and fine particles are present simultaneously in the electrolytic copper foil so that there is no warp and the strength can be maintained. The electrolytic copper foil of the present invention is particularly useful as a copper foil for a secondary battery negative electrode current collector.
Specifically, the presence of columnar particles can reduce the amount of warpage, and the presence of fine particles can maintain strength.
That is, thereby pulling in the normal state of the electrodeposited copper foil strength (hereinafter, referred to as "normal tensile ^strength."), And ^{45kgf / mm 2 ~55kgf / mm 2} , the average value of the floating amount of the four corners of 100mm square It can be 2 mm or less.

The higher the current density, the smaller particles can be formed and the strength can be increased. However, even if it is low, it does not fall below the lower limit of the present invention. Rather, the problem of warping is large. That is, when the current density is less than 60 A / dm ² , there is no temperature condition that can reduce the warp to 2 mm or less. This is presumably because the effect becomes small even when the whole particle becomes large and columnar particles are present.
On the other hand, when the current density exceeds 120 A / dm ² , the whole becomes too fine, and even if the liquid temperature is raised, columnar particles are hardly generated, and it is considered that warpage increases.

From the above, it can be seen that an appropriate range is a combination of the electrolyte temperature and the current density. When the current density is low within the range of the appropriate current density, it can be said that the liquid temperature is preferably low. In addition, when the current density is low, the particles are originally larger, and therefore, when the liquid temperature is increased, the overall particle size is larger than the increase of the columnar particles, so that the warp increases even if there are columnar particles.
On the other hand, when the current density is high in the appropriate current density range, it is desirable that the liquid temperature is high. This is probably because when the current density is high, the particle diameter is originally small, so that the columnar grains are difficult to develop unless the liquid temperature is high.

  The particle shape in the structure of the electrolytic copper foil can be known by observing the cross section of the electrolytic copper foil. For fine particles, the aspect ratio (ratio between the maximum height and minimum width of the particles) can be less than 2.0, and for columnar particles, the aspect ratio is 2.0 or more, and the two are distinguished. be able to. The particle shape in the structure of the electrolytic copper foil of the present invention is determined by this aspect ratio.

In the present invention, the total area of the columnar particles can be 10% to 55%, and the remainder can be fine particles. Here, the “area of columnar particles” means “area of columnar particles” that can be observed in the cross section of the electrolytic copper foil. This is a preferred form that can suppress warping of the electrolytic copper foil and maintain strength.
When the amount of columnar particles is too small, that is, when it is less than 5%, warpage increases, which is not preferable. On the other hand, if it exceeds 30%, the number of fine particles is relatively decreased, which is not preferable because the strength is lowered. Therefore, it can be said that the preferable condition is that the total area of the columnar particles is 5% to 30%.

  Moreover, in this invention, it is desirable that the average particle diameter of the fine particle which exists in electrolytic copper foil, ie, the fine particle whose aspect ratio is less than 2.0, is 0.2 micrometer or less. As described above, the fine particles play a role of increasing the strength, and the lower limit value of the average particle size is not particularly limited. When the average particle size of the fine particles is large, even if columnar particles are present, the effect of columnar particles in reducing warpage tends to be reduced. Therefore, it is a desirable form that the average particle size of the fine particles is 0.2 μm or less. In addition, regarding the foil thickness of the copper foil for secondary battery negative electrode collectors, 20 micrometers or less are desirable and 10 micrometers or less are more preferable.

  The electrolytic copper foil of the present invention is produced by an electrolytic method using a sulfuric acid-based copper electrolytic solution. The present invention relates to a conventional electrolytic copper foil in which a rotating drum made of titanium or stainless steel having a diameter of about 3000 mm and a width of about 2500 mm and an electrode is disposed with a distance of about 5 mm around the drum in an electrolytic cell. It can manufacture using a manufacturing apparatus. The example of this apparatus is an example and there is no restriction | limiting in particular in the specification of an apparatus.

