TW506153B - Apparatus and method of manufacturing current collector for secondary battery - Google Patents

Abstract

Provided are an apparatus and method for manufacturing a current collector for a secondary battery. In the current collector manufacturing method, a current collector source material is first prepared, pro-treated and then passed between rollers, one of which has patterns shaped like openings to be formed in the source material to then coat a pattern forming composition. Then, the resultant is dried and etched to form the openings, thereby completing the current collector. The current collector manufacturing apparatus includes a main roller, a guide roller coupled to the main roller so that the current collector passes therebetween, and a pattern forming composition storage unit installed under the main roller, for supplying the pattern forming composition to a patterned portion.

Description

506153

This is the equipment buckle for manufacturing the current collector of the secondary battery, so as to form an opening on the current collector. Injury and method 2 · Relevant technical description: Pass, 'the secondary battery can be charged and discharged and passed N :, pool, sickle-hydrogen (Ni-MH) battery, clock secondary = special, from energy density per unit The concept of weight. For batteries such as NbCc ^ tNi-MH, · = Gao exists relative to the requirement. The M secondary battery has a growing demand for liquid electrolyte batteries and solid electrolyte batteries. The first, the second, and the second kind of degraded batteries are called bell polymer batteries ... the secondary battery type 70, which has _ L including batteries_) and-negative plates stacked in sequence; and an outer and a separator (Ca-The positive and negative plates each have a current collector and a plurality of openings formed on the two to provide ion conductivity between the surfaces of the open: collector. The active material liquid electrolyte formed on the surface The battery system is called clock ion = two rounds of decomposed batteries are called lithium battery. ^ ^. Using ^ compound type electricity According to the opening formation method, the positive and negative current collectors can be classified as punched metal (punched) metal type), where openings are formed on the current collector via pressure t (pres — sing); expan — ded metal type 'wherein all openings are formed on the current collector and then expand to Openings on either side; and etched metal

V. Description of the invention (2) -1 No. =), in which the current collector is etched to form an opening Procedure for sequential steps of collectors] ,, and “The two-cut method for manufacturing currents” refers to Section 1®. Here we briefly explain the tradition of manufacturing current collectors: ίν This preparation is used as a source material for positive and negative current collectors From > White or copper tears (step S10). Then, a dry film resist layer is applied to one surface p y ′ of the aluminum electrode material used for the gold material ^ longer than the source Λ P (step S30). The pattern of the ancient radiation applied to the openings < the mask 乂 will be formed with the source on the material and then exposed to the resist layer, and the resulting radiation is radiated (step S40). At the end of the exposure, each door should be enriched to form a pattern, which is the same as the coating of the film barrier layer (Bu Cong 0). Then, the agent should be evenly ==; ί At temperature: the inhibitor (step 7 °) and then not throwing it, 70% of positive or negative current collector (step S80). However, the conventional technology has the following problems. Use source ^ ^ ^ Yun carved metal current collector, tied to the positive or negative current collector ^ ^ on the surface of a complete application of a film barrier layer, exposed it, part of the state 'and you made the etching That is, there are many processing steps, and because the cost is increased. In addition, compared to other technologies, it requires far more time to etch, which is disadvantageous from the viewpoint of productivity. It is not good for expanded metals. f. In the manufacture of the current collector, "the current collector is not cut in the plane" because the direction of elongation and the direction of tension are applied, so 506153 V. Description of the invention (3) The current collector production program is a In the electrode plate collector, the shape of the film is not properly extracted. < Invention In order to understand the current collector of a secondary battery, the present invention uses a device and a brush of the same shape to directly print and develop steps to reduce and produce the current collector source material used to reach the current collector through two rollers to become as important Overview of plasticizers that open and adjust with negative current and current in the case where the base is coated with the material.> The second method of forming the current set surface is described above. Its pattern can be changed to the above method in current and rate. In between, the source electrode is permanently deformed with a picture, which is not suitable for continuous mass production. Furthermore, when the current collector is cut into, a rough hole edge may be generated at the cut part, resulting in an electrode plate. A short circuit occurs between the holes. The source material used in the punched metal current collector is a thin film of metal foil, which is easy to deform. Therefore, the size of the opening may not be smooth or may be caused in the subsequent battery manufacturing process. Ion conductivity deteriorates. The purpose of the openings of the various poles is followed by the collector pole. The various features of the source are material problems, and the present invention The first purpose is to propose a device and a method to efficiently produce a secondary battery current collection and to be formed on the current collector by using a source material used for general lithography or rubber to form a current collector. It does not need to be etched and stripped, which leads to pre-treatment of the electrode material for the secondary battery, which is produced by manufacturing and printing on the negative phase of the negative electrode. The source material, a roller, has a pattern. The pattern is the shape of the opening formed on the meridian, and then a composition is formed at the source. The pattern forming composition is characterized in that it includes the following steps:

Page 7

The source material is etched to form the pattern on the f material to form a composition flow collector. In the coating on the source material, it is preferred that the pattern forming group is coated entirely on the side where the openings are not formed. In addition, the pattern-forming composition on the residue is preferably according to another part of the present invention, a device for collecting poles, the device including a guide roller to the main roller for guiding the guide roller and the main roller. The opening formed on the source material of the current collector between the rollers forms a composition storage unit, which is supplied with the pattern forming composition to the sampled portion of the main as if to be formed on the current collector. In the present invention, the graphical polymer is a copolymerization product of a monomer forming a main chain, the main chain forming monomer and a water-resistant polymerization product, a colorant, and a cross-linking composition. The material may include an aqueous propylene-forming monomer, an acid-resistant copolymerization of a propylene-based propylene-based monomer, and a solvent. Opening, and removing the residue remaining in the source 'is to complete the step of forming the composition with the electrical overlay pattern having the opening, and the product is only coated on the source material, and the other source material is left The patterned portions of the drum are all transferred to the source material. A current main roller for manufacturing a secondary battery is formed. Once the source material of the current collector is rotatably coupled to form a pattern having a shape similar to the shape of the electricity, and a pattern is installed on the main roller The bottom is used for rollers. The main drum preferably has an opening-shaped pattern. The pattern-forming composition may include an acidic monomer and an acid-resistant propylene-based water-resistant polymer, which is a propylene-based monomer. Co-agent and a solvent. In addition, the pattern-based resin is a main chain-based monomer and a water-resistant product, a colorant, a cross-linking agent & explanation (5) This J brief description > attached The drawings detail Z t and its advantages can be made clearer by referring to Figure 1 for manufacturing practices for its specific examples, where: Figure 2 shows the flow of the method used for the current collector of the secondary battery. Figure 2 ~ ~-Figure 3 is based on: i battery-part of the enlarged perspective view. Figure 4 shows the perspective view of the Jingjing unit. FIG. 5 is a side view of the roller unit shown in FIG. ^ Manufactured by She Wei ==, the steps included in the sequence are current collectors. Figure 6 is a diagram using the third functional element. Figures 3 and 4 show the flowchart of the 7th episode. The electric current diagrams for the production of 疋 早 疋 are shown in Figs. 3 and 4. _ The side view shows a partial enlargement of the electric steam 隼 f70 ^ The pattern is used to form an opening through the stone. The state of enlightenment on the source material of the current collector-a specific example is shown in Figure δ A. The process of opening / opening is shown, in which the source of the pattern-coating pattern is formed: two = cross-sectional view above it Fig. 8B of the engraved state is a cross-sectional view showing the state of Fig. ΔA. The material has been etched and Fig. 8C is shown in Fig. 8B without the source material.

Face view. No variation of poor adjustment according to the present invention 'is a cross-sectional view showing a state in which a pattern is formed by overlaying a pattern on the pattern. A cross-sectional view of the state of the source material shown in Figure A after cutting the surface. The second specific example of the current collector manufacturing is the 9th and 9th states. Figure 9A and 9 are the source of the 9th product. Figure 9B is the outline of the display. 1; shows the cross-section B of the sample to show the A view of the ninth invaded invention of the pole material. Figure 0 shows a partial enlarged side view of the current from the rubber element > barrel unit in a state in which an open plate is formed and printed on the source material of the collector. 11 ... Positive electrode plate lib ... Positive electrode sheet 13 ... Negative electrode sheet 13b ... Negative electrode sheet 13c ... Opening 15 ... Negative electrode tab 17 ... Negative electrode end 19 ... Space 18b ... Housing part 31 ... Main drum 3 00 ... Patterned part 302 ... Unpatterned groove part < Description of component numbers in the picture > I 0 ... Polymer battery II a .. Positive current set Pole 12 spacer 13a. Negative current set 11c .. Opening 1 4 ... Positive fin 1ββ .. Positive electrode terminal 1 8 .. Case 18a. Upper case part 30. Roller unit 32 .. .Guide roller 301. Pattern groove

Page 10

Composition storage unit Another pattern formation composition pre-treatment unit nozzle nozzle bobbin first support roller ink supply drum 3 3 a · blade edge 42 · · pattern formation composition 6 1 · · · bobbin 6 3 · · · Curing unit 6 5 · · · First cleaning unit 6 7 · · · First cleaning unit 1 0 0 · · Patterned part 120 · · Second support roller < Description of preferred embodiments > As shown in FIG. 2, a lithium polymer battery cell belonging to a secondary battery has a plurality of electrode laminates, and a positive electrode plate 11, a spacer 12, and a negative electrode plate 13 are arranged in this order. Zhenglei 2 Ϊ 511 includes a layered body (lamina) such as a machine collector lla made of Ming pig, and the conductivity must be adhered to the positive current collector Ua. Mixed with auxiliary ingredients such as plastic, plastic, adhesive or the like. && 1 The negative electrode plate 1 1 includes a negative electrode composed of a layer such as a copper drop. The collector 1 3a, and the electric motor which is adhered to the relay, and the electric motor A negative electrode sheet 13b on at least one side of the collector 13a. The negative electrode sheet 13b includes a negative electrode. Human poverty # MATERIAL 'is basically a material composed of a mixture of auxiliary ingredients such as a mixture or the like. Get T biomass, stick to at least one side of each-positive electrode plate Η and each negative electrode ㈣

