KR101675336B1 - Eletrod collector of fiber type for secondary battery and Manufacturing method thereof - Google Patents

Eletrod collector of fiber type for secondary battery and Manufacturing method thereof Download PDF

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KR101675336B1
KR101675336B1 KR1020150118680A KR20150118680A KR101675336B1 KR 101675336 B1 KR101675336 B1 KR 101675336B1 KR 1020150118680 A KR1020150118680 A KR 1020150118680A KR 20150118680 A KR20150118680 A KR 20150118680A KR 101675336 B1 KR101675336 B1 KR 101675336B1
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polyurethane
thin film
layer
film coating
coating layer
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KR1020150118680A
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Korean (ko)
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홍종윤
권오경
정원욱
김효정
이창민
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주식회사 비 에스 지
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/747—Woven material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y02E60/12—

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The present invention relates to a fiber-type electrode current collector for a secondary battery and a method of manufacturing the same, and more particularly, to an invention capable of providing a secondary battery for various wearable devices by introducing a fabric as a base layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a collector of a fibrous electrode for a secondary battery,

The present invention relates to a fiber-type electrode current collector for a secondary battery and a method of manufacturing the same, and more particularly, to a method of forming an electrode for a secondary battery using a fabric of a fiber material.

IT equipment that meets the convenience of living has evolved into a wearable device that can be mounted on a garment or body by rapidly advancing the miniaturization of the IT device due to the development of technology. However, the secondary battery, which is an indispensable element for operating the IT device, is manufactured based on a metal material so far and is heavy and deformable, and it is difficult to apply to a wearable device product family.

In recent years, in order to provide a secondary battery for use in a wearable device product, a technique has been studied in which a pattern is formed on a current collector of a secondary battery or a bending and / or a flexible is formed by forming a pore However, even if such a pattern is formed, not only the banding is limited but also the weight loss is limited.

In order to overcome such a problem, a secondary battery for a wearable device having excellent flexibility is being actively developed by applying electrical conductivity to a relatively light and flexible fiber material and applying it to a secondary battery.

Korea Patent Publication No. 2011-0108194 (published on October 10, 2011)

As a result, the inventors of the present invention have conducted research and development to be able to apply a collector of a fibrous electrode to a secondary battery. As a result, impurities are added in a plating process for producing a fibrous electrode current collector, In order to solve this problem, a fiber knitted fabric having a light weight of about 4 times or more as compared with a conductive metal material was introduced, and a conductive metal The present invention provides a method of manufacturing a fiber-type electrode current collector capable of producing a lightweight and excellent secondary battery by compositing the electrode with a material, and a fiber-type electrode current collector manufactured by the method.

To achieve the above object, the present invention provides a fibrous electrode current collector for a secondary battery, comprising: a polyester fabric layer; A polyurethane thin film coating layer; And an electrode having a conductive metal layer or a conductive polymer layer, the polyester fabric layer; A polyurethane thin film coating layer; And a conductive metal layer or a conductive polymer layer; a conductive metal layer or a conductive polymer layer stacked in this order; A polyester fabric layer; A polyurethane thin film coating layer; And a conductive metal layer or a conductive polymer layer are stacked in this order.

Another method for producing a fibrous electrode current collector for a secondary battery according to the present invention includes a first step of calendering a polyester fabric to produce a calendering fabric; Casting a polyurethane mixed resin on one side of the calendering fabric to form a polyurethane thin film coating layer, and then drying the polyurethane thin film coating layer; And forming a conductive metal layer by sputtering a conductive metal on the upper surface of the polyurethane thin film coating layer.

In addition, as a preferred embodiment of the present invention, the method for manufacturing a fibrous electrode current collector for a secondary battery of the present invention comprises the steps of: 1) preparing a calendering fabric by calendering a polyester fabric; Casting a polyurethane mixed resin on one side of the calendering fabric to form a polyurethane thin film coating layer, and then drying the polyurethane thin film coating layer; And a third step of sputtering a conductive metal on the upper surface of the polyurethane thin film coating layer and the lower end surface of the calendering fabric to form a conductive metal layer, thereby manufacturing a fibrous electrode current collector can do.

