KR20180090736A - Surface treated copper foil,and current collector,electrode,and battery using the surface treated copper foil - Google Patents

Abstract

The present invention provides a surface treated copper foil for a battery in which falling of roughened particles is less and which can obtain good adhesion with an active material. The surface treated copper foil for a battery of the present invention comprises: a copper foil; and a surface treated layer on at least one surface of the copper foil. The surface treated layer has a primary particle layer and a secondary particle layer. A surface of the surface treated layer has a 10-point average roughness (Rz) of 1.8 μm or more when measuring by using a laser microscope with a wavelength of 405 nm based on JIS B0601 1994.

Description

TECHNICAL FIELD [0001] The present invention relates to a surface treated copper foil, a current collector using the same,

The present invention relates to a surface-treated copper foil, a current collector, an electrode and a battery using the same.

A rolled copper foil and an electrolytic copper foil are used as a current collector for a negative electrode or an electrode of a battery, particularly a secondary battery. In either copper foil, high adhesion of the positive electrode or the negative active material and the copper foil as the current collector is required. In order to improve the adhesion, there is an example in which surface treatment for forming irregularities on the surface of the copper foil is performed. For example, as disclosed in Patent Document 1, the surface of a copper foil is polished with emery paper to form irregularities to improve the adhesion.

Patent Document 1: Japanese Patent Publication No. 3733067

However, as described in Patent Document 1, there is a problem in that sufficient adhesion between the current collector and the active material can not be obtained even if the copper foil is simply polished with abrasive paper such as emery paper to form irregularities.

In addition, when the copper foil is provided with the roughened layer by plating with harmonization to form irregularities, there is a problem in that the roughening particle layer looses much of the coarse particles.

An object of the present invention is to provide a surface-treated copper foil for a battery, in which coarse particles are less likely to fall off and good adhesion with an active material can be obtained.

The present inventors have earnestly studied the reason why sufficient adhesion can not be obtained in the prior art, and found that the harmful particles formed on the surface of the copper foil by the roughening treatment using the copper sulfate plating bath have a problem of non-uniformity due to superposition of non-large, did. That is, there is a problem that the coarse particles fall off from the superposed portion of the coarse particles to the copper powder, and sufficient adhesion between the current collector copper foil and the active material can not be obtained. Here, the present inventors have found that adhesion to the active material is improved by controlling the 10-point average roughness (Rz) of the surface treatment layer obtained by forming the primary particle layer and the secondary particle layer on the surface side of the copper foil. The present invention has been completed based on the above findings.

That is, the present invention is a surface treated copper foil for a battery having a surface treatment layer on the surface side of at least one of a copper foil and a copper foil, wherein the surface treatment layer is formed by laminating a primary particle layer and a secondary particle layer in this order Treated surface-treated copper foil for a battery has a 10-point average roughness (Rz) of 1.8 占 퐉 or more when measured using a laser microscope having a wavelength of 405 nm according to JIS B0601 1994.

Further, in an embodiment of the present invention, the surface treatment layer surface of the battery surface-treated copper foil is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994, and the arithmetic average roughness Ra is 0.26 탆 or more to be.

In one embodiment of the present invention, the primary particle layer includes at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, do.

In one embodiment of the present invention, the secondary particle layer includes at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, do.

In one embodiment of the present invention, the surface treatment layer is made of at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, 100 mu g / dm < 2 > or more.

In one embodiment of the present invention, the surface treatment layer is made of at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, 10000 占 퐂 / dm2 or less.

In one embodiment of the present invention, the surface treatment layer contains Ni and the adhesion amount of Ni is 100 占 퐂 / dm2 or more.

In one embodiment of the present invention, the surface treatment layer contains Ni and the adhesion amount of Ni is 4500 占 퐂 / dm2 or less.

In one embodiment of the present invention, the surface treatment layer contains Co, and the amount of adhesion of Co is 100 占 퐂 / dm2 or more.

Further, in an embodiment of the present invention, the surface treatment layer contains Co, and the adhesion amount of Co is 6000 占 퐂 / dm2 or less.

Further, in an embodiment of the present invention, the primary particle layer is made of Cu.

Further, in an embodiment of the present invention, the secondary particle layer is made of Cu, Co, and Ni.

In one embodiment of the present invention, the copper foil is made of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, By mass and not more than 5% by mass and not more than 0.3% by mass in total.

In one embodiment of the present invention, the copper foil is made of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, At least 5 mass ppm and not more than 300 mass ppm.

In one embodiment of the present invention, the copper foil is made of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, By mass and not more than 0.3% by mass in total.

Further, in an embodiment of the present invention, the surface treatment layer may further comprise, on the secondary particle layer, at least one selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment layer, a plated layer, It has more than two layers.

Further, in one embodiment of the present invention, the surface-treated copper foil for a battery of the present invention is for a secondary battery.

Further, in one embodiment of the present invention, the surface-treated copper foil for a battery of the present invention is for a secondary battery current collector.

Further, the present invention is a current collector having the above-described surface-treated copper foil for a battery.

The present invention is also an electrode having a surface-treated copper foil for a battery described above.

Further, the present invention is a battery having the above-described surface-treated copper foil for a battery or a current collector or an electrode.

According to the present invention, it is possible to obtain a surface-treated copper foil for a battery having less loose coarse particles and having good adhesion to an active material. Further, according to some embodiments of the present invention, it is possible to obtain a surface-treated copper foil for a battery having a surface treatment further excellent in heat resistance.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual diagram showing the appearance of harmonized particles when a conventional roughening treatment is performed on the surface of a copper foil. Fig.
2 is a conceptual view showing a surface treatment layer of a surface treated copper foil for a battery having a surface treatment layer of the present invention.

<Battery-surface-treated copper foil>

The surface-treated copper foil for a battery (including the copper alloy foil) of the present invention can be produced by, for example, forming a current collector of a battery or a secondary battery by forming an active material thin film thereon and finally forming an electrode Or a negative electrode), or a secondary battery can be manufactured. The method of forming the active material thin film on the current collector is not particularly limited. For example, a liquid containing a CVD method, a sputtering method, a vapor deposition method, a spraying method, and an active material is applied on a current collector, A post-drying method or a plating method. Of these thin film forming methods, CVD method, sputtering method, and vapor deposition method are particularly preferably used. Further, an intermediate layer may be formed on the current collector, and an active material thin film may be formed on the intermediate layer. The surface-treated copper foil for a battery of the present invention can be used for a known electrode, a known current collector, and a known battery. Examples of the known battery include a lithium ion secondary battery, a full solid secondary battery, an air battery (lithium-air battery, zinc-air battery, etc.), a sodium ion battery, a magnesium ion battery, A secondary battery using a sulfur-based material in the anode, a secondary battery using an organic material showing redox activity on the anode, a nickel-cadmium battery, a manganese battery (dry battery), an alkaline battery (dry battery), a lithium battery (dry battery), etc. . Known electrodes and known collectors include electrodes and collectors used in the above-described known batteries.