Into this electrolytic cell, a copper concentration: 80 to 110 g / L, a sulfuric acid concentration: 70 to 110 g / L, and a glue concentration: 2.0 to 10.0 ppm are introduced to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 1.5 to 5.0 m / s, the electrolyte temperature is adjusted to 60 ° C. to 65 ° C., and the current density is set to 60 to 120 A / dm ² to deposit copper on the surface of the rotating drum, The copper deposited on the surface of the rotating drum is peeled off to continuously produce a copper foil.
That is, as described above, electrolysis with an electrolyte temperature of 60 to 65 ° C. and a current density of 60 to 120 A / dm ² is a preferable condition for obtaining an electrolytic copper foil having the above characteristics. In particular, the adjustment of the electrolyte temperature is important. Details will be described in Examples and Comparative Examples.

A roughening treatment can be applied to the surface or back surface of this electrolysis, or both surfaces as necessary. For example, the average surface roughness Ra can be set to 0.04 to 0.20 μm. In this case, the reason why the lower limit of the average surface roughness Ra is 0.04 μm is to form fine particles and improve the adhesion.
Thereby, for example, it becomes possible to apply as much active material as possible for the secondary battery, and the electric capacity of the battery can be increased. On the other hand, the reason for setting the upper limit to 0.20 μm is to reduce variation in weight thickness. Thereby, for example, the charge / discharge characteristics of the secondary battery can be improved. These surface roughnesses show an example and can be appropriately adjusted according to the use of the electrolytic copper foil.

  Moreover, when taking a copper foil for a negative electrode current collector for a secondary battery as an example, it is desirable that the average diameter of the roughened particles on the roughened surface be 0.1 to 0.4 μm. It is desired that the roughened particles are fine particles and the fine particles are more uniform. Similarly to the above, this is a preferable mode for improving the adhesion of the battery active material and applying as much active material as possible to increase the electric capacity of the battery.

Moreover, as for the copper foil for negative electrode collectors for secondary batteries, it is desirable for the maximum height of a roughening process layer to be 0.2 micrometer or less. This is also a preferable mode for reducing the thickness variation of the roughening treatment layer, improving the adhesion of the battery active material, and increasing the electric capacity of the battery by applying as much active material as possible.
The present invention can be managed and achieved based on an index that makes the thickness of the roughened particles 0.2 μm or less.

  The copper foil for a negative electrode current collector for a secondary battery can form one type of plating of copper, cobalt, nickel or two or more types of alloy plating as roughened particles. Usually, roughened particles are formed by three-part alloy plating of copper, cobalt, and nickel. Furthermore, the copper foil for the negative electrode current collector for the secondary battery has a cobalt-nickel alloy plating layer on the roughened surface on both the front and back sides of the rolled copper alloy foil in order to improve heat resistance and weather resistance (corrosion resistance). It is an element of a desirable form to form one or more rust-proofing layers or heat-resistant layers and / or silane coupling layers selected from zinc-nickel alloy plating layers and chromate layers.

  As described above, the copper foil for a negative electrode current collector for a secondary battery of the present invention can reduce the thickness variation in the copper foil width direction of the rolled copper alloy foil after the front and back surface roughening treatment to 0.5% or less. An excellent copper foil for a negative electrode current collector for a secondary battery can be provided.

The roughening treatment on the copper foil for the negative electrode current collector for the secondary battery of the present invention can be, for example, a copper roughening treatment or a copper-cobalt-nickel alloy plating treatment.
For example, the copper roughening treatment is as follows.
Copper roughening treatment Cu: 10 to 25 g / L
H ₂ SO _4: 20~100g / L
Temperature: 20-40 ° C
Dk: 30 to 70 A / dm ²
Time: 1-5 seconds

Moreover, the roughening process by a copper-cobalt-nickel alloy plating process is as follows. It is carried out so as to form a ternary alloy layer having an adhesion amount of 15 to 40 mg / dm ² copper-100 to 3000 μg / dm ² cobalt-100 to 500 μg / dm ² nickel by electrolytic plating. This ternary alloy layer also has heat resistance.

The general bath and plating conditions for forming such ternary copper-cobalt-nickel alloy plating are as follows.
(Copper-cobalt-nickel alloy plating)
Cu: 10-20 g / liter Co: 1-10 g / liter Ni: 1-10 g / liter pH: 1-4
Temperature: 30-50 ° C
Current density D _k : 20 to 50 A / dm ²
Time: 1-5 seconds

After the roughening treatment, a cobalt-nickel alloy plating layer can be formed on the roughened surface. The cobalt-nickel alloy plating layer has a cobalt adhesion amount of 200 to 3000 μg / dm ² and a cobalt ratio of 60 to 70 mass%. This treatment can be regarded as a kind of rust prevention treatment in a broad sense.