The fibrous electrode current collector for a secondary battery of the present invention has a fiber material which is not only chemically stable but also light and has excellent bending property without causing swelling phenomenon in a water and electrolyte environment, The present invention can be applied to a rechargeable battery for a wearable device that is highly flexible and can be made lighter and more comfortable to wear.

Figs. 1 and 2 show photographs of the cathode current collector manufactured in Example 1 and Comparative Example 1, respectively.
3 and 4 are SEM photographs of the anode current collector manufactured in Comparative Example 2-1 and Comparative Example 2-2.

Hereinafter, the fibrous electrode current collector for a secondary battery of the present invention and a method for producing the same will be described in more detail.

The present invention provides a fiber-type electrode current collector for a secondary battery comprising: a polyester fabric layer; A polyurethane thin film coating layer; And an electrode having a conductive metal layer or a conductive polymer layer, the present invention comprising a polyester fabric layer; A polyurethane thin film coating layer; And a conductive metal layer or a conductive polymer layer; a three-layer structure or a conductive metal layer or a conductive polymer layer stacked in this order; A polyester fabric layer; A polyurethane thin film coating layer; And a conductive metal layer or a conductive polymer layer may be stacked in this order to form a four-layer structure.

In the present invention, the polyester fabric layer may be a base layer, and a general polyester fabric used in the art may be used. The fabric constituting the polyester fabric layer may include polyester fibers having 9 to 20 denier.

The polyester fabric layer preferably has an average thickness of 20 to 50 mu m, preferably 35 to 45 mu m. When the polyester fabric layer has an average thickness of less than 20 mu m, the fabric density is insufficient, Or there may be a problem that the conductivity is not sufficiently exhibited after plating. If the average thickness exceeds 50 탆, there may be a problem that the bending property is lowered. Therefore, it is preferable to form the fabric layer so as to have the above thickness.

The polyurethane thin film coating layer is for producing a highly efficient electrode current collector by controlling the voids existing in the polyester fabric layer corresponding to the base layer. If the size of the gap of the base layer is large, the cut surface of the metal layer becomes large, In order to overcome such a problem, it is possible to improve the plating performance by filling the pores with a thin film of a polyurethane material secured in the electrolyte. More specifically, the electrode current collector should have high electrical conductivity, and the electrical conductivity of the electrode current collector is determined by the diameter and density of the yarn in the polyester fabric. During the deposition for the conductive metal layer, the polyester fabric is exposed to a high temperature of 180 ° C to 200 ° C. At this time, since the tension is applied in an oblique direction, the space between the wefts is widened through the process, And the conductivity is lowered. Therefore, the deposition rate of the metal layer can be improved by coating the polyurethane thin film to control the void of the polyester fabric as the base layer.

The polyurethane thin film coating layer of the present invention comprises a polyurethane resin; And a solvent; and a polyurethane mixed resin which is a one-pack type resin. The solvent of the polyurethane mixed resin may be a mixture of one or more kinds selected from methyl ethyl ketone, toluene, dimethyl formamide and methanol, and preferably two or three kinds of solvents for multi- Are mixed and used.

When a solvent is used in combination, it is preferable to add 10 to 30 parts by weight of methyl ethyl ketone, 5 to 15 parts by weight of toluene and 5 to 20 parts by weight of dimethylformamide to 100 parts by weight of the polyurethane resin, 12 to 20 parts by weight of methyl ethyl ketone, 8 to 12 parts by weight of toluene and 6 to 15 parts by weight of dimethyl formamide per 100 parts by weight of the polyurethane resin to prepare a polyurethane mixed resin. The polyurethane mixed resin thus prepared has a viscosity of 80,000 to 120,000 cps (25 ° C), preferably 85,000 to 110,000 cps (25 ° C), a solid content of 25 to 35% by weight, preferably 28 to 32% More preferably from 29 to 31% by weight. If the viscosity of the polyurethane mixed resin is less than 80,000 cps (25 캜), there may be a problem that the rigidity of the film is lowered due to a lack of the solid content in the film forming viscosity. If the viscosity exceeds 120,000 cps (25 캜) There may be a problem that formation of the polyurethane resin and the solvent becomes impossible. Therefore, it is preferable to adjust the mixing amount of the polyurethane resin and the solvent so as to maintain the viscosity within the above range.