<Copper>

The form of the copper foil usable in the present invention is not particularly limited, and a known copper foil can be used. Typically, the copper foil used in the present invention may be a copper foil formed by dry plating or wet plating, an electrolytic copper foil or a rolled copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel. The rolled copper foil is produced by repeating plastic working and heat treatment by a rolling roll. Rolled copper foil is often applied to applications requiring flexibility. In the case of using the above-described copper foil, for example, a rolled copper foil, a copper foil subjected to annealing treatment (annealing treatment) may be used after producing a copper foil after rolling. It is preferable to use a rolled copper foil subjected to annealing treatment.

Examples of the copper foil material are tough pitch copper (JIS H3100 alloy No. C1100), oxygen free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011), indaturated copper (JIS H3100 alloy No. C1201, C1220 or C1221) Cu, Sn, Zn, Mn, Mo, Co, Ni and Si are added to the above-mentioned high-purity copper, for example, , Copper alloy containing at least one selected from the group consisting of Zr, B and / or Mg, and copper alloy such as Colson copper alloy containing Ni and Si added can also be used. A copper foil and a copper alloy foil having a known composition can also be used. In the present specification, when the term &quot; copper foil &quot; is used singly, copper alloy foil is also included. As the copper foil material, a group of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B and Mg is added to the above- , Preferably not less than 15 mass ppm, preferably not less than 20 mass ppm, preferably not less than 25 mass ppm, preferably not more than 30 mass ppm, more preferably not less than 30 mass ppm, Preferably not less than 35 mass ppm, preferably not less than 40 mass ppm, preferably not less than 45 mass ppm, preferably not less than 50 mass ppm, preferably not less than 301 mass ppm, preferably not less than 310 mass ppm Or more, preferably 350 mass ppm or more, preferably 380 mass ppm or more, preferably 400 mass ppm or more, preferably 500 mass ppm or more. As the copper foil material, a group of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B and Mg is added to the above- , Preferably not more than 30 mass%, preferably not more than 20 mass%, preferably not more than 10 mass%, preferably not more than 5 mass%, more preferably not more than 5 mass% Preferably not more than 0.5 mass%, preferably not more than 0.3 mass%, preferably not more than 0.28 mass%, more preferably not more than 0.5 mass%, preferably not more than 0.8 mass% Preferably not more than 0.25 mass%, preferably not more than 0.23 mass%, preferably not more than 0.20 mass%, preferably not more than 0.17 mass%, preferably not more than 0.15 mass%, preferably not more than 300 mass ppm It is also possible to use one copper alloy. A metal selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B and Mg added to the above- (For example, 301 mass ppm or more), the strength of the copper foil becomes higher, which is effective. The total concentration of one or more elements selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, (For example, not more than 300 mass ppm) is excellent because of excellent flexibility.

<Surface Treatment Layer>

The surface treatment layer has a primary particle layer and a secondary particle layer in this order from the copper foil side. The surface treatment layer has a primary particle layer and a secondary particle layer in this order from the copper foil side, and the case where the powder falls off due to the fall off of the coarse particles is reduced. Further, the surface treatment layer has an effect that the adhesion between the copper foil and the active material is improved by having the primary particle layer and the secondary particle layer in this order from the copper foil side. This is presumably due to the fact that the harmonic particles are not folded well by providing the primary particle layer and the secondary particle layer. Further, the surface treatment layer has the primary particle layer and the secondary particle layer in this order from the copper foil side, so that the heat resistance of the copper foil is improved. The primary particle layer and the secondary particle layer can be formed of the above-mentioned plating layer. The characteristics of the secondary particles are one or a plurality of particles grown on the primary particles. Or the secondary particle layer is a normal plating layer grown on the primary particle. The secondary particles may be dendritic. That is, when the term "secondary particle layer" is used in the present specification, a normal plating layer such as coating plating is also included. The secondary particle layer may be a layer having one or more layers formed by coarsely grained particles or a layer having one or more normal plating layers and may be a layer formed by coarsely grained particles and a layer having one or more normal plating layers . The surface treatment layer may have one or a plurality of different layers other than the primary particle layer or the secondary particle layer. The normal plating means plating performed under the condition of a current density equal to or lower than the critical current density.

The primary particle layer is a layer in which the coarse particles directly formed on the copper foil and the coarse particles superimposed on the coarse particles have the same composition as the coarse particles directly formed on the copper foil or the coarse particles directly formed on the copper foil Is a layer containing harmonic grains having the same element as the element contained in the grains. The secondary particle layer is a coarse particle formed on the coarse particle contained in the primary particle layer and has a composition different from that of the coarse particle forming the primary particle layer or an element containing no coarse particles forming the primary particle layer As a layer containing harmonic particles.

When the presence or absence of the elements constituting the primary particles and / or the secondary particles and / or the concentration or the amount of the elements can not be measured, the primary particles and the secondary particles are, for example, When observed with an electron microscope photograph, the particles existing on the copper foil side (lower side) and the non-overlapping particles as the overlapping particles are regarded as primary particles and the particles existing on other particles as overlapping particles are judged as secondary particles . When the base plating layer (normal plating layer) such as copper is provided on the copper foil, the above-mentioned &quot; coarsely grained particles directly formed on the copper foil &quot; includes coarsely grained particles directly formed on the base plating layer.

The surface-treated copper foil for a battery of the present invention has a 10-point average roughness (Rz) of 1.8 占 퐉 or more when the surface treatment layer surface is measured using a laser microscope having a wavelength of 405 nm in accordance with JIS B0601 1994. If Rz is less than 1.8 占 퐉, as shown in the conceptual diagram of Fig. 1, the coarse grains of the copper foil are distributed in the form of elongated dendrites, and the elongated dendritic particles are easily broken by external force, Therefore, the adhesion to the active material is not good. On the other hand, if Rz is 1.8 占 퐉 or more, the sharp start is lost as shown in the conceptual diagram of Fig. 2, and the rounded shape of the particles grows, so that the resin does not break well and does not fall off well from the root. As a result, the adhesion with the active material improves. From this viewpoint, the 10-point average roughness Rz is more preferably 1.9 占 퐉 or more, more preferably 2.0 占 퐉 or more, further preferably 2.1 占 퐉 or more, further preferably 2.2 占 퐉 or more, further preferably 2.3 Mu m or more, and more preferably 2.35 mu m or more. The upper limit of the 10-point average roughness (Rz) is not particularly limited, but is typically 10 μm or less, preferably 8 μm or less, more preferably 5 μm or less, further preferably 3.30 μm or less, More preferably not more than 3.20 占 퐉, still more preferably not more than 3.10 占 퐉, still more preferably not more than 3.05 占 퐉, still more preferably not more than 3 占 퐉, still more preferably not more than 2.95 占 퐉, still more preferably not more than 2.90 占 퐉 Is not more than 2.85 占 퐉, and more preferably not more than 2.80 占 퐉. It is presumed that when the Rz is small to 3 탆 or less, the coarsened particles are less likely to fall off and the adhesion with the active material becomes better. When the surface treatment layer is present on both surfaces of the copper foil, the effects of the present invention are exhibited when one of the ten-point average roughness Rz falls within the above range. Therefore, if one of the ten- And the 10-point average roughness (Rz) on both sides may be within the above range.

When the surface-treated copper foil for a battery has a plurality of layers such as a primary particle layer, a secondary particle layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment layer and a plated layer Means the outermost layer surface of the plurality of layers.

