Art
[1]
This application claims priority based on Korea Patent Application No. 10-2016-0090985, filed on July 18, 2016 The present invention is directed to a method of producing whole, and it houses an electrochemical device. In addition, the present invention is the flexibility made according to the method is for an improved current collector and electrode.
[2]
BACKGROUND
[3]
In recent years the technology development of the electronic industry mobile phones, game consoles, PMP (Portable Multimedia Player), as well as MP3 (MPEG Audio Layer-3) player, smart phone, smart pad, e-books, watch-type phones, portable medical devices that attach to the body the market for various portable electronic devices, such as large and growing. Grows above the market for portable electronic equipment such, there is also growing demand for battery suitable for driving these portable electronic devices. In particular, for ease of use of the portable electronic device, the demand for flexibility of the battery is becoming gradually increase. There is also becoming increasingly growing demand for flexibility of the battery to be easily charged into the battery in a small space of these portable electronic devices.
[4]
Typically the electrode is prepared by drying after coating the slurry for forming an electrode on the surface of the metal thin film such as aluminum or copper. However, the production by such method is difficult to apply the electrode to the flexible type (flexible type), or double type Ben (bendable type) cells since the flexibility of the metal thin film limited. Figure 3 is a schematic illustration of an electrode made in accordance with the prior art conventional method. Typically by coating and drying the electrode active material layer slurry to the whole of the metallic thin film to produce an electrode house. Prepared according to the conventional manufacturing method has a problem arises that the electrode is damaged when the electrode active material layer which forms the deformation of the flexible electrode.
[5]
Korea Patent Publication 10-2012-0131779 discloses an electrode active material is a penetration portion in the pores of the membrane separator and the electrodes are integrated into the cell. However, there is a limit to the manufacture of battery of the flexible type, since such a metallic thin film of this low flexibility in the current collector used in the case.
[6]
Detailed Description of the Invention
SUMMARY
[7]
Thus, the invention serves to solve the above-described problem, the object of the present invention is to provide an electrode covering the entire flexible-type cell or a van flexibility that can be used in the double-cell type improved collector and the current collector. Other objects and advantages of the other invention will be readily appreciated that this can be realized by the means as claimed and combinations thereof.
[8]
Problem solving means
[9]
The invention The present invention provides an electrode made by the method and the method for manufacturing an electrode to solve the above technical problem.
[10]
A first aspect of the present invention comprises the steps of heating a, the method comprising: (S10) for collecting metal thin film as for the method for producing the electrode jejoeul; (S20) step of stretching said heated metallic foil; And a; and (S30) step of cooling said heated metal thin film.
[11]
A second aspect of the present invention may be the first side, to the metal as a thin film metal layer for the current collector, including copper and / or aluminum.
[12]
A third aspect of the present invention may be the first or the second aspect, heating of the (S10) step is carried out under vacuum conditions or in an inert gas-substituted atmosphere to prevent oxidation of the metal thin film.
[13]
A method according to any one of the fourth aspect of the first to third aspect of the invention, the (S20) step is to stretch a thin metal film as an elongation of 2% to 25%.
[14]
A fifth aspect of the present invention, the first aspect to the fourth method according to any one of the aspects, further includes a to (S31) to (S33) the step (S30) steps: (S31) the temperature of the metal thin film a (S20) step is heated over a temperature cooled to -100 ~ -150 ℃ in; (S32) step of applying the electrode active material layer-forming slurry was heated to 60 ℃ to 100 ℃ on the surface of the metal foil; And (S33) drying the slurry for forming the coated electrode coating.
[15]
The sixth aspect of the present invention is the fifth aspect in the (S33) and at the same time or step (S33) the cooling of the electrode after performance of the step to perform more.
[16]
A method according to any of the seventh aspect is the first aspect to the fourth aspect of the invention one, to the (S30) step further comprises the (S34) to (S35) steps: (S34) the extended metal thin film applying the slurry for forming electrode active material layer on the surface; And (S35) drying the slurry for forming the coated electrode coating.
[17]
An eighth aspect of the present invention is according to the seventh aspect, the (S34) The slurry for forming an electrode active material layer in the step is at room temperature (25 ℃) +/- 10 ℃.