The polyurethane thin film coating layer is preferably formed to have an average thickness of 5 탆 to 25 탆, preferably an average thickness of 5 탆 to 20 탆, and more preferably 8 탆 to 15 탆, wherein the average of the polyurethane thin film coating layer If the thickness is less than 5 mu m, there may be a problem of being damaged 500 times or more after bending, and if the average thickness of the polyurethane thin film coating layer exceeds 25 mu m, it is disadvantageous in peeling and no further increase in metal layer deposition effect and electrode efficiency increase It is uneconomical.

In the present invention, the polyurethane thin film coating layer has a 100% modulus value of 40 to 50 kg / cm 2, a tensile strength of 400 to 600 kg / cm 2, preferably 420 to 550 kg / cm 2, %, Preferably from 750% to 850%.

In the present invention, the conductive metal layer may be formed of at least one conductive metal selected from the group consisting of aluminum, nickel, copper, stainless steel, platinum (Pt), silver (Ag) Pt, silver (Ag), and gold (Au), and more preferably aluminum or nickel. Depending on the type of electrode, components of the conductive metal layer may be different. For example, when the electrode is a cathode, a metal layer is formed of nickel, and when the electrode is an anode, aluminum is formed to manufacture an electrode current collector including the cathode and the anode.

The conductive metal layer may further include a conductive polymer.

Alternatively, instead of the conductive metal layer, the conductive polymer may be used to form a conductive polymer layer on the upper surface of the polyurethane thin-film coating layer to produce an electrode current collector.

In the present invention, the conductive metal layer preferably has an average thickness of 100 nm to 600 nm, preferably an average thickness of 200 nm to 500 nm, and more preferably 250 nm to 350 nm. If the average thickness of the conductive metal layer is less than 100 nm, Or deteriorated in physical properties, and the efficiency of the electrode may be deteriorated. It is uneconomical that the average thickness exceeds 600 nm, which is disadvantageous in the peeling screen.

The total average thickness of the fibrous electrode current collector (three-layer or four-layer structure) of the present invention is 27 탆 to 75 탆, preferably 30 탆 to 55 탆, and more preferably 32 탆 to 48 탆 . ≪ / RTI >

The fibrous electrode current collector of the present invention comprises a first step of calendering a polyester fabric to produce a calendering fabric; Casting a polyurethane mixed resin on one side of the calendering fabric to form a polyurethane thin film coating layer, and then drying the polyurethane thin film coating layer; And a third step of sputter depositing a conductive metal on the upper surface of the polyurethane thin film coating layer to form a conductive metal layer.

In addition, instead of the above three steps, a conductive metal layer is formed by sputtering a conductive metal on the upper end surface of the polyurethane thin film coating layer and the lower end surface of the calendering fabric, thereby preparing a fibrous electrode current collector having a four- You may.

The kind, composition and characteristics of the polyester fabric, the polyurethane mixed resin and the conductive metal used in the production of the fibrous electrode current collector of the present invention are the same as those described above.

In the manufacturing method of the present invention, the calendering in the first step may be calendering at a temperature of 70 ° C to 90 ° C and a pressure of 40 to 60 kg / cm 2 at a rate of 30 to 60 m / min, If the calendering temperature is less than 70 캜, there is a problem that the smoothness of the fabric is insufficient and the thickness of the plated layer is unevenly formed. If the pressure during calendering is less than 40 kg / cm 2, the conductivity can be deteriorated due to insufficient calendering of the tangent points of warp and weft. If the pressure exceeds 60 kg / cm 2, the fabric may be damaged during the process, There may be a problem. If the calendering speed is less than 30 m / min, the productivity is excessively decreased. If the calendering speed is more than 60 m / min, the fabric may be damaged during the process.

