Copper foil for current collector of lithium secondary battery with improved wrinkle characteristics

Abstract

A copper foil for a current collector of a lithium secondary battery has a crystalline structure, in which a ratio of the sum of texture coefficients of a (111) surface and a (200) surface to the total sum of texture coefficients of the (111), (200) and (220) surfaces is 60 to 85%, a ratio of the texture coefficient of the (111) surface to the total sum of texture coefficients of the (111), (200) and (220) is 18 to 38%, a ratio of the texture coefficient of the (200) surface thereto is 28 to 62%, and a ratio of the texture coefficient of the (220) surface thereto is 15 to 40%. The copper foil has surface roughness (Rz-JIS) of 2 mum or less, weight deviation of 3% or less, tensile strength of 30 to 40 kgf/mm2, elongation of 3 to 20%, and thickness of 1 to 35 mum.

Claims

1. A wrinkle-free copper foil for a current collector of a lithium secondary battery, wherein, in a crystalline structure, a ratio of a sum of texture coefficients of a (111) surface and a (200) surface to a total sum of texture coefficients of the (111) surface, the (200) surface and a (220) surface is 60 to 85%, a ratio of a texture coefficient of the (111) surface to the total sum of texture coefficients of the (111) surface, the (200) surface and the (220) surface is 18 to 38%, a ratio of the texture coefficient of the (200) surface to the total sum of texture coefficients of the (111) surface, the (200) surface and the (220) surface is 28 to 62%, and a ratio of the texture coefficient of the (220) surface to the total sum of texture coefficients of the (111) surface, the (200) surface and the (220) surface is 15 to 40%, wherein the texture coefficient satisfies the following equation: $\mathrm{TC}\left(\mathrm{hkl}\right)=\frac{\frac{I\left(\mathrm{hkl}\right)}{I_0\left(\mathrm{hkl}\right)}}{\frac{1}{n}\frac{I\left(\mathrm{hkl}\right)}{I_0\left(\mathrm{hkl}\right)}}$ where TC(hkl) represents a texture coefficient of a (hkl) surface, I(hkl) represents a measured diffraction intensity with respect to the (hkl) surface, and I.sub.0(hkl) represents a standard diffraction intensity of the (hkl) surface obtainable from ASTM (American Society of Testing Materials) standard powder-shaped diffraction data, wherein the wrinkle-free copper foil has a surface roughness (R.sub.z-JIS) of 2 m or less, wherein the wrinkle-free copper foil has a weight deviation of 3% or less, wherein the wrinkle-free copper foil has a tensile strength of 30 to 40 kgf/mm.sup.2, wherein the wrinkle-free copper foil has an elongation of 3 to 20%, wherein the wrinkle-free copper foil has a thickness of 1 to 35 m, and wherein the wrinkle-free copper foil is treated to prevent corrosion.

2. The wrinkle-free copper foil according to claim 1, wherein the wrinkle-free copper foil is surface-chromated to prevent corrosion.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Other objects and aspects of the present invention will become apparent from the following description of embodiments with reference to the accompanying drawing in which:

(2) FIG. 1 is a photograph showing that a wrinkle is generated at a conventional copper foil for a current collector of a lithium secondary battery; and

(3) FIG. 2 is a graph showing a result of X-ray diffraction (XRD) to calculate a texture coefficient of a copper foil for a current collector of a lithium secondary battery according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(4) Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Therefore, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.

(5) A copper foil for a current collector of a lithium secondary battery according to the present invention gives surface characteristics in which factors such as crystal structure, surface roughness, weight deviation, tensile strength and elongation are optimized not to generate a wrinkle.

(6) Preferably, the copper foil for a current collector of a lithium secondary battery according to the present invention is made by adding a small amount of organic additives to a copper sulfate solution containing copper sulfate, sulfuric acid and chlorine. Here, the additive may be a sulfonate-based additive containing sulfide as a brightener to polish a plating surface and obtain a fine plating layer, gelatin having a low molecular weight of 1,000 to 100,000 as a leveler added to obtain a low roughness copper foil, or a cellulose-based additive serving as a suppressor to realize a stable low roughness. As the process condition, copper is electrodeposited on a drum surface of a foil making machine with a current density of 30 to 80 ASD (A/dm.sup.2) at a temperature of 30 to 60 C., and the surface of the copper foil is chromated to prevent corrosion.

(7) A crystalline structure of the copper foil should satisfies a condition that a ratio of the sum of texture coefficients of the (111) surface and the (200) surface, to the total sum of texture coefficients of the (111) surface, the (200) surface and the (220) surface, is 60 to 85%. Also, a ratio of the texture coefficient of the (111) surface to the total sum of the texture coefficients of the (111) surface, the (200) surface and the (220) surface should be 18 to 38%, a ratio of the texture coefficient of the (200) surface thereto should be 28 to 62%, and a ratio of the texture coefficient of the (220) surface thereto should be 15 to 40%. Such a crystalline structure may be obtained by controlling additives or plating conditions during an electroplating process for making a copper foil. In detail, the plating solution for obtaining the crystalline structure basically includes a copper sulfate plating solution having copper sulfate, sulfuric acid and chlorine, to which at least two kinds of organic additives selected from the following group are added in the range of 1 to 50 ppm, respectively. The organic additive includes a gelatin-based compound with a molecular weight of 1,000 to 100,000 or a cellulose-based compound in addition to a mercapto compound. As the plating conditions to obtain the crystalline structure, copper is electrodeposited onto a drum surface of a foil making machine with a current density of 30 to 80 ASD at a temperature of 30 to 60 C. to make an original foil, and a nodule is formed thereat as necessary. After that, the surface of the copper foil is finally chromated to prevent corrosion.