[18]
A method according to any of the ninth aspect is the first to fourth aspects of the invention one, to to the above (S30) steps (S36) to further comprise a (S38) steps: (S36) the temperature of the metal thin film surface a step of cooling to room temperature (25 ℃); (S37) applying the slurry for forming electrode active material layer on the surface of the metal thin film of the cooling; And (S38) drying the slurry for forming the coated electrode coating.
[19]
A tenth aspect of the invention according to the ninth aspect, the (S38) step is carried out by means of blowing a cooling and / or cold air cooling, the metallic thin film at a rate of 5 ℃ / min to 20 ℃ / min It will be cooled.
[20]
The eleventh aspect of the present invention is the first to claim 10 according to any one of the aspect, the metal thin film has a thickness of 5 ㎛ to 30 ㎛.
[21]
A method according to any one of the 12th aspect, the first to eleventh aspects of the invention, (S40) is further comprising the step of forming the heat-resistant layer comprising inorganic particles and a binder polymer on the surface of the electrode.
[22]
In addition, the 13th aspect includes the electrode active material layer formed on a surface of a collector and the current collector, the current collector has a wrinkle generated spontaneously in accordance with the heat expansion and cooling shrinkage the electrode active material layer of the present invention will have a surface pattern corresponding to the wrinkles of the current collector, to the first side to claim 12 prepared according to the either side of the side surfaces.
[23]
In addition, the 14th aspect of the present invention includes a membrane interposed between the cathode, the anode and the cathode and the anode, the cathode and / or anode here is prepared according to the either side of the first aspect to twelfth aspect to the electrode.
[24]
Effects of the Invention
[25]
Collector and the electrode according to the present invention there is a wrinkle caused by the thermal expansion and cooling shrinkage in the current collector is formed is effective, the flexibility of the electrode is improved. In addition, when using such an electrode for manufacturing a curved-type cell so modified form cracks decrease the electrode active material layer even by the low desorption of the electrode active material has the effect that the moldability of the electrode active material layer to improve.
[26]
Brief Description of the Drawings
[27]
Intended to illustrate the following figures attached to the specification are exemplary of the invention, the components which serve to further understand the spirit of the invention and together with the description of which will be described later invention, the details of this invention is described in such figures be construed as limited only is not.
[28]
[29]
1 is a process flow diagram showing the schematic view showing the electrode manufacturing process according to an embodiment of the invention.
[30]
Figure 2 shows the schematic illustrates the wrinkle formation mechanism of the collector according to the specific exemplary embodiments of the present invention.
[31]
Figure 3 shows the schematic illustrates the conventional manufacturing method of the electrode.
[32]
Figure 4 shows the crack and desorption phenomenon electrode of Example 1-1.
[33]
Figure 5 is a process flow diagram illustrating one embodiment of the electrode manufacturing process according to the invention for each step.
[34]
Mode for the Invention
[35]
Hereinafter, a detailed description of a structure and operation according to the present invention with reference to the accompanying drawings. The specification and are should not be construed as limited to the terms or general and dictionary meanings used in the claims, the inventor can adequately define terms to describe his own invention in the best way be based on the principle that the interpreted based on the meanings and concepts corresponding to technical aspects of the present invention. Accordingly, the configuration shown in the examples and figures disclosed herein are merely nothing but the embodiment most preferred embodiment of the invention, a not intended to limit the scope of the present invention, that can be made thereto according to the present application point there can be various equivalents and modifications.
[36]
[37]
The present invention relates to an improved electrode flexibility. The electrode is a whole is formed the wrinkles caused by the expansion and contraction of the metal on the surface of the metal current collector and an electrode active material layer formed on at least one side surface of a house, and the metal of the metal home. In the present invention, the electrode active material layer may have recesses and protrusions in accordance with the folds formed in the current collector.
[38]
[39]
In the present invention, the electrode is acceptable electrochemical device. In the present invention, the electrochemical device includes any devices in which electrochemical reactions, capacitor (capacitor), such as all kinds of primary batteries, secondary batteries, fuel cells, solar cells or a super capacitor element as a specific example and the like. In particular, a lithium secondary battery including the secondary battery of the lithium metal secondary battery, lithium ion secondary batteries, lithium polymer secondary batteries or lithium ion polymer secondary battery are preferred.