The polyurethane thin film coating layer was dried at 65 ° C to 75 ° C for 1 minute to 3 minutes, followed by secondary drying at 90 ° C to 110 ° C for 30 seconds to 2 minutes , And it is preferable to carry out tertiary drying at 160 ° C to 190 ° C for 20 seconds to 1 minute 30 seconds. The reason why the drying temperature is different is that the solvent (methyl ethyl ketone, toluene, dimethyl formamide) In order to obtain a dewatered polyurethane coating layer.

Electroless plating and sputtering are the typical methods for imparting conductivity to fiber materials. In the case of electroless plating, electrons generated in the oxidation reaction of hypophosphorous acid (H 2 PO 2 ) And phosphorus (P) generated in this process remains on the current collector. Taking nickel as an example of this reaction, the following reaction formula 1 is given.

[Reaction Scheme 1]

H 2 PO 2 - > H 2 PO 3 - + 2e -

Ni 2 + + 2e - > Ni

In the present invention, a conductive metal layer is formed by introducing a sputtering deposition method instead of an electroless plating method in order to control the impurities of the electrode current collector in the formation of the conductive metal layer in three stages. At this time, In order to prevent non-uniform growth, it is possible to minimize the void of the polyester fabric layer by thinly coating polyurethane on one side of the polyester fabric.

The sputtering deposition process in the third step is performed at a temperature of 250 to 350 ° C. in an argon gas pressure and a degree of vacuum (5 to 8) × 10 -3 , preferably in a range of 280 to 320 S CCM under an argon gas pressure and a degree of vacuum of 6 to 7 × 10 -3 , It is preferable to perform the sputtering deposition process at a power of 6 to 10 kW, preferably 7 to 8 kW.

The fibrous electrode current collector of the present invention manufactured by the above-described method has an electrical conductivity of 5 x 10 1 S / cm to 1 x 10 3 S / cm, preferably, 7 x 10 1 S / cm to 5 × 10 2 S / cm, more preferably 1 × 10 2 S / cm to 4.5 × 10 2 S / cm.

In addition, the fibrous electrode current collector of the present invention has a bending strength of 0.100 to 0.220 g · cm 2 / cm, preferably 0.100 to 0.175 g · cm 2 / cm, as measured by the Kawabata test method (bending propertie) Preferably 0.150 to 0.150 g · cm 2 / cm 2.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.

[Example]

Preparation Example 1: Preparation of one-pack type polyester mixed resin

15 parts by weight of methyl ethyl ketone (MEK), 10 parts by weight of toluene and 10 parts by weight of dimethylformamide (DMF) were mixed with 100 parts by weight of one-pack type polyurethane resin (trade name: SPH- A polyurethane mixed resin having a viscosity of 100,000 cps (25 캜) and a solid content of 30% by weight was prepared.

Preparation Example 2 ~ Preparation Example 9

Polyurethane mixed resins were prepared in the same manner as in Preparation Example 1, except that polyurethane mixed resins were prepared so as to have compositions and composition ratios as shown in Table 1 below, and Preparation Examples 2 to 9 were respectively performed.

division
(Parts by weight) Polyurethane resin menstruum Viscosity
(cps, 25 < 0 > C) Solids content
(weight%) MEK toluene DMF Preparation Example 1 100 15 10 10 10,000 30 Preparation Example 2 100 27 12 10 9,000 30 Preparation Example 3 100 10 10 10 12,000 30 Preparation Example 4 100 15 8 14 10,000 30 Preparation Example 5 100 - 15 20 10,000 30 Preparation Example 6 100 20 - 15 10,000 30 Preparation Example 7 100 28 12 - 8,800 30 Preparation Example 8 100 35 8 6 9,000 30 Preparation Example 9 100 15 18 3 10,000 30