In view of the above, the surface-treated copper foil for a battery of the present invention has an arithmetic mean roughness (Ra) of 0.26 탆 or more when measured using a laser microscope with a wavelength of 405 nm in accordance with JIS B0601 1994 . The arithmetic average roughness Ra is more preferably 0.28 占 퐉 or more, more preferably 0.30 占 퐉 or more, still more preferably 0.32 占 퐉 or more, still more preferably 0.34 占 퐉 or more, and still more preferably 0.36 占 퐉 or more Preferably not less than 0.38 mu m, and more preferably not less than 0.40 mu m. The upper limit of the arithmetic average roughness (Ra) is not particularly limited, but is typically 5.0 탆 or less, preferably 4.5 탆 or less, more preferably 4.0 탆 or less, further preferably 3.5 탆 or less Preferably 3.0 μm or less, more preferably 2.5 μm or less, further preferably 2.0 μm or less, further preferably 1.5 μm or less, further preferably 1.0 μm or less, further preferably 0.5 μm or less, Is not more than 0.45 mu m, more preferably not more than 0.44 mu m, further preferably not more than 0.41 mu m, further preferably not more than 0.40 mu m. When the surface treatment layer is present on both surfaces of the copper foil, the effect of the present invention is exhibited when the arithmetic mean roughness Ra of one side is within the above range. Therefore, the arithmetic average roughness Ra of one of the surfaces may be within the above- The arithmetic mean roughness Ra of both sides may be within the above range.

It is preferable that the primary particle layer has an average particle diameter of 0.1 to 0.6 탆. The average particle size of the secondary particle layer is preferably 0.01 to 0.45 mu m. Here, the particle diameter means the diameter of the minimum circle surrounding the particles when the coarse particles are observed by photographing from above the copper foil with a scanning electron microscope. The average particle diameter means an arithmetic mean value of the particle diameters of a plurality of coarsely grained particles. Specifically, the average particle diameter of the primary particle layer means an arithmetic average value of the particle diameters of the primary particle layer coarsening particles existing in the region of 4 占 퐉 x 3 占 퐉 in the photograph taken by the scanning electron microscope described above . The average particle diameter of the secondary particle layer means an arithmetic average value of the particle diameter of the secondary particle layer coarsening particles present in the region of 4 占 퐉 占 3 占 퐉 in the photograph taken by the scanning electron microscope described above.

The average particle diameter of the primary particle layer can be adjusted by adjusting the concentration of elements attached to the copper foil by plating and / or by increasing the current density and / or the surface treatment The time can be increased by lengthening the time (energizing time for plating) and / or increasing the number of times of plating. The average particle diameter of the primary particle layer can be adjusted by increasing the concentration of elements attached to the copper foil by plating and / or by lowering the current density and / or surface treatment The time can be reduced by shortening the time (energizing time at the time of plating) and / or reducing the number of times of plating.

The average particle diameter of the secondary particle layer is preferably set such that the concentration of the element adhered to the copper foil is lowered by plating and / or the current density is increased and / or the surface treatment The time can be increased by lengthening the time (energizing time at the time of plating) and / or increasing the number of times of plating. The average particle diameter of the secondary particle layer can be adjusted by increasing the concentration of elements attached to the copper foil by plating and / or by lowering the current density and / or surface treatment The time can be reduced by shortening the time (energization time at the time of plating) and / or reducing the number of times of plating.

In the surface-treated copper foil for a battery of the present invention, the primary particle layer in the surface treatment layer is one or more selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, It may have two or more kinds of elements. It is preferable that the primary particle layer in the surface treatment layer has at least one element selected from the group consisting of Cu, W, Ti, As, Cr and P. It is preferable that the primary particle layer in the surface treatment layer has at least one element selected from the group consisting of Cu, W, As and P. This makes it easier to prevent the powder from falling off. The secondary particle layer may have one or more elements selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. The total deposition amount of at least one element selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn contained in the above- , For example, 100 占 퐂 / dm2 or more. The upper limit of the total adhesion amount is not particularly limited, but may be, for example, 10000 占 퐂 / dm2 or less. In addition, one or two or more elements selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn contained in the primary particle layer and the secondary particle layer Can be, for example, 100 占 퐂 / dm2 or more. The upper limit of the total adhesion amount is not particularly limited, but may be, for example, 10000 占 퐂 / dm2 or less.

From the standpoint of improving the battery capacity, a composite active material obtained by mixing a silicon-based material or a plurality of materials from a simple carbon-based active material has been studied. When such a silicon-based active material is used, a polyimide-based binder may be used, and heating at 300 DEG C or more is required for bonding. Therefore, it is more preferable that the copper foil is a copper foil for a secondary battery current collector having heat resistance characteristics that does not cause oxidative discoloration on the surface of the copper foil even after heating at 300 DEG C or higher, although the object of the present invention can be achieved when the adhesion with the active material is good. Wherein at least one element selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn is selected and a secondary particle layer is formed in accordance with the above- The heat resistance characteristics can be improved.

The surface treatment layer of the surface-treated copper foil for a battery of the present invention may not contain Ni, or the surface treatment layer may contain Ni. When the surface treatment layer contains Ni, the amount of Ni adhered to the surface treatment layer is preferably 100 占 퐂 / dm2 or more. If the adhesion amount of Ni is less than 100 / / dm 2, a problem that the heat resistance remarkably deteriorates may occur. When the surface treatment layer contains Ni, it is preferable that the amount of Ni deposited on the surface treatment layer is 4500 占 퐂 / dm2 or less. If it exceeds 4500 占 퐂 / dm2, the Ni film thickness becomes thick, and the above-mentioned resistance value rises and there is a possibility that the above-mentioned characteristic as the copper foil for current collector is lowered. The adhesion amount of Ni is more preferably 200 占 퐂 / dm2 or more, further preferably 300 占 퐂 / dm2 or more, and further preferably 400 占 퐂 / dm2 or more. The deposition amount of Ni is more preferably 4,400 占 퐂 / dm2 or less, still more preferably 4,300 占 퐂 / dm2 or less, still more preferably 4,200 占 퐂 / dm2 or less, still more preferably 4,100 占 퐂 / dm2 More preferably 4000 占 퐂 / dm2 or less, and further preferably 3950 占 퐂 / dm2 or less. When the surface treatment layer contains Ni, the chemical resistance of the surface-treated copper foil may be improved as compared with the case where the surface treatment layer does not contain Ni.