(8) If the texture coefficients are not within the above ranges, many wrinkles are created in a width direction of the copper foil, and accordingly the adhesion of active material to the surface of the copper foil may be deteriorated when the active material is coated. Here, the texture coefficient (TC) is determined by applying the X-ray diffraction (XRD) to obtain a diffraction intensity peak of each crystal surface as shown in FIG. 2 and then comparing the diffraction intensity peak with a criterion peak to convert it within the range defined by the following equation 1. In the equation 1. I(hkl) represents a measured diffraction intensity with respect to the (hkl) surface, and I.sub.0(hkl) represents a standard diffraction intensity of an ASTM (American Society of Testing Materials) standard powder-shaped diffraction data.

(9) $\begin{array}{cc}\mathrm{TC}\left(\mathrm{hkl}\right)\frac{\frac{I\left(\mathrm{hkl}\right)}{I_0\left(\mathrm{hkl}\right)}}{\frac{1}{n}\frac{I\left(\mathrm{hkl}\right)}{I_0\left(\mathrm{hkl}\right)}}& \mathrm{Equation}1\end{array}$

(10) Surface roughness (R.sub.z) of the copper foil should be 2 m or less, based on JIS (Japanese Industrial Standards). In case the surface roughness (R.sub.z) exceeds 2 m, the surface is irregular, so a short circuit may occur during a charging or discharging process. In addition, the coating state of the anode active material becomes irregular.

(11) The weight deviation of the copper foil should be 3% or less. If the weight deviation exceeds 3%, property deviations occur at the surface of the copper foil, which may increase the number of wrinkles and make properties of the current collector irregular. Here, the weight deviation is obtained by cutting a copper foil by an area of 5 cm5 cm to make a test piece, measuring weight of the test piece and converting the weight into a weight of the copper foil per a unit area, cutting the test piece along a width direction of the copper foil, repeating the above processes to measure weights of copper foils of every test piece, and then calculating a standard deviation. At this time, the copper foil is preferably an electrodeposited copper foil that is surface-chromated for the prevention of corrosion.

(12) In addition, the copper foil should satisfy the following conditions: a tensile strength of 30 to 40 kgf/mm.sup.2, an elongation of 3 to 20%, and a thickness of 1 to 35 m. Out of the above ranges, the properties of the copper foil are deviated to increase the number of wrinkles, and the properties of the current collector become irregular.

(13) The following table 1 shows measurement results of wrinkle characteristics of the copper foils for a current collector of a lithium secondary battery according to examples 1 to 7 of the present invention and comparative examples 1 to 9. In the table 1, the tensile strength was measured by using a UTM (Universal Testing Machine), and at this time the gauge length was set to 5 cm.

(14) TABLE-US-00001 TABLE 1 Examples Comparative examples 1 2 3 4 5 6 7 1 2 3 4 5 6 7 8 9 Copper foil Electrodeposited copper foil Thickness of 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 copper foil [m] (111) + (200) 76 62 83 70 72 81 66 64 73 62 83 87 57 80 75 76 ratio [%] (111) ratio 26 31 32 20 35 22 36 16 41 37 19 34 26 30 23 25 [%] (200) ratio 50 31 51 50 36 59 30 48 32 25 64 53 31 49 51 50 [%] (220) ratio 24 38 17 30 29 19 34 36 27 38 17 13 43 21 26 25 [%] Tensile 32.2 33.7 345 32.6 32.1 37.2 33.1 36.8 33.2 31.4 37.1 33.1 32.4 27.4 41.5 31.8 strength [kg/mm.sup.2] Weight 0.4 0.7 0.8 1.6 0.4 2.6 1.2 0.5 0.9 0.5 0.9 0.7 0.8 0.6 0.9 3.4 deviation [%] Number of 0 0 0 0 0 0 0 2 3 3 4 2 3 2 2 5 wrinkles [ea]

(15) Seeing the table 1, it would be understood that the copper foils according to the examples 1 to 7 of the present invention satisfy all conditions of the texture coefficient ratio, the tensile strength, the weight deviation and the copper foil thickness, so no wrinkle occurs. Meanwhile, it would be also found that the copper foils according to the comparative examples 1 to 9 have inappropriate characteristics as a current collector of a lithium secondary battery since a lot of winkles occur.

(16) The copper foil for a current collector of a lithium secondary battery according to the present invention may have an improved wrinkle characteristic in comparison to conventional cases even if it satisfies only the condition of texture coefficient ratio. However, if other conditions such as tensile strength and weight deviation are out of the above numerical ranges, bad influences are given to the improved characteristics, thereby deteriorating the wrinkle characteristic. Thus, it is most preferable to satisfy all conditions of the texture coefficient ratio, the tensile strength, the weight deviation and the copper foil thickness.

(17) The copper foil for a current collector of a lithium secondary battery according to the present invention has excellent peel strength since a sufficient adhesive force is ensured when the copper foil is contacted with anode active material such as carbon-based slurry, so it is possible to realize a lithium secondary battery that may stably keep a battery capacity.

(18) The present invention has been described in detail. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.