TW567630B - Lithium ion polymer secondary battery, electrode thereof and polymer synthesizing method of binder used for adhesion layer thereof - Google Patents

Abstract

This invention relates to a lithium ion polymer secondary battery comprising an electrode exhibiting excellent adhesion between a current collector and an active substance layer, excellent conductivity and enhanced cycle capacity sustaining characteristics in which an adhesion layer for bonding the current collector and the active substance layer is stable against organic solvent in electrolyte and exhibits long term shelf life and corrosion of the current collector due to strong acid, e.g. hydrofluoric acid, produced in the battery is suppressed. The lithium ion polymer secondary battery comprises a positive electrode formed by providing a positive pole active substance layer containing a first binder and an active substance on the surface of a positive pole current collector, a negative electrode formed by providing a negative pole active substance layer containing a second binder identical to or different from the first binder and an active substance on the surface of a negative pole current collector, and electrolyte. A first adhesion layer is provided between the positive pole current collector and the positive pole active substance layer and a second adhesion layer is provided between the negative pole current collector and the negative pole active substance layer in which the first and second adhesion layers contain a third binder and a conductive substance, respectively, and third binder is a polymer compound obtained by modifying the first or second binder with a modifying substance.

Description

567630 A7 B7 V. Description of the invention (1) Technical field (please read the precautions on the back before filling out this page) The present invention relates to a lithium ion polymer with an adhesive layer between the current collector of the electrode and the active material. Method for synthesizing secondary battery and adhesive used in the adhesive layer of the battery. 2. Description of the Related Art In recent years, the demand for thin batteries has increased due to the spread of discrete devices such as video cameras and notebook computers. This thin battery has, for example, a lithium ion polymer secondary battery formed by laminating a positive electrode and a negative electrode. A positive electrode active material layer is formed on the surface of the sheet-shaped positive electrode current collector to produce the positive electrode, and a negative electrode active material layer is formed on the surface of the sheet-shaped negative electrode current collector to produce the negative electrode. An electrolyte layer is provided between the positive electrode active material layer and the negative electrode active material layer. In this battery, a positive electrode terminal and a negative electrode terminal which take out a potential difference between two active materials in a current form are provided on a positive electrode current collector and a negative electrode current collector, and thus the laminate package is sealed to form a lithium ion polymer secondary battery. This lithium ion polymer secondary battery uses the positive terminal and the negative terminal pulled out from the case as the terminals of the battery, and can obtain the required electricity. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Lithium-ion polymer secondary batteries with this structure have high battery voltage and high energy density, and are highly valued. An adhesion layer may be provided between the current collector and the active material. The characteristics required for this adhesion layer are, for example, adhesion to the current collector material, adhesion to the binder contained in the active material layer, stability to the organic solvent in the electrolyte, and excellent long-term storage stability, heat stability, and No peeling at high temperatures, electrochemical stability, resistance to repeated charge and discharge, etc., but these characteristics have not yet been completely solved. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 567630 Α7 Β7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) For example, to increase the lithium ion polymerization In the secondary battery's discharge capacity, the area of the plate-shaped positive electrode or negative electrode must be enlarged. Simply increasing the area of the positive electrode or the negative electrode is difficult due to the wide area. In order to solve this problem, it is considered that the enlarged plate-shaped positive electrode or negative electrode is folded or wound to a desired size. (However, when the plate-shaped positive electrode or negative electrode is folded or wound, the positive electrode or negative electrode of the folded line portion will generate elasticity, and the positive electrode plate or negative electrode plate of this portion is peeled off from the electrolyte layer such as the polymer electrolyte layer, so that The effective surface area of the interface between the electrode and the electrolyte is reduced, and the discharge capacity is reduced. At the same time, the internal resistance of the battery is increased, which sometimes causes the cycle characteristics of the discharge capacity to be deteriorated. (/ Similarly, due to the elasticity of the broken line, the positive or negative electrodes are formed separately. The active material layer will peel off from the current collector.) During charging or discharging of this battery, lithium ions are occluded and released in the positive and negative active materials, causing the positive and negative active material layers to expand and contract. As a result, stress is generated, causing the problem that the active material layer is peeled from the current collector. In order to solve these problems, it is proposed to form an adhesive layer between the current collector and the active material layer, so that the adhesive layer prevents the two from peeling or dense. The method of reducing the sensitivity is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the positive electrode active material layer and the positive electrode set. The adhesion layer provided between the electrical bodies and between the negative electrode active material layer and the negative electrode current collector must have the function of bonding the two and the function of conductivity. Therefore, the conductive material serving as electron conduction is dispersed in the two having the bonding. Among the polymer materials of functional adhesive materials, in order to solve these problems, for example, in the following prior documents (1) to (5), it is proposed to provide an adhesion layer between the current collector and the active material layer, This adhesive layer prevents the peeling of the two or the adhesiveness is reduced. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 567630 A7 _ B7_ V. Description of the invention () Technology. (1) Japanese special The Japanese Patent Publication No. 7-70328 proposes a current collector covered with a conductive coating film composed of a conductive adhesive (filler), and the materials of the adhesive in this invention include phenol resin, melamine resin, urine resin, Vinyl resin, alkyd resin, synthetic rubber, etc. (2) Japanese Unexamined Patent Publication No. 9-3 5 707 proposes forming a negative electrode material layer containing a binder composed of carbon powder and polyvinylidene fluoride (PVdF) on a negative electrode current collector, and on the negative electrode current collector. An adhesive layer composed of an acrylic copolymer mixed with a conductive agent is formed. In the present invention, the negative electrode plate formed of a copper foil using a copper foil uses an acrylic copolymer having high adhesion to copper, and can obtain a high adhesion effect. (3) Japanese Unexamined Patent Publication No. 10-149801 is to form a polyurethane resin or epoxy resin undercoat layer between the current collector and the active material layer to improve the active material coating film layer of the electrode and The tightness between the current collectors improves the cycle capacity maintenance characteristics of the battery. (4) Japanese Unexamined Patent Publication No. 10-144298 provides an adhesive layer composed of graphite and a binder between a negative electrode current collector and an active material layer. This invention is that the graphite contained in the adhesive layer has the function of improving the current collecting efficiency of the negative electrode. (5 Γ Japanese Unexamined Patent Publication No. 9-2 1 3370, the graft polymerized PVdF is used as the electrolyte part of the battery active material layer and the binder of the electrolyte layer. This invention uses graft polymerized PVdF as the battery active material layer. The use of a binder for the electrolyte part and the electrolyte layer can improve the contact efficiency with the current collector. I The characteristics required for the adhesion layer include, for example, adhesion to the current collector material and adhesion of the binder contained in the active material layer It is stable to organic solvents in the electrolyte, and has excellent long-term storage stability, thermal stability and no peeling at high temperatures, electrochemical stability, resistance to repeated charge and discharge, etc. ^ This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) 6 dagger —！ 丨 4 | — 丨 (Please read the precautions on the back before filling this page)

II Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, W Industrial Consumer Cooperative, 567630 A7 B7 V. Description of the invention () 4 (Please read the notes on the back before filling this page) But in the technology shown in (1) above, it is used as an adhesive The butyl rubber or phenylhydrazone resin will invade the uranium by the electrolyte, causing the problem of peeling. In the technique shown in the above (2), the acrylic copolymer is strongly adhered to the PVdF contained in the negative electrode material layer or the negative electrode current collector. Therefore, a conductive mixture is formed between the negative electrode current collector and the negative electrode layer. Adhesive layer of acrylic copolymer as the main component of the agent can improve the adhesion between the negative electrode current collector and the negative electrode material layer, but the acrylic copolymer will invade the uranium by the electrolyte and cause the problem of separation. When a polyurethane resin is used for the above undercoat layer, although the peel strength and the cycle number of 80% capacity are higher than those of the battery without the undercoat layer, it cannot be practically used. When epoxy resin is used, uranium is invaded by the electrolyte, and the active material layer may be peeled from the current collector. In the technology shown by (4) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the adhesive layer uses the same substance as the binder contained in the active material, so it has good adhesion with the sexual material layer of the adhesive layer, but has The adhesion of the current collector is not significantly different from that of an active material layer formed directly on the current collector, and the adhesion is insufficient. In addition, the electrolyte penetrates the adhesive, so the adhesive strength between the adhesive layer and the current collector is weak. (5) In the technique shown, a graft polymer polymer having high adhesion to the current collector is used as an adhesive for the active material layer, so it is not necessary to provide an adhesion layer, and it can be formed directly on the current collector. An active material layer, but this polymer is poorly soluble, so the available solvents are limited. The solvent inside the battery cannot be completely removed, and if the solvent remains inside the battery, the battery performance will be adversely affected. In the second conventional technique for solving the above-mentioned various problems, a carbon material powder of a conductive substance is dispersed in an adhesion layer. However, the paper size of this carbon material powder is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 567630 A7 _ B7__ V. Description of the invention ("5 (Please read the precautions on the back before filling this page) The conductivity is not Good, in order to obtain good conductivity, the mass ratio of carbon material to adhesive material (carbon material / adhesive material) must be increased. When the ratio of carbon material in the adhesive layer is increased, the amount of adhesive material in the adhesive layer The proportion is reduced, and the contact area with the current collector or active material layer of the binder material is reduced due to the bulk density of the carbon material, and the adhesion ability is insufficient. Either a stripe or a grid-like electrode for a battery coated with a patterned adhesive layer (Japanese Patent Application Laid-Open No. 1 1-73947). The paint for forming the above adhesive layer is formed by spraying or printing the battery electrode. The ratio of the coating area of the adhesive layer to the area of the active material layer holding surface of the current collector is 30 to 80% ° The battery electrode configured as described above is between the current collector and the active material An adhesive layer having a predetermined coating pattern is formed between the layers, so that it does not hinder the transfer of electrons between the current collector and the active material layer, which can improve the adhesion between the two and improve the cycle characteristics. Specifically, by The adhesive layer with a predetermined coating pattern ensures the adhesion between the current collector and the active material layer. In the uncoated part, the electron transfer between the current collector and the active material layer is smooth, which can reduce the resistance. Intellectual Property Bureau, Ministry of Economic Affairs Employee Consumer Cooperatives printed another technology (Japanese Patent Application Laid-Open No. 7-6752) that belongs to the third prior art. It was proposed that the binder constituting the battery electrode be uniformly dispersed in the electrode material. An electrode is formed on the current collector. Adhesive-dispersed electrode material, this electrode material is dried and press-formed, and then the electrode is manufactured by heat treatment. Using the electrode composed of the above two documents can produce high-performance secondary batteries with excellent discharge capacity characteristics, especially excellent cycle characteristics. In the third prior art mentioned above, the paper size of Japanese Unexamined Patent Publication No. 1 1-73947 applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by the Employees' Cooperatives of the Ministry of Economic Affairs of the Ministry of Finance 567630 A7 B7

V. Description of the Invention (J 6 In the past, the battery electrode had to form an adhesive layer on a dot, stripe, or grid-like coating pattern. The formation of the adhesive layer was difficult. The current collector and the active material layer When the area of the uncoated part that is used for electronic acceptance is large, the adhesion of the part cannot be ensured, and the problem of peeling must be solved. The conventional electrode system described in Japanese Patent Application Laid-Open No. 7-6752 mentioned above will be bonded. The polymer of the agent or the polymer electrolyte with adhesive effect is completely dissolved in the solvent, and then uniformly mixed with the carbon and active materials of other materials to prepare the coating slurry. Therefore, the active material layer and the current collector are dense. Insufficient strength and the reduction of the charge-discharge cycle characteristics of the battery still need to be solved. The reason may be that a large amount of powder materials such as carbon added to the coating slurry exist at the interface between the current collector and the active material layer. It is disclosed that the f-th object of the present invention is to provide a positive electrode current collector and a positive electrode active material layer or a negative electrode current collector and a negative electrode active material layer with excellent adhesion and conductivity, and A lithium ion polymer secondary battery with improved cycle capacity maintenance characteristics. A second object of the present invention is to provide an adhesion layer between a positive electrode current collector and a positive electrode active material layer or a negative electrode current collector and a negative electrode active material layer. Lithium-ion polymer secondary battery with stable organic solvent in the liquid and excellent long-term storage stability. A third object of the present invention is to provide a lithium-ion polymer II that can suppress the strong acid such as fluoric acid from corroding the current collector in the battery. The secondary / battery. The first / objective of the present invention is to provide a dense paper size set between the positive electrode current collector and the positive electrode active material layer or between the negative electrode current collector and the negative electrode active material layer. The Chinese paper standard (CNS) A4 is applicable. Specifications (210X 297mm) (Please read the notes on the back before filling this page)