The surface treatment layer of the surface-treated copper foil for a battery of the present invention may contain Co, or the surface treatment layer may include Co. When the surface treatment layer contains Co, the adhesion amount of Co in the surface treatment layer is preferably 100 占 퐂 / dm2 or more. If the coating amount of Co is less than 100 / / dm 2, the heat resistance may be significantly deteriorated. When the surface treatment layer contains Co, it is preferable that the Co deposition amount in the surface treatment layer is 6000 占 퐂 / dm2 or less. If it is more than 6000 占 퐂 / dm2, the thickness of Co becomes thick and magnetic property is developed, and there is a possibility that a problem that the electric characteristics are deteriorated as a battery copper foil, especially a copper foil for current collecting, may arise. The coating amount of Co is more preferably not less than 200 μg / dm 2, more preferably not less than 300 μg / dm 2, more preferably not less than 400 μg / dm 2, more preferably not less than 500 μg / More preferably at least 600 μg / dm 2, more preferably at least 700 μg / dm 2, even more preferably at least 800 μg / dm 2, even more preferably at least 900 μg / dm 2, / d &lt; 2 &gt; The coating amount of Co is more preferably 5500 占 퐂 / dm2 or less, more preferably 5000 占 퐂 / dm2 or less, still more preferably 4500 占 퐂 / dm2 or less, still more preferably 4300 占 퐂 / dm2 More preferably not more than 4200 μg / dm 2, more preferably not more than 4100 μg / dm 2, more preferably not more than 4000 μg / dm 2, and still more preferably not more than 3950 μg / dm 2. When the surface treatment layer contains Co, the effect of improving the weather resistance of the surface-treated copper foil may be enhanced as compared with the case where the surface treatment layer does not include Co.

The deposition amount of elements such as Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, Sn and P in the surface treatment layer is specified in the present invention. And defines the total amount of adhesion of elements present in the surface treatment layer including the tea particle layer. When these surface treatment layers are present on both surfaces of the copper foil, the total amount of elements (for example, Ni) contained in the surface treatment layer defined on the surface treatment layer of one surface It is not a value.

When the adhesion amount of elements such as Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, Sn and P in the surface treatment layer of the surface treatment copper foil for a battery of the present invention is within the above range, The deposition amount can be changed as necessary, but it is preferable that the primary particle layer is made of Cu from the viewpoint of further improving the adhesion with the active material thin film. Here, "the primary particle layer is made of Cu" is a concept that "the primary particle layer contains only Cu" and that "the primary particle layer contains Cu and inevitable impurities". From the viewpoint of improving the heat resistance of the surface-treated copper foil, it is preferable that the secondary particle layer is made of Cu, Co and Ni. Here, &quot; the secondary particle layer is made of Cu, Co, and Ni &quot; means that the secondary particle layer contains Cu, Co, and Ni only and that the secondary particle layer contains only Cu, Co and Ni and inevitable impurities And the like.

The adhesion amount of the element contained in the surface treatment layer can be adjusted by increasing the concentration of the element in the surface treatment liquid used for forming the surface treatment layer and / or increasing the current density when the surface treatment is plating, And / or by increasing the surface treatment time (electrification time at the time of plating), or the like. The deposition amount of the element contained in the surface treatment layer is preferably set such that the concentration of the element in the surface treatment liquid used when forming the surface treatment layer is lowered and / or when the surface treatment is plating, the current density is lowered , And / or by shortening the surface treatment time (electrification time at the time of plating), and the like.

<Formation Conditions of Primary Particle Layer and Secondary Particle Layer>

The surface treatment layer of the surface-treated copper foil for a battery of the present invention forms a primary particle layer and a secondary particle layer in this order from the surface side of the copper foil. The primary particle layer and the secondary particle layer may be formed directly from the surface side of the copper foil or the base plating layer may be formed on the surface side of the copper foil and then the primary particle layer and the secondary particle layer may be formed in order. The above-mentioned base plating layer may be a Cu plating layer. The conditions for forming the primary particle layer and the secondary particle layer are shown below. However, this is only a preferable example, and the surface treatment layer surface is measured using a laser microscope having a wavelength of 405 nm in accordance with JIS B0601 1994 If the 10-point average roughness (Rz) is 1.8 占 퐉 or more, the plating conditions other than those shown below are not adversely affected.

The 10-point average roughness (Rz) when the surface treatment layer surface is measured using a laser microscope having a wavelength of 405 nm according to JIS B0601 1994 is used for forming the primary particle layer and / or the secondary particle layer And / or the surface treatment time (electrification time at the time of plating) is made long, and / or the electroplating is carried out, It can be increased by increasing the number of times. The 10-point average roughness (Rz) measured when the surface treatment layer surface is measured using a laser microscope with a wavelength of 405 nm in accordance with JIS B0601 1994 can be measured by using the surface roughness of the primary particle layer and / By increasing the concentration of the element to be adhered to the copper foil and / or lowering the current density and / or shortening the surface treatment time (electrification time at the time of plating) in the surface treatment liquid, Can be made small.

The arithmetic mean roughness (Ra) when the surface treatment layer surface is measured using a laser microscope having a wavelength of 405 nm in accordance with JIS B0601 1994 is preferably in the range of It is possible to increase the concentration of the element to be adhered to the copper foil by plating and / or by increasing the current density and / or by lengthening the surface treatment time (plating time for plating) have. The arithmetic mean roughness (Ra) when the surface treatment layer surface is measured using a laser microscope having a wavelength of 405 nm in accordance with JIS B0601 1994 is preferably in the range of It is possible to increase the concentration of the element attached to the copper foil and / or lower the current density and / or to shorten the surface treatment time (energization time at the time of plating) by plating and / Or the like can be reduced.

Primary particle layer

In the case of treatment with the primary particle plating solution (B) after the treatment with the primary particle plating solution (A), the primary particle layer can be formed under the following conditions.

(Treatment with primary particle plating solution (A)) [

<Electrolyte Composition>

Copper: 5 ~ 15g / L

Sulfuric acid: 70 to 80 g / L

<Manufacturing Conditions>

Current density: 40 to 60 A / dm 2

Electrolyte temperature: 25 ~ 35 ℃

Delivery time: 0.5-1.6 seconds

(Treatment with primary particle plating solution (B)

<Electrolyte Composition>

Copper: 20 to 50 g / L

Sulfuric acid: 60 to 100 g / L

<Manufacturing Conditions>

Current density: 4 to 10 A / dm 2

Electrolyte temperature: 35 ~ 55 ℃

Delivery time: 1.4 to 2.5 seconds

In the case where the primary particle layer is formed only by the treatment with the primary particle plating solution (I), the treatment with the primary particle plating solution (I) or the treatment with the primary particle plating solution (I) .

(Treatment with primary particle plating solution (I) 1)

<Electrolyte Composition>

Copper: 10 ~ 45g / L

Cobalt: 5 ~ 30g / L

Nickel: 5 to 30 g / L

pH: 2.8 to 3.2

<Manufacturing Conditions>

Current density: 30 ~ 45A / dm2

Electrolyte temperature: 30 ~ 40 ℃

Delivery time: 0.3 to 0.8 seconds

(Treatment with primary particle plating solution (I) 2)

<Electrolyte Composition>

Copper: 5 ~ 15g / L

Nickel: 3 to 30 g / L

pH: 2.6-3.0

<Manufacturing Conditions>

Current density: 50 to 70 A / dm 2

Electrolyte temperature: 30 ~ 40 ℃

Electrolysis time: 0.3 to 0.9 seconds

Secondary particle layer

In the case of forming the secondary particle layer, it can be carried out by treatment with the following secondary particle plating solution (I) or secondary particle plating solution (II).