[40]
[41]
The present invention is also characterized in that as for the process for preparing the flexibility is improved electrode, the method comprising cooling by heat expansion and contraction of the metal thin film used as a current collector to form a crease on the surface of the current collector.
[42]
[43]
Figure 1 shows the schematic illustrates a method of manufacturing an electrode according to an embodiment of the invention. Less than or equal to the reference even when the one to be described the present invention in more detail.
[44]
[45]
First, prepare the metal film for the whole house. In a specific exemplary embodiment of the invention, the current collector may be a positive electrode collector or negative electrode collector. The current collector as long as it is stable without causing chemical changes in the electric cell is not particularly limited. If the whole house of corrosion, depending on the cell cycle is repeated it can not exert sufficient current collection capacity, thereby shortening the battery life. The current collector with will a stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel the surface of carbon, nickel, titanium, in the treatment with the surface, the aluminum-surface-treated with a cadmium alloy, a conductive material, a non-conductive may be used is manufactured by using the polymer, or a conductive polymer.
[46]
[47]
In a specific exemplary embodiment of the invention, the metal thin film is an anode current collector include copper, and is suitably for, the entire positive electrode collector include aluminum for suitable.
[48]
The metal thin film has a tensile strength of 20kgf / mm 2 or higher, or kgf 30 / mm 2 is preferably. In addition, the metallic thin film will have an elongation of 2% to 25% by weight is the 5㎛ to 30㎛. For example, when aluminum is used, the thin film thereof has a tensile strength 20kgf / mm 2 is preferably not less than. Then, the elongation of the aluminum thin film is preferably 2% to 10%, or 2% to 5%, or 2% to 4%, and the thickness will 10㎛ to 20㎛.
[49]
In the present invention, in the case of using a copper thin film thereof it has a tensile strength of 30kgf / mm 2 is preferably not less than. Then, the elongation of the copper foil is preferably from 2% to 10%, or 2% to 5%, or 2% to 4%, and the thickness will 10㎛ to 20㎛.
[50]
[51]
Herein elongation shows a value obtained by dividing the gage length to the original gauge length of the car to the first gauge length after stretched as on the gauge length as a percentage. Will display the two different points on the surface of the gauge length thin metal film according to the present invention, it means the distance between the two points gauge length.
[52]
[53]
The above-mentioned range will described example a copper film or an aluminum thin film for example, the thickness of the collector The thicker be an appropriate thickness according to the material and the tensile strength becomes small as opposed elongation is larger, because consideration of the flexibility, the side of the wrinkle formation and the electrode It can be set.
[54]
[55]
When the metal thin film is prepared, and heat the metal thin film to the next (S10). The heating in the specific exemplary embodiment of the present invention can be carried out through a heating apparatus such as a furnace, an oven. In addition, the heating apparatus can be equipped with a temperature control device. In the present step to the metal thin film has a surface temperature of more than 200 ℃ under 300 ℃ of the metal thin film can be heated to more than 400 ℃ or up to 500 ℃ below. Is the ductility of the metal of the metal thin film increases due to the heating can be stretched in the step which will be described later.
[56]
[57]
In a specific exemplary embodiment of the invention the heating is evacuated to the heating device, or may be performed in an inert gas-substituted atmosphere to prevent oxidation of the metal thin film when heat-treated. By doing this it is possible to suppress the reduction of the metal thin film due to oxygen during heat treatment.
[58]
[59]
And then stretching the heated metal thin film (S20). In the present invention, the stretching is carried out to maximize the wrinkles caused by the cooling shrinkage of the metal thin film to be described later. The stretching may be a uniaxial stretching or biaxial stretching according to a specific exemplary embodiment of the invention, preferably is a biaxially stretched. Stretching ratio is different depending on the material of the metal thin film, it is 2% to 25%, as described above.
[60]
[61]
Next, by cooling the metal thin film to form a crease in the metal thin film surface (S30). Cooling method of the metal thin film according to the present invention, that is a method of introducing the wrinkles on the metal thin film can be selected any one of the methods described below 1-3.