Ι ^ ρι 1 ^ · Page 11 506153

A positive electrode 1 4 extends outward and is concentrated and bent at the end 16. Similarly, the negative electrode terminal 17. The fins 14 are wedge-shaped with a negative wing, and the negative fins 15 such as the ends thereof also pass through the fins 15. The positive electrode fins are all welded to a positive electrode and concentratedly bent, and the welded tabs can be accommodated in a casing 18 having a space 19. The casing 18 is a pouch-shaped outer casing. The outer casing includes an upper casing part 18a and a piece 18b, which is hinged to the upper casing part on one side thereof. A novel feature of the present invention lies in the The positive current collector 1a and the negative current collector 13a are individually formed with openings 11a and 13c through the equipment used to form the openings. Fig. 3 shows a roller in a current collector manufacturing equipment used to form openings in the current collectors. Unit 30. Referring to FIG. 3, the drum unit 30 includes a main drum 31 and a guide drum 32, which can be rotated in contact with the main drum 31. The positive or negative current collector 1a or 1 3a shown in FIG. The source material used passes between the main roller 31 and the guide roller 32. A patterned portion 3 0 0 is formed on the central surface of the main drum 31. The patterned portion 300 has a width corresponding to that of the source material used for the current collector 11a (13a). The patterned portion 3 q 〇 is used to 'source material used in the current collector 11 a or 1 3 a when the source material passes between the main roller 31 and the guide roller 32. The opening 11 c (1 3 c) on one surface is patterned. For this purpose, the patterned portion 300 has the form of a screen.

Genera 153

化 ί =. For example, φ is the same as the pattern groove 301 of the second elc (13c). At the turn of the pattern, the individual pattern grooves 301 of the patterned part 300 were carved into the ^ t to be used for lithography. These pattern grooves • a predetermined amount of pattern formation in Dingjian Temple Land Reserve This part will be described later with reference to Figure 4. When the source material passes between the main roller 31 and the guide roller 32, the composition 42 is transferred to the current collector 11a (13a ) On the source material used. The patterned portion 300 can be formed directly on the main roller 31. In addition, a pattern corresponding to the openings 11c (13c) can be adhered to the surface of the main roller 31 The lead roller 32 is made of an elastic material, such as rubber, so that the current collector 11 a (1 3a) can be brought into complete close contact with the patterned portion 300. When the main When the drum 31 rotates, the pattern-forming composition 42 supplied from the composition storage unit 41 (as shown in FIG. 4) is scattered on the main drum 31, that is, even in the unpatterned groove portion 3 〇2. If this state is continued, it cannot be in the current collector 丨 a (丨 3a) A desirable opening pattern is obtained on the source material used. To prevent this, a scraper 33 in contact with the main roller 31 is installed in front of the main roller 31 in contact with the guide roller 32. It is used to remove the pattern formed on the unpatterned groove portion 3 02 to form the composition 42. The edge 33a of the scraper 33 is kept in close contact with the main roller 31 so that the unpattern contained in the main roller 31 is adhered. The pattern forming composition 4 2 on the groove portion 3 0 2 does not remain on the surface of the main drum 31. So far, it will be explained that using the above-mentioned drum unit 30 at the current collector 11 a

Page 13 V. Description of the invention (10) () The procedure for forming an opening 1 1 C (1 3 c) on the source material used.

Had4): shows the current collector according to the first specific example of the present invention. The equipment used to form the opening UC (13C) on the material in Figure 5 is shown in Figure 4. = The steps in the procedure of the opening UC (13C) are illustrated by the openings and components, and the closed opening is shown in Figure 6. Form a private sequence flow chart. Referring to the drawings, first, prepare a layered body such as aluminum foil or copper foil to be used as the source material of positive and negative a 13 =) (step, preferably, the aluminum or copper wire is wound on a supply Above the bobbin b 1 for continuous supply. Then, in order to remove impurities such as water vapor or dust from the surface of the current collector 11a (13a) source material, the prepared source material is passed through a pre- The saponin 62 is processed for washing or degreasing (step T20). After the pretreatment, a pattern is formed on the source material and surface of the current collector na (13a) to form a composition 42 (step T30). In other words, the source material used for the current collector core supplied from the supply bobbin 61 passes between the main roller 31 and the guide roller 32. Here, the main roller 31 is formed with Openings 丨 lc (13c) sample forming part 300. The main drum 31 is rotated in the following state, that is, it is continuously maintained by the pattern forming composition 42 stored in the composition storage unit 41 According to this, as shown in FIG. 7, the pattern forms the composition 42 It is supplied to the pattern groove 301 formed on the main drum 31 and then transferred to the source material used for the current collector 11a (13a). Here, every 506153 5. Invention Description (11) a pattern The bottom surface of the groove 3 0 1 is preferably formed with irregular unevenness 30 la to help the storage of the pattern forming composition 42. If the pattern forming composition 42 overflows the pattern groove 301 and is sprinkled on Above the unpatterned trench portion 30 2, it is difficult to form a desirable opening pattern in the source material used for the current collector 11 a (1 3 a) unless the scattering composition 42 is removed. To avoid this, The pattern forming composition 42 scattered on the unpatterned groove portion 302 of the main drum 3 and above the unpatterned portion can be removed and collected into the composition storage unit 41.

In this way, an opening 11c (13c) pattern can be formed on one side of the source material used in the current collector 11a (13a). In addition, another pattern-forming composition 43 is also coated on the entire surface of the source material having the opening 11 c (1 3 c) on the side opposite to the pattern side. In other words, the pattern-forming composition 42 used to form the blue opening 丨 丨 c (丨 3 c) is selectively coated on one side of the source material used in the current collector Ua (13a) and the other A pattern-forming composition 43 is coated on the entire surface of the opposite side of the source material used for the current collector 11a (13a). Applying the pattern-forming composition 43 on an entire side of the source material may selectively coat the pattern-forming composition 42 on the source material.