Experimental Example 1

The polyurethane mixed resin prepared in Preparation Examples 1 to 9 was cast on a glass substrate to a thickness of 10 占 퐉 on a glass substrate and dried at 70 占 폚 for 1 minute and then at 100 占 폚 for 1 minute and then at 180 占 폚 And dried for 1 minute to prepare a polyurethane thin film, and the physical properties thereof were measured. The results are shown in Table 2 below.

division 100% modulus (kg / ㎠) Tensile strength (kg / cm 2) Elongation (%) Preparation Example 1 43 515 790 ~ 792 Preparation Example 2 40 475 625 to 627 Preparation Example 3 41 386 512 to 514 Preparation Example 4 43 510 788-790 Preparation Example 5 42 to 43 511 790 to 793 Preparation Example 6 42 to 43 510 792 to 794 Preparation Example 7 16 367 482 to 485 Preparation Example 8 35 475 618 to 622 Preparation Example 9 43 508 783-787

Example 1: Production of positive electrode current collector

Calendering was carried out at a temperature of 80 캜, a pressure of 50 kg / cm 2 and a speed of 50 m / min in order to increase the smoothness of the polyester fabric of 20 deniers to form a polyester fabric layer having an average thickness of 40 탆.

Next, the polyurethane mixed resin prepared in Preparation Example 1 was cast on one side of the polyester fabric to a thickness of 10 mu m with a doctor knife coater. Then, it was dried at 70 ° C for 1 minute, then dried at 100 ° C for 1 minute, and then dried at 180 ° C for 1 minute to form the polyurethane thin film layer of the present invention on the polyester fabric.

Next, a vapor deposition process was performed to impart electrical conductivity to the polyester fabric layer coated with the polyurethane thin film. In order to control the content of impurities, an aluminum target with a purity of 99.99% was subjected to a deposition process under an argon (Ar) gas of 300SCCM at a power of 7 to 8 kW to form a conductive metal layer having an average thickness of 350 nm. 10 -3 mmHg.

Fig. 1 shows a photograph of the produced positive electrode current collector. Referring to FIG. 1, it can be seen that there is almost no pore.

Examples 2 to 4

A positive electrode current collector was prepared in the same manner as in Example 1 except that the polyurethane mixed resin of Preparation Examples 2 to 4 was used instead of the polyurethane mixed resin of Preparation Example 1 to prepare a positive electrode collector, 2 to 4 were respectively performed.

Example 5

A 20-denier polyester fabric having an average thickness of 25 占 퐉, calendered in place of the 20 denier polyester fabric having an average thickness of 40 占 퐉, was produced in the same manner as in Example 1, Thereby producing a positive electrode current collector.

Example 6

A positive electrode current collector was manufactured in the same manner as in Example 1, and a conductive metal layer was formed to a thickness of 200 nm to prepare a positive electrode current collector.

Comparative Example 1

The same polyester fabric as that of the polyester fabric of Example 1 was calendered at a temperature of 80 캜, a pressure of 50 kg / cm 2 , and a speed of 50 m / min.

Next, an aluminum target having a purity of 99.99% was subjected to a deposition process at a power of 7 to 8 kW under 300SCCM argon (Ar) gas pressure and a process vacuum degree of 6.5 x 10-3 mmHg to the polyester fabric layer to form an average thickness of the conductive metal layer 350 nm. Thus, a positive electrode current collector formed of a polyester woven layer and a conductive metal layer was produced, and a photograph thereof is shown in Fig. Referring to FIG. 2, it is confirmed that pores of the fabric layer exist.

Comparative Example 2

A cathode electrode current collector was produced in the same manner as in Example 1 except that the polyester fabric having an average thickness of 16 탆 and a denier of 20 탆 obtained by calendering instead of the 20 denier polyester fabric having an average thickness of 40 탆 was used as a polyester fabric layer Thereby producing a positive electrode current collector.