[62]
[63]
[Cooling method 1]
[64]
According to the specific exemplary embodiments of the present invention, by forming an electrode active material layer on the surface of the extended metallic thin film to produce an electrode. The electrode active material layer can be formed by coating the slurry on a surface of the thin metal film after the stretching for preparing a slurry for forming electrode active material layer and dried.
[65]
[66]
In the present invention, the slurry for forming the electrode active material layer is prepared by dispersing the electrode active material and a binder resin, conductive in a suitable solvent, in addition to the above components it is appropriate additives may further be included. In a specific exemplary embodiment of the present invention, the electrode slurry can be heated to the range of 60 ℃ to 120 ℃. When the temperature of the slurry satisfies the above range does not cause the rapid shrinkage when applied to the heating and stretching a thin metal film, the deterioration of the electrode active material it can be prevented.
[67]
[68]
In a specific exemplary embodiment of the present invention, the temperature of the metal thin film may be cooled to an appropriate temperature before the slurry is applied after the stretching. In one embodiment of the invention, the cooling is cooled to -100 ~ -150 ℃ the heating temperature compared. For example, the temperature of the metal thin film can be adjusted to a temperature of about 100 ℃ ~ 200 ℃ or about 100 ℃ ~ 150 ℃.
[69]
[70]
Next, by drying the slurry. The drying is preferably performed by a method such as natural drying, blast drying, hot air drying, cold drying, heat drying. In a specific exemplary embodiment of the invention, by cooling the electrode at the same time with the drying of the electrode slurry, or drying the electrode slurry may promote contraction of the current collector with a surface wrinkle formation. The cooling is preferably carried out at a cooling rate of 5 ℃ / min to 10 ℃ / min in terms of the surface temperature of the electrode. In addition, the drying and / or cooling can be carried out until the electrode surface the temperature is room temperature (25 ℃).
[71]
[72]
Depending on the cooling shrinkage of metal thin films that were expanded due to heating, and wrinkles are formed in accordance with the case retracted over the entire surface of the house. Further, in accordance with the folds to the current collector formed of shrinkage it is formed concave and convex corresponding to the wrinkles of the current collector to the electrode active material layer. According to house, and the whole of wrinkles are formed due to thermal expansion / contraction cooling, the electrode active material layer has a surface roughness corresponding to the wrinkle contour of the current collector.
[73]
[74]
The accompanying Figure 1 illustrates to an electrode fabrication process in accordance with one embodiment of the present invention illustrates that performed by a continuous process. It may be carried out in a heating oven 100 in a sequential heating and stretching of the copper foil. In addition, the stretching of the metal thin film is made through a rotating roller of a continuous process. The control rotation direction of the copper film transport roller as shown in Figure 1, for example, it is possible to draw both the direction of rotation of the rollers to control each other in the opposite direction (A direction), the metal thin film arranged in a sequential order.
[75]
[76]
Figure 2 shows the schematic view showing the mechanism that folds the metal thin film is used as the current collector is formed in the concrete exemplary embodiment according to the present invention. According to this air flow in the drying apparatus 200 (e.g. cool air) while heating and stretching the metal thin film is cooled by the wrinkles are formed on the metal thin film, whereby the electrode active material layer is also formed in the form corresponding to the wrinkles of the current collector do. Of the house wrinkle of the total it will schematically shown for a better understanding of the invention, in practice the shape of the wrinkles formed on the current collector is the result of the expansion and contraction of the material depend on the nature of the material used in its amorphous shown in Figure 2, have a random pattern.
[77]
[78]
[Cooling method 2]
[79]
In one embodiment of the invention, the cooling can be performed by applying an electrode slurry to the surface of the metal thin film is heated and stretched. In the present invention, the electrode active material, by dispersing a conductive agent and a binder resin in an appropriate solvent to prepare a slurry for forming the electrode active material layer. The slurry for forming an electrode active material layer may further contain appropriate additives in addition to the above components. Here, in a state maintained the temperature of the slurry to room temperature (25 ℃) +/- 10 ℃ then applied to the surface of the metal thin film to induce shrinkage and cooling of the entire home.