Before, after or simultaneously on the other side of the material. When the pattern forming composition 43 is used as a solid phase (such as a thin film), the coating system of the pattern forming composition 43 and step T3O, that is, when the pattern forming composition 42 is applied in step f Attack. When the pattern forming composition 43 is used in a liquid phase, the coating of the pattern forming composition 43 is preferably performed before or after step T30.

The thicknesses of the compositions 42 and 43 are preferably in the range of 3 to 10 µm ', and more preferably, in this range, it is only possible to be thin. When the thickness of the composition 42 3 is less than 3 micrometers, the acid resistance is deteriorated. If it is larger than 10 micrometers, the 'peeling time will be undesirably prolonged.

After Ik ', the source material used for the current collector 11 a (1 3 a) having the composition 4 2 and 4 3 is cured in a curing unit 63 (step T40). Preferably, its curing temperature is in the range of 60 to 140 ° C and its curing time is in the range of 10 to 20 seconds.

After this curing step, a neodymium etchant is uniformly coated on the known source material through a nozzle 64 (step T 5). In the present invention, it is preferable to use vaporized iron (FeC 13) as an etchant, the etching temperature is in a range of about 30 to 50 ° C, and the etching time is about 30 to 60 seconds.

Here, the source material used for the current collector 11a (13a) is configured such that the surface having the pattern-forming composition 42 faces downward, and one or more nozzles 64 are arranged below it. This is because the current collector 11a3a) is etched due to the accumulation of the etchant. In detail, the surface coated with the composition 4 2 faces upward, and the opposite surface coated with the composition 43 faces downward, and the silver etching agent is used from the current collector 11 a (1 3 a). In the case where the source material is sprayed downward, as shown in FIG. 9A. In this case, during the etching process, the etchant may be concentrated on the bottom surface of the current collector 丨 丨 a (丨 3a) which is entirely coated with the composition 43, resulting in the current collector. The dip # phenomenon occurs in the lower end portion of the wall portion of the opening formed in the source material used in the electrode 11 a (13a). Therefore, as shown in Fig. 9B, the contour of the surface after the button engraving may be uneven and may be etched inward. Special

Page 16 V. Description of the invention (13) ′ As the current collector 1] a knows] q0 ㈣. Therefore, these nozzles and 丄 === they are very susceptible to the source material used in a) ;: both must be mounted on the current collector Ua (13, in other words, the ancestor κ 目 1 1, η ο X m, the above mentioned problems can be solved by spraying the source from the current collector engraving agent 1 through the nozzle 64, fc, not shown in Figure 8A. During the etching process , This down: this: this: the electrode material collides and then drops um due to its own weight, the etchant will not accumulate, so the current collector is prevented from going to a, and less t Φ is etched with the source material. Therefore, the opening 11c (13c) pattern is made in the source material used in π = Gu = collector 1 la (13a) as shown in Fig. 8B. "Then L is used to wash the patterned After the source material is removed, the stripping agent sprayed with the nozzle 66 will form the composition 42 and the "step T6Q) pattern remaining on the source material used in the current collector l ^ a (1a). Here 'Preferred is the use of trough water> grain solution as the stripping agent. After removing the delta pattern forming compositions 42 and 43, the source material used for the current collector Ua (13a) is washed in the first and main cleaning units 67. π After the procedure described above is completed, another post-processing procedure may be further performed according to the source material used for the current collector lla (13a). For example, in the case of two copper foils, an anti-oxidation procedure can be implemented to maintain product performance requirements. The patterned aluminum or steel foil may then be re-produced onto a receiving bobbin 68. In some cases, pigs or copper boxes can be cut to a predetermined size for wrapping. , ^

1M

Page 17 506153 V. Description of the invention (14) Next, an opening 1 1 c (1 3 c) having a desired size is formed in the source material used in the current collector 1 1 a (1 3 a), and the current is thereby completed. Collector 1 1 a (1 3 a), as shown in Figure 8C. FIG. 10 shows a device for forming an opening 1 1 c (1 3 c) in a source material used in a current collector 1 1 a (1 3 a) according to a second specific example of the present invention. Here, the same reference numerals as those shown in the drawings used in the first specific example represent the same functional elements. Referring to FIG. 10, the current collector 1 1 a (13 a) supplied from the supply bobbin 61 is wound around a first gift drum 110 and passes through a guide drum 3 2 and a main drum 3 1 and then passed the second support roller 1 2 0 to the last winding on the accommodating winding officer 6 2. In addition, an ink supply roller 1 3 0 is rotatably engaged and contacts the main roller 3 1. The main roller 31 and the guide roller 32 are rotatably supported on a supporting member (not shown). The lower end portion of the ink supply roller 1 3 0 is immersed in the pattern forming composition 4 2 stored in a composition storage unit 41 1 so that the composition 42 can follow the ink supply roller 1 3 0 Is continuously supplied to the main drum 31. A patterned portion 100 is formed on the surface of the main cylinder 31 and is in contact with the ink supply cylinder 130. For this reason, the composition 42, which is supplied in accordance with the rotation of the ink supply roller 130, can be continuously applied to the main roller 31. The patterned portion 100 is formed by a pattern having an opening corresponding to the current collector 1 1 a (1 3 a). A second support roller 120 is installed along the path of the current collector 1 1 a (1 3 a) through the main roller 31 and the guide roller 32, which can change the electric current.