(Treatment with secondary particle plating solution (I)) [

<Electrolyte Composition>

Copper: 10 ~ 15g / L

Cobalt: 5 to 15 g / L

Nickel: 5 to 15 g / L

pH: 2.8 to 3.2

<Manufacturing Conditions>

Current density: 20 to 40 A / dm 2

Electrolyte temperature: 33 ~ 37 ℃

Electrolysis time: 0.5 to 1.0 second

(Treatment with secondary particle plating solution (II)) [

<Electrolyte Composition>

Copper: 5 ~ 12g / L

Nickel: 2 to 11 g / L

pH: 2.8

<Manufacturing Conditions>

Current density: 55 to 65 A / dm 2

Electrolyte temperature: 35 ~ 40 ℃

Electrolysis time: 0.3 to 0.9 seconds

&Lt; Coating plating &

Coating on the secondary particle layer can be carried out. By forming the coating plating, the effect of improving the heat resistance can be expected. The layer formed by the coating plating may be a Zn-Cr alloy layer, a Ni-Mo alloy layer, a Zn layer, a Co-Mo alloy layer, a Co-Ni alloy layer, a Ni-W alloy layer, A Ni-P alloy layer, a Ni-Fe alloy layer, a Ni-Al alloy layer, a Co-Zn alloy layer, a Co-P alloy layer, a Zn-Co alloy layer, a Ni layer, a Co layer, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo, Co, etc., such as a Sn-Ni layer, a Ni-Sn layer or a Zn- And a metal layer composed of one kind of element selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo and Co An alloy layer containing two or more kinds, or an alloy layer comprising two or more kinds of elements selected from the above-mentioned element group.

Coating plating can be carried out by treating with the following coating plating solution or the like, or by combining them. The metal layer and / or alloy layer which can not be provided by wet plating can be provided by a dry plating method such as sputtering, physical vapor deposition (PVD), or chemical vapor deposition (CVD).

· Treatment with plating solution (1) Zn-Cr

Liquid composition: Potassium dichromate 1 ~ 10g / L, Zn 0.1 ~ 5g / L

Solution temperature: 40 to 60 ° C

pH: 0.5 to 10

Current density: 0.01 to 2.6 A / dm 2

Energization time: 0.05 to 30 seconds

· Treatment with plating solution (2) Treatment with Ni-Mo

Liquid composition: 270 to 280 g / L of nickel sulfate, 35 to 45 g / L of nickel chloride, 10 to 20 g / L of nickel acetate, 1 to 60 g / L of sodium molybdate, 10 to 50 g / Sodium sulfate 50 to 90 ppm

Temperature: 20 to 65 ° C

pH: 4-12

Current density: 0.5 to 5 A / dm 2

Power-on time: 0.1 to 5 seconds

· Treatment with plating solution (3) Zn

Solution composition: Zn 1 ~ 15g / L

Solution temperature: 25 ~ 50 ℃

pH: 2-6

Current density: 0.5 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

(4) Treatment with Co-Mo

Liquid composition: Co 1 ~ 20g / L, sodium molybdate 1 ~ 60g / L, sodium citrate 10 ~ 110g / L

Solution temperature: 25 ~ 50 ℃

pH: 5 to 7

Current density: 1 to 4 A / dm 2

Power-on time: 0.1 to 5 seconds

· Treatment with coating solution (5) Co-Ni

Liquid composition: Co 1 to 20 g / L, Ni 1 to 20 g / L

Temperature: 30 ~ 80 ℃

pH: 1.5 to 3.5

Current density: 1 to 20 A / dm 2

Power supply time: 0.1 to 4 seconds

· Treatment with plating solution (6) Treatment with Zn-Ni

Solution composition: Zn 1 to 30 g / L, Ni 1 to 30 g / L

Solution temperature: 40 ~ 50 ℃

pH: 2 to 5

Current density: 0.5 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

· Treatment with plating solution (7) Treatment with Ni-W

Solution composition: Ni 1 to 30 g / L, W 1 to 300 mg / L

Temperature: 30 ~ 50 ℃

pH: 2 to 5

Current density: 0.1 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

· Treatment with coating plating solution (8) Treatment with Ni-P

Solution composition: Ni 1 to 30 g / L, P 1 to 10 g / L

Temperature: 30 ~ 50 ℃

pH: 2 to 5

Current density: 0.1 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

<Other Surface Treatment>

The surface-treated layer of the surface-treated copper foil for a battery of the present invention may further comprise a heat-resistant layer, a rust-preventive layer, a chromate treatment layer, a silane coupling treatment layer, a plated layer and a resin layer on the secondary particle layer or the above- May be used. The heat-resistant layer, the rust-preventive layer, the chromate treatment layer, the silane coupling treatment layer, the plating layer, and the resin layer may each have a plurality of layers (for example, two or more layers, three layers or more).

As the heat-resistant layer and the rust-preventive layer, known heat-resistant layers and rust-preventive layers can be used. For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Or a layer containing at least one element selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, May be a metal layer or an alloy layer composed of at least one element selected from the group of Further, the heat-resistant layer and / or the anticorrosion layer may contain an oxide, a nitride, or a silicide including the above-described elements. Further, the heat resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc, except for unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m 2, preferably 10 to 500 mg / m 2, and preferably 20 to 100 mg / m 2. It is also preferable that the ratio of the nickel adhesion amount to the zinc adhesion amount (= adhesion amount of nickel / adhesion amount of zinc) of the nickel-zinc alloy layer or the nickel-zinc alloy layer is 1.5 to 10. The adhesion amount of the nickel-zinc alloy layer or nickel in the nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2, more preferably 1 mg / m 2 to 50 mg / m 2. When the heat-resistant layer and / or the rust-preventive layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is not eroded well by the liquid when the inner wall of the through hole, the via hole, The adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a nickel or nickel alloy layer having an adhesion amount of 1 mg / m2 to 100 mg / m2, preferably 5 mg / m2 to 50 mg / m2 and an adhesion amount of 1 mg / m2 to 80 mg / m2, M 2 to 40 mg / m 2, and the nickel alloy layer may be formed of a nickel-molybdenum alloy, a nickel-zinc alloy, a nickel-molybdenum-cobalt alloy, or a nickel-tin alloy It may be composed of one kind.

In the present specification, the chromate treatment layer refers to a layer treated with a liquid containing chromic acid anhydride, chromic acid, bichromic acid, chromic acid salt or dichromate. The chromate treatment layer contains elements (metals, alloys, oxides, nitrides, sulfides and the like) such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As and Ti Maybe. Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc, and the like.

The silane coupling treatment layer may be formed using a well-known silane coupling agent, or may be formed using an epoxy silane, an amino silane, a methacryloyl clock silane, a mercapto silane, a vinyl silane, an imidazole silane, a triazine silane, Of a silane coupling agent or the like. These silane coupling agents may be used in combination of two or more. Among them, it is preferable to use an amino-based silane coupling agent or an epoxy-based silane coupling agent.

The surface of the copper foil, the surface treatment layer, the heat resistant layer, the rust preventive layer, the silane coupling treatment layer or the chromate treatment layer may be coated with a surface treatment agent such as those described in International Publication Nos. WO2008 / 053878, Japanese Laid-open Patent Publication No. 5024930, International Publication Nos. WO2006 / 028207, Japanese Patent Publication No. 4828427, International Publication Nos. WO2006 / 134868, JP 5046927, WO2007 / 105635, JP 5180815, -19056 can be carried out.