[80]
[81]
Depending on the cooling shrinkage of metal thin films that were expanded due to heating, and wrinkles are formed in accordance with the case retracted over the entire surface of the house. Further, in accordance with the folds to the current collector formed of shrinkage it is formed concave and convex corresponding to the wrinkles of the current collector to the electrode active material layer. In this case, it is not necessary for heating the slurry, or to use a separate cooling device has a high process efficiency advantages.
[82]
[83]
Next, by drying the slurry. The drying may select natural drying, blast drying, hot air drying, at least one of methods, such as cold air drying, heat drying to be performed in a proper manner and is not limited to any one particular method. In one embodiment of the invention, wrinkling of the collector surface can be formed through the step of drying, as well as the cooling step.
[84]
[85]
[Cooling Method 3]
[86]
In one embodiment of the invention, it is possible to form the electrode active material layer on the surface of the cooled thin metal film and then cooling the metal thin film. First by cooling the heated and stretched in the metal thin film (S20) to obtain a metal thin film formed on the wrinkled surface and uses it as the current collector. In one embodiment of the invention, the cooling of the metal thin film can be carried out by selecting one or more appropriately, etc. natural cooling, cooling air flow, the cold air cooling. It can be preferably used a method of blowing a cooling and / or cold air cooling. In this case it is preferred that the side of the metal thin film surface temperature at a cooling rate of 5 ℃ / min or more, and, less than 20 ℃ / min or less, or 10 ℃ / min to perform the cooling. Also, the cooling may be carried out until the surface temperature of the metal thin film to be a room temperature (25 ℃). Less than the above-described cooling rate, it does not generate a lot of surface wrinkles.
[87]
[88]
After obtaining the current collector in accordance with the method described above the following it can be formed by coating and drying the slurry for forming electrode active material layer on the surface of the current collector. The slurry for forming the electrode active material layer is prepared by dispersing the electrode active material and a binder resin, conductive in a suitable solvent, and in addition to the above components is suitable additives may further be included.
[89]
[90]
The slurry is then dried. The drying is preferably carried out by appropriately selecting and combining natural drying, blow drying, cold drying, hot air drying, heating method for drying including one or more of the methods.
[91]
[92]
The electrode for an electrochemical device was obtained in accordance with the aforementioned method. The electrode produced by the method according to the invention comprises an electrode active material layer formed on a surface of a collector and the current collector. In addition, the current collector has a wrinkle generated spontaneously in accordance with the heat expansion and cooling contraction, the electrode active material layer is characterized by having a surface pattern corresponding to the wrinkles of the current collector.
[93]
[94]
Thus, the present invention is the naturally-occurring wrinkles in the current collector is formed wrinkles shape corresponding electrode active material layer, because the electrode to the curved electrode active material by the deformation of the electrodes when the battery or bending is applied to the flexible battery that is formed according to the there is a problem that a crack occurs in the electrode active material layer or desorption can be reduced.
[95]
[96]
Further, in the electrode manufacturing process according to the invention can form an adequate pattern by heating and cooling the current collector without having to perform a separate patterning process in order to introduce a pattern in a current collector or electrode coating process efficiency is very high.
[97]
[98]
Conventionally, if the introduction of the pattern on the electrode after forming the electrode active material layer, this method were applied to a method for removing a portion of the electrode coating or rolling the electrode active material layer to a patterned member is a lot consumption of the electrode active material rolled It was likely to cause deterioration in the electrode process. However, in the electrode manufacturing process according to the invention it has the effect that such process removing the drawbacks.
[99]
[100]
Further, in one specific embodiment of the invention, it is possible to further perform the step of forming a heat-resistant layer to a surface of the electrode.
[101]
[102]
Prepared by the method described above the electrode it may not be in close contact with the separation membrane by the unevenness of the surface. Therefore, the heat-resistant layer is a flat surface on the electrode may be further formed in order to prevent this. In a specific exemplary embodiment of the present invention, the heat-resistant layer may comprise a plurality of inorganic particles and a binder resin. The heat-resistant layer as the inorganic binder particles is that the binder and / or surface integrated to the binder resin in the intermediate layer wherein the coating layer has a porous structure due to interstitial volumes (interstitial volume) between the inorganic particles. By forming such heat resistant layer can be achieved which is capable of promoting the flattening of the electrode surface as it is possible to improve the heat resistance of the polymer membrane, which will be described later.