Page 18 506153 V. Description of the invention (15) The direction of the current collector 11a (13a). Downstream of the second supporting drum 120 is one or more nozzles 64. The remainder is sprayed from the nozzles 64 to the current collector 11a (13a). At this point, the procedure for forming the opening 11c (13c) in the source material used in the current collector 1a (3a) using the equipment described above will be explained. The current collector 1 ia (i3a) wound on the supply bobbin 61 is guided to a pre-processing unit (not shown) as the supply bobbin 61 is unwound, and then washed . After the pre-treatment, the current collector 丨 a (13a) and the first roller no and then is guided between the main roller 31 and the guide roller 32. The pattern contained in the patterned portion 100 is protruded from the surface of the patterned portion 100 so that the pattern forming composition 42 adhered to the surface of the ink supply roller 3 can be transferred to the patterned portion Copy 丨 〇〇. Here, the ink supply roller 130 is partially immersed in a composition storage unit 41 equipped with the pattern forming composition 42 to transfer the composition 42 to the ink supply roller 130 as it is rotated. This main roller 31. One side of the current collector 11a (13a) will be partially coated according to the shape of the patterned part 100, and the opposite side will be patterned by a pattern (not shown). To ground. As shown in FIG. 11, various patterns in the patterning section 丨 〇 are structured to protrude from the surface of the main drum 3, and the patterns are applied to form the composition 42. For this reason, the pattern-forming composition 42 can be transferred onto the source material used for the current collector 11a (13a). After the pattern forming composition 42 is applied to the main roller 31 and the guide

P.19 506153 V. Description of the invention (16) After the current collector iia (i3a) between the rollers 32 is wound, the current collector 11a (13a) is wound on the second support roller 120 to In the subsequent application of solid 4 dagger. Here, the 'cure temperature' is preferably in the range of 60 to 140 ° C and the better cure time is in the range of 10 to 20 seconds. Then, the etchant is uniformly sprayed from the nozzle 64 on the patterned source material, and the etching is performed. Here, one or more nozzles 64 are installed below the current collector 11a (13a) and the etchant is sprayed upward from them.

Immediately after the opening pattern is formed by engraving, the pattern-forming composition 42 remaining on the source material used for the current collector 11a (13a) is removed. Then, the current collector 11a (3a) is wound again on the receiving bobbin 68 and stored. After engraving 'and then removing the pattern to form the composition 42, another post-processing step can be performed according to the source material used. Finally, the openings 11c (13c) of each desired size are formed in the source material used in the current collector 11a (13a), so that the current collector 11a (13a) is completed.

The pattern forming composition used in the current collector of the secondary battery according to the present invention includes an acid-resistant polymer, which is a copolymerization product of a main chain-forming monomer and an acidic propylene-based monomer; A water-resistant polymer is a copolymerization product of a main chain-forming monomer and a water-resistant propylene-based monomer; a colorant, a cross-linking agent, and a solvent. In addition, the pattern used in the current collector of the secondary battery according to the present invention may include a water-based propylene-based resin, which has a main chain shape.

Page 20 506153 V. Description of the invention (π) forming monomer, a copolymerization product of an acid-resistant monomer based on propylene and a water-resistant monomer based on acrylic, a colorant, a Crosslinking agent and a solvent. The pattern forming composition used for the current collector can be directly printed on the current collector without using an exposure and / or development step by using lithographic printing or rubber printing, and can be etched and stripped. So far, the various components contained in the pattern composition and the method for preparing the composition will be explained in more detail. The pattern forming rainbow used for the current collector of the secondary battery according to the present invention includes an acid-resistant polymer, which is a copolymerized product of a main chain-forming monomer and an acid-resistant propylene-based monomer. A resistant polymer, which is a copolymerization product of a main chain-forming monomer and a water-resistant propylene-based monomer; a colorant, a cross-linking agent, and a ^ μ agent. The acid-resistant polymer has excellent acid resistance and ordinary or poor alkali resistance, and is obtained by mixing 50 to 70 parts by weight of a main chain-forming monomer and 30 to 50 parts by weight of acid resistance to propylene. The base-based monomer is copolymerized to make it. ^ Α 1 Water-based polymer is a general term used for trees having excellent alkali resistance and considerable water resistance, and is obtained by combining 60 to 90 parts by weight of a main chain-forming monomer and 10 to 40 parts by weight. Parts of acid-resistant monomers based on propylene groups are copolymerized to make them. Here, the main chain-forming single system forms the main chain of the polymer, and includes 5 to 75 parts by weight of an aromatic vinyl monomer and 20 to 55 parts by weight of an alkyl (meth) acrylate. The aromatic vinyl ΙΒΙΒΠβΗ Page 21 V. Description of the invention (18) Examples of the monomers are styrene, and examples of the alkyl (meth) acrylate are methyl methacrylate and methyl acrylate g will. Useful examples of the acid-resistant propylene-based monomer include a propylene-based (meth) acrylate having a carboxyl group (-COOH) in the molecule. The water-resistant propylene-based monomer is a compound having an aromatic vinyl acrylate in its main chain and a hydroxyl group (-OH) in its molecule, and an example thereof is (hydroxy) acrylic hydroxyalkane Based ester. Specific examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate. A better weight ratio of the acid-resistant polymer to the water-resistant polymer is in the range of 1 ·· 4 to 4 ·· 1. If the content of the acid-resistant polymer exceeds the I 巳 ® ′, the surface of the current collector may be corroded improperly. If the content of the acid-resistant polymer falls below this range, the acid resistance will deteriorate. The total content of the acid-resistant polymer and the water-resistant polymer is preferably in the range of 1 to 90 parts by weight, and more preferably in the range of 40 to 60 weight. If the total polymer content is less than 丨 parts by weight, the composition will exhibit weak acid resistance, and if it is more than 90 parts by weight, the printability of the composition will become poor. The weight average component of the acid-resistant polymer and the water-resistant polymer is preferably in the range of 10,000 to millions, and the glass transition temperature of the polymer is preferably in the range of -40 to 90 t: In the range. For the cross-linking agent used for cross-linking the acid-resistant polymer and the water-resistant polymer, from the standpoint of low-temperature curability of the mask layer as the surname, aziridine: ^ The content of the cross-linking agent is 0 5