The conditions for cobalt-nickel alloy plating are as follows.
(Cobalt-nickel alloy plating)
Co: 1-20 g / liter Ni: 1-20 g / liter pH: 1.5-3.5
Temperature: 30-80 ° C
Current density D _k : 1.0 to 20.0 A / dm ²
Time: 0.5-4 seconds

A zinc-nickel alloy plating layer can be further formed on the cobalt-nickel alloy plating. The total amount of the zinc-nickel alloy plating layer is 150 to 500 μg / dm ² and the nickel ratio is 16 to 40% by mass. This has the role of a heat and rust preventive layer.

The conditions for zinc-nickel alloy plating are as follows.
(Zinc-nickel alloy plating)
Zn: 0-30 g / liter Ni: 0-25 g / liter pH: 3-4
Temperature: 40-50 ° C
Current density D _k : 0.5 to 5 A / dm ²
Time: 1-3 seconds

  Then, the following rust prevention process can also be performed as needed. A preferable antirust treatment is a coating treatment of chromium oxide alone or a mixture coating treatment of chromium oxide and zinc / zinc oxide. Chromium oxide and zinc / zinc oxide mixture coating treatment is zinc or zinc comprising zinc oxide and chromium oxide by electroplating using a plating bath containing zinc salt or zinc oxide and chromate. It is the process which coat | covers the antirust layer of a chromium group mixture.

As the plating bath, typically, at least one kind of dichromate such as K ₂ Cr ₂ O ₇ and Na ₂ Cr ₂ O ₇ and CrO ₃ and a water-soluble zinc salt such as ZnO ₄ and ZnSO ₄ · 7H are used. A mixed aqueous solution of at least one kind such as ₂ O and an alkali hydroxide is used. A typical plating bath composition and electrolysis conditions are as follows. The copper foil thus obtained has excellent heat resistance peel strength, oxidation resistance and hydrochloric acid resistance.

(Chromium rust prevention treatment)
K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / liter NaOH or KOH: 10 to 50 g / liter ZnO or ZnSO ₄ · 7H ₂ O: 0.05 to 10 g / liter pH: 3-13
Bath temperature: 20-80 ° C
Current density D _k : 0.05 to 5 A / dm ²
Time: 5 to 30 seconds Anode: Pt—Ti plate, stainless steel plate, etc. Chromium oxide requires a coating amount of 15 μg / dm ² or more, and zinc requires a coating amount of 30 μg / dm ² or more.

  Finally, if necessary, silane treatment for applying a silane coupling agent to at least the roughened surface on the rust preventive layer is performed mainly for the purpose of improving the adhesive force between the copper foil and the resin substrate. Examples of the silane coupling agent used for the silane treatment include olefin silane, epoxy silane, acrylic silane, amino silane, and mercapto silane, which can be appropriately selected and used. .

The application method may be any of spraying a silane coupling agent solution by spraying, coating with a coater, dipping, pouring and the like. For example, Japanese Examined Patent Publication No. 60-15654 describes that the adhesion between the copper foil and the resin substrate is improved by performing a chromate treatment on the rough side of the copper foil followed by a silane coupling agent treatment. . Refer to this for details. Thereafter, if necessary, an annealing treatment may be performed for the purpose of improving the ductility of the copper foil.
About the above, although the additional surface treatment layer to the electrolytic copper foil of this invention applied mainly to the negative electrode collector for secondary batteries was demonstrated, these can be arbitrarily applied according to the use of electrolytic copper foil. Needless to say. The present invention includes all of these.

  Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited only to this example. That is, other aspects or modifications included in the present invention are included.

Example 1
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity was adjusted to 3.0 m / s, the electrolyte temperature: 60 ° C., and the current density: 84 A / dm ² , copper was deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum was peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 50%, the size of the fine particles was less than 0.2 μm, the strength (normal tensile strength) was 51.4 kgf / mm ² , and the amount of warpage was 1.5 mm.
All satisfied the conditions of the present invention. The results are also shown in Table 1. In addition, in Table 1, “columnar particles” are described as “columnar crystals”, both of which mean “particles composed of columnar crystals” and are used in the same meaning. The same applies hereinafter.