567630 A7 B7 V. Description of the invention (7) A method for synthesizing the aforementioned binder for the adhesion layer of a lithium ion polymer secondary battery with excellent adhesion and electrical conductivity. (Please read the precautions on the back before filling this page.) The ninth aspect of the present invention is to provide excellent adhesion and conductivity between the current collector and the active material layer, and improve the cycle capacity maintenance characteristics of the secondary battery. Electrode for secondary battery and secondary battery using the electrode. The first aspect of the present invention is provided with a first binder containing a polymer compound on the surface of the positive electrode current collector and a positive electrode containing a positive electrode active material layer, and the same as or the same as the first binder is provided on the surface of the negative electrode current collector. In the second binder of different polymer compounds, the negative electrode of the negative electrode active material layer containing the negative electrode active material, and the lithium ion polymer secondary battery of the electrolyte, there is a first electrode between the positive electrode current collector and the positive electrode active material layer. Adhesive layer, a second adhesive layer between the negative electrode current collector and the negative electrode active material layer, and the first and second adhesive layers contain a third adhesive and a conductive substance, respectively, and the third adhesive contains a borrow One or both of the polymer compounds contained in the first adhesive or the second adhesive is made of a denatured substance, or the repeating unit of any one of these polymer compounds is the height of the repeating unit. Lithium-ion polymer secondary battery obtained by denaturation of molecular compounds, and the third adhesive contained in the first and second adhesion layers when printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Employees ’Cooperative The high-molecular compound in the present invention is one or both of the first or second high-molecular compounds contained in the positive electrode active material layer or the negative electrode active material layer by a denatured substance, or contains (these (A) Any one of the repeating units of the polymer compound is a polymer compound obtained by denaturing the polymer compound of the repeating unit, so each adhesive layer has a higher adhesive force to the positive electrode active material layer or the negative electrode active material layer. The third adhesive is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) by changing the paper size. -10- 567630 A7 B7 V. Description of the invention (8) (Please read the precautions on the back before filling in this Page) The substance is one or both of the polymer compounds contained in the first adhesive or the second adhesive, or the repeating unit containing any one of the polymer compounds (these) is the repeating unit. Since the polymer compound obtained by denaturing the polymer compound, the adhesion of each adhesive layer to the positive electrode current collector or the negative electrode current collector is greatly improved compared with the conventional adhesive. The first aspect of the present invention includes a first binder provided on the surface of the positive electrode current collector and a positive electrode containing a positive electrode active material layer, and a second binder provided on the surface of the negative electrode current collector which contains the same or different from the first binder. A negative electrode containing a negative electrode active material layer containing a negative electrode active material and a lithium ion polymer secondary battery having an electrolyte, wherein the positive electrode current collector and the positive electrode active material layer have a first adhesion layer between the positive electrode current collector and the negative electrode current collector. There is a second adhesive layer between the negative electrode active material layer and the first and second adhesive layers, respectively, containing a third binder and a conductive substance, and the third binder contains a fluorine-containing polymer compound by a denaturing substance. Lithium-ion polymer secondary battery of denatured polymer compound. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. According to the second aspect, one or both of the polymer compounds contained in the aforementioned first and second adhesives is preferably a fluorine-containing polymer compound. The fluorine-containing polymer compound or the fluorine-containing polymer compound of the third binder in the second or third aspect is preferably selected from polytetrafluoroethylene, polychlorotrifluoroethylene, PVdF, and vinylidene fluoride-hexafluoropropylene copolymer. Or fluorine-containing polymer compounds of polyvinyl fluoride. The polytetrafluoroethylene and PVdF of the above-mentioned fluorine-containing polymer compound are preferable because of their high durability in the electrolytic solution. In the first or second aspect, from the viewpoint of obtaining good adhesion with the current collector, the aforementioned denatured substance is preferably selected from ethylene, styrene, butadiene, and the Chinese paper standard (CNS) A4 is applied to the paper size. Specifications (210X297 public director) '-11-567630 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7_ V. Description of the invention () 9 Vinyl acetate, acrylic acid, methyl acrylate, methyl vinyl ketone, acrylic 醯Compounds of amines, acrylonitrile, vinylidene chloride, methacrylic acid, methyl methacrylate or isoprene. The aforementioned denatured substances are more preferably acrylic acid, methyl acrylate, methacrylic acid, and methyl methacrylate. In the first or second aspect, the thickness of the first and second adhesion layers is preferably 0.5 to 30 μm. When the thickness of the first and second adhesion layers is 0.5 μm or less, the current collector is protected. The function of the body to be corroded is reduced, and the cycle characteristics of the discharge capacity are deteriorated. When the first and second adhesion layers are formed, it is difficult to uniformly disperse the conductive powder, which leads to an increase in internal resistance. When the thickness of the first and second adhesion layers exceeds 30 m, the volume and mass of the part not participating in the battery reaction will increase, so the volume and mass energy density will decrease. The thickness of the adhesion layer is preferably 1 to 15 μm. In the 1st or 2nd aspect, it is preferable that the said 1st and 2nd adhesion layer contain 0.1-20 mass% of dispersing agents. The first and second adhesion layers contain a dispersant in an amount of 0.1 to 20% by mass, and the conductive material can be uniformly dispersed in the first and second adhesion layers. Examples of the dispersant include an acidic polymer-based dispersant, a basic polymer-based dispersant, and a neutral polymer-based dispersant. When the dispersant content is 0.1% by mass or less, the dispersion of the conductive powder is the same as that in the case where no dispersant is added, and there is no addition effect. When the content of the dispersant exceeds 20% by mass, the dispersion state of the conductive powder is not changed, and no battery reaction is involved, so it is not necessary to add an excessive amount. The content of the dispersant is more preferably 2 to 15% by mass. In the first or second aspect, the particle size of the aforementioned conductive substance is 0.5 to 30 μ (please read the precautions on the back before filling in this page) This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm)- 12- 567630 Printed by A7 B7, Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (^ m, this material uses a carbon material with a graphitization degree of 50% or more, and the third adhesive contained in the first and second adhesive layers The mass ratio of the agent to the conductive substance (third binder / conductive substance) is preferably 13/87 to 50/50. When the aforementioned mass ratio is 13/87 or less, the proportion of the third binder in the adhesion layer is present. When the mass ratio exceeds 50/50, there is less conductive material in the adhesion layer, the electron movement between the current collector and the active material layer is insufficient, and the internal resistance increases. The third adhesive and The mass ratio of the conductive material is more preferably 14/86 to 33/67. Ί The synthesis method of the third binder contained in the adhesion layer of the lithium ion polymer secondary battery of the first / morphological system of the present invention, the third The bonding agent is the first bonding of (a) the first form by a denaturing substance One or both of the polymer compounds contained in the agent or the second binder, or (b) a polymer compound containing repeating units of any one of these polymer compounds as repeating units, Or (c) The second form of the fluorine-containing polymer compound is denatured. When the third binder is 100% by mass, the ratio of the denatured substance contained in the third binder is 2 to 50% by mass. Synthesis method. (When the ratio of the denatured material contained in the third adhesive is the above ratio, a third adhesive with excellent adhesion and conductivity can be obtained. The ratio of the denatured material contained in the third adhesive is 2 When the content is less than mass%, the adhesive strength to the current collector is low, and when it exceeds 50% by mass, it is not easy to dissolve in the solvent. The proportion of the denatured substance contained in the adhesive is preferably 10 to 30% by mass. It is ideal to mix the denatured substance and the irradiated substance for graft polymerization after the above-mentioned (a) (b) or (c) polymer compound is irradiated with radiation. The aforementioned denaturation of the denatured substance can also be adapted to the paper size. Closed House Standard (CNS) A4 Specification— (YlGX297 Gongchu) — -13- (Please read the precautions on the back before filling out this page) 567630 A7 B7 V. Description of the invention () " 11 ) (b) or (c) the polymer compound is mixed and then irradiated with radiation to carry out graft polymerization. (Please read the precautions on the back before filling out this page) of the above (a) (b) or (c) The radiation of the polymer compound is performed by irradiating r rays so that the absorption line of the polymer compound (a) (b) or (C) becomes 1 to 1 20 kGy. When the absorption line is below 1 kGy or exceeds 120 kGy, the adhesive strength of the obtained adhesive decreases. The fourth aspect of the present invention is the aforementioned lithium ion polymer secondary battery of the first or second aspect, (the first and second conductive substances contain a metal or a partial metal oxide having a particle diameter of 0.1 to 20 μm, and the first dense Mass ratio of the third adhesive and the first conductive substance contained in the adhesion layer (the third adhesive / the first conductive substance) and the ratio of the third adhesive and the second electrically conductive substance contained in the second adhesion layer Lithium-ion polymer secondary batteries with mass ratios (third binder / second conductive substance) of 13/87 to 75/25, respectively. The Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs printed the aforementioned first and second dense Because the first or second conductive substance contained in the coating layer contains a metal or part of a metal oxide, due to the good electrical conductivity of the metal, the amount of carbon added to the adhesion layer is higher than that of carbon used as a conductive material in the past. With less material, good electron conductivity can be obtained. The particle size of the first or second conductive material, and the mass ratio of the third adhesive to the first conductive material contained in the first adhesive layer (the third adhesive / The first conductive substance) and the quality of the third adhesive and the second conductive substance contained in the second adhesive layer The range of the ratio (the third binder / the second conductive substance) is limited to each predetermined range, and good adhesion, electronic conductivity, and cycle capacity maintenance characteristics can be obtained.? The first and second conductive substances described above Contains materials selected from aluminum, copper, and iron. Paper standards applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm) -14- 567630 A7 B7 V. Description of the invention (^, nickel, cobalt, silver, gold, platinum, palladium And one or two or more mixtures or alloys of which some of these metals are partially oxidized and some of the metal oxides are grouped together. The first and second adhesion layers are more preferably containing an acidic polymer-based dispersant and a basic polymer. Dispersant or neutral polymer-based dispersant. The f-th aspect of the present invention is a secondary battery in which an active material layer is provided on one or both sides of a current collector in an adhesive layer containing a polymer binder. For the electrode, a part of the polymer binder is present in the adhesive layer in the form of particles, and the volume-average particle diameter of the particulate polymer binder is 1 to 100 μm for an electrode for a secondary battery. Particles in landing Polymer binders are conductive substances that exist in the form of particles, and are also present at the interface between the current collector and the adhesion layer, and at the interface between the active material layer and the adhesion layer, improving the adhesion of these interfaces. Particle-free There is a conductive substance at the interface between the current collector and the adhesion layer of the polymer binder, and at the interface between the active material layer and the adhesion layer. The conductive substance allows the electron transfer at the interface to proceed smoothly, and low resistance can be maintained. As the particulate polymer binder is contained in the adhesive layer, the cohesive force inside the adhesive layer can be improved, and the cycle capacity maintenance characteristics of the battery can be improved. The main component of the polymer adhesive is preferably a fluorine-based resin. The main component of the binder is a fluorine-based resin to obtain an electrolyte-resistant secondary battery electrode. The aforementioned polymer binder is preferably a compound obtained by graft-polymerizing a monomer of acrylic acid or methacrylic acid with polyvinylidene fluoride. The use of acrylic acid or methacrylic acid as a denaturing substance can provide an electrode for a secondary battery containing a good adhesion to a current collector. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling out this page}-Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives -15- 567630 A7 B7 V. Description of the invention (^ The area density of the aforementioned particulate polymer binder is 1 to 100 pieces / cm2, which can bond the particulate polymer at the interface between the current collector and the adhesion layer and the interface between the active material layer and the adhesion layer. The distribution density of the agent is appropriate to ensure the adhesion and conductivity of the interface. When the area density exceeds 100 pieces / cm2, the conductivity of the interface decreases, and when the area density is 1 piece / cm2 or less, the adhesion of the interface decreases. The more desirable area density is 10 to 80 pieces / cm2. The sixth aspect of the present invention is a secondary battery including the aforementioned secondary battery electrode of the fifth aspect. This secondary battery has excellent cycle capacity maintenance characteristics. Brief description Fig. 1 is a partial cross-sectional structural view showing a current collector of a lithium ion polymer secondary battery of the present invention. Fig. 2 is a view showing a third binder obtained in Examples 5 to 11 and Comparative Examples 5 and 6. Evaluation test ② Results. Fig. 3 shows the results of the evaluation test ④ of the third adhesive obtained in Examples 5 to 11 and Comparative Examples 5, 6. Fig. 4 shows the results of Examples 12 to 16 and Comparative Examples 7, 8 The results of the third adhesive evaluation test ②. Fig. 5 shows the results of the third adhesive evaluation test ④ obtained in Examples 12 to 16 and Comparative Examples 7 and 8. Fig. 6 shows the third adhesive of the present invention. Form of the lithium ion polymer secondary battery: AA line cross-sectional structure diagram of Figure 7. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 567630 A7 ________ B7 V. Description of the invention (^ 117 Negative electrode current collector layer 118 Negative electrode 121 Polymer electrolyte layer 119 Second adhesion layer 122 Roller 122a End edge 123 Positive terminal 124 Negative terminal 122b Side edge 125 Package body 152 Bend body 152a Ideal implementation of side edge (please read the precautions on the back before filling this page) Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative, printed this invention The first and second adhesive layers of the lithium ion polymer secondary battery of the first embodiment contain a third binder and a conductive substance, respectively. The third binder is a first binder or a second binder by a denatured substance. The polymer compound obtained by denaturing the binder. "Denaturation" refers to changing properties. In this specification, a polymer compound is denatured with a denaturing substance, which not only has the properties of the polymer compound before denaturation, but also has Have properties, or have properties that are absent from both. The polymer compound after the denaturation is mainly the first binder or the second binder in the active material layer, and therefore has high adhesion to the active material layer. In addition, this paper size applies the Chinese National Standard (CNS) A4 specification (210X29? Mm) — -18- 567630 A7 B7 V. Description of the invention (^ (Please read the precautions on the back before filling this page) The denatured material with high body adhesion is denatured, and the adhesion with the current collector is much greater than when the same binder as the active material layer is used. Therefore, the active material layer can be prevented from peeling off the current collector and the cycle can be improved. Characteristics. After denaturation, the denatured polymer compound has better chemical stability than the adhesive used for the active material layer, and it will not dissolve in the electrolyte, which can inhibit the active material layer from peeling off the current collector. The same reason The conductive substance dispersed in the adhesive layer will not collapse, so it can maintain good electronic conduction, and it has excellent long-term storage or cycling characteristics. The current collector is coated on a chemically stable layer, even for batteries When fluoric acid occurs inside, the adhesion layer becomes a protective layer, which can suppress the corrosion of the current collector. ^ The thermal stability of the denatured polymer compound printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs after denaturation, It is better than the binder used in the active material layer. Even if the battery is at high temperature, it will not dissolve in the electrolyte in the battery, which can inhibit the deterioration of the battery. The electrochemical stability of the denatured polymer compound after denaturation Better than the binder used for the active material layer, even when the positive electrode is fully charged, it will not deteriorate at high potential, maintain stable adhesion and conductivity. Because the electrolyte is difficult to penetrate into the denatured polymer compound, so Almost no electrolyte adheres to the current collector, which can suppress the dissolution of the positive electrode current collector when fully charged. Next, the manufacturing sequence of the lithium ion polymer secondary battery of the present invention will be described. First, the second embodiment of the present invention is The binder contained in the positive electrode active material layer or the negative electrode active material layer is denatured by the denaturing material, and the denatured polymer compound is used as the third binder of the first and second adhesion layers. The layer requires chemical, electrochemical, and thermal stability, so this paper size applies the Chinese National Standard (CNS) A4 specification (210'〆297 mm)-Yin-567630 A7 B7 ((Please read the precautions on the back before filling out this page) The polymer compound contained in the first and second binders for the active material and used as the raw material of the denatured polymer compound is ideally high in fluorine in the molecule Molecular compounds. Examples of fluorine-containing polymer compounds include polytetrafluoroethylene, polyvinylidene fluoride, PVdF, vinylidene chloride-hexafluoropropylene copolymer, and polyvinyl fluoride. Methods for denaturing fluorine-containing polymer compounds For example, there are graft polymerization, cross-linking, etc. Denatured substances used for graft polymerization include ethylene, styrene, butadiene, ethyl chloride, ethyl acetate, propionic acid, methyl propionate, methyl ester, etc. Compounds of vinyl vinyl ketone, acrylamide, acrylonitrile, vinylidene chloride, methacrylic acid, methyl methacrylate, etc. In particular, acrylic acid, methyl acrylate, methyl acrylate, methacrylic acid, and methyl methacrylate are used. In the case of an ester, good adhesion to a current collector can be obtained. Denatured substances used for crosslinking are compounds having more than two unsaturated bonds, such as butadiene, isoprene, and the like. It can also be cross-linked by vulcanization.) Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by Du, an example of this embodiment is graft polymerization. Methods of the graft polymerization include, for example, a catalyst method, a chain transfer method, a radiation method, a photopolymerization method, and a mechanical cutting method. For example, in the radiation method, a polymer compound is mixed with a compound that becomes a grafted material, and radiation is intermittently or continuously irradiated to polymerize, so that the polymer compound and the grafted material are brought into contact with the polymer compound that is irradiated with the main component in advance. Specifically, after a polymer compound is irradiated with radiation, a denatured substance that becomes a grafted material is mixed with the above-mentioned irradiated substance to obtain a denatured polymer compound having a polymer compound as a main chain and a denatured substance as a side chain. The radiation used for the graft polymerization is, for example, electron beam, X-ray or r-ray. Irradiation of r-rays makes the absorption line of the polymer compound 1 to 120 kGy. The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -20- 567630 A7 — ^ -— V. Description of the invention (j 丨 丨 丨 If (please read the precautions on the back before filling this page) Radiation is irradiated on the high molecular compound of the main component, and radicals can be formed at a single end to make the grafted material easily polymerized. The following chemical formula (η and chemical formula (2)) represents the graft polymerization of PVdF and acrylic acid by radiation method. Η Γ Η HF Η II., Ir radiation 1 i Η, -CC-fCHeC ^ C —-— CC-tCH ^ CFgj ^ C- — (1)

a F Η Η H

H F 珏 H F H H * R H CH2-CH2 fl

COOH As shown in Chemical Formula (1), PVdF is irradiated with r-rays to form free radicals in the molecules of PVdF. Acrylic acid is brought into contact with PVdF having radicals in the molecule, and the double bond portion of acrylic acid is graft-polymerized with PVdF radicals. In addition, chemical formulas (3) and (4) represent graft polymerization of PVdF and fluorinated propionic acid. ) Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economy fl F Η 1 " 1 (3)