[Example]

Hereinafter, the present invention will be described based on Examples and Comparative Examples. Note that this embodiment is merely an example, and is not limited to this example.

<Primary Particle Layer and Secondary Particle Layer>

First, the ingot having the composition shown in the column of &quot; Composition of the copper foil base material &quot; in Table 1 was melted and the ingot was hot-rolled from 900 DEG C to obtain a plate having a thickness of 10 mm. Thereafter, cold rolling and annealing were repeated, and finally, cold rolled to a copper foil having a thickness of 12 탆 to obtain a rolled copper foil. Further, as the electrolytic copper foil of Example 7, an HLP foil of 9 占 퐉 thick made by JE X-Metal Co., Ltd. was prepared.

TPC in the "composition of the copper foil substrate" in Table 1 means tough pitch copper (JIS H3100 alloy number C1100) and OFC means oxygen-free copper (JIS H3100 alloy number C1020). That is, for example, "190 ppm Ag-TPC" in Example 2 means that 190 mass ppm of Ag is added to tough pitch copper. For example, "1200 ppm Sn-OFC" in Example 4 means 1200 mass ppm Sn added to oxygen-free copper.

Subsequently, the surface of the rolled copper foil or the surface of the electrolytic copper foil on the side of the mat surface (precipitated surface, M side) was subjected to electrolytic degreasing, water washing and pickling, Thereby forming a particle layer and / or a secondary particle layer. In Examples and Comparative Examples in which "Primary Particle Layer Plating Current Condition A" and "Primary Particle Layer Plating Current Condition B" are listed in Table 1, the plating was performed under the conditions described in A, It means that plating is further performed. The conditions of the plating solution for forming the primary particle layer and the secondary particle layer are shown in Table 1 below in the "primary particle layer plating solution A", "primary particle layer plating solution B", "secondary particle layer plating solution" For example, when (1) is described in the column of &quot; primary particle layer plating solution A &quot;, the primary particle layer A is formed by using "plating solution (1)" of the "plating solution condition in primary particle layer A formation step" .

(Plating solution condition in the primary particle layer A forming step)

· Plating solution (1)

Liquid composition: copper 11 g / L, sulfuric acid 50 g / L

Solution temperature: 25 ℃

pH: 1.0 to 2.0

· Plating solution (2)

Liquid composition: copper 11 g / L, tungsten 3 mg / L, sulfuric acid 50 g / L

Solution temperature: 25 ℃

pH: 1.0 to 2.0

· Plating solution (3)

Liquid composition: copper 11 g / L, arsenic 100 mg / L, sulfuric acid 50 g / L

Solution temperature: 25 ℃

pH: 1.0 to 2.0

· Plating solution (4)

Liquid composition: copper 11 g / L, titanium 6 mg / L, sulfuric acid 50 g / L

Solution temperature: 25 ℃

pH: 1.0 to 2.0

· Plating solution (5)

Liquid composition: copper 11 g / L, chromium 3 mg / L, sulfuric acid 50 g / L

Solution temperature: 25 ℃

pH: 1.0 to 2.0

(Plating solution condition in the primary particle layer B formation step)

· Plating solution (1)

Liquid composition: copper 22 g / L, sulfuric acid 100 g / L

Solution temperature: 50 ° C

pH: 1.0 to 2.0

(Plating conditions in the secondary particle layer formation step)

· Plating solution (1)

Liquid composition: Copper 15 g / L, Nickel 8 g / L, Cobalt 8 g / L

Solution temperature: 36 ℃

pH: 2.7

· Plating solution (2)

Liquid composition: copper 15 g / L, nickel 8 g / L, phosphorus 1 g / L

Solution temperature: 36 ℃

pH: 2-3

· Plating solution (3)

Liquid composition: Copper 15 g / L, Nickel 8 g / L, Cobalt 8 g / L, Molybdenum 8 g / L

Temperature: 36

pH: 2-3

· Plating solution (4)

Liquid composition: Copper 15 g / L, Nickel 8 g / L, Tungsten 3 g / L

Solution temperature: 36 ℃

pH: 2-3

· Plating solution (5)

Liquid composition: copper 15 g / L, molybdenum 8 g / L, cobalt 8 g / L

Solution temperature: 36 ℃

pH: 2-3

&Lt; Coating plating &

Subsequently, only the primary particle layer was formed on the primary particle layer in which the primary particle layer and the secondary particle layer were formed, on which the coated plating shown in Table 1 was formed on the secondary particle layer. Each specific condition will be described below.

(1) Ni layer

Composition of plating solution: Ni 10 g / L

pH: 2.5

Temperature: 50 ° C

Current density (Dk): 12 A / dm &lt; 2 &gt;

Plating time: 0.5 seconds

Plating: 2 times

(2) Ni-Co alloy layer

Plating bath composition: Ni 10 g / L, Co 5 g / L

pH: 2.5

Temperature: 50 ° C

Current density (Dk): 10 A / dm &lt; 2 &gt;

Plating time: 0.5 seconds

Plating: 2 times

(3) Ni-Zn alloy layer

Plating bath composition: Ni 10 g / L, Zn 5 g / L

pH: 3.5

Temperature: 40 ° C

Current density (Dk): 2A / dm &lt; 2 &gt;

Plating time: 1 second

Plating: 2 times

<Electrolytic chromate treatment>

After the coated plating was formed, the following electrolytic chromate treatment was carried out in Examples 1 to 7 and Comparative Examples 2 and 3.

Liquid composition: potassium dichromate 3 g / L, Zn 0.5 g / L

Solution temperature: 40 to 60 ° C

pH: 4.0

Current density (Dk): 2.0 A / dm &lt; 2 &gt;

Plating time: 0.6 seconds

Plating: 2 times

&Lt; Silane coupling treatment &gt;

In Examples 1 to 7 and Comparative Examples 2 and 3, electrolytic chromate treatment was carried out, and further, the following silane coupling treatment was carried out.

Silane coupling agent: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane

Silane coupling agent concentration: 1.0 vol%

Processing temperature: 25 ° C

Processing time: 3 seconds

In Comparative Example 4, as shown in Table 1, instead of forming the primary particle layer and the secondary particle layer under the above-described predetermined conditions, the surface roughly roughened with a rolling roll was heat-oxidized in an atmospheric environment, % CO in a nitrogen atmosphere.

In Comparative Example 5, as shown in Table 1, instead of forming the primary particle layer and the secondary particle layer under the above-described predetermined conditions, the first Cu plating, the second Cu plating, and the third Cu plating were carried out successively under the following conditions .