Comparative Example 3

A positive electrode current collector was manufactured in the same manner as in Example 1, and a polyurethane thin film coating layer was formed to a thickness of 32 탆 to prepare a positive electrode current collector.

Comparative Example 4

A positive electrode current collector was manufactured in the same manner as in Example 1, and a conductive metal layer was formed to a thickness of 70 nm to prepare a positive electrode current collector.

Comparative Example 5

A positive electrode current collector was produced in the same manner as in Example 1 except that a polyurethane mixed resin was cast on one side of a polyester fabric to a thickness of 10 mu m and then dried at 100 DEG C for 3 minutes to form a polyurethane thin film layer Next, a conductive metal layer was formed in the same manner as in Example 1 to produce a positive electrode current collector.

Experimental Example 2: Electrical Conductivity Measurement

The electric conductivity of each of the positive electrode collectors prepared in Examples 1 to 6 and Comparative Examples 2 to 5 was measured by a 4-point probe method. The results are shown in Table 3 below.

division Electrical conductivity Example 1 1 x 10 2 S / cm Example 2 1.45 x 10 2 S / cm Example 3 1.79 x 10 2 S / cm Example 4 2.83 × 10 2 S / cm Example 5 4.20 × 10 2 S / cm Example 6 3.89 × 10 2 S / cm Comparative Example 2 10.87 × 10 2 S / cm Comparative Example 3 9.70 × 10 2 S / cm Comparative Example 4 9.27 x 10 2 S / cm Comparative Example 5 8.45 x 10 2 S / cm

As a result of the electrical conductivity measurement test of Table 3, it was confirmed that the electrical conductivity of Examples 1 to 6 was in the range of 1 × 10 2 S / cm to 5 × 10 2 S / cm. However, in the case of Comparative Examples 2 to 5, the electrical conductivity was 8.45 × 10 2 S / cm or more, which was relatively high as compared with the Examples.

Experimental Example 3: Measurement of bending strength of a fiber current collector

Each of the positive electrode collectors prepared in Examples 1 to 6 and Comparative Examples 2 to 5 was measured for bending strength per unit length by the Kawabata test method (Bending propertie). The results are shown in Table 4 below.

division Bending strength (g · cm 2 / cm) Example 1 0.119 Example 2 0.124 Example 3 0.122 Example 4 0.130 Example 5 0.126 Example 6 0.109 Comparative Example 2 0.270 Comparative Example 3 0.267 Comparative Example 4 0.260 Comparative Example 5 0.264

Example 2: Production of an anode current collector

The same polyester fabric as that of the polyester fabric of Example 1 was calendered at a temperature of 80 캜, a pressure of 50 kg / cm 2 , and a speed of 50 m / min.

Next, the polyurethane mixed resin prepared in Preparation Example 1 was cast on one side of the polyester fabric to a thickness of 10 mu m with a doctor knife coater. Then, it was dried at 70 ° C for 1 minute, then dried at 100 ° C for 1 minute, and then dried at 180 ° C for 1 minute to form the polyurethane thin film layer of the present invention on the polyester fabric.

Next, a vapor deposition process was performed to impart electrical conductivity to the polyester fabric layer coated with the polyurethane thin film. In order to control the content of impurities, a nickel target having a purity of 99.99% was subjected to a deposition process under a pressure of 7 to 8 kW under a 300S CCM argon (Ar) gas pressure to form a conductive metal layer having an average thickness of 500 nm. 10 -3 mmHg.

The impurities of the conductive metal layer of the negative electrode collector were measured, and the results are shown in Table 5 below.

Comparative Example 2: Production of an anode current collector

The same polyester fabric as that of the polyester fabric of Example 1 was calendered at a temperature of 80 캜, a pressure of 50 kg / cm 2 , and a speed of 50 m / min.