Η F I C

H a

, I f H «H IH ch2-ch-ch3 COOH ⑷ This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-567630 A7 —_B7 V. Description of the invention (^ (Please read the back first) Please note that this page is to be filled in again.) As shown in chemical formula (3), irradiate PVdF with r rays to form free radicals in the molecule of PVdF. As shown in chemical formula (4), methacrylic acid has free radicals in the molecule. When PVdF is contacted, the double bond portion of methyl propionate is graft polymerized with the free radical of PVdF. Graft polymerization is a polymer that is radiated due to the contact time between the activated polymer main chain and the grafted monomer. The degree of preparatory activity of the main chain, the ability of the aforementioned monomer to penetrate the polymer main chain, the temperature at which the grafted polymer and the monomer come into contact produce different grafted products. The grafted monomers are When acid is used, a graft reaction solution containing monomers is taken at any time, and the residual monomer concentration is measured by titration. The degree of graft polymerization reaction can be observed. The grafting ratio in the obtained composition is preferably the final quality. 1 0 ～ 30 from the above The graft polymerized denatured polymer compound is the third adhesive of the adhesion layer. This third adhesive is dissolved in a solvent to prepare a polymer solution, and the conductive substance is dispersed in the polymer solution to prepare the first and second denses. Coating layer paste. The particle size of printed conductive materials used by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is 0. 5 ~ 30μm carbon materials with a graphitization degree of more than 50%. The mass ratio of the third bonding agent to the conductive material (third bonding agent / conductive material) is 13/87 to 50/50, and the slurry of the adhesive layer is prepared. As the solvent, DiMethyl Acetamide (hereinafter referred to as DMA), acetone, dimethylformamide, and N-methylpyrrolidone can be used. Next, plate-shaped positive and negative electrode current collectors are prepared, and the prepared first and second adhesive layer pastes are applied to the positive and negative electrode current collectors by a doctor blade method, respectively. The thickness of the adhesion layer is 0. 5 ~ 30μm This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297mm) -22- 567630 A7 B7 V. Description of the invention ((Please read the precautions on the back before filling this page) The positive and negative electrode current collectors of the second adhesion layer. The thickness of the positive and negative electrode adhesion layers after drying is preferably 1 to 15 μm. The plate-shaped positive electrode current collector is, for example, A1 foil, and the negative electrode current collector is, for example, There is Cu foil. The scraper method here refers to the thickness of the slippery mud carried on a carrier such as a carrier film or an endless belt. The thickness of the board is precisely controlled by adjusting the distance between the blade edge called the scraper and the carrier. Next, the components required for the positive electrode active material layer, the negative electrode active material layer, and the electrolyte layer are mixed separately to prepare a slurry for coating a positive electrode active material layer, a slurry for coating a negative electrode active material layer, and a slurry for coating an electrolyte layer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the prepared positive electrode active material layer coating slurry was applied to the positive electrode current collector having the first adhesion layer by a doctor blade method, and dried and extended to form a positive electrode. . The electrodes are the same, and the prepared slurry for coating the negative electrode active material layer is spread on the negative electrode current collector having the second adhesion layer by a doctor blade method, and the negative electrode is dried and stretched to form a negative electrode. Positive electrode or negative electrode active material layer The thickness after drying is 20 to 250 μm. The electrolyte layer is coated on the release paper by a doctor blade method, and dried to form a dry thickness of the electrolyte layer of 20 to 250 μm. The formed layer is peeled off. The slurry for coating the electrolyte layer is coated on the surface of the positive electrode or the surface of the negative electrode and dried to form the electrolyte layer. The formed positive electrode, electrolyte layer, and negative electrode are sequentially laminated, and the laminate is heated. Press-bonding can form a plate-shaped electrode body as shown in Fig. 1. Finally, a positive electrode conductor and a negative electrode conductor made of Ni are welded to the positive electrode collector and the negative electrode collector on the electrode body, and the electrode body is stored and processed to have an opening. In a bag-like laminated packaging material, under pressure, the openings are closed by hot pressing to produce a plate-shaped lithium ion polymer secondary battery. This paper is applicable to the Chinese National Standard (CNS) A4 Grid (210X297 mm) -23- 567630 A7 _ B7 V. Description of the invention (21 Next, the third embodiment of the present invention will be described based on the drawings. As shown in FIG. 6, the lithium ion polymer secondary battery 111 is provided in A positive electrode 113 composed of a positive electrode binder and a positive electrode active material layer 112 containing a positive electrode active material is provided on the surface of the positive electrode current collector layer 112; a negative electrode binder and a negative electrode active material containing a negative electrode active material are provided on the surface of the negative electrode current collector layer 117. The negative electrode 118 of the material layer 116; a polymer electrolyte layer 121 provided between the surface of the positive electrode active material layer 111 of the positive electrode 113 and the surface of the negative electrode active material layer 116 of the negative electrode 118. The positive electrode current collector layer 112 is Formed from A1 foil, the positive electrode active material layer 111 contains a positive electrode active material and a binder for a positive electrode. As the positive electrode active material, powders such as LiCoCh, LiNiCh, and LiMn04 can be used. The negative electrode current collector layer 117 is formed of a Cu foil, and the negative electrode active material layer 116 includes a negative electrode active material and a binder for a negative electrode. As the negative electrode active material, a powder of a carbon material such as graphite can be used. The binder for the positive electrode and the binder for the negative electrode require chemical, electrochemical, and thermal stability. Therefore, the main component of the binder for the positive electrode and the binder for the negative electrode is preferably a polymer compound containing fluorine in the molecule. Examples of the fluorine-containing polymer compound include polytetrafluoroethylene, polychlorotrifluoroethylene, PVdF, vinylidene fluoride-hexafluoropropylene copolymer, and polyvinyl fluoride. The polymer electrolyte layer 1 2 1 can be used, for example, containing a lithium salt (for example, etc.) dissolved in an organic solvent (for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl ethyl carbonate, butadiene). Ester, etc.) polymer plate of electrolyte (such as fluororesin of polyvinylidene fluoride or polyvinylidene fluoride-hexafluoropropylene copolymer, or polymer plate of polyethylene oxide, etc.). This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) 丨 — 丨 — 1! —, #! (Please read the precautions on the back before filling this page)

、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-24- 567630 A7 B7________ V. Invention Description (j (please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives I positive set A first adhesive layer 114 including a first binder and a first conductive material is provided between the electric current layer 112 and the positive electrode active material layer 111. A second binder is provided between the negative electrode current collector layer 117 and the negative electrode active material layer 116. The second adhesive layer 119 of the second conductive material is formed by dispersing the first conductive material in the first adhesive. Similarly, the second adhesive layer 119 is the second conductive material The first adhesive layer 114 or the second adhesive layer 119 is formed by dispersing a substance in the second binder. The chemical, electrochemical, and thermal stability are required, and the adhesiveness with the current collector layer and the active material layer is required. Therefore, the main component of the first binder or the second binder is the main component of the positive electrode binder or the negative electrode binder contained in the positive electrode active material layer or the negative electrode active material layer. The first and second conductive materials are Use particle size of 0. 1 ~ 20μm of metal or part of metal oxide. The particle size of these first and second conductive materials is 0. 1 ~ 20μιη. Ideal is 0. 3 ~ 15μιη. The particle size is 0. When the length is less than μμη, the particles are agglomerated and the conductive material cannot be sufficiently dispersed on the current collector, so the electron conductivity is reduced, and the output characteristics are deteriorated. The ratio of the agglutinating agent is small, the adhesion is poor, and the cycle characteristics are also poor. When the particle diameter exceeds 20 µm, the thickness of the adhesive layer increases, so the volume energy density decreases. Since conductive materials are difficult to contact with each other, the electron conductivity is reduced, and the output characteristics are deteriorated. Examples of the metal include aluminum, copper, iron, nickel, cobalt, silver, gold, platinum, and palladium. Some metal oxides include oxides in which a part of the metal is oxidized. As the first and second conductive materials, a mixture or an alloy selected from the group consisting of the above-mentioned metals or partial metal oxides may be used. The first and second conductive materials are metals or partial metal oxides, and good electronic conductivity can be obtained with a small amount of addition, so the volume of the conductive materials can be greatly reduced. This paper applies Chinese National Standard (CNS) A4 specifications ( 210 × 297 mm) 567630 A7 ____ B7 _—__ 5. Description of the invention () 23. Therefore, the adhesion amount can be increased to obtain good adhesion. (Please read the precautions on the back before filling this page.) (The composition of the first embodiment of the present invention is mixed so that the mass ratio of the first adhesive and the first conductive substance contained in the first adhesive layer 114 (the first 1 adhesive / first conductive substance) and the mass ratio of the second adhesive to the second conductive substance (the second adhesive / the second conductive substance) contained in the second adhesive layer 119 are 13/87, respectively. ~ 7 5/25. The mass ratio of the first adhesive and the first conductive substance contained in the first adhesive layer 114 and the ratio of the second adhesive and the second conductive substance contained in the second adhesive layer 119 are changed. The mass ratios are respectively limited to the ranges specified above, and the positive electrode current collector and the positive electrode active material layer or the negative electrode current collector and the negative electrode active material layer can be obtained with excellent adhesion and conductivity, and can improve the cycle capacity maintenance characteristics Lithium-ion polymer secondary battery. The first binder / the first conductive substance and the second binder / the second conductive substance are 13/87 to 75/25, respectively, and preferably 14/86 to 3 3/67. When the mass ratio is 13/87 or less, the ratio of the binder decreases, and sufficient adhesion cannot be obtained. When the mass ratio exceeds 75/25 There are few conductive materials in the adhesion layer, the electron movement between the current collector and the active material layer is insufficient, and the internal impedance increases. When the positive electrode 113 is printed and produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it is prepared to use plate A1 foil. The formed positive electrode current collector is coated with the first adhesive layer slurry on this positive electrode current collector 112, and dried to form a dried first adhesive layer having a thickness of 0. A positive electrode current collector with a first adhesion layer of 5 to 30 m. The thickness of the first adhesive layer after drying is preferably 1 to 15 μm. A desired component is mixed in the positive electrode active material layer to prepare a slurry for coating a positive electrode active material layer. The prepared positive electrode active material layer coating slurry was applied on the surface of a positive electrode current collector having a first adhesion layer, and dried and rolled to form a positive electrode 11 3. The thickness of the positive electrode active material layer after drying is 20 ^ Paper size is applicable to China National Standard (CNS) A4 (210X297 mm) • 丨 -26- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 567630 A7 B7

Fives, Description of the invention (J 24 to 250 μm 〇 When making the negative electrode 118, Prepare a negative electrode current collector made of plate-shaped Cu foil, Apply the prepared second adhesive layer paste on this negative electrode current collector, After drying, a negative electrode current collector having a second adhesion layer with a thickness of 0.5 to 30 m after the drying of the second adhesion layer was formed. The thickness of the adhesive layer of the negative electrode after drying is preferably 1 to 15 μm. The desired components are mixed in the negative electrode active material layer, respectively. A slurry for coating a negative electrode active material layer was prepared. Same as the manufacturing method of the positive electrode, Apply the prepared negative electrode active material layer coating slurry on the surface of a negative electrode current collector having a second adhesion layer, After drying, The rolling forms a negative electrode. The thickness of the negative electrode active material layer after drying is 20 to 250 μm.  When manufacturing the polymer electrolyte layer 121, The desired components are mixed in the polymer electrolyte layer. A slurry for coating a polymer electrolyte layer was prepared. Apply the electrolytic layer coating slurry on a release paper, After drying, The dry thickness of the electrolyte layer is 10 ~ 150 μm. A polymer electrolyte layer can be obtained by peeling from a release paper.  The polymer electrolyte layer 121 is laminated at a slightly reversed center, To cover both sides of the base end of the negative electrode 11 8 After fragrant, the positive electrode 113 was laminated on this part of the laminate, Make a laminate. Then the laminate is rolled into a flat roll, The roller body 122 is produced (Figs. 6 and 7). As shown in Figure 7, One end of the positive electrode current collector 112 of the roller body 122 electrically connected to the positive electrode terminal 123 of a single plate-shaped Ni is provided on one of the end edges 122a of the roller body 122, A negative electrode terminal 124 composed of a single plate-shaped Ni which is electrically connected to the negative electrode current collector 117 of the roller body 122 at one end is provided on the other side edge 122b of the roller body 122 in a protruding state. Make the other paper end of the positive terminal 123 and the negative terminal 124 above the Chinese paper standard (CNS) A4 (210X25) 7 mm) ~ -27- (Please read the precautions on the back before filling this page )

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 567630 A7 ____B7_ V. Description of the invention (^ The other end is exposed, and the above-mentioned roller body 122 is sealed by the package 125 (FIG. 6 and FIG. 7). When one end and the other end of the negative terminal 124 are exposed, the above-mentioned roller body 1 22 is housed in a laminated packaging body 125 processed into a bag shape having an opening portion, and the opening portion is closed by hot pressing under reduced pressure to produce A plate-shaped lithium ion polymer secondary battery. Next, the fourth embodiment of the present invention will be described. In FIG. 8, the same reference numerals as those in FIG. 6 indicate the same components. "Here, this laminated body is zigzag" means that the laminated body is bent into a zigzag shape (such as a snake). Except for the above, its structure is the same as that of the first embodiment. The manufacturing process will be described using the positive electrode 113 and the negative electrode 118. Method for a secondary battery. First, a negative electrode 118, a polymer electrolyte layer 121, and a positive electrode 113 are laminated to form a laminate, and the laminate is folded into a zigzag shape to produce a flat bent body 1 52 (Fig. 8 and Fig. 9). As shown in Figure 9, one end is electrically connected A single plate-shaped positive electrode terminal 123 of the positive electrode current collector 112 of the bent body 152 is provided on a side edge 152a of the bent body 152 in a protruding state, and a single plate of the negative electrode current collector 117 of the bent body 152 is electrically connected at one end. The negative electrode terminal 124 is provided on the other edge of the bent body 152 in a protruding state. The other end of the positive terminal 1 23 and the other end of the negative terminal 1 24 are exposed through the package 125 (FIG. 8 And FIG. 9) The bent body 152 is sealed. The lithium ion polymer secondary battery 150 having the above structure has fewer assembly steps than the first embodiment. Next, the fifth embodiment of the present invention will be described. As shown in FIG. The lithium-ion polymer secondary battery has a laminated positive electrode 11 and this paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling this page)