[103]
[104]
The present invention provides an electrode assembly including an electrode prepared according to the method described above. In the present invention, the electrode assembly refers to a laminated structure consisting of a cathode / separator / cathode are sequentially stacked. The electrode assembly is a cathode, a separator and a positive electrode containing one or more, respectively. The present invention also provides an electrochemical device such as a battery, a battery module and / or a battery pack including one or more of the electrode assembly.
[105]
[106]
In the present invention, the case where the electrode is the anode, the electrode is a positive electrode active material, for example, lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 as a layer compound and one or more transition metals, etc.) substituted compounds; Formula Li 1 + x Mn 2 - x O 4 (where, x is from 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 Li-Mn oxide and the like; Lithium copper oxide (Li 2 CuO 2 ); LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5, Cu 2 V 2 O 7 of vanadium oxide and the like; Formula LiNi 1 - x M x O 2 (where, the M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, x = 0.01 ~ 0.3 Im) Ni site type lithium nickel oxide which is represented by; Formula LiMn 2 - x M x O 2 (where, M = Co, Ni, Fe , Cr, and Zn, or Ta, x = 0.01 ~ 0.1 Im) or Li 2 Mn 3 MO 8 (where, M = Fe, Co, lithium manganese composite oxide represented by Ni, Cu or Zn); A portion of Li is substituted with alkaline earth metal ions formula LiMn 2 O 4 ; Disulfide compounds; Fe 2(MoO 4 ) 3 , LiNi x Mn 2 - x O 4 and the like can be used (0.01 ≤ x ≤ 0.6).
[107]
[108]
Furthermore, in the specific exemplary embodiment of the present invention, the negative electrode active material is, for example, natural graphite, artificial graphite, expanded graphite, carbon fiber, I carbon such as graphitizable carbon, carbon black, carbon nanotube, fullerene, activated carbon and graphite materials; Compound including lithium and a metal such as alloys capable of Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, Pd, Pt, Ti, and these elements; Metals and their compounds and composites of carbon and graphite materials; It includes lithium-containing nitrides and the like. In particular, and preferably the carbon-based material, Non-limiting examples, the carbon-based material may be at least one selected from the group consisting of graphite carbon, hard carbon and coke-based carbon.
[109]
[110]
In the present invention, the separation membrane is to serve as the ion conducting barrier that transmits ions while blocking electrical contact between the cathode and the anode. According to a specific exemplary embodiment of the invention the separator may include porous polymer substrate having a plurality of fine pores. A porous polymer substrate, for example, polyolefin, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, Opole polyphenylene oxide, polyphenylene sulfide, but the porous polymeric base material, such as a polymer resin formed of at least any one of polyethylene, such as naphthalene is not particularly limited here. Further, in the porous polymer substrate it can be used for both the non-woven fabric form in which integration of the filaments obtained by melt spinning the melt to form a film or sheet of a film-forming polymer resin, a polymer resin. Preferably the melt is / molding the polymer resin, a porous polymer substrate made of a sheet form.
[111]
[112]
Further, in addition to the battery device is not described herein, for example, be used are elements commonly used in the cell, particularly in a lithium secondary battery or the like for the field separator, the conductive material, a binder resin, a liquid electrolyte.
[113]
[114]
Next, it will be described in more detail by the herein in the Examples. However, the following examples are only intended to illustrate the invention, without being limited by the following examples, the contents of the present application.
[115]
[116]
1. Example
[117]
[118]
Examples 1-1 to 1-3
[119]
[120]
(1) Preparation of the collector
[121]
Thickness was prepared from about 20㎛ a copper thin film. The copper makmak is a tensile strength of approximately 30kgf / mm2, elongation was about 5%. Next it was heated until the surface of the copper thin film to be a specified temperature. It was then uniaxially stretching the heated copper film. The heating temperature for each test sample, the elongation is the same as the information gathered up to Table 1.