(First Cu plating condition)

Plating bath composition: Cu 150 g / L to 250 g / L, sulfuric acid 100 g / L

pH: 1.0

Temperature: 40 ° C

Current density (Dk): 5 A / dm &lt; 2 &gt;

Plating time: 7 seconds

Plating: 1 time

(Second Cu plating condition)

Plating bath composition: Cu 50 g / L to 150 g / L, sulfuric acid 130 g / L

pH: 1.0

Temperature: 25 ℃

Current density (Dk): 40 A / dm 2

Plating time: 7 seconds

Plating: 1 time

(Third Cu plating condition)

Plating bath composition: Cu 150 g / L to 250 g / L, sulfuric acid 100 g / L

pH: 1.0

Temperature: 40 ° C

Current density (Dk): 5 A / dm &lt; 2 &gt;

Plating time: 7 seconds

Plating: 1 time

(Measurement of ten-point average roughness (Rz)) [

The surface roughness (Rz) of the copper foil after the surface treatment in each of the experimental examples was measured with a laser microscope OLS4000 manufactured by Olympus. Rz is in accordance with JIS B0601 1994. The measurement was carried out by measuring the direction (TD) perpendicular to the rolling direction with respect to the rolled copper foil under the condition of an evaluation length of 258 탆 and a cutting edge by observing the surface of the copper foil using an objective lens 50 times, And the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil at the measurement position was changed 10 times to obtain an average value in 10 measurements. The measurement environment temperature of the surface roughness (Rz) by the laser microscope was 23 to 25 占 폚. For the copper foil provided with the surface treatment layer on both sides, the 10-point average roughness (Rz) on both surfaces became the same value.

(Measurement of arithmetic mean roughness (Ra)) [

The surface roughness (Ra) of the copper foil after surface treatment in each of the experimental examples was measured with a laser microscope OLS4000 manufactured by Olympus. Ra is in accordance with JIS B0601 1994. (TD) perpendicular to the rolling direction with respect to the rolled copper foil under the condition of an evaluation length of 258 占 퐉 and a cutting edge by observing the surface of the copper foil using an objective lens 50 times or by the measurement of the electrolytic copper foil By measuring the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the apparatus, the measuring positions were changed 10 times to obtain an average value in 10 measurements. The measurement environmental temperature of the surface roughness (Ra) measured by a laser microscope was 23 to 25 占 폚. With respect to the copper foil provided with the surface treatment layer on both sides, the arithmetic mean roughness (Ra) was the same on both sides.

(Measurement of deposition amount of Co, Ni and other elements)

Co, Ni, and other elements were determined by ICP emission analysis by dissolving the surface treated layer of the copper foil sample in an aqueous solution of acetic acid (nitric acid) having a concentration of 20 mass%. In Examples and Comparative Examples in which the surface treatment layer was provided on both surfaces of the copper foil, one surface was masked with an anti-acid tape or the like, and the surface treatment layer on one surface was dissolved to adjust the adhesion amount of Co, Ni, Respectively. Thereafter, the amount of Co, Ni and other elements deposited on the other side was measured by the masking described above, or the amounts of Co, Ni and other elements deposited on the other side were measured using other samples. In addition, the values shown in Table 1 were values on one side. With respect to the copper foil provided with the surface treatment layer on both surfaces, the adhesion amounts of Co, Ni and other elements on both surfaces became the same value. When Co, Ni and other elements do not dissolve in an aqueous acetic acid solution having a concentration of 20 mass%, it is dissolved by using a solution capable of dissolving Co, Ni and other elements, and then measured by ICP issuance analysis . In addition, as the solution capable of dissolving Co, Ni and other elements, a known solution, a known acid solution, or a known alkaline solution may be used.

(Particle drop evaluation)

(1) Tape testing

A transparent mending tape was stuck on the surface-treated side of the surface-treated copper foil, and when the tape was peeled off in the direction of 180 DEG, the falling of the powder due to the discoloring particles adhering to the tape sticking surface was evaluated. Quot ;, &quot;? &Quot;, &quot;? &Quot;, and &quot; x &quot; when the tape turns black.

(2) Checking the transport roll

In the manufacturing process of the secondary battery, when the electrode active material is coated on the copper foil for current collector, a roll-to-roll transfer line is used. For this reason, it is a problem that the coarse grains of the copper foil surface treatment for current collector fall off on the roll of the conveying line. The yield of the conveying roll was evaluated according to the contamination state of the roll, although the conveying roll was often cleaned once every several thousands meters of the conveying of the copper foil by using the slit line device used for adjusting the product width of the copper foil for collectors. The state in which the roll was hardly dirty was indicated by &quot; &quot;, the state in which the fixing was slightly observed was indicated by &quot; &quot;, and the state in which the roll was remarkably dirty was indicated by &quot;

(Evaluation of adhesion with active material)

The adhesion with the active material was evaluated according to the following procedure.

(1) Artificial graphite having an average diameter of 9 占 퐉 and polyvinylidene chloride were mixed at a weight ratio of 1: 9 and dispersed in solvent N-methyl-2-pyrrolidone.

(2) The active material is applied to the surface of the copper foil.

(3) The copper foil coated with the active material is heated in a drier at 90 占 폚 for 30 minutes. At this time, the silane coupling agent hardly reacts with the copper surface due to the dehydration reaction with the unreacted silane coupling agent because the OH group is not bonded to the copper surface.

(4) After drying, cut into 20 mm square and apply a load of 1.5 ton / m ㎡ × 20 seconds.

(5) A mark formed by cutting the sample with a cutter in a lattice shape is formed, a commercially available adhesive tape (Cellotape (registered trademark)) is attached, and a roller having a weight of 2 kg is placed and reciprocated once to press the adhesive tape.

(6) The adhesive tape was peeled off, and the surface image of the active material remained on the copper foil was introduced into the PC to distinguish the metallic luster portion of the copper surface from the black portion where the active material remained by binarization, and the residual ratio of the active material was calculated. The residual ratio was the average value of three samples. , &Quot;? &Quot;, &quot;? &Quot;, &quot;? &Quot;, and &quot; The above was called "◎ ◎".

(Heat resistance evaluation)

The surface-treated copper foil was cut into a size of 20 cm x 20 cm, and then the copper foil cut sample was put into an oven heated to 300 캜. After 15 seconds passed, the copper foil sample was taken out of the oven to evaluate the oxidative discoloration degree of the surface treatment. , &Quot;? &Quot;, &quot;? &Quot;, &quot; C &quot;, and &quot; x &quot;

[Table 1-1]

[Table 1-2]

(Evaluation results)

In all of Examples 1 to 14, particle drop evaluation was good, adhesion with active material was good, and heat resistance was good.

In Comparative Example 1, since the secondary particle layer was not provided, the 10-point average roughness (Rz) and the arithmetic mean roughness (Ra) deviated from a predetermined range, and therefore, both the dropout evaluation and the adhesion were all poor. Further, since the secondary particle layer was not formed and no coating was provided, the heat resistance was also poor.

In Comparative Example 2, since the primary particle layer was not provided, the 10-point average roughness (Rz) deviated from the predetermined range, and therefore, the dropout evaluation and adhesion were all poor.

In Comparative Example 3, the primary particle layer and the secondary particle layer were provided. However, since the 10-point average roughness (Rz) and the arithmetic mean roughness (Ra) were out of the predetermined range, the evaluation of the adhesion remained at?.

In Comparative Example 4, the 10-point average roughness (Rz) was within a predetermined range, but the adhesion was insufficient because the primary particle layer and the secondary particle layer could not be formed sequentially by the rolling treatment alone. In addition, since no coated plating layer was provided, the heat resistance was poor.