-28- 567630 A7 _ B7 V. Description of the invention (j (Please read the precautions on the back before filling this page) The electrode body 10 formed by the negative electrode 14. This positive electrode 11 is formed by the plate-shaped positive electrode current collector 12 The positive electrode active material layer 13 is provided on the surface, and the negative electrode 14 is a plate-shaped negative electrode current collector 16 provided with the negative electrode active material layer 17 on the surface. It is interposed between the positive electrode active material layer 13 and the negative electrode active material layer 17. In the state of the provided electrolyte layer 18, the positive electrode 11 and the negative electrode 14 are laminated to form an electrode body 10. At this time, the positive electrode active material layer 13 contains a second binder in addition to an active material such as LiCoCh. The positive electrode current collector 12 and the positive electrode A first adhesion layer 19 is provided between the active material layers 1 3, and a second adhesion layer 21 is provided between the negative electrode current collector 16 and the negative electrode active material layer 17. The first and second adhesion layers 19 and 21 each contain polymerization. Polymer adhesive and conductive material. The polymer adhesive in this embodiment is a polymer compound obtained by denaturing the first adhesive or the second adhesive with a denaturing substance. "Denaturation" means the same as in the first embodiment. Meaning. Secondary power in this embodiment Part of the polymer binder for the pool electrode exists in the adhesive layer 19, 21 in the form of particles. The volume average particle diameter of the particulate polymer binder is 1 to 100 μm. 0 Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs The battery electrodes 11 and 14 having such a structure are printed by a cooperative, and the particulate polymer binder existing in the adhesive layers 19 and 21 is a conductive substance existing in a particle state and also existing in the current collector 1 2 The interface between 16 and the adhesion layer 19, 21, and the interface between the active material layers 13, 17 and the adhesion layer 19, 21 improve the adhesion of these interfaces. It does not contain a collection of particulate polymer binders A conductive substance is present at the interface portion between the electric body 12, 16 and the adhesion layer 19, 21 and an active material layer 13, 17 and the adhesion layer 19, 21. The electronic acceptance of this interface is carried out smoothly, and low resistance can be maintained. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -29- 567630 A7 B7 5. Description of the invention (because part of the polymer adhesive is based on The state of particles exists in the adhesion layers 19, 21, The mechanical strength of the adhesive layers 19 and 21 can also increase the strength of the adhesive layers 19 and 21 through the active material layers 13 and 17 which are laminated. A stripe or grid-like coating pattern is restricted, and the formation of the adhesive layer 19, 21 is easier than when a predetermined coating pattern is required to be formed. Next, the second embodiment of the fifth embodiment of the present invention will be described. Manufacturing sequence of electrodes for secondary batteries. First, the binder contained in the positive electrode active material layer or the negative electrode active material layer is denatured with a denaturing material, so that the denatured polymer compound becomes the polymer adhesion of the first and second adhesion layers. Agent. The first and second adhesive layers 19 and 21 require chemical, electrochemical, and thermal stability. Therefore, the polymer compounds used as the first and second adhesives of the active material layer and the raw materials of the denatured polymer compounds are preferably A polymer compound containing fluorine in its molecule. Examples of the fluorine-containing polymer compound include polytetrafluoroethylene, polychlorotrifluoroethylene, PVdF, vinylidene fluoride-hexafluoropropylene copolymer, and polyfluoroethylene. Methods for denaturing the fluorine-containing polymer compound include, for example, graft polymerization and crosslinking. Denatured substances used for graft polymerization include, for example, ethylene, styrene, butadiene, vinyl chloride, vinyl acetate, acrylic acid, methacrylate, fluorenyl vinyl ketone, acrylamide, acrylonitrile, vinylidene chloride, Compounds such as methacrylic acid and methyl methacrylate. In particular, when acrylic acid, methyl acrylate, methyl acrylate, methacrylic acid, or methyl methacrylate is used, good adhesion to the current collector can be obtained. This paper size applies to China National Standard (CNS) Α4 specification (210 × 29? Mm) 丨 丨 丨 —— (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -30- 567630 A7 B7 V. Description of the invention (j. The denatured substance used for cross-linking is a compound with more than two unsaturated bonds. A storage, etc. It can also be cross-linked by vulcanization. The denatured polymer compound obtained above is used as a polymer binder for the adhesive layer. This polymer binder is locally dissolved in a solvent to make a granular polymer-containing solution. The conductive material is dispersed in this polymer solution to prepare the first and second adhesive layer pastes. The conductive material uses a carbon material having a particle size of 0.5 to 30 μm and a degree of graphitization of 50% or more. Polymer bonding The mass ratio of the agent to the conductive substance (polymer binder / conductive substance) is 13/87 ~ 50/50, and the slurry of the adhesive layer is prepared. The solvent can use DiMethyl Acetamide (hereinafter referred to as DMA), acetone, dimethylformamide, and N-methylpyrrolidone. Next, plate-shaped positive and negative electrode current collectors were prepared, 2, 16, and the first and second preparations were prepared by the doctor blade method, respectively. Adhesive layer slurry is applied to the positive and negative electrode current collectors On the bodies 12 and 16, the positive and negative electrode current collectors 1 and 2 having the first and second adhesive layers 19 and 21 having a thickness of 0.5 to 30 μm after drying are formed to dry. The thickness of the subsequent adhesion layer is preferably 1 to 15 μm. The plate-shaped positive electrode current collector 12 includes, for example, A1 foil, and the negative electrode current collector 16 includes, for example, Cu foil. The doctor blade method here refers to placing on a carrier film or The thickness of slippery mud carried on a carrier such as an endless belt is a method of precisely controlling the thickness of the plate by adjusting the distance between the blade edge called the scraper and the carrier. Next, the positive electrode active material layer 13 and the negative electrode active material layer 17 are mixed separately. The required components are prepared separately for the positive electrode active material layer coating slurry and the negative electrode active material layer coating slurry. The prepared positive electrode active material layer coating slurry is applied to a substrate having a first density by a doctor blade method. The positive electrode current collector of layer 19 is in accordance with the Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T-31-567630 A7 B7__ V. Description of the Invention (12), the positive electrode is formed by drying and calendering. The negative electrode 14 is also the same. The negative electrode active materials prepared by the scraper method are respectively The layer coating slurry is spread on the negative electrode current collector 16 having the second adhesive layer 21, and dried and stretched to form a negative electrode. The thickness of the positive electrode or negative electrode active material layers 13, 17 after drying is 20 to 250 μm. A positive electrode for a secondary battery of the present invention and a negative electrode for a secondary battery of the present invention are thus formed. Next, a secondary battery of the sixth embodiment of the present invention including an electrode of the fifth embodiment of the present invention will be described. The secondary battery of the electrode of Embodiment 5 is characterized by including the above-mentioned positive electrode 11 for a secondary battery and the negative electrode 14 for a secondary battery of the present invention. The specific manufacturing sequence is to first prepare the above-mentioned positive electrode 11 for a secondary battery and the present invention. A negative electrode 14 for a secondary battery. The necessary components are mixed with the electrolyte layer 18 to prepare a slurry for coating the electrolyte layer. The slurry for coating the electrolyte layer is applied to a release paper by a doctor blade method, and After drying, the electrolyte layer 18 has a dry thickness of 10 to 150 μm and is formed by peeling off from a release paper. The electrolyte layer coating slurry is applied to the surface of the positive electrode 11 or the surface of the negative electrode 14 and dried to form The electrolyte layer 18 is also acceptable. The formed positive electrode 11, the electrolyte layer 18, and the negative electrode 14 are sequentially laminated, and this laminate is formed by hot pressing to form a plate-shaped electrode body 10 as shown in Fig. 1. Although not shown, thereafter On this electrode body 10, a positive electrode lead and a negative electrode lead made of Ni are respectively welded to the positive electrode current collector 12 and the negative electrode current collector 16 to be stored in a bag shape processed with an opening. The lithium ion polymer secondary battery of the present invention is made by hot-pressing and closing the opening under pressure reducing conditions. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the back Note: Please fill in this page again) Order f Printed by the 8th Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-32- 567630 A7 B7_ V. Description of the invention (Secondly, the examples and comparative examples of the present invention will be explained. (Please read the precautions on the back) (Fill in this page again) < Implement Example 1 > First, 50 g of PVdF powder of the first and second binders and 260 g of a 15% by mass acrylic acid aqueous solution of a denatured substance were prepared. The PVdF powder was placed in a polyethylene box to form a vacuum box, and cobalt 60 was irradiated. The source of r-rays made the absorption line of PVdF 50 kGy. Next, the PVdF powder irradiated with r-rays was taken out of a polyethylene box, moved to a nitrogen atmosphere, and PVdF was supplied to 260 g of the aforementioned 15 mass% acrylic acid aqueous solution and maintained at 80 ° C. Then, it is reacted with an acrylic acid aqueous solution to synthesize the acrylic acid grafted PVdF (Acrylic Acid grafting Polyvinyliene Fluoride, hereinafter referred to as AA-g-PVdF) generated by graft polymerization as shown in the above chemical formula (2). A sample of the reaction solution was taken, and the decrease in acrylic acid by graft polymerization with PVdF was measured by titration one by one. The reaction was stopped when the content ratio of the grafted acrylic acid group in AA-g-PVdF became 17% by mass. The obtained solid product was washed and dried with pure water, and used as a third binder. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs < Example 2 > A third adhesive was obtained in the same manner as in Example 1 except that the denatured substance was changed to 260 g of a 15% by mass aqueous methacrylic acid solution. < Example 3 > A third binder was obtained in the same manner as in Example 1 except that the denatured substance was changed to 260 g of a 15% by mass methyl acrylate aqueous solution. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) -33- 567630 A7 B7 V. Description of the invention () 31 < Example 4 > (Please read the precautions on the back before filling this page) A third binder was obtained in the same manner as in Example 1 except that the denatured substance was changed to 260 g of a 15% by mass methyl methacrylate aqueous solution. < Comparative Example 1 > A commercially available acrylate-methacrylate copolymer was prepared as a third binder. < Comparative Example 2 > A commercially available PVdF homopolymer was prepared as a third binder. < Comparative Example 3 > A commercially available PVdF-HFP copolymer was prepared as a third binder. < Comparative Example 4 > Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs, except that the denatured substance was changed to 260 g of 1% by mass aqueous solution containing oleic acid, and the third method was obtained in the same manner as in Example 1. < Comparative evaluation 1 > The following evaluation tests were performed using the third adhesive obtained in Examples 1 to 4 and Comparative Examples 1 to 4. ① Solubility test for dimethylvinylpyrrolamine This paper is in accordance with the Chinese Standard (CNS) A4 (210X297 mm) -34- 567630 A7 _____B7__ 5. The description of the invention (j (please read the precautions on the back first) (Fill in this page) Take 4g of the third adhesive obtained from Examples 1 to 4 and Comparative Examples 1 to 4, respectively. Add 56g of DMA to this sample, heat to 60 ° C and stir to form a polymer solution. This solution is stored in a glass bottle Then, check the state of precipitation in the solution after being left for one day. 0 Adhesion test for copper foil and aluminum foil First, the third adhesive obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was used to prepare and evaluate the above. The polymer solution of test ① is the same polymer solution. Then, these solutions were evenly coated on a Cu foil with a width of 30 mm, a length of 200 mm, and a thickness of 14 μm. The width of the surface was deesterified. 〇mm, length 100mm, thickness 20μm, make peeling sample for adhesion test. The produced sample is dried in a dryer at 80 ° C for 5 days in the air. Then the dried sample is evaluated with a peel tester for Cu foil and Adhesive for A1 foil. Peeling test method: During the measurement, the Cu foil side of the sample is fixed on the § type test stand. The A1 fan adhered to the Cu fan is pulled upward at a speed of 100mm / min to measure A1. The force required for the foil to be pulled away by Cu foil. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ③ Battery cycle capacity maintenance characteristics test when used as the adhesive layer of the battery First, 2g of each of Examples 1 to 4 and In the third adhesive obtained in Comparative Examples 1 to 4, 200 g of DMA was added to this sample, and the polymer solution was heated to 6 CTC and stirred to form a polymer solution. 8 g of graphite powder having a specific surface area of 150 mVg and a dispersant ug for dispersing the graphite powder were added to the solution to prepare Adhesive layer slurry. Then prepare A1 foil with a thickness of 20 μm and a width of 250 μm as a positive electrode current collector, and apply the above-mentioned prepared adhesive layer slurry to the A1 foil by a doctor blade method. The paper size is suitable for China after drying. National Standard (CNS) A4 specification (no, 〆297 meals) --- -35- 567630 A7 ___ ___B7 _____ V. Description of the invention (^ After drying, the thickness of the adhesive layer after drying is controlled to 1 〇 ± 1 μιη range In addition, a Cu foil with a thickness of 14 μm and a width of 250 μm was prepared as a negative electrode current collector, and the prepared adhesive layer slurry was coated on the Cu foil by a doctor blade method. The thickness of the adhesive layer is controlled within a range of 10 ± Ιμηη. Then, each component shown in the table below is mixed for 2 hours using a ball mill to prepare a slurry for coating the positive electrode active material layer and a slurry for coating the negative electrode active material layer, respectively. And electrolyte layer coating paste. (Please read the precautions on the back before filling out this page.) The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is sized for the Chinese National Standard (CNS) Α4 (210X 297 mm). • 36- 567630 A7 B7 V. Description of the invention (j __-__ ^ 1 Coating slurry-component mass positive electrode active material layer LiCo〇2 90 graphite powder 6 PVdF 4 N-methylpyrrolidone 45 negative electrode active material layer graphite Powder 90 PVdF 10 N-methyl methyl ketone 50 Electrolyte layer vinylidene fluoride-hexafluoropropylene copolymer 17 propylene carbonate 15 vinyl carbonate 30 diethyl carbonate 30 LiPFa 8 Acetone 80 (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and apply the prepared positive electrode active material layer coating slurry to the adhesive layer by the doctor blade method. On the surface of the A1 foil, the positive electrode active material layer was dried to a thickness of 80 μm, and a positive electrode was formed by rolling. Similarly, the prepared negative electrode active material layer coating slurry prepared by a doctor blade method is coated on a Cu surface having an adhesive layer, and dried to make the dry thickness of the negative electrode active material layer 80 μm. The rolling forms a negative electrode. The slurry for coating the electrolyte layer was coated on the positive electrode and the negative electrode by a doctor blade method to a dry thickness of 50 μm, and the positive electrode and the negative electrode having these electrolyte layers were laminated and hot-pressed. (CNS) A4 specification (210 × 297 mm) -37- 567630 A7 ______B7_ V. Description of the invention ("(Please read the precautions on the back before filling out this page) Plate-shaped electrode bodies. The electrode bodies will be made of Ni respectively The positive electrode lead and the negative electrode lead are welded to the positive electrode current collector and the negative electrode current collector, and then stored in a laminated packaging material processed into a bag shape with an opening portion, and the opening portion is closed by hot pressing under reduced pressure. Make a plate-shaped battery. Next, charge the prepared plate-shaped battery for 2.5 hours under the conditions of a maximum charge voltage of 4V and a charge current of 0.5A, discharge at a constant current of 0.5A, and discharge to make the discharge voltage become the minimum discharge voltage. The discharge step until it reaches 2.75V is one cycle. Repeat the charge and discharge cycle, measure the charge and discharge capacity of each cycle, and reduce the measurement to less than 80% of the initial charge and discharge capacity. Number of cycles. ④ Adhesion test of the adhesion layer to the current collector when used for the adhesion layer of the battery. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Firstly, the samples used in Examples 1 to 4 and Comparative Examples 1 to 4 were used. The obtained third binder was used to prepare plate-shaped batteries identical to the plate-shaped battery of the above-mentioned evaluation test ③. Then, this battery was subjected to a charge-discharge cycle of 100 cycles under the same conditions as the above-mentioned evaluation test ③ under a 7 ° C environment. Then remove the storage packaging material of the plate-shaped battery that has completed the 100 cycle, peel off the positive and negative electrodes of the battery, and separate them. When the separated positive electrode and negative electrode adhesive layers are clamped and stretched by the clamp, Observe whether the adhesion layer will peel off from the current collector. The evaluation results of the above evaluation tests ① to ④ are shown in Table 2. The symbols in the evaluation test ① table in Table 2 have the following meanings: 均匀: uniform and no precipitation solution. The meanings of the symbols in the evaluation test ④ column in Table 2 are as follows: ◎: The adhesion layer and the current collector have excellent adhesion without peeling off. This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) -38- 5676 30 A7 B7 V. Description of the invention ((Please read the precautions on the back before filling this page) 〇: A part of the adhesive layer is peeled off from the current collector. △: A large area of the adhesive layer is peeled off from the current collector. χ: The adhesive layer and the current collector are completely peeled off. Table 2 Evaluation test evaluation test Evaluation test evaluation test ④ ① ② ③ After 100 cycles of the third adhesive battery, the adhesive layer has a capacity of 80% for Cu, A1 and The number of peeling strong cycles of the adhesive DMA of the current collector [the positive electrode current collector negative electrode current collector solubility [N / cm] times] Mftfl Example 1 ◎ 16.46 635 ◎ ◎ Example 2 ◎ 10.09 480 ◎ 〇 Example 3 ◎ 15.58 565 ◎ ◎ Example 4 ◎ 13.15 523 ◎ ◎ Comparative Example 1 ◎ 6.89 194 X Δ Comparative Example 2 ◎ 0.98 183 XX Comparative Example 3 ◎ 0.98 157 XX Comparative Example 4 ◎ 1.96 92 Δ Δ Intellectual Property of the Ministry of Economy Printed by the Consumer Cooperative of the Bureau. The evaluation test is obtained from Table 2. ① Dissolution characteristics of DMA: The third adhesives obtained from Examples 丨 ~ 4 and Comparative Examples 1-4 can be completely dissolved in DMA. No precipitation occurs even after the solution is left for one day, and it is suitable as a coating slurry. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 39- 567630 A7 _B7____ V. Description of the invention (Evaluation test ② Adhesion test for copper foil and aluminum foil, using Comparative Examples 2 to 4 The test of the third adhesive was 2N / cm or less, and the adhesion effect of the adhesive layer material was insufficient. However, the third adhesive obtained in Examples 1 to 4 was A1 foil adhered to the Cu foil, which was in contact with the Cu foil. The peel strengths were all 100N / cm or more, showing sufficient adhesion strength between the active material and the current collector of the battery. Evaluation test ③ In the cycle capacity maintenance characteristic test, the battery using the third binder of Examples 1 to 4 was used. The 80% capacity cycles are higher than the 80% capacity cycles of the batteries using the third binder of Comparative Examples 1 to 4. This is because the third binder of Examples 1 to 4 has excellent adhesion and is excellent for electrolytes. Since the durability is high, the cycle capacity maintenance characteristics can be improved. Evaluation Test ④ Adhesive layer adhesion test to the current collector, the adhesion layer using the third adhesive of Examples 1 to 4 is more than the comparative example. 3rd to 4th adhesive layer It is not easy to peel from the current collector and has excellent adhesion to the current collector. Comparative Example i, which uses a fluorine-containing copolymer as the third binder, has high adhesion properties to Cu foil and A1 foil, but has electrolyte resistance. Insufficient, after the charge and discharge cycle is repeated, the adhesion layer and the current collector of the battery are peeled off. Based on the above evaluation test, it is known that denatured substances, especially acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate and The denatured polymer compound obtained by PVdF grafting is suitable for use as the third adhesive of the first and second adhesive layers. ≪ Examples 5 to 11 and Comparative Examples 5, 6 > CNS) Α4 size (210X 297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T -40- 567630 A7 _B7_ V. Description of the invention ((Please read the precautions on the back before filling this page) First, prepare the PVdF powder for the first and second adhesives, respectively 50g, 260g of a 15% by mass acrylic acid aqueous solution of denatured material. Then put the PVdF powder into a polyethylene box to form a vacuum box, and irradiate the r-ray with cobalt 60 as the r-ray source, so that the absorption line of PVdF becomes 50kGy. The PVdF powder irradiated with r rays was taken out of a polyethylene box, moved to a nitrogen atmosphere, and PVdF was supplied to the aforementioned 15 mass% acrylic acid aqueous solution at 260g and maintained at 80 ° C, and then reacted with the acrylic acid aqueous solution to synthesize AA-g-PVdF. The sample of the solution was subjected to titration to successively measure the decrease in the amount of acrylation with the graft polymerization reaction with PVdF. The proportion of the content of the grafted acrylate group in AA-g-PVdF was 2% by mass (Example 5), 7 % By mass (Example 6), 10% by mass (Example 7), 13% by mass (Example 8), 17% by mass (Example 9), 25% by mass (Example 10), 40% by mass (Example 11), 1% by mass (compared to (Comparative Example 5) and 55% by mass (Comparative Example 6), the reaction was stopped, and the obtained solid product was washed and dried with pure water. These were used as Examples 3 to 11 and Comparative Examples 5 and 6 as the third adhesion. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs < Comparative Evaluation 2 > Using the third adhesives obtained in Examples 5 to 11 and Comparative Examples 5 and 6, an evaluation test with Comparative Evaluation 1 was performed ① to an evaluation test ④ The same test 'reviewed the influence of the content ratio of propionic acid group in 9 kinds of AA-g _ PV d F on the adhesion characteristics or battery electrical characteristics. The results of the evaluation test ① and evaluation test ④ are shown in Table 3. Evaluation The results of the test ② are shown in Figure 2 and the results of the evaluation test ③ are shown in Figure 3. The meaning of the evaluation test ① column in Table 3 is as follows. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). ) -41-567630 A7 --_ B7—— _ V. Description of the invention (^ description. ◎: Uniform solution without precipitation. 〇: Although dissolved in DMA, a small amount of precipitation occurs in the solution. X: Insoluble in DMA. Table Evaluation test in 3①The meaning of the symbol in the column ◎: Excellent adhesion between the adhesive layer and the current collector, without peeling off. 〇: A part of the adhesive layer is peeled off from the current collector. X: The adhesive layer and the current collector completely peel off. (Please first (Please read the notes on the back and fill in this page again.) Printed in Table 3 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. Evaluation Test ① Evaluation Test ④ The solubility of the 3rd adhesive to DMA after 110 cycles, the adhesion layer and the current collector Adhesive positive current collector and negative current collector Example 5 ◎ 〇 Example 6 ◎ ◎ ◎ Example 7 ◎ ◎ ◎ Example 8 ◎ ◎ Example 9 ◎ ◎ ◎ Example 10 ◎ ◎ Instance 11 〇 ◎ 〇Comparative example 5 ◎ XX comparative example 6 XXX This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm)