[122]
[123]
TABLE 1
The heating temperature Elongation
Examples 1-1 200℃ 5%
Example 1-2 300℃ 5%
Examples 1-3 400℃ 5%

[124]
[125]
(2) Preparation of the electrodes
[126]
Then the slurry for forming electrode active material layer on the surface of the current collector prepared in Preparation Example 1 was applied to a thickness of 90㎛. The slurry will ready to inject the artificial graphite, carbon black and PVdF in NMP and injection, 90 in the slurry with the artificial graphite, carbon black and PVdF has a weight ratio of: is mixed at a ratio of 6: 4. In addition, the slurry was prepared by heating to be 150 ℃. An electrode to cool air drying the slurry was prepared. The dried electrode was rolled in thickness of the active material layer such that the 55㎛. The cool air drying, the electrode surface temperature was carried out until a temperature of about 7 (25 ℃) at a cooling rate of ℃ / min.
[127]
[128]
[129]
Examples 2-1 to 1-2
[130]
[131]
(1) Preparation of the collector
[132]
Thickness was prepared from about 20㎛ a copper thin film. The copper makmak is a tensile strength of approximately 30kgf / mm2, elongation was about 5%.
[133]
After following the heating until the surface of the copper thin film to be a certain temperature is reached and the temperature was maintained at this temperature for about 5 seconds. It was then uniaxially stretching the heated copper film. Stylized and then stops the heating and cooling to room temperature (25 ℃) a copper thin film surface temperature was added to the cold air in the upper and lower direction of the stretched thin copper film, the cooling rate was about 7 ℃ / min. The heating temperature and elongation of each test sample are shown in Table 2 below.
[134]
[135]
TABLE 2
The heating temperature Elongation
Examples 2-1 200℃ 5%
Example 2-2 300℃ 5%

[136]
[137]
(2) Preparation of the electrodes
[138]
Artificial graphite, carbon black and PVdF was prepared electrode slurry is mixed with NMP. In the electrode slurry as artificial graphite, carbon black and PVdF has a weight ratio of 90: was mixed in a ratio of 6: 4. An electrode by coating the slurry to a thickness of 90㎛ on the surface of the copper thin film prepared by the above production example, dry air blowing was prepared. After the dried electrode was rolled in thickness of the active material layer such that the 55㎛.
[139]
[140]
2. Comparative Example
[141]
Thickness was prepared from about 20㎛ a copper thin film. The copper makmak is a tensile strength of approximately 30kgf / mm2, elongation was about 5%. Artificial graphite, carbon black and PVdF was prepared electrode slurry is mixed with NMP. In the electrode slurry as artificial graphite, carbon black and PVdF has a weight ratio of 90: was mixed in a ratio of 6: 4. Applying the slurry to 90㎛ thickness on the surface of the copper thin film prepared by the Preparation Example 1 and was prepared by air flow drying the electrode. The dried electrode was rolled in thickness of the electrode active material layer so that the 55㎛.
[142]
[143]
Experiment A.
[144]
In bar (bar) having a diameter of 1R (1mm radius) wrapped around the electrodes prepared in Examples 1 to 3 and Comparative Examples ryeoteumyeo bend the bar by 90 ° it was repeated 150 times. Examples 1 to 3dml if there after bending 70 times, but the elimination of cracks and / or the electrode active material occurs, when the comparative example, after repeating the bending 10 times occurred with a tally of the crack and the electrode active material.
[145]
[146]
B. The sheet resistance increases
[147]
The surface resistance around the bend for each of Examples and Comparative Examples were measured electrode. Next, close the electrode prepared in the above Examples and Comparative Examples in bar (bar) of the 15R (radius 15mm) diameter ryeoteumyeo bend the bar by 90 ° was repeated 1,500 times. The. After measured the sheet resistance of the electrode. The sheet resistance was measured using the 4-probe (probe) sheet resistance measuring equipment (CMT-SR2000N). According to this embodiment, the case or've found to have a sheet resistance of less than 110% the rate, the comparative example case, the sheet resistance increase rate is found to be 200%.