Page 22 5. Description of the invention (19) to 5 parts by weight. ^ If the content of the cross-linking agent is less than 0.5 parts by weight, the force will be reduced if the content of the cross-linking agent is less than 5 parts by weight. Medium, τ ^:, and printing adaptability. The crosslinking reaction uses an acid: a cross-link between the polymer and a cross-linking agent, a second or third amine, 3 = two: fatty acid, or a derivative thereof. The colorant is ΓΓ; Is °, 1 to 1 part by weight. And its examples include distinguishable ethers that have a uit4 pattern forming composition. It can be clear that: acidic agents = hydrocarbons; -hydrocarbons, alcohols, organic solvents; In the pattern forming composition used for the current collector of the invention, for the time required for the coating formed from the composition, the surface state of the coating and other purposes, it is necessary to add: an additive. Here, examples of their additives include leveling agents (such as syringone, high melting point or eight purposes; foaming agents, such as azodicarbamide UDCA), and defoamers, and Its preferred amount is 5 parts by weight or less. If the amount of the additive used is more than 5 parts by weight, the coating cannot be formed due to the difference in surface tension, and various unfavorable effects such as set-off, eyeholes, and cratering may occur. . In addition, recoating is difficult and phase separation can occur disadvantageously. In addition, according to the present invention, the pattern for the electricity and current collectors of the secondary battery is formed.

506153 V. Description of the invention (20) --- The composition may also have the following composition. In other words, the composition ΊΓ of the present invention includes a water-based acrylic resin, which is a main chain-forming monomer, an acid-based propylene-based monomer, and a water-resistant propylene-based monomer. Copolymerization product of the body; a colorant, a crosslinking agent and a solvent. In some cases, an ethylene-modified unsaturated monomer may be further added in the preparation of the aqueous acrylic resin. The content of the main chain-forming monomer is in the range of 25 to 13 parts by weight. The content of the monomer based on propylene based on acid resistance is in the range of 1 to ^ parts by weight. The content of copolymerization products of monomers based on propylene groups is in the range of i to 40 parts by weight. Here, the main chain-forming monomer includes 5 to 75 parts by weight of an aromatic vinyl monomer and 20 to 55 parts by weight of an alkyl (meth) acrylate. Preferably, the water-based acrylic resin has an acid value in the range of 30 to 25 ° and a glass transition temperature in the range of -40 to 90 ° C. The aqueous = enoic acid-based resin has a weight-average molecular weight in the range of 100,000 to millions and its content is in the range of 1 to 80 parts by weight, more preferably 40 to 60 in weight. In the range. When the content of the water-based acrylic resin is less than 1 part by weight, the acid resistance becomes weak. If it is more than 80 parts by weight, the printability will be deteriorated. The content of the cross-linking agent is in the range of 1 to 10 parts by weight, and the content of the solvent is in the range of 5 to 80 parts by weight. So far, the present invention will be described in more detail with reference to the embodiments. Do not

However, it must be understood that the present invention is by no means limited by their particular embodiments. Implementation H

Page 24 506153 V. Description of the invention (21) Add 50 parts by weight of water to 5 parts by weight of styrene, 25 parts by weight of methyl methacrylate and 20 parts by weight of acrylic type acrylic acid. , And 2 parts by weight of benzamyl peroxide (βρ〇) was added as a polymerization catalyst, and then the polymerization reaction was performed at 85 ° C for 6 hours. Therefore, there was a synthesis of 3,000,000 to 800. , 0 00 weight-average molecular weight acid-resistant polymer 0 In addition, 50% by weight of water and 5 parts by weight of methacrylic acid were added to 20 parts by weight of styrene, 25 parts by weight of methyl Methyl acrylate and 0.5 reset the number of propionate via propyl propyl vinegar, and add 2% by weight of BP0 as a polymerization catalyst, and then perform a polymerization reaction at 85 ° C, From this, a water-repellent polymer with a weight average molecular weight of 300,000 to 800, Q00 was synthesized. = 20 parts by weight of the acid-resistant polymer is mixed with 28 parts by weight of the cross-resistant β Ϊ ί, and then 3 parts by weight are added and mixed as a catalyst = pyridine, 8 parts by weight of pigment, 0.3 parts by weight were used as cross-linked water / ethylmethylpropane, 1 part by weight of wax, and 38 parts by weight of β / combination solvent, and a composition was prepared by forming a pattern. P. Etching is performed. Then, a 4% solution with a 011 aqueous solution was used to produce a copper current collector in the following manner. The material is degreased through the surface of the source material used for the current collector to form the source material surface. The roller has a pattern like the shape of the current collector I port on the current collector. And the composition is coated on the copper electrode as the αΪ face. Thereafter, the resultant was dried at 120 ° C, and the surface was contacted with FeClS of the etchant to spray the entire surface of the two copper current collectors.