1T -42- 567630 A7 B7 V. Description of the invention (d) Table 3 shows the dissolution characteristics of DMA in the evaluation test ①: the third adhesive of Examples 5 to 9 in the proportion of acrylic group content is 25% by mass or less The solution was completely dissolved in DMA, and no precipitation occurred after the solution was left for one day. The third adhesive of Example 10 with an acrylic group content of 25% by mass was not easily dissolved in DMA, and a small amount of precipitation occurred after the solution was left for one day. This small amount of precipitated solution was stirred again with a homogenizer for a long time and dissolved again. This degree did not affect the adhesion of copper foil or aluminum foil. Comparative Example 6 with an acrylic group content ratio of 55% by mass was almost insoluble in DMA and was not suitable for use in Adhesion of copper foil or aluminum foil. Comparative Example 5 in which the content ratio of acrylic group is 1% by mass can be dissolved in DMA. In the adhesion test of copper foil and aluminum foil in evaluation test 0, as shown in FIG. 2, AA-g- The adhesion strength of the copper foil and aluminum foil to which PVdF adheres is related to the content ratio of the acrylic group contained in AA-g-PVdF. According to the result of Comparative Example 6, when the content ratio is 55% by mass or more, the adhesion effect is reduced. This From the results of the evaluation test ①, it is known that the solubility of AA-g-PVdF to DMA is not good. In Comparative Example 5 in which the content ratio of the acrylic group is 1% by mass, the adhesive strength is reduced. Results from Examples 5 to 11 It is learned that in order to obtain sufficient adhesion characteristics, the content ratio of the acrylic group in AA-g-PVdF must be 2 to 50% by mass, ideally 10 to 30% by mass. Evaluation test ③ In the cycle capacity maintenance characteristics test, such as As shown in Fig. 3, it shows the same tendency as the test result of the adhesion strength of the evaluation test ②. In the adhesion test of the adhesion layer to the current collector of the evaluation test ④, Table 3 shows the battery after analyzing the charge-discharge cycle. The result of the adhesion layer, the adhesion characteristics of the adhesion layer are the same as the evaluation test ② and evaluation test ③. The paper size of AA-g-PVdF in this paper applies the Chinese National Standard (CNS) A4 specification (210 × 29? Mm) (please (Please read the precautions on the back before filling out this page)

， 1T Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-43- 567630 A7 ___B7_ V. Description of the invention () When the content ratio of acrylic group in 41 must be 2 ~ 50% by mass, it is suitable as a battery binder, ideally 10 ~ 30% by mass. < Examples 1 to 2 and Comparative Examples 7, 8 > First, 50 g of PVdF powder of the first and second binders and 260 g of a 15% by mass acrylic acid aqueous solution of a denatured substance were prepared. The PVdF powder was put into a polyethylene box to form a vacuum box, and irradiated with r-rays using cobalt 60 as an r-ray source, so that the absorption lines of PVdF were 90 kGy (Example 12), 70 kGy (Example 13), and 50 kGy (implementation). Example 14), 20 kGy (Example 15), 10 kGy (Example 16), 130 kGy (Comparative Example 7), and 0.5 kGy (Comparative Example 8). Next, the PVdF powder irradiated with r rays was taken out of a polyethylene box, moved to a nitrogen atmosphere, and PVdF was supplied to 260 g of a 15% by mass aqueous acrylic acid solution and maintained at 80 ° C, and then reacted with the acrylic acid aqueous solution to synthesize AA-g-PVdF. A sample of the reaction solution was taken, and the decrease in acrylic acid by graft polymerization with PVdF was measured successively by titration. When the content ratio of the grafted acrylic acid group in AA-g-PVdF became 17% by mass, the reaction was stopped. The obtained solid product was washed and dried with pure water, and was used as the third adhesive agent in Examples 1 2 to 16 and Comparative Examples 7 and 8, respectively. < Comparative evaluation 3 > Using the third adhesives obtained in Examples 12 to 16 and Comparative Examples 7, 8 were subjected to the same tests as the evaluation tests ① to ④ of the comparative evaluation 1, respectively. The results of the evaluation test ① and evaluation test ④ are shown in Table 4. The paper size of the evaluation test ② applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (please read the precautions on the back before filling this page). ·

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-44- 567630 A7 B7 V. Description of the invention (2 The results are shown in Figure 4, and the results of the evaluation test ③ are shown in Figure 5. The evaluation tests in Table 4 ① and The symbols in the evaluation test ④ have the same meanings as those used in the comparative evaluation 2. Table 4

Evaluation test ① Evaluation test ④ The solubility of the DMA of the third binder after 110 cycles, the adhesion between the adhesion layer and the current collector positive electrode current collector negative electrode current collector Example 1 2 〇 ◎ 〇 Example 1 3 ◎ ◎ Example 14 ◎ ◎ ◎ Example 15 5 ◎ ◎ Example 16 6 ◎ 〇 Example 7 XXX Example 8 XX XX From Table 4, the dissolution characteristics for DMA in the evaluation test ①: the absorption line amount is The AA-g-PVdF synthesized in Examples 13-16 below 70 kGy can be dissolved in DMA at room temperature. The AA-g-PVdF synthesized in Example 12 with an absorption line of 90 kGy can be dissolved in DMA maintained at a high temperature (85 ° C).

Comparative Example 7 with an absorption line of 130 kGy is almost insoluble in DMA even when stirred 〇 Evaluation test ② In the adhesion test for copper foil and aluminum foil, as shown in Figure 4 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) Li)-(Please read the precautions on the back before filling this page) Order the Intellectual Property Bureau of the Ministry of Economic Affairs, 8th Industrial Cooperation, Du-print-45- 567630 Α7 Β7 V. Description of the invention () 43, AA-g The adhesion strength of the copper foil and aluminum foil to which -PVdF adheres is related to the content ratio of the acrylic group contained in AA-g-PVdF. As a result of Comparative Examples 7 and 8, it was found that when the absorption line amount is lkGy or less or exceeds 120 kGy, the adhesive strength of AA-g-PVdF is reduced, and it is not suitable as an adhesive. This reason is because when the absorption line is less than lkGy, the grafted acrylic group is small, and when it exceeds 120 kGy, the dissolution of AA-g-PVdF is poor. As shown in FIG. 5, the cycle capacity maintenance characteristic test of the evaluation test ③ showed the same tendency as the test result of the adhesion strength of the evaluation test ②. From this result, it was found that in order to make 400 cycles and maintain 80% of the battery, the absorption line is ideally in the range of lkGy to 120kGy. Evaluation test ④ Adhesion layer adhesion test to the current collector, Table 4 shows the results of analyzing the battery adhesion layer after the charge-discharge cycle. AA-g-PVdF is suitable as a binder for batteries. In order to obtain stable adhesion characteristics, it is preferable to use PVdF having a T-ray absorption line of lkGy ~ 120kGy as a raw material. < Example 17 > First, 2 g of AA-g-PVdF by graft polymerization of 17% by mass of acrylic acid and PVdF was prepared as a third binder. 98 g of solvent DMA was added to 2 A of AA-g-PVdF 'and dissolved in a homogenizer to form a polymer solution. 8 g of graphite powder having a specific surface area of 150 m2 / g of a conductive material was prepared, and this graphite powder was dispersed in 80 g of DMA to prepare a dispersion. This dispersion is added to the polymer solution to prepare an adhesive layer slurry. Prepare A1 foil with a thickness of 20μηι and a width of 250μιη as a positive current collector. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

、 1T f Printed by R Industrial Consumer Cooperative, Intellectual Property Bureau, Ministry of Economy -46- 567630 A7 ______B7

V. Description of the invention (J 44 The doctor blade method applies the above-mentioned prepared adhesive layer slurry on this A1 foil, and after drying, forms an A1 foil with an adhesive layer with a thickness of 5 μm after drying. Also prepare a thick A 10 μm Cu foil with a width of 250 μm was used as the negative electrode current collector. The above-mentioned prepared adhesive layer paste was coated on this Cu foil by a doctor blade method, and dried to form a dense adhesive layer with a thickness of 5 μm after drying. Next, the components shown in Table 1 were mixed for 2 hours using a ball mill to prepare a slurry for coating a positive electrode active material layer, a slurry for coating a negative electrode active material layer, and a slurry for coating an electrolyte layer. The positive electrode active material layer coating slurry prepared by the doctor blade method was applied on the surface of an A1 foil having an adhesive layer, and dried to make the dry thickness of the positive electrode active material layer 80 μm, and a positive electrode was formed by rolling. Similarly, the prepared negative electrode active material layer coating slurry prepared by a doctor blade method was coated on the surface of a Cu foil having an adhesive layer, and dried to make the dry thickness of the negative electrode active material layer 80 μm. A negative electrode was formed. The coating material for coating the electrolyte layer was coated on a release paper having a thickness of 25 μm and a width of 250 μm by a doctor blade method. After drying, the dry thickness of the electrolyte layer was 50 μm. An electrolyte layer is formed below. The positive electrode, the electrolyte layer, and the negative electrode formed in this order are sequentially laminated, and the laminate is hot-pressed to form a plate-shaped electrode body. On this electrode body, a positive electrode wire composed of Ni is respectively formed. And the negative electrode lead are welded to the positive electrode current collector and the negative electrode current collector, and then stored in a laminated packaging material processed into a bag shape with an opening portion, and the opening portion is closed by hot pressing under reduced pressure to produce a plate shape &Lt; Example 1 8 &gt; This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) &quot; ~ &quot; -47- (Please read the precautions on the back before filling this page) Clothing · Order printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 567630 A7 B7 V. Description of the invention ((Please read the precautions on the back before filling out this page) In addition to changing the denatured polymer compound used in the adhesion layer to 7% by mass Acrylic Except for the modified polymer compound (Methacrylic Acid Grafting Polyvinyliene Fluoride, MA-g, PVdF) graft-polymerized with polyvinylidene fluoride as shown in the above chemical formula (2), the battery was fabricated in the same manner as in Example 1. &lt; Examples 19 &gt; The same as Example 17 except that the conductive substance was dispersed in the solvent in the preparation of the adhesive layer, dispersant 1.2 g was added, and the content of the acidic polymer-based dispersant was 10.7% by mass in the solid substance. A battery was made. &Lt; Example 20 &gt; In addition to the preparation of the adhesive layer slurry, when dispersing the conductive substance in the solvent, dispersant 1.2 g was added, and the content of the acidic polymer-based dispersant was 10.7% by mass in the solid substance. The rest were made in the same manner as in Example 18. &lt; Example 21 &gt; Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that the dry thicknesses of the adhesive layers provided on the positive electrode current collector and the negative electrode current collector were set to 0.5 μm, respectively, the rest were the same as in the examples. 17 Make the same battery. <Example 22 &gt; Except that the dry thicknesses of the adhesive layers provided on the positive electrode current collector and the negative electrode current collector were set to be ΐ μm, respectively, the paper sheets produced in the same manner as in Example 17 were prepared in accordance with Chinese national standards ( CNS) A4 specification (210X 297 mm) -48- 567630 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7_ V. Description of the invention (pool. &Lt; Example 23 &gt; Except that the dry thickness of the adhesion layer on the current collector was set to 10 μm, the rest were fabricated in the same manner as in Example 17. &lt; Example 24 &gt; Except that the positive electrode current collector and the negative electrode current collector were provided Except that the dry thickness of the adhesive layer was set to 15 μm, the rest were fabricated in the same manner as in Example 17. &lt; Example 25 &gt; Except that the graphite powder of the conductive material of the paste for coating the adhesive layer was changed to 2 g, and adhered. A battery was produced in the same manner as in Example 17 except that the mass ratio of the agent and the conductive substance was changed to 50/50. &Lt; Example 26 &gt; Except that the graphite powder of the conductive substance of the paste for coating the adhesive layer was changed to 4 g , Adhesives and guides The battery was fabricated in the same manner as in Example 17 except that the mass ratio of the active substance was changed to 33/67. &Lt; Example 27 &gt; The graphite powder of the conductive substance of the paste for coating the adhesive layer was changed (please read the back first) Please pay attention to this page, please fill in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) -49-Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 567630 A7 B7 _ V. Description of invention (j is 12 g, except that the mass ratio of the binder to the conductive substance was changed to 14/86, and the battery was produced in the same manner as in Example 17. &lt; Example 28 &gt; A graphite powder of the conductive substance except for a paste for coating an adhesive layer It was changed to 14 g, and the mass ratio of the binder to the conductive material was changed to 13/87, and the battery was produced in the same manner as in Example 17. &lt; Comparative Example 9 &gt; Except for the coating layer, the battery was fabricated in the same manner as in Example 17. &lt; Comparative Example 10 &gt; Except that the adhesive for coating the coating for the adhesive layer was changed from AA-g-PVdF to butyl rubber, and the solvent was changed from DMA to Except for toluene, the rest were produced in the same manner as in Example 17. &Lt; Comparative Example 11 &gt; Except that the binder of the paste for coating the adhesive layer was changed from AA-g-PVdF to an acrylate-methacrylate copolymer, and the solvent was changed from DMA to water, the rest were related to A battery was fabricated in the same manner as in Example 17. &lt; Comparative Example 1 2 &gt; Except that the adhesive for the coating paste for the adhesive layer was changed from AA-g-PVdF to ^ paper size, the Chinese National Standard (CNS) A4 specification (210x297 Gongchu) --- -50- (Please read the precautions on the back before filling this page)