Next, the polyurethane mixed resin prepared in Preparation Example 1 was cast on one side of the polyester fabric to a thickness of 10 mu m with a doctor knife coater. Then, it was dried at 70 ° C for 1 minute, then dried at 100 ° C for 1 minute, and then dried at 180 ° C for 1 minute to form the polyurethane thin film layer of the present invention on the polyester fabric.

Next, an electroless plating was performed using nickel (Ni) to form a nickel metal layer having an average thickness of 120 占 퐉 to prepare an anode current collector formed of a polyester woven layer, a polyurethane thin film coating layer, and a conductive metal layer. The photograph is shown in Fig.

The impurities of the conductive metal layer of the negative electrode collector were measured, and the results are shown in Table 5 below.

Comparative Example 2-2: Production of an anode current collector

The same polyester fabric as that of the polyester fabric of Example 1 was calendered at a temperature of 80 캜, a pressure of 50 kg / cm 2 , and a speed of 50 m / min.

Next, the polyurethane mixed resin prepared in Preparation Example 1 was cast on one side of the polyester fabric to a thickness of 10 mu m with a doctor knife coater. Then, it was dried at 70 ° C for 1 minute, then dried at 100 ° C for 1 minute, and then dried at 180 ° C for 1 minute to form the polyurethane thin film layer of the present invention on the polyester fabric.

Next, an electroless plating was carried out using nickel to form a nickel metal layer having an average thickness of 120 탆 to prepare a negative electrode current collector formed of a polyester fabric layer, a polyurethane thin film coating layer and a conductive metal layer. Respectively.

The components of the conductive metal layer of the anode current collector thus prepared were measured, and the results are shown in Table 5 below.

division Example 2 Comparative Example 2-2 Comparative Example 2-2 weight% At.% weight% At.% weight% At.% C 2.41 10.90 2.31 9.79 2.31 9.79 O 1.34 4.00 1.19 3.79 1.19 3.79 P 0 0 3.48 5.73 3.48 5.73 Ni 96.25 85.1 93.02 80.69 93.02 80.69

As shown in Table 3, unlike Example 2-1 in which sputtering deposition was performed, impurities such as carbon, oxygen, and phosphorus were added to the conductive metal layer of the negative electrode current collector produced by forming the conductive metal layer by electroless plating And it was confirmed that it included.

Through the above-described Examples and Experimental Examples, it was confirmed that the electrode current collector (anode and / or cathode) of the method and the form of the present invention exhibited not only a uniform conductive metal layer but also excellent electric conductivity. It can be confirmed that a flexible secondary battery having excellent charging efficiency can be provided by using the electrode current collector of the present invention, and it can be provided to a variety of wearable device products using the electrode current collector.

Claims (18)