In Comparative Example 5, the 10-point average roughness (Rz) was within the predetermined range. However, since the primary particle layer and the secondary particle layer can not be formed sequentially in this plating condition, the result of particle drop test is not preferable, did.

Claims (28)

Copper foil; And
A surface treatment layer on the surface side of at least one of the copper foils,
Wherein the surface treatment layer has a primary particle layer and a secondary particle layer,
Wherein the surface-treated surface has a 10-point average roughness (Rz) of 1.8 占 퐉 or more when measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994,
Copper foil for surface treatment of batteries. The method according to claim 1,
Wherein the surface treatment layer surface has an arithmetic mean roughness (Ra) of 0.26 탆 or more when measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994. The method according to claim 1,
Wherein the primary particle layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. 3. The method of claim 2,
Wherein the primary particle layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. The method according to claim 1,
Wherein the secondary particle layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. 3. The method of claim 2,
Wherein the secondary particle layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. The method of claim 3,
Wherein the secondary particle layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. 5. The method of claim 4,
Wherein the secondary particle layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn in a total surface area of 100 mu g / Copper foil. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer comprises at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P and Sn in a total amount of 10000 / / Copper foil. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer contains Ni and the adhesion amount of Ni is 100 占 퐂 / dm2 or more. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer contains Ni and the adhesion amount of Ni is 4500 占 퐂 / dm2 or less. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer contains Co and the amount of Co is 100 mu g / dm &lt; 2 &gt; or more. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer contains Co and the amount of Co deposited is 6000 占 퐂 / dm2 or less. 9. The method according to any one of claims 1 to 8,
Wherein the primary particle layer is made of Cu. 9. The method according to any one of claims 1 to 8,
Wherein the secondary particle layer is made of Cu, Co, and Ni. 9. The method according to any one of claims 1 to 8,
The surface treated copper foil for a battery satisfies any one or two or three or four or five or six or seven or eight of the following (17-1) to (17-8).
(17-1) The surface-treated layer contains at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, Include
(17-2) The surface treatment layer may contain at least one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, Include
(17-3) The surface treatment layer contains Ni and the adhesion amount of Ni is 100 占 퐂 / dm2 or more
(17-4) The surface treatment layer contains Ni and the adhesion amount of Ni is 4500 占 퐂 / dm2 or less
(17-5) The method according to (17-5), wherein the surface treatment layer contains Co and the adhesion amount of Co is 100 占 퐂 /
(17-6) the surface treatment layer contains Co, and the amount of deposited Co is 6000 占 퐂 / dm2 or less
(17-7) The primary particle layer is made of Cu
(17-8) The secondary particle layer is made of Cu, Co, Ni 9. The method according to any one of claims 1 to 8,
A surface-treated copper foil for a battery satisfying any one or two of the following (18-1) and (18-2).
(18-1) The 10-point average roughness (Rz) when the surface treatment layer surface is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 is as follows: 18-1-1 and 18 -1-2) &lt; / RTI &gt;
(18-1-1) The 10-point average roughness (Rz) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· It is more than 1.9㎛
· It is 2.0 μm or more
· It is more than 2.1㎛
(18-1-2) The 10-point average roughness (Rz) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· 10 μm or less
· 8 μm or less
· 5 μm or less
3.30 μm or less
· It is less than 3.20㎛
· Less than 3.10 μm
· Less than 3.05 μm
2.85 μm or less
(18-2) The arithmetic mean roughness (Ra) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm in accordance with JIS B0601 1994 is (18-2-1) and (18-2-1) 2-2) &lt; / RTI &gt;
(18-2-1) The arithmetic average roughness (Ra) when the surface of the surface treatment layer is measured using a laser microscope having a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· It is more than 0.28 μm
· It is more than 0.30 μm
· It is more than 0.32 μm
(18-2-2) Arithmetic mean roughness (Ra) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· It is 5.0 μm or less
· 4.5 μm or less
· It is 4.0 μm or less
· Less than 3.5 μm
· It is 3.0 μm or less
· Less than 2.5 μm
· Not more than 2.0 μm
· It is 1.5 μm or less
· It is not more than 1.0 μm
· 0.45 μm or less
· 0.44 μm or less
· 0.41 μm or less
· It is not more than 0.40 μm 18. The method of claim 17,
A surface-treated copper foil for a battery satisfying any one or two of the following (19-1) and (19-2).
(19-1) The 10-point average roughness (Rz) when the surface treatment layer surface is measured using a laser microscope with a wavelength of 405 nm in accordance with JIS B0601 1994 is (19-1-1) and -1-2) &lt; / RTI &gt;
(19-1-1) The 10-point average roughness (Rz) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· It is more than 1.9㎛
· It is 2.0 μm or more
· It is more than 2.1㎛
(19-1-2) The 10-point average roughness (Rz) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· 10 μm or less
· 8 μm or less
· 5 μm or less
3.30 μm or less
· It is less than 3.20㎛
· Less than 3.10 μm
· Less than 3.05 μm
2.85 μm or less
(19-2) The arithmetic mean roughness (Ra) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm in accordance with JIS B0601 1994 is (19-2-1) and (19-2-1) 2-2) &lt; / RTI &gt;
(19-2-1) The arithmetic mean roughness (Ra) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· It is more than 0.28 μm
· It is more than 0.30 μm
· It is more than 0.32 μm
(19-2-2) Arithmetic mean roughness (Ra) when the surface of the surface treatment layer is measured using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 satisfies any one of the following
· It is 5.0 μm or less
· 4.5 μm or less
· It is 4.0 μm or less
· Less than 3.5 μm
· It is 3.0 μm or less
· Less than 2.5 μm
· Not more than 2.0 μm
· It is 1.5 μm or less
· It is not more than 1.0 μm
· 0.45 μm or less
· 0.44 μm or less
· 0.41 μm or less
· It is not more than 0.40 μm 9. The method according to any one of claims 1 to 8,
Wherein the copper foil is at least one selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, 5 mass ppm or more and 0.3 mass% or less. 9. The method according to any one of claims 1 to 8,
Wherein the copper foil is at least one selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, 5 mass ppm or more and 300 mass ppm or less. 9. The method according to any one of claims 1 to 8,
Wherein the copper foil is at least one selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, A surface-treated copper foil for a battery comprising 301 mass ppm or more and 0.3 mass% or less. 9. The method according to any one of claims 1 to 8,
Wherein the surface treatment layer further comprises at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment layer, a plating layer and a resin layer on the secondary particle layer. 9. The method according to any one of claims 1 to 8,
A surface - treated copper foil for a secondary battery. 9. The method according to any one of claims 1 to 8,
Copper foil for surface treatment of batteries for secondary batteries. 9. A current collector having a surface-treated copper foil for a battery according to any one of claims 1 to 8. 9. An electrode having a surface-treated copper foil for a battery according to any one of claims 1 to 8. A battery having any one of the following (28-1) to (28-3).
(28-1) The surface-treated copper foil for a battery according to any one of claims 1 to 8,
(28-2) A current collector having a surface-treated copper foil for a battery according to any one of claims 1 to 8,
(28-3) An electrode having a surface-treated copper foil for a battery according to any one of claims 1 to 8.

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