1T 567630 A7 __ B7 V. Description of the invention (2 Polyurethane resin, solvent changed from DMA to methyl ethyl ketone 10 8g and methyl isobutyl ketone 72 g mixed solvent, the rest are the same as in Example 17 Manufacture of battery 〈Comparative Example 13〉 In addition to changing the adhesive for the adhesive layer coating paste from AA-g-PVdF to epoxy resin, the solvent was changed from DMA to 108 g of methyl ethyl ketone and methyl isocyanate. A battery was produced in the same manner as in Example 17 except for a mixed solvent of 72 g of methyl ethyl ketone. &Lt; Comparative Example 14 &gt; When a conductive material was dispersed in the solvent except for preparing an adhesive layer slurry, 3.5 g of a dispersant and a dispersant were added. A battery was produced in the same manner as in Example 17 except that the content was 26% by mass. &Lt; Comparative Example 15 &gt; Except that the dry thicknesses of the adhesion layers provided on the positive electrode current collector and the negative electrode current collector were set to 40 μm, respectively. The rest were fabricated in the same manner as in Example 17. &lt; Comparative Example 16 &gt; Except that the graphite powder of the conductive material of the paste for coating the adhesive layer was changed to 20 g, and the mass ratio of the binder to the conductive material was changed to 9 Except for / 9 1, the rest were made in the same manner as in Example 17. This paper size Use Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) Clothing-Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economy -51-Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 567630 A7 _B7____ 5. Description of the Invention (^ &lt; Comparative Evaluation &gt; Evaluation tests were performed on the batteries obtained in Examples 17-28 and Comparative Examples 9-16. ⑤ The resistance test of the adhesive layer to the electrolytic solution will have examples The negative electrode current collector of the adhesion layer obtained in 17 to 28 and Comparative Examples 9 to 16 was immersed in an electrolytic solution composed of 20 parts by mass of propylene carbonate, 40 parts by mass of ethylene carbonate, and 40 parts by mass of diethyl carbonate. On the week, the mass increase amount of the negative electrode current collector having the adhesion layer was measured, and it was confirmed whether the denatured polymer compound of the third adhesive of the adhesion layer was swollen by the electrolyte. The fingers were also used to wipe the negative electrode current collector Cu foil. Check whether the adhesion layer will peel off. ⑥ Test the current collector protection performance of the adhesion layer against hydrogen fluoride (HF). Drop 2ml of 5ppm hydrogen fluoride aqueous solution to the locations with Examples 17-28 and Comparative Examples 9-16. On the surface of the negative electrode current collector of the adhesion layer, confirm the state of the current collector after being left for 24 hours. 试验 Adhesion test of the adhesion layer to the active material layer Adhesive tape was adhered to Examples 17 to 28 and Comparative Examples The surfaces of the positive and negative electrode current collectors of the positive electrode and the negative electrode obtained from 9 to 16 were rolled with a rubber roller. The positive electrode current collector and the negative electrode current collector adhered to the adhesive tape were cut to a width of 10 mm and 10 mm, respectively. The wide current collector was pulled up vertically, and the force required to peel the active material layer was measured. At the same time, visually confirm the peeling method. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order-52- 567630 A7 B7 V. Description of the invention (^ ⑧ Cyclic capacity maintenance characteristics test for The plate batteries obtained in Examples 17 to 28 and Comparative Examples 9 to 16 were subjected to a charge-discharge cycle test. The charging steps were performed under the conditions of a maximum charging voltage of 4V and a charging current of 0.5 people for 2.5 hours, and 0.5-8 Discharge at a constant current until the discharge voltage reaches 2.75V (minimum discharge voltage), repeat this charge-discharge cycle, measure the discharge capacity of each cycle, and measure the number of cycles reduced to less than 80% of the initial discharge capacity. The above evaluation test ⑤ The evaluation results of ～ ⑧ are shown in Table 5. The evaluation tests in Table 5 have the following meanings: 符号: Excellent, not peeled. ○: Good, not peeled. △: Partially peeled. X: Completely peeled The meanings of the symbols in the evaluation test column in Table 5 are as follows. ◎: Excellent, non-corroded. 〇: Good, non-corroded. △: Partially rotted X: Completely corroded. Size of this paper Use Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) Printed by the staff and consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-53- 567630 A7 B7 V. Description of the invention () 51 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 Evaluation Tests ⑤ Evaluation Tests ⑧ Evaluation Tests ⑦ Evaluation Tests 浸渍 Impregnation of electrolytes to protect HF {N} 80% of capacity cycles [times] Increasing amount [% by mass] Peel resistance Example 17 0.8 ◎ ◎ 12.1 635 Example 1 8 1.1 ◎ ◎ 11.8 565 Example 19 0.9 ◎ ◎ 12.3 6.04 Example 20 1.0 ◎ ◎ 11.8 539 Example 21 0.5 ◎ 〇12.2 346 Example 22 0.7 ◎ 9.0 545 Example 23 1.9 ◎ ◎ 10.8 589 Example 24 2.5 ○ 10.6 444 Example 25 0.4 ◎ ◎ 12.0 329 Example 26 0.6 ◎ ◎ 11.0 566 Example 27 1.2 〇10.0 468 Example 28 1.8 〇〇9.3 375 Comparative Example 9-X 0.5 15 Comparative Example 10 83.2 X Δ 2.1 135 Comparative Example 11 34.8 Δ X 3.6 194 Comparative Example 12 51.1 Δ Δ 3.7 203 Comparative Example 1 3 25.7 Δ Δ 2.6 178 Comparative Example 14 0.9 Δ 〇5.6 280 Comparative Example 1 5 6.0 Δ ◎ 14 213 Comparative Example 16 2.9 Δ 〇 4.8 187 (Please read the precautions on the back before filling this page) The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -54- 567630 A7 B7 5. Description of the invention (j ⑤ In Comparative Examples 10 to 13 for the resistance test of the adhesion layer to the electrolyte, the adhesion layer has The increase amount of the negative electrode current collector was large, and it was found that the adhesive forming the adhesion layer was wet with the electrolyte. On the other hand, even if Examples 17 to 28 were immersed in the electrolytic solution for one week, the increase amount of the negative electrode current collector having the adhesion layer was extremely small, and the resistance to the electrolytic solution was exhibited. Test of Protective Performance of the Adherent Layer for Hydrogen Fluoride (HF) Current Collector The comparative examples 9 and 11 were corroded by HF. Comparative Examples 10, 2 and π are partially rotten uranium. The current collectors of Examples 17 to 28 were not corroded by HF, and the adhesive layer had a protective function.试验 Adhesion test of the adhesion layer to the active material layer In Examples 17 to 28, the force required to peel the active material layer was greater than that of Comparative Examples 9 to 16. Regarding the method of peeling, Comparative Examples 9 to 16 were uneven on the inner surface and had peeled and unpeeled parts. Example 1 The 7 to 28 series were uniformly and completely peeled in the plane.试验 Cycle capacity maintenance characteristic test Compared to the 80% capacity cycle number of Comparative Examples 9 to 16, Examples π to 28 each show a high cycle number, and have excellent cycle maintenance characteristics during charge and discharge. &lt; Example 29 &gt; First, a polymer material (Acrylic Acid grafting Poly vinyliene Fluoride) of 17% by mass of acrylic acid and PVdF graft polymerization was prepared, and the following paper dimensions are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ( (Please read the precautions on the back before filling out this page)

Printed by 1T Consumer Intellectual Property Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-55- 567630 A7 B7 V. Invention Description (^ (Please read the notes on the back before filling this page) is called AA-g-PVdF) 2g as the first and 2nd adhesive. 98 g of the solvent DiMethylAcetamide (hereinafter referred to as DMA) was added to this 2 AA-g-PVdF and dissolved in a homogenizer to form the first and second binder material solutions. Prepare 8 g of each conductive material. The first conductive material is aluminum with a particle size of 1 μm, and the second conductive material is copper with a particle size of 1 μm. This metal powder is dispersed in 80 g of DMA to prepare the first And a second dispersion. These first and second dispersions are added to the above-mentioned binder material solution to prepare first and second adhesive layer pastes. An A1 foil having a thickness of 20 μm and a width of 250 μm was prepared as a positive electrode current collector. The first adhesive layer slurry prepared above was coated on the A1 foil, and dried to form a first adhesive layer having a thickness of 5 μm after drying. Adhesive layer of Al foil. In addition, a Cu foil with a thickness of 10 μm and a width of 250 μm was prepared as a negative electrode collector. The second adhesive layer slurry prepared above was coated on this Cu foil, and dried to form a second adhesive layer with a thickness of 5 μm after drying. Adhesive layer of Cu foil. Next, each component shown in Table 6 below was mixed using a ball mill for 2 hours to prepare a slurry for coating a positive electrode active material layer, a slurry for coating a negative electrode active material layer, and a slurry for coating an electrolyte layer. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, S Industry Consumer Cooperative, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -56- 567630 A7 B7 54 Substance-electrolyte component mass LiCo〇2 90 graphite powder 90 vinylidene fluoride-hexafluoro17 graphite powder 6 polyvinylidene fluoride 10 propylene copolymer polyvinylidene fluoride 4 N-methylpyrrole 50 propylene carbonate 15 N-formyl Base pyrrole 45 Alkanone vinyl carbonate 30 Alkanone diethyl carbonate 30 LiPF6 8 Acetone 80 V. Description of the invention ((Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives The obtained positive electrode active material layer coating slurry was coated on an A1 foil having an adhesive layer, and dried to make the dry thickness of the positive electrode active material layer 80 μm, and the positive electrode was formed by rolling. Similarly, the obtained positive electrode was prepared. The slurry for coating an anode active material layer is coated on a Cu foil having an adhesive layer, and the anode active material layer is dried after drying. The dry thickness becomes 80 μm, and the negative electrode is formed by rolling. The slurry for coating the electrolyte layer is coated on a release paper having a thickness of 25 μm and a width of 250 μm. After drying, the dry thickness of the electrolyte layer is 50 μm. The electrolyte is peeled off from the release paper to form an electrolyte. Laminates: The positive electrodes, electrolyte laminates, and negative electrodes formed in this order are laminated sequentially, and the laminates are hot-pressed to produce plate-shaped electrode bodies. On this electrode body, positive and negative leads composed of Ni are respectively formed. It is welded on the positive electrode current collector and the negative electrode current collector, and then stored in a laminated packaging material processed into a bag shape with an opening. Under reduced pressure, the paper is hot-pressed. The dimensions of this paper are applicable to China National Standards (CNS). A4 specification (210X 297 mm) -57- 567630 A7 B7 V. Description of the invention ("Seal the opening and make a plate-shaped battery. &Lt; Example 30 &gt; Except the aluminum which is the first conductive substance and the second conductive substance A lithium ion polymer secondary battery was produced in the same manner as in Example 29 except that the particle diameter of copper was set to 1 μm. &Lt; Example 3 1 &gt; A lithium ion polymer secondary battery was produced in the same manner as in Example 29 except that the particle diameter of copper of the electrical substance was set to 20 μm. &Lt; Example 32 &gt; The mass of the first binder and the first conductive substance were changed. The mass ratio of the ratio (the first adhesive / the first conductive material) and the mass ratio between the second adhesive and the second conductive material (the second adhesive / the second conductive material) were changed to 13/87, The rest was produced in the same manner as in Example 29. &lt; Example 3 3 &gt; Except the mass ratio of the first adhesive to the first conductive substance (the first adhesive / the first conductive substance) and the mass ratio of the second adhesive to the second conductive substance ( The mass ratios of the second binder / the second conductive substance) were changed to 75/25, respectively. The rest were the same as in Example 29 to produce a lithium ion polymer secondary battery. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) Clothing · Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives -58- 567630 A7 Economy Printed by the Consumers ’Cooperative of the Ministry of Intellectual Property Bureau B7 V. Description of the invention (&lt; Example 34 &gt; A lithium-ion polymer secondary battery was produced in the same manner as in Example 29 except that the first conductive substance used platinum. Example 35 A lithium ion polymer secondary battery was produced in the same manner as in Example 29 except that nickel was used as the second conductive material. &Lt; Example 36 &gt; An acidic polymer was added to the first and second adhesion layers, respectively. Except for the dispersant, a lithium ion polymer secondary battery was fabricated in the same manner as in Example 29. &lt; Example 37 &gt; A neutral polymer dispersant was added to the first and second adhesive layers, respectively, and the rest were the same as A lithium ion polymer secondary battery was produced in the same manner as in Example 29. &lt; Comparative Example 17 &gt; A carbon battery powder having a specific surface area of 150 m2 / g was used for the first and second conductive materials, and the rest were manufactured in the same manner as in Example 29. Lithium-ion polymer secondary battery. &Lt; Comparative Example 1 8 &gt; The same as Example 29 except that the particle diameters of aluminum of the first conductive substance and copper of the second conductive substance were set to 0.05 μm, respectively. For making lithium ions, this paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling out this page) Order -59- 567630 A7 B7 V. Description of the invention (5j polymer secondary Batteries. (Please read the precautions on the back before filling in this page} &lt; Comparative Example 19 &gt; Except for setting the particle size of aluminum of the first conductive substance and copper of the second conductive substance to 25 μm, the rest A lithium ion polymer secondary battery was produced in the same manner as in Example 29. &lt; Comparative Example 20 &gt; Except for the mass ratio of the first binder to the first conductive substance (the first binder / the first conductive substance) and the first The mass ratio of the mass ratio of the 2 binder and the second conductive substance (the second binder / the second conductive substance) was changed to 10/90 respectively, and the rest were the same as in Example 29 to produce a lithium ion polymer secondary battery. &lt; Comparative Example 21 &gt; Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Cooperative society prints the mass ratio of the first adhesive to the first conductive substance (the first adhesive / the first conductive substance) and the mass ratio of the second adhesive to the second conductive substance (the second adhesive / Except that the mass ratio of the second conductive substance) was changed to 80/20, the rest were fabricated in the same manner as in Example 29. &lt; Comparative evaluation &gt; For Examples 29 to 37 and Comparative Example 17 to The obtained batteries were subjected to the following evaluation tests. (1) Peeling test This paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) -60- 567630 A7 B7 58 5. Description of the invention ((Please read the precautions on the back before filling this page) This test system After the plate-shaped electrode bodies were cut into 50 mm widths, a tensile tester (Orientech tensiron UCT-500) was used. In other words, the electrode bodies with a width of 50 mm were set on a pair of jigs having a 100 mm interval, and then measured therein. One of the clamps is stretched at a tensile speed of 300 mm / min until the electrode body breaks. This is the adhesion force. (2) Output characteristics test When the discharge capacity of these batteries is expressed as 1C [mAh], 1 / The current indicated by 5C [mA] is charged until the voltage between the terminals of the battery becomes 4.0 [V], and then held at 4.0 [V]. After charging for 5 hours in total, it is left for 1 hour, and then expressed as 3C [mA] Measure the discharge capacity at a current of 直到 until the voltage reaches 2.7 [V]. Calculate the discharge capacity obtained when the current is expressed in 3C [mA] and the discharge capacity obtained when the current is expressed in 1 / 5C [mA]. (3) Cycle capacity maintenance characteristics test The first time when the discharge capacity is Cmax, the intellectual property bureau of the Ministry of Economic Affairs, the number of charge and discharge cycles when the discharge capacity is 80% of Cmax is the cycle life, and the cycle life of each battery is measured. The evaluation test results of the above (1) ~ (3) are shown in Table 7. The paper size printed by the consumer cooperative is applicable to the Chinese National Standard (CNS) A4 (210x297)-61 _ 567630 A7 B7 V. Description of the invention (2 Table 7 Adhesion [N] Output characteristics [%] Characteristics [times] Example 29 59.2 95.8 _ 851 Example 30 47 97.4 _ 699 Example 3 1 51.2 94.6 893 Example 32 67 98.7 658 Example 33 46.2 92.4 994 Example 34 55.8 97.7 814 Example 35 58 96.7 772 Example 36 52.8 97.9 781 Example 37 57 96.3 732 Comparative Example 17 36.2 90.8 635 Comparative Example 1 8 40.8 90.2 534 Comparative Example 1 9 40 87.5 473 Comparative Example 20 25.6 88.5 139 Comparative Example 21 45.8 67.5 758 (Please read the precautions on the back before filling this page). Clothing. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 2 is not used for adhesion of a metal battery, from the results of the peeling test found that low density focus, easily peeled off. Also, the batteries of Comparative Examples 18 and 19 whose particle diameters of the metals contained in the first and second adhesion layers were outside the scope of the present invention had small particle diameters and were easy to aggregate (Comparative Example 18), and had large particle diameters. Since the particles are coarse and the contact between the conductive materials is insufficient (Comparative Example 19), the results of each evaluation test show a low number. The battery of Comparative Example 20 has very low adhesion and cycle characteristics. The battery of Comparative Example 21 has a paper size that conforms to the Chinese National Standard (CNS) A4 specification (210X297 mm) -62- 567630 A7 ______B7 _ V. Description of the invention (D The output characteristics are very low. The batteries of Examples 29 to 37 showed better adhesion, output characteristics, and cycle characteristics than conventional batteries. (Please read the precautions on the back before filling out this page) &lt; Example 38 &gt; Preparation 2 g of granular acrylic acid grafting polyvinyliene fluoroide (hereinafter referred to as AA-g-PVdF) with an average particle diameter of 200 μm was used as a binder to prepare a solvent of DiMethylAcetamide (DiMethylAcetamide, Hereinafter referred to as DMA) 98g, the two are mixed. This mixed solution is heated to 80 ° C while continuing to stir with a homogenizer. The stirring solution is occasionally taken and applied on a transparent glass substrate to form a liquid film thickness of about 200 μm. The average particle diameter of polymer binder particles (undissolved particles) and the number of polymer binder particles (undissolved particles) with a particle size of 1 μm or more were measured with an optical microscope. The measurement of the particle size of particles printed by the Employees' Cooperative of the Ministry of Intellectual Property of Jibei uses the definition of the diameter of the projected circle and its measurement method. In other words, the particle size is the diameter of a circle equivalent to the projected area of the particle. The measurement method is optical Microscopes, electron microscopes, close-up shots, etc. observe particles arranged on a plane from directly above, and determine the particle size from the projection of the particles. The particle size obtained according to the above measurement method is d, and the number of the particles is η, The average particle diameter D is obtained according to the following formula: D = [Σηά3 / Ση] 1/3 The average particle diameter of the polymer binder particles is 30 ± 10 μm, and the number of polymer binder particles having a particle size of 1 μm or more is 20 When ± 10 pcs / cm2, the size of the paper is subject to the Chinese National Standard (CNS) A4 (210X297 mm) -63- 567630 A7 ____ B7__ __ V. Description of the invention (61) Stop stirring. Contains this polymer binder particle The solution was the polymer solution of Example 38. &lt; Example 39 &gt; 1.5 g of granular AA-g-PVdF having an average particle diameter of 200 μm was prepared as a binder and mixed with 98 g of DMA. This mixed solution was heated to 85 ° C At the same time, continue to disturb with homogeneous theft. After this AA-g-PVdF is completely dissolved, add 0.5 g of granular AA-g-PVdF with an average particle size of 100 μm, and stir for 5 minutes with a homogenizer to form a polymer containing this polymer. Solution of binder particles. The prepared solution was applied on a transparent glass substrate to form a liquid film thickness of about 200 μm. The average particle size and particle size of polymer binder particles (undissolved particles) were measured with an optical microscope. The number of polymer binder particles (undissolved particles) above 1 μm. As a result, when the average particle diameter of the polymer binder particles became 20 ± 10 μm, and the number of the polymer binder particles having a particle size of ΐ μm or more became 20 ± 10 particles / cm2, the stirring was stopped. The solution containing the polymer binder particles was the polymer solution of Example 39. &lt; Example 40 &gt; In the same manner as in Example 38, AA-g-PVdF 2g and DMA 98g having an average particle diameter of 200 m were prepared, and the two were continuously mixed under the same conditions as in Example 38. The stirring solution was taken occasionally, and the average particle diameter of the polymer binder particles (undissolved particles) and the polymer binder particles (undissolved particles) having a particle diameter of 1 μm or more were measured using an optical microscope under the same conditions as in Example 38. Number of them. The average particle size of the polymer binder particles is 10 ± 5μm, and the particle size is ΐμ. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297mm) (Please read the precautions on the back before filling this page). ·