[148]
[149]
TABLE 3
Damage due to bending The sheet resistance increase
Example 1-1 Cracks and desorption occurs after the 70th 110%
1-2 125 times after cracking and desorption occurs 70%
1-3 Cracks and desorption occurs after 110 times 85%
2-1 80 times after cracking and desorption occurs 105%
2-2 Cracks and desorption occurs after 110 times 73%
Comparative Example 1-1 Cracks and desorption occurs after 10 200%
1-2 Cracks and desorption occurs after the 13th 203%

[150]
[151]
As described above, the present invention has been been described by exemplary embodiments and drawings, the invention is not limited thereto, under the teachings of the present invention by one of ordinary skill in the art various modifications and variations within the equivalent scope of the claims to be described are possible, of course.
[152]
[153]
Reference Numerals
[154]
10 current collectors (metal thin film), the electrode active material layer 20, the heating device 100, the drying apparatus 200, 300 the slurry applicator, conveying rollers 400, 500 drying apparatus

Claims
[Claim 1]
(S10) heating the current collector for a thin metal film; (S20) step of stretching said heated metallic foil; And (S30) step of cooling said heated metallic foil; Electrode production method comprising a.
[Claim 2]
The method of claim 1, wherein as said thin metal film is a metal thin film for the current collector, the electrode production method comprises a copper and / or aluminum.
[Claim 3]
The method of claim 1, wherein the electrode manufacturing method of the heating (S10) step is carried out under vacuum conditions or in an inert gas-substituted atmosphere to prevent oxidation of the metal thin film.
[Claim 4]
2. The method of claim 1, wherein (S20) step of the electrode manufacturing method of stretching a thin metal film to 102% to 125%.
[Claim 5]
2. The method of claim 1, wherein (S30) step is to (S31) of the electrode manufacturing method to further comprises a (S33) steps: (S31) against heating temperature in the temperature of the metal thin film (S20) - phase is cooled to 100 ~ -150 ℃; (S32) step of applying the electrode active material layer-forming slurry was heated to 60 ℃ to 100 ℃ on the surface of the metal foil; And (S33) drying the slurry for forming the coated electrode coating.
[Claim 6]
Method, the electrode manufacturing method above (S33) phase and which at the same time, or (S33) performing step further cooling of the electrode after performance of the claim 5.
[Claim 7]
2. The method of claim 1, wherein (S30) step is to (S34) is to further comprises a (S35) step, the electrode production method: (S34) applying the slurry for forming the extended electrode active material on a metal thin film layer the method comprising; And (S35) drying the slurry for forming the coated electrode coating.
[Claim 8]
Claim 7, wherein (S34) the slurry for forming electrode active material layer of step is prepared in like a normal temperature (25 ℃) +/- 10 ℃ on.
[Claim 9]
The method of claim 1, wherein the electrode production method in that the (S30) step further comprises the (S36) to (S38) steps: (S36) to cool to room temperature (25 ℃) the temperature of the metal thin film surface step; (S37) applying the slurry for forming electrode active material layer on the surface of the metal thin film of the cooling; And (S38) drying the slurry for forming the coated electrode coating.
[Claim 10]
10. The method of claim 9, wherein (S38) step is carried out by means of blowing a cooling and / or cold air cooling, the electrode manufacturing method of the metal thin film is cooled at a rate of 5 ℃ / min to 20 ℃ / min.
[Claim 11]
According to claim 1, wherein the metal thin film is a thickness of 5 to 30 ㎛ ㎛, electrode method.
[Claim 12]
According to claim 1, (S60) electrode method further comprising a step of forming a heat-resistant layer comprising inorganic particles and a binder polymer on the surface of the electrode.
[Claim 13]
The collector and comprises an electrode active material layer formed on the surface of the current collector, the current collector has a wrinkle generated spontaneously in accordance with the heat expansion and cooling shrinkage the electrode active material layer surface corresponding to the wrinkles of the current collector It will have the pattern of any one of claims 1 to 12 is manufactured according to any one of claims, wherein the electrode.
[Claim 14]
Which comprises a separator interposed between the cathode, anode and the cathode and the anode, the cathode and / or anode here is the electrode manufactured according to any one of claims 1 to 12, wherein the electrode assembly.