In the embodiment, the current density is 84 A / dm ² . Furthermore, the microscope picture which shows the particle shape of the cross section of this electrolytic copper foil is shown in FIG. FIG. 1 shows a feature that columnar particles having an aspect ratio of 2.0 or more and fine particles having an aspect ratio of less than 2.0 are mixed.

(Example 2)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 63 ° C., the current density is 84 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 29%, the size of the fine particles: 0.2 μm, the strength (normal tensile strength): 50.7 kgf / mm ² , and the warpage amount: 1.7 mm.
All satisfied the conditions of the present invention. The results are also shown in Table 1.

(Example 3)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 63 ° C., the current density is 109 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 42%, the size of the fine particles was less than 0.2 μm, the strength (normal tensile strength) was 51.1 kgf / mm ² , and the amount of warpage was 1.8 mm. All satisfied the conditions of the present invention. The results are also shown in Table 1.

Example 4
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 65 ° C., the current density is 84 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 23%, the size of the fine particles was 0.2 μm, the strength (normal tensile strength) was 48.8 kgf / mm ² , and the amount of warpage was 1.4 mm. All satisfied the conditions of the present invention. The results are also shown in Table 1.

(Example 5)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 65 ° C., the current density is 97 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 32%, the size of the fine particles was 0.2 μm, the strength (normal tensile strength) was 49.2 kgf / mm ² , and the amount of warpage was 1.6 mm. All satisfied the conditions of the present invention. The results are also shown in Table 1.

(Example 6)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 65 ° C., the current density is 109 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 28%, the size of the fine particles: 0.2 μm, the strength (normal tensile strength): 49.5 kgf / mm ² , and the warpage amount: 1.7 mm.
All satisfied the conditions of the present invention. The results are also shown in Table 1.

(Example 7)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 65 ° C., the current density is 120 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 52%, the size of the fine particles: 0.2 μm, the strength (normal tensile strength): 51.0 kgf / mm ² , and the warpage amount: 1.8 mm. All satisfied the conditions of the present invention. The results are also shown in Table 1.

(Comparative Example 1)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 57 ° C., the current density is 84 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 6%, the size of the fine particles was less than 0.2 μm, the strength (normal tensile strength) was 60.6 kgf / mm ² , and the amount of warpage was 7.5 mm. FIG. 2 is a photomicrograph showing the shape of the cross-sectional particles of the electrolytic copper foil of Comparative Example 1.
In FIG. 1 of Example 1, columnar particles having an aspect ratio of 2.0 or more and fine particles having an aspect ratio of less than 2.0 are in a mixed state. FIG. 2 shows an undesirable tendency that the number of columnar particles having an aspect ratio of 2.0 or more is small, and the fine particles having an aspect ratio of less than 2.0 are almost all. That is, the requirement of the present invention that the total area of the columnar particles was 10% or more was not satisfied. The results are shown in Table 1, which caused the amount of warpage to increase as compared with the example.

(Comparative Example 2)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 57 ° C., the current density is 97 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 0%, the size of the fine particles was less than 0.2 μm, the strength (normal tensile strength) was 64.4 kgf / mm ² , and the amount of warpage was 6.9 mm. None of them satisfied the conditions of the present invention. The results are also shown in Table 1.

(Comparative Example 3)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 57 ° C., the current density is 109 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 0%, the size of the fine particles was less than 0.2 μm, the strength (normal tensile strength) was 66.7 kgf / mm ² , and the amount of warpage was 8.1 mm. None of them satisfied the conditions of the present invention. The results are also shown in Table 1.

(Comparative Example 4)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity was adjusted to 3.0 m / s, the electrolyte temperature: 60 ° C., and the current density: 61 A / dm ² , copper was deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum was peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 5%, the size of the fine particles was less than 0.2 μm, the strength (pile strength) was 50.3 kgf / mm ² , and the warpage amount was 6.2 mm.
None of them satisfied the conditions of the present invention. The results are also shown in Table 1.

(Comparative Example 5)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity was adjusted to 3.0 m / s, the electrolyte temperature: 60 ° C., and the current density: 109 A / dm ² , copper was deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum was peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 6%, the size of the fine particles was less than 0.2 μm, the strength (normal tensile strength) was 60.4 kgf / mm ² , and the amount of warpage was 6 mm. None of them satisfied the conditions of the present invention. The results are also shown in Table 1.