IH Page 25 506153 V. Description of the invention (22) The pattern remaining on the current collector is formed into a composition. Example 2 45 parts by weight of water was added to 0.3 parts by weight of acrylic acid hydroxyethyl vinegar '13 parts by weight of parts of styrene '26 parts by weight of methacrylic methyl acrylate, 10 parts by weight Parts of a propylene-based acrylate, 2.5 parts by weight of a methacrylic acrylate and 2 parts by weight of an ethylenically unsaturated monomer, such as M305, which are available under the trade name Aronix M305 Toagosei Chemical Industries, etc., and added 3 parts by weight of BP0 as a polymerization catalyst, and then polymerized at 85 ° C for 5 hours to synthesize a water-based acrylic resin. 48 parts by weight of this aqueous acrylic resin having a weight average molecular weight of 300,000 to 800,000 and 3 parts by weight of aziridine as a crosslinking agent, 8 parts by weight of a pigment, 0.3 parts by weight of aminomethylpropane as a cross-linking catalyst, 1 part by weight of hydrazone, and 38 parts by weight of a water / ethanol mixed solvent are mixed, and then a cross-linking reaction is performed to prepare a pattern. A composition is formed. Using this composition, a copper current collector was manufactured in the same manner as in Example 1. Example 1 25 parts by weight of a melamine resin having a weight average molecular weight of 100,000 to 300,000 was used. 40 parts by weight of cellulose oxalate and 20 parts by weight of maleic acid The resin is mixed with 10 parts by weight of a pigment, such as yellow D-581, to prepare a composition for lithographic printing. Using this composition, a copper current collector was manufactured in the same manner as in Example 1. Example 2

Page 26 506153 V. Description of the invention (23) 70 parts by weight of urethane resin with NCO group, 20 parts by weight of acrylic polyol and 10 parts by weight of pigment, such as yellow D- 581 'Mixed into a composition for lithography. Using this composition, a copper current collector was manufactured in the same manner as in Example 1. Example 3 60 parts by weight of polyethylene gas, 30 parts by weight of maleic acid resin, and parts by weight of pigment, such as yellow D-58i, were mixed to prepare a composition for lithographic printing. Using this composition, a copper current collector was manufactured in the same manner as in Example 1. Example 4 A polymer obtained by modifying 60 parts by weight of epoxypropyl methacrylate and 30 parts by weight of epoxy resin by using maleic acid, that is, via epoxy resin -0H group and -C00H group of maleic acid esterified resin, the resin has a double bond, and 0 parts by weight of pigment > such as yellow D-581, prepared for supply Composition for lithography. Using this composition, a copper current collector was manufactured in the same manner as in Example 丨. In manufacturing copper current collectors according to Examples 1 and 2 and Comparative Example 4, the pattern-forming composition and the lithographic composition were evaluated and rated on a scale of 1 to 5, with 1 being the worst And 5 is the best. (2) Adhesion: ί: The adhesion between the formed coating and the source material used in the copper current collector j pattern forming composition and the copper electrode material is f. K source estimate. The scored tape peeling test is performed to make the scored tape adhere to

506153 V. Description of the invention (24) The printing plane is peeled off suddenly to check whether the coating will be transferred to the tape. (2) Chemical resistance: ^ The chemical resistance was examined by dipping the pattern-forming composition formed on the copper current collector at 25 ° C for 3 minutes in an FeC3 solution as an etchant. Conditional. (3) Peelability: The peelability of the pattern-forming composition is obtained by immersing the composition in a 4% NaOH aqueous solution as a cleaning solution for about 2 minutes at 35 to 40 ° C. And evaluated. (4) Printing adaptability: Visually inspect the shape of the printed object, for example, circular or prismatic, and compare it with the original pattern used for printing. (5) Water resistance ... In order to compare the degree of removal of coatings formed by these compositions, the coatings were immersed in ion-exchanged water at 40-50 ° C for 10 to 60 minutes. Table 1 shows the evaluation results of the adhesive properties, chemical resistance, peelability, printability, and water resistance.

Table 1 Adhesive properties Chemical resistance Peelability Printing adaptability Water resistance Example 1 5, -------5 4 '' 5 5 Example 2 5 4-5 5 4-5 -------- --- · —— 一-5 Comparative Example 1 5 __ 3 5 5-4 3 Comparative Example 2 5 —-___ 2 One 5 L 5 2 Page 28 V. Description of the Invention (25) Comparative Example 3 Implementation Example 4