、 1T Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-64- 567630 A7 ______B7_ 5. Description of the invention (When the number of polymer binder particles above 2 m becomes 10 ± 5 particles / cm2, stop stirring. Contain this The solution of the polymer binder particles was the polymer solution of Example 40. &lt; Example 41 &gt; 2 g of granular methacrylic acid-grafted polyvinylidene fluoride having an average particle diameter of 200 μm was prepared as a binder and 98 g DMA. The two were continued to be mixed under the same conditions as in Example 38. The stirring solution was occasionally taken, and the average particle diameter and particle diameter of the polymer binder particles (undissolved particles) were measured using an optical microscope under the same conditions as in Example 38. The number of polymer binder particles (undissolved particles) above 1 μm. The average particle size of the polymer binder particles is 30 ± 5 μm, and the number of polymer binder particles with a particle size of 1 μm or more When it becomes 20 ± 10 particles / cm2, the stirring is stopped. The solution containing the polymer binder particles is the polymer solution of Example 41. &lt; Comparative Example 22 &gt; As in Example 38, an average particle diameter of 200 m was prepared. As a binder, 2 g of AA-g-PVdF is mixed with 98 g of DMA solvent. This mixed solution is heated to 85 ° C, while continuing to stir with a homogenizer to make this AA-g-PVdF completely dissolved solution appear transparent. The obtained polymer solution was applied on a transparent glass substrate to form a liquid film thickness of about 200 μm, and it was confirmed by an optical microscope that there were no polymer binder particles (undissolved particles) having a particle size of 1 μm or more. This solution is a comparative example. Polymer solution of 22. The paper size applies to the Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297 mm) (Please read the precautions on the back before filling this page) Order P. Intellectual Property Bureau, Ministry of Economic Affairs Printed by Employee Consumer Cooperatives-65- 567630 A7 B7 V. Description of the invention (&lt; Comparative Example 23 &gt; As in Example 39, 1.5 g of granular AA-g-PVdF with an average particle diameter of 200 μm was prepared as a binder , Mixed with 98g of DMA. This mixed solution is heated to 85. (:, while continuing to stir with a homogenizer. After this AA-g-PVdF is completely dissolved, add a granular AA-g-PVdF with an average particle size of 200μm. 0.5g, and stirred in the homogenizer for another 1 minute to form a polymer Take the prepared solution and apply it on a transparent glass substrate to form a liquid film with a thickness of about 200 μm. Measure the average particle diameter of polymer binder particles (undissolved particles) with an optical microscope and particle diameters of 1 μm or more. The number of polymer binder particles (undissolved particles). As a result, the average particle size of the polymer binder particles was 120 ± 10 μm, and the number of polymer binder particles with a particle size of 1 μm or more was 80 ± 10 particles / cm2. The solution containing the polymer binder particles was the polymer solution of Comparative Example 23. &lt; Comparative Example 24 &gt; As in Example 39, a granular AA-g-PVdF lg having an average particle diameter of 200 µm was prepared as a binder and mixed with 98 g of DMA. This mixed solution was heated to 85 ° C while continuing to stir with a homogenizer. After this AA-g-PVdF was completely dissolved, 0.5 g of granular AA-g-PVdF having an average particle diameter of 100 µm was added, and the mixture was further stirred in a homogenizer for 2 minutes to form a polymer solution. The prepared solution was applied on a transparent sloped glass substrate to form a liquid film thickness of about 200 μm, and the average particle diameter of polymer binder particles (undissolved particles) and the polymerization with a particle diameter of 1 μm or more were measured with an optical microscope. The number of particles (undissolved particles) of the binder. Results The average particle size of the polymer binder particles was 60 ± 10 μm. The size of the paper was in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back before filling in this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-66- 567630 A7 B7 V. Description of the invention (J; 64 The number of polymer binder particles with a diameter of 1 μm or more is 150 ± 10 / cm2. Contains this polymer bond The solution of the agent particles is the polymer solution of Comparative Example 24 (please read the precautions on the back before filling this page). 〈Comparative Example 25〉 Same as Example 41, the granular methyl group with an average particle diameter of 200 μm 2 g of acrylic grafted polyvinylidene fluoride was mixed with 98 g of DMA, and the mixed solution was heated to 85 ° C while being stirred with a homogenizer until the polytetrafluoroethylene was completely dissolved. The prepared polymer solution was applied and coated A polymer film having a thickness of about 200 μm was formed on a transparent glass substrate, and it was confirmed with an optical microscope that there were no polymer binder particles (undissolved particles) having a particle size of 1 μm or more. This solution was the polymer solution of Comparative Example 25. &lt; Comparative test & Evaluation &gt; Adhesion test for copper foil and aluminum foil Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs First, the polymer solutions obtained in Examples 38 to 41 and Comparative Examples 22 to 25 were used to uniformly coat these solutions, respectively. On a Cu foil with a width of 30 mm, a length of 200 mm, and a thickness of 14 μm on the surface of which is degreased, an A1 foil with a width of 10 mm, a length of 100 mm, and a thickness of 20 μm on which the surface is degreased is bonded to prepare an adhesive test Peel the sample. The produced sample is dried in the air at 80 &lt; t for 5 days in a dryer. Then the peel tester is used to evaluate the adhesion of the dried sample to the Cu foil and A1 foil. The peel test method is to measure the The Cu foil side is fixed on the test 'table' and the A1 foil adhered to the Cu foil is pulled vertically upward at a speed of 100 mm / min 'to measure the force required to pull the A1 foil away from the Cu foil (peel strength Paper size applies Chinese National Standard (CNS) M specification (21〇 &gt; &lt; 297 meals) -67- 567630 A7 _ B7 V. Description of the invention ("degree"). It was coated with the polymer solution of Example 38 Electron microscopy of copper particles after drying on copper foil The photograph is shown in Fig. 10. Test for maintaining the cycle capacity of the battery when used in the adhesive layer of the battery First, graphite with a specific surface area of 150 m2 / g was added to the polymer solutions obtained in Examples 38 to 41 and Comparative Examples 22 to 25. 8g of powder and 80g of DMA were stirred to prepare the adhesive layer slurry. Then, A1 foil with a thickness of 20 μm and a width of 250 μm was prepared as a positive electrode current collector, and the prepared adhesive layer slurry was coated on the A1 foil by a doctor blade method. After drying, the thickness of the dried adhesive layer is controlled within a range of 20 ± 1 μm. In addition, a Cu foil with a thickness of 14 μm and a width of 250 μm was prepared as a negative electrode current collector. The above-mentioned prepared adhesive layer slurry was coated on the Cu foil by a doctor blade method, and the thickness of the dried adhesive layer was controlled to 20 by drying. Within ± 1 μιη. Next, each component shown in Table 8 below was mixed using a ball mill for 2 hours to prepare a slurry for coating a positive electrode active material layer, a slurry for coating a negative electrode active material layer, and a slurry for coating an electrolyte layer. (Please read the notes on the back before filling this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese National Standard (CNS) Α4 specifications (210 × 297 mm) -68- 567630 Α7 _ Β7 Explanation ("_______ Table 8 Coating slurry-component mass positive electrode active material layer LiCo〇2 90 graphite powder 6 PVdF 4 N-methylpyrrolidone 45 negative electrode active material layer graphite powder 90 PVdF 10 N-methylpyrrolidone 50 Electrolyte layer vinylidene fluoride hexafluoropropylene copolymer 17 propylene carbonate 15 ethylene carbonate 30 diethyl carbonate 30 LiPFa 8 acetone 80 (Please read the precautions on the back before filling out this page) Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs The positive electrode active material layer coating slurry prepared by the doctor blade method was printed on the surface of an A1 foil having an adhesive layer, and dried to make the dry thickness of the positive electrode active material layer 80 μm, and formed by rolling. Positive electrode: Similarly, the prepared negative electrode active material layer coating slurry was applied to Cu having an adhesive layer by a doctor blade method. On the surface of the foil, after drying, the dry thickness of the negative electrode active material layer was 80 μm, and the negative electrode was formed by calendaring. The slurry for coating the electrolyte layer was applied to the positive electrode and the negative electrode by a doctor blade method, so that the dry thickness was 50 μm. The positive electrode and negative electrode with these electrolyte layers are laminated and hot-pressed to make this paper. This paper applies Chinese National Standard (CNS) A4 (210 × 297 mm) -69- 567630 A7 ___ B7__