(Comparative Example 6)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is 63 ° C., the current density is adjusted to 61 A / dm ² , copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 9%, the size of the fine particles was 0.2 μm, the strength (normal tensile strength) was 55.3 kgf / mm ² , and the amount of warpage was 12.6 mm. None of them satisfied the conditions of the present invention. The results are also shown in Table 1.

(Comparative Example 7)
In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum. A copper concentration: 90 g / L, a sulfuric acid concentration: 80 g / L, and a glue concentration: 3 ppm were introduced into this electrolytic cell to obtain an electrolytic solution.
Then, the linear velocity is adjusted to 3.0 m / s, the electrolyte temperature is set to 70 ° C., and the current density is set to 109 A / dm ² to deposit copper on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off. The copper foil was continuously manufactured.

This condition is shown in Table 1. The area ratio of the columnar particles, the size of the fine particles, the strength (normal tensile strength), and the amount of warpage of the electrolytic copper foil thus produced were examined. As a result, the area ratio of the columnar particles was 83%, the size of the fine particles: 0.5 μm, the strength (normal tensile strength): 43.0 kgf / mm ² , and the warpage amount: 0.5 mm. None of them satisfied the conditions of the present invention. The results are also shown in Table 1.

  INDUSTRIAL APPLICABILITY The present invention is particularly useful for an electrolytic copper foil for a negative electrode current collector for a secondary battery because it can provide an electrolytic copper foil having a high normal tensile strength and a high heating tensile strength and little warpage.

Claims (9)

The tensile strength in the normal state (hereinafter referred to as “normal tensile strength”) is 45 kgf / mm ^{2 to} 55 kgf / mm ² , and the average value of the lifting height at the four corners of 100 mm square is 2 mm or less. Electrolytic copper foil. 2. The electrolytic copper foil according to claim 1, wherein the crystal particles of the cross section of the electrolytic copper foil are composed of fine particles having an aspect ratio of less than 2.0 and columnar particles having an aspect ratio of 2.0 or more. The total area of the columnar particles is 10% to 55%, the electrolytic copper foil according to claim 2, wherein the remainder being the fine particles. Tensile at normal strength (hereinafter, referred to as "normal tensile strength.") Is a ^{45kgf / mm 2 ~55kgf / mm 2} , the average value of the floating amount of the four corners of 100mm angle is not more 2mm or less, an aspect ratio An electrolytic copper foil, wherein the average particle size of the fine particles having a particle size of less than 2.0 is 0.2 μm or less,
Or
The total area of columnar particles having an aspect ratio of 2.0 or more, which are crystal particles in the cross section of the electrolytic copper foil, is 10% to 55%, and the remaining crystal particles in the cross section of the electrolytic copper foil have an aspect ratio of 2.0. Electrolytic copper foil, characterized by being fine particles that are less than
Because
You characterized electrostatic Kaidohaku an average particle size of the fine particles having an aspect ratio of less than 2.0 is 0.2μm or less.   It is a copper foil for secondary battery negative electrode collectors, The electrolytic copper foil as described in any one of Claims 1-4 characterized by the above-mentioned.   The surface or back surface or both surfaces of the electrolytic copper foil are provided with a roughened surface having an average surface roughness Ra of 0.04 to 0.20 μm. Electrolytic copper foil. In this method, an electrolytic copper foil is produced by an electrolytic method using a sulfuric acid-based copper electrolytic solution. In the electrolytic cell, copper concentration: 80 to 110 g / L, sulfuric acid concentration: 70 to 110 g / L, glue concentration: 2 0.0 to 10.0 ppm is used as an electrolytic solution, and electrolysis is performed at a linear velocity of 3.0 to 5.0 m / s, an electrolytic solution temperature of 60 to 65 ° C., and a current density of 60 to 120 A / dm ^2. The manufacturing method of the electrolytic copper foil characterized by manufacturing the electrolytic copper foil as described in any one of Claims 1-6. The method according to claim 7 , wherein the electrolytic solution does not contain 1.4 ppm or more of chloride ions. The method according to claim 7 , wherein the electrolyte temperature is 63 to 65 ° C. and the current density is 84 to 120 A / dm ^2, or the electrolyte temperature is 60 ° C. and the current density is 84 A / dm ² .