~ ^ J 4-3 3 3 1 3-2 "5 Ancients? Table 1 ~ Yes, sure, the current collectors produced in Examples 1 and 2 are very special. 22 ft 2 The composition and properties of the lithographic printing of the prior art, ΐΓ :: Γ-4 are compared with substantially the same adhesion, σ '彳 11, printing adaptability, and water resistance. Also gi7 In addition: According to Examples 1 and 2 The processing steps can be greatly reduced. (2) The following steps need to be implemented: a dry film resistance layer is adhered to the surface of the electro-collector for exposure and development, so as to increase the processing speed. As explained above, In the production of a secondary set according to the present invention: in the apparatus and method, the current collector is passed through the roller I; θ :; I roller has openings as to be formed on the current collector: two · P 2, Then, and then etched, and in the positive and negative electrode plates, openings are formed on the \ τ ΐ f current collector, so that according to the present month, the following effects can be obtained. A Α Ϊ First, because the system has The roll of the pattern with the shape like the opening to transfer the pattern to form the composition Without the need for a dry current, surface, exposure, development, and shoe engraving steps, two or two j consume Φ expensive source materials such as dry film barrier layer. Moreover, because exposure and development are no longer implemented, Therefore, the number of processing steps can be reduced, which is advantageous from a manufacturing point of view. Second, because the burr that often occurs at the end of the expanded metal when the bobbin-type current collector is cut to a desired size, ^ ^ Will not be 506153 5. The invention description (26) is generated, so it can be used. Third, because it can be smoothly adjusted to the desired size, fourth, and the opening formed by the etching material is sprayed upwards. Fifth, the pattern Although the source, water resistance, and printing used for the current collector are illustrated in the present invention, the true scope of the patent application attached is not intended to prevent short-circuit currents that occur between the positive electrode plate and the negative electrode plate. Due to the adaptability of the material of the wall-forming group, the reference material has been referred to. In the process of forming the battery only for the upper surface of the collector, the lower part of this material has excellent adhesion. It can be specially explained. All the nozzles used after repairing can prevent the formation of the joints at the end parts to facilitate the realization of the examples. The dimensions of the modified product of the present invention and the opening of the attached application are the plasticizer extraction steps in the sequence from the current. The pattern of erosion that occurs near the collector of the collector exhibits phase and good resistance to stripping. And the range is intended to cover equivalents only. Therefore, the scope of the patent is given to the source material below. For electrochemical properties The implementation is defined later in this article.

Claims (1)

506153 ^ —1 丨 _ 丨 I .. 6. Scope of patent application • A method for manufacturing a secondary battery, 4 steps: The method for the battery motor collector, which includes the following sources of gas backup current collectors Pre-treatment of the source material; passing the source material between the two rollers, the pattern is formed as if there is a pattern to make up in Feng ns /, "M # ϋ π Opening formed on source material 'A pattern is formed on the source material to form a group of objects. The pattern forming composition is cured; " leaving the source material to form an opening for a while; and removing the remaining The pattern on the source material is based on the pattern forming composition described above, and the current collector having an opening is formed by the element 4. 2. :: Please patent the first! The method of item, wherein in the step of forming a composition on the source material, the pattern is formed into a composition and coated on a portion of the source material on which the openings are not formed, The other side of the source material is entirely coated. 3. If the method of applying for the patent scope μ, wherein the pattern-forming composition remaining on the patterned part of the drum is transferred to the source material 4. If the scope of patenting is applied! The method of item, wherein in the step of engraving the source material into the second name, the side of the source material is coated with a patterned part / 衮 琦 coated with a 忒 pattern forming composition and the side is configured The surface is facing down, and the money engraving agent is sprayed upward toward the source material. 5. The method of claim 1 in which the current collector is etched during the bobbin to bobbin process. ΙΒΙ Page 31 Equipment for current collectors, including: A main roller for manufacturing a secondary battery; a guide roller which is rotatably passed through a source material of the current collector to form a pattern having a shape like a shape to be formed in the electrical opening, and is coupled to the main electrode; The roller is used for guiding the source material of the current collector between the guide roller and the main roller to form a composition storage unit, which is installed on the main roller to supply the pattern to form the composition. To the main drum. For example, if the equipment of the patent scope item δ is applied, wherein the main drum has a shape like the shape of the opening to be formed on the current collector, the equipment of the patent scope item 6 is further included, The ink supply roll-off is in contact with the patterned portion to continuously supply the pattern-forming composition to the patterned portion. 9. The device according to item 6 of the patent application, further comprising a nozzle unit below the patterned source material to spray the etchant upward toward the source material. 10. The device according to item 6 of the scope of patent application, wherein the pattern is formed to form a composition resistant polymer 'It is a copolymer of a main chain-forming monomer and an acidic propylene-based monomer. Product; a water-resistant polya which is a copolymerization product of a main chain-forming monomer and a water-resistant acrylic-based monomer; a colorant, a cross-linking agent, and a agent. ‘11. The device according to item 6 of the patent application, wherein a group is formed on the pattern 506153 VI. Scope of patent application ----- In the product, the total content of the acid-resistant polymer and the water-resistant polymer is in the range of 1 to 90 parts by weight, and the content of the colorant is 1 The content of the crosslinking agent is in the range of 0.5 to 50 parts by weight, and the content of the solvent is in the range of 5 to 80 parts by weight. 12. The device as claimed in claim 6 in which the main chain-forming monomer comprises 5 to 75 parts by weight of an aromatic vinyl monomer and 20 to 55 parts by weight of an (f-based) acrylic alkyl group Ester, the acid-resistant propylene-based monomer propylene-based (meth) acrylate, and the water-resistant propylene-based monomer is hydroxyalkyl (meth) acrylate. 13. The device according to item 6 of the scope of patent application, wherein the content of the main chain-forming monomer in the acid-resistant polymer is in the range of 70 to 95 parts by weight, and the acid resistance is based on a propylene group. The content of the basic monomer is in the range of / to 30 parts by weight, and in the water-resistant polymer, the content of the main chain-forming monomer is in the range of 70 to 99 parts by weight. The content of the propylene-based monomer is in the range of 1 to 30 weight parts, and the fine content of the acid-resistant polymer and the water-resistant polymer is in the range of 1 to 90 weight parts. 1