A polyester fabric layer having an average thickness of 20 탆 to 50 탆; A polyurethane thin film coating layer having an average thickness of 8 mu m to 20 mu m; And an electrode having a conductive metal layer or a conductive polymer layer having an average thickness of 100 nm to 600 nm,
A polyester fabric layer; A polyurethane thin film coating layer; And a conductive metal layer or a conductive polymer layer are stacked in this order, or
A conductive metal layer or a conductive polymer layer; A polyester fabric layer; A polyurethane thin film coating layer; And a conductive metal layer or a conductive polymer layer are stacked in this order,
Wherein the polyester fabric layer comprises polyester fibers of 9 to 20 denier,
The polyurethane thin film coating layer is formed of a polyurethane mixed resin containing 12 to 20 parts by weight of methyl ethyl ketone, 8 to 12 parts by weight of toluene and 6 to 15 parts by weight of dimethylformamide based on 100 parts by weight of the polyurethane resin, The polyurethane mixed resin has a viscosity of 85,000 to 110,000 cps (25 DEG C) and a solid content of 28 to 32 wt%
The polyurethane thin film coating layer has a 100% modulus value of 40 to 50 kg / cm 2, a tensile strength of 400 to 600 kg / cm 2, an elongation of 700 to 900%
When the electrode is a cathode, the conductive metal layer is formed of nickel, and when the electrode is an anode, the conductive metal layer is formed of aluminum,
Wherein the electrode collector has a conductivity of 7 × 10 1 S / cm to 4.5 × 10 2 S / cm when measured by a 4-point probe method and a bending strength of 0.100 to 0.220 g · cm 2 / cm. delete delete delete delete delete delete delete delete delete delete Calendering a polyester fabric to produce a calendering fabric;
Casting a polyurethane mixed resin on one side of the calendering fabric to form a polyurethane thin film coating layer, and then drying the polyurethane thin film coating layer; And
And forming a conductive metal layer by sputtering a conductive metal on the upper surface of the polyurethane thin film coating layer,
The polyurethane mixed resin is formed of a polyurethane mixed resin containing 12 to 20 parts by weight of methyl ethyl ketone, 8 to 12 parts by weight of toluene and 6 to 15 parts by weight of dimethyl formamide based on 100 parts by weight of the polyurethane resin, The polyurethane mixed resin has a viscosity of 85,000 to 110,000 cps (25 DEG C) and a solid content of 28 to 32 wt%
The polyester fabric has an average thickness of 20 탆 to 50 탆, the polyurethane thin film coating layer has an average thickness of 8 탆 to 20 탆, the metal layer has an average thickness of 100 nm to 600 nm,
The polyurethane thin film coating layer is dried at 65 ° C to 75 ° C for 1 minute to 3 minutes, followed by secondary drying for 30 seconds to 2 minutes at 90 ° C to 110 ° C, followed by drying at 160 ° C Followed by tertiary drying at < RTI ID = 0.0 > 190 C < / RTI > for 20 seconds to 1 minute 30 seconds,
Wherein the sputtering deposition is performed at a power of about 6 to about 10 kW under a vacuum of about 250 to about 350 SCCM argon gas pressure and a degree of vacuum of about 5 to about 8 to about 10 to about 3 mmHg. ≪ / RTI > A step of calendering a polyester fabric to produce a calendering fabric;
Casting a polyurethane mixed resin on one side of the calendering fabric to form a polyurethane thin film coating layer, and then drying the polyurethane thin film coating layer; And
And forming a conductive metal layer by sputtering a conductive metal on the upper surface of the polyurethane thin film coating layer and the lower surface of the calendering fabric,
The polyurethane mixed resin is formed of a polyurethane mixed resin containing 12 to 20 parts by weight of methyl ethyl ketone, 8 to 12 parts by weight of toluene and 6 to 15 parts by weight of dimethyl formamide based on 100 parts by weight of the polyurethane resin, The polyurethane mixed resin has a viscosity of 85,000 to 110,000 cps (25 DEG C) and a solid content of 28 to 32 wt%
The polyester fabric has an average thickness of 20 탆 to 50 탆, the polyurethane thin film coating layer has an average thickness of 8 탆 to 20 탆, the metal layer has an average thickness of 100 nm to 600 nm,
The polyurethane thin film coating layer is dried at 65 ° C to 75 ° C for 1 minute to 3 minutes, followed by secondary drying for 30 seconds to 2 minutes at 90 ° C to 110 ° C, followed by drying at 160 ° C Followed by tertiary drying at < RTI ID = 0.0 > 190 C < / RTI > for 20 seconds to 1 minute 30 seconds,
Wherein the sputtering deposition is performed at a power of about 6 to about 10 kW under a vacuum of about 250 to about 350 SCCM argon gas pressure and a degree of vacuum of about 5 to about 8 to about 10 to about 3 mmHg. ≪ / RTI > The method according to claim 12 or 13, wherein said calendering in one step is calendering at a rate of 30 to 60 m / min under a temperature of 70 ° C to 90 ° C and a pressure of 40 to 60 kg / cm 2 Wherein the step of forming the second electrode comprises the steps of: delete delete delete delete
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