V. Description of the invention (I 67 Plate-shaped electrode body. On this electrode body, a positive lead and a negative lead made of Ni are welded to the positive current collector and the negative current collector, respectively, and then stored in an electrode processed into an opening. Inside the bag-shaped laminated packaging material, the opening was closed by heat pressing under reduced pressure to produce a plate-shaped battery. Next, the plate-shaped battery obtained was charged under the conditions of a maximum charging voltage of 4V and a charging current of 0.5A. The charging step of 2.5 hours, discharge at a constant current of 0.5A, and the discharging step until the discharge voltage reaches the minimum discharge voltage of 2.75V is 1 cycle, repeat the charge and discharge cycle, measure the charge and discharge capacity of each cycle, The number of cycles reduced to less than 80% of the initial charge-discharge capacity. ③ Adhesion test of the adhesion layer to the current collector when used for the adhesion layer of the battery First, Examples 3 to 4-1 and Comparative Examples were used. 2 The polymer solutions obtained from 2 to 2 5 were each made into the same plate-shaped battery as the plate-shaped battery of the above-mentioned evaluation test ②. Then, this battery was subjected to a phase similar to that of the above-mentioned evaluation test ② at 70 ° C. The charging and discharging cycle of the conditions is 100 cycles. Then remove the storage packaging material of the plate-shaped battery that ends the 100 cycles, peel off the positive and negative electrodes of the battery, and separate them. When clamping and stretching, observe whether the adhesion layer is peeled from the current collector. The evaluation results of the above evaluation tests ① to ④ are shown in Table 9. The symbols in the evaluation test ③ column in Table 9 have the following meanings. ◎ : Excellent adhesion between the adhesive layer and the current collector, without peeling off. 〇: Part of the adhesive layer is peeled off from the current collector. X: The adhesive layer and the current collector are completely peeled off. This paper size applies Chinese national standards (CNS) A4 specification (210'〆297 mm) (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-70- 567630 A7 B7 i. Description of the invention ( 9 Evaluation test Evaluation test Evaluation test ④ ② ③ 80% of the adhered Cu battery After 100 cycles, the adhesion layer and the capacity peeling strength of the current collector of A1 capacity cycling number [times] Electric body [ N / cm] Example 3 8 20.58 680 ◎ ◎ Example 39 19.60 675 ◎ ◎ Example 40 18.62 657 ◎ ◎ Example 4 1 19.70 648 ◎ 〇 Comparative Example 22 15.68 523 ◎ ◎ Comparative Example 23 13.72 506 ◎ ◎ Comparative Example 24 13.72 459 ◎ 〇 Comparative Example 25 15.29 495 ◎ ○ (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs from the evaluation test in Table 9 In the adhesion test, using the polymer solution obtained in Examples 38 to 41, and the A1 foil adhered to the Cu foil, the peel strength with the Cu foil was both 18.6 N / cm or more. The peel strength of the polymer solutions obtained using Comparative Examples 22 to 25 was 4.41 to 5.88 N / cm, which was lower than that of Examples 38 to 41. This is due to the presence or absence of the particulate polymer binder, and the presence of the particulate polymer binder can improve adhesion. Next, in the test of the cycle capacity maintenance characteristics of the evaluation test ②, the 80% capacity cycle of the battery using the polymer binder of Example 3 8 to 41 was used. 1 Moderate sheet-paper I, standard bidder (〇 奶) 8 4 Specifications (210 乂 297 mm) -71-567630 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention This is because the polymer binders of Examples 38 to 41 have excellent adhesion characteristics and high durability to the electrolyte, so the cycle capacity maintenance characteristics can be improved. The average particle size of the particles present in the polymer solution is Examples 38 to 40 in which the number of particles of 1 to 100 μm is 100 particles / cm2 or less, the number of cycles is higher than the average particle size of more than 100 μm, or the number of particles having an average particle size of ΐ μm or more exceeds 100 particles / cm2 23 and 24. In the adhesion test of the adhesion layer to the current collector of the evaluation test ③, Examples 38 and 39 were used, and Comparative Examples 22 and 23 showed the same high adhesion. Examples 38 to 40 and Example 41 For comparison, methacrylic acid When branched polyvinylidene fluoride is used as a binder, its adhesive properties are lower than when using AA-g-PVdF. However, methacrylic acid grafted polyvinylidene fluoride with poor adhesion properties is used as a polymer binder. Part 41 of the polymer adhesive was present in the adhesive layer in the form of particles. Compared with Comparative Example 25, which was used after the polymer adhesive was completely dissolved, the adhesion of the adhesive layer to the current collector after 100 cycles (③Evaluation test) There is almost no difference, but in the evaluation test ① (adhesive Cu, peeling strength of A1) and the evaluation test ② (80% capacity cycle number of the battery) (these are the generalized measures of adhesion) On the one hand, Example 41, in which a part of the polymer binder was present in the adhesive layer in the form of particles, improved the adhesion in a broader sense and improved battery characteristics than Comparative Example 25, which was used after the polymer binder was completely dissolved. Exploitability

(Please read the notes on the back before filling out this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -72- 567630 A7 B7 V. Description of the invention (4 According to the first of the invention In the form, the lithium ion polymer secondary battery has a first adhesion layer between the positive electrode current collector and the positive electrode active material layer, a second adhesion layer between the negative electrode current collector and the negative electrode active material layer, and the first The first and second adhesive layers each contain a third adhesive and a conductive substance, and the third adhesive contains one or both of the polymer compounds contained in the first adhesive or the second adhesive by a denaturing substance. Or a polymer compound obtained by denaturing a polymer compound in which any of the repeating units of the polymer compound is a repeating unit, so the first adhesive or the second adhesive is mainly denatured. The polymer system has higher adhesion to the positive electrode active material layer or the negative electrode active material layer, and the adhesiveness with the current collector is greatly improved by denaturation than with conventional binders. As a result, the active material layer can be suppressed from the current collector. Stripped, big It increases the conductivity of the current collector and the active material layer. Since the electrolyte is difficult to penetrate into the denatured polymer compound, the adhesion layer is stable to the organic solvent in the electrolyte and has excellent long-term storage stability. Even if fluorine occurs in the battery In the case of a strong acid such as an acid, the denatured polymer compound becomes a protective layer, which can suppress the corrosion and erosion of the current collector. According to the first aspect of the present invention, the lithium ion polymer secondary lithium ion secondary battery excellent as described above can be provided. The secondary battery contributes to the industry. According to the second aspect of the present invention, in the lithium ion polymer secondary battery, there is a first adhesion layer between the positive electrode current collector and the positive electrode active material layer, and the negative electrode current collector and There is a second adhesion layer between the negative electrode active material layers, and the first and second adhesion layers each contain a third binder and a conductive substance, and the third binder contains a fluorine-containing polymer compound that is modified by a denatured substance. The polymer compound obtained by denaturation, so for the paper size of the positive electrode current collector or the negative electrode current collector, the national paper standard (CNS) A4 (210X297 mm) is applicable (please read first) Read the notes on the back and fill in this page again), printed by the Consumer Cooperative of the Intellectual Property Bureau of 1T Ministry of Economic Affairs-73- 567630 A7 B7 V. Description of the invention () 71 The adhesion is greatly improved compared with the past adhesives. The results can inhibit the activity The separation of the material layer from the current collector greatly improves the conductivity between the current collector and the active material layer, which can improve the cycle capacity maintenance characteristics. Because the electrolyte is difficult to penetrate into the denatured polymer compound, the adhesion layer is resistant to electrolysis. The organic solvent in the liquid is stable and has excellent long-term storage stability. Even when strong acid such as fluoric acid occurs in the battery, the denatured polymer compound becomes a protective layer, which can suppress the decay of uranium by the current collector. According to the second aspect of the present invention, it can provide The excellent lithium-ion polymer secondary battery as described above contributes to the industry. According to the third aspect of the present invention, a method for synthesizing a third adhesive suitable for use in the first and second adhesive layers can be provided. Therefore, the third aspect of the present invention has industrially useful characteristics. The lithium ion polymer secondary batteries of the third and fourth aspects of the present invention include a positive electrode composed of a positive electrode active material layer containing a positive electrode binder and a positive electrode active material provided on a surface of a positive electrode current collector; The surface of the body is provided with a negative electrode composed of a negative electrode binder and a negative electrode active material layer of a negative electrode active material; and a polymer electrolyte layer provided between the surface of the positive electrode active material layer of the positive electrode and the negative electrode active material layer of the negative electrode; A first adhesive layer containing a first binder and a first conductive material is provided between the current collector and the positive electrode active material layer, and a second binder and a second conductive layer are provided between the negative electrode current collector and the negative electrode active material layer. Improved lithium ion polymer secondary battery of the second adhesive layer of the active substance, the main component of the first binder is the main component of the binder for the positive electrode, and the main component of the second binder is the main component of the binder for the negative electrode . The conductive substances contained in the first and second adhesion layers are metals or partial metal oxides with a particle size of 0.1-20 μm. Due to the good electrical paper size of the metal, the Chinese National Standard (CNS) A4 is applicable. Specifications (210X297 mm) (Please read the notes on the back before filling out this page) Clothing · Order Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-74- 567630 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Disclosure of the Invention (d) The conductivity is higher than that of carbon materials used as conductive materials in the past, and even a small amount of addition can form a dense layer with good electronic conductivity. At this time, the DC resistance component generated in the battery is reduced, so it can be produced with A battery with good output characteristics (speed characteristics). A small amount of addition can obtain good electronic conductivity, which can greatly increase the volume ratio of the binder material in the adhesion layer, and increase the contact between the binder material of the active material layer and the collector. Area, you can get higher adhesion. The mass ratios of the binder and conductive material contained in the first and second adhesion layers are set at predetermined ranges, respectively. Inside, good adhesion and electron conductivity can be obtained. As a result, peeling of the active material layer from the current collector due to winding or folding, external impact, and expansion and contraction of the active material layer during charging and discharging can be prevented, Therefore, good charge-discharge cycle characteristics (long life) can be obtained. Therefore, the fourth aspect of the present invention has industrially useful characteristics. According to the fifth aspect of the present invention, it is interposed between an adhesive layer containing a polymer binder In the electrode for a secondary battery in which an active material layer is provided on one or both sides of the current collector, a part of the polymer binder exists in a dense state in a particle state, and the volume of the particulate polymer binder is average. The particle size is 1 ~ 100μm. Therefore, the particulate polymer binder existing in the adhesion layer is a conductive substance in a particle state, and is also present at the interface between the current collector and the adhesion layer, and at the interface between the active material layer and the adhesion layer. The interface of the landing layer can improve the adhesion of these interfaces. The interface between the current collector and the adhesion layer without the particulate polymer binder, and the interface between the active material layer and the adhesion layer contain a conductive layer. The conductive material allows the electron transfer at the interface to proceed smoothly and maintain low resistance. At this time, when the main component of the polymer binder is a fluororesin, electricity can be obtained (please read the precautions on the back before filling (This page)

、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -75- 567630 A7 B7 V. Description of the invention (j Electrolyte secondary battery electrode with high durability, polymer binder is acrylic When a monomer that stores acid or methacrylic acid is graft polymerized with polyvinylidene fluoride, a secondary battery electrode containing a good adhesion to the current collector can be obtained. The surface of the adhesion layer is parallel to the surface of the adhesion layer When the area density of the particulate polymer binder is 1 to 100 pieces / cm2, the distribution of the particulate polymer binder at the interface between the current collector and the adhesion layer and the interface between the active material layer and the adhesion layer can be adjusted. 'Ensure the adhesion and conductivity of this interface. The secondary battery (sixth aspect of the present invention) using an electrode for a secondary battery is one that improves cycle capacity maintenance characteristics. 0 // Therefore, the fifth aspect and the fifth aspect of the present invention 6 Forms have industrially useful characteristics. (Please read the notes on the back before filling out this page.) Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm -76-

Claims (1)

567630 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 VI. Application for Patent Scope 1 Patent Application No. 9 1 1 07248 Chinese Application for Patent Scope Amendment August 1, 1992 Amendment 1. A lithium ion polymer secondary battery, which is A positive electrode composed of a positive electrode active material layer containing a first binder and a positive electrode active material is provided on the surface of the electric body, and the first binder is a polymer compound; a second binder and a negative electrode are provided on the surface of the negative electrode current collector. A negative electrode composed of a negative electrode active material layer of an active material. The second binder is a lithium ion polymer secondary battery containing the same or different high molecular compound as the first binder; and an electrolyte, which is characterized by the positive electrode. A first adhesion layer is provided between the current collector and the positive electrode active material layer, and a second adhesion layer is provided between the negative electrode current collector and the negative electrode active material layer. The first and second adhesion layers each include a first adhesion layer. 3 bonding agent and conductive material, the third bonding agent contains one or both of the polymer compound contained in the first bonding agent or the second bonding agent by a denaturing substance, or a combination thereof (these High score A compound according to any one of the repeat unit of the resulting polymer compound is a polymer compound of denatured repeat units. 2. For a lithium-ion polymer secondary battery according to item 1 of the patent application, wherein one or both of the first binder or the second binder contains a fluorine-containing high molecular compound. 3. The lithium-ion polymer secondary battery according to item 2 of the patent application, wherein the fluorine-containing polymer compound is selected from the group consisting of polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and vinylidene fluoride-hexafluoro. Copolymer of propylene or polyvinyl fluoride. 4. For example, the lithium ion polymer secondary battery of item 1 of the patent scope, wherein the denatured substance is selected from the group consisting of ethylene, styrene, butadiene, vinyl chloride, and vinegar. (210 X 297 mm) (Please read the notes on the back before filling this page) 567630 A8 B8 C8 D8 々, patent application scope 2 (please read the notes on the back before filling this page) vinyl acid ester, acrylic acid, methyl acrylate, methyl vinyl ketone, acrylamide, acrylonitrile, vinylidene chloride , Methacrylic acid, methyl methacrylate or isoprene compounds. 5. The lithium ion polymer secondary battery according to item 1 of the patent application, wherein the thickness of the first and second adhesion layers is 0.5 to 30 m, respectively. 6. The lithium ion polymer secondary battery according to item 1. in the patent application scope, wherein the first and second adhesive layers further contain 0.1 to 20% by mass of a dispersant. A lithium ion polymer secondary battery according to item 1, wherein the conductive material has a particle diameter of 0.5 to 30 μm, a carbon material having a degree of graphitization of 50% or more, and a third adhesion contained in the first and second adhesion layers The mass ratio of the agent to the conductive substance (third binder / conductive substance) is 13/87 to 50/50. Printed by an employee of the Intellectual Property Bureau of the Ministry of Economic Affairs, a cooperative. 8. A lithium-ion polymer secondary battery having a positive electrode provided with a positive electrode active material layer containing a first binder and a positive electrode active material on the surface of a positive electrode current collector. ; On the surface of the negative electrode current collector, a negative electrode containing a negative electrode active material layer of a second adhesive agent and a negative electrode active material that is the same as or different from the first binder, and an electrolyte lithium ion polymer secondary battery, which is characterized by There is a first adhesion layer between the positive electrode current collector and the positive electrode active material layer, and there is a second adhesion layer between the negative electrode current collector and the negative electrode active material layer, and the first and second adhesion layers each contain A third binder and a conductive substance, the third binder contains a polymer compound obtained by denaturing a fluorine-containing polymer compound with a denaturing substance. 9. For a lithium-ion polymer secondary battery with the scope of patent application No. 8, in which one or both of the first or second binder contains a fluorinated polymer compound, the paper standard is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 567630 A8 B8 C8 D8 A, patent application scope 3 items. (Please read the precautions on the back before filling out this page) 10. If the lithium-ion polymer secondary battery in item 9 of the patent application scope, the content of one or both of the first or second binders contains The fluorine polymer compound is a fluorine-containing polymer compound selected from polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, or polyfluoroethylene. The lithium-ion polymer secondary battery according to item 8, wherein the fluorine-containing polymer compound contained in the third binder is selected from the group consisting of polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and vinylidene fluoride-six Fluorinated propylene copolymer or fluorine-containing polymer compound of polyvinyl fluoride. 12. The lithium-ion polymer secondary battery according to item 8 of the application, wherein the denatured substance is selected from the group consisting of ethylene, styrene, butadiene, vinyl chloride, vinyl acetate, acrylic acid, methyl acrylate, and methyl ethylene. Compounds of ketone, acrylamide, acrylonitrile, vinylidene chloride, methacrylic acid, methyl methacrylate or isoprene. 13. The lithium ion polymer secondary battery according to item 8 of the patent application, wherein the thickness of the first and second adhesion layers is 0.5 to 30 m, respectively. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 14. If the lithium ion polymer secondary battery of item 8 of the patent application scope, the first and second adhesion layers further contain 0.1 to 20% by mass of a dispersant. 15. The lithium ion polymer secondary battery according to item 8 of the patent application, wherein the conductive material has a particle diameter of 0.5 to 30 μm, a carbon material having a degree of graphitization of 50% or more, and the first and second adhesions The mass ratio of the third adhesive contained in the layer to the conductive substance (third adhesive / conductive substance) is 13/87 to 50/50. This paper size is applicable to China National Standard (CNS) 8 4 specifications (210X297 mm) -3- 567630 A8 B8 C8 _D8 VI. Patent application scope 4 16 · —A method of synthesizing the third adhesive, such as the scope of patent application A method for synthesizing a polymer compound in a third binder contained in an adhesive layer of a lithium ion polymer secondary battery according to the first item, which comprises a method in which the first or second binder is contained in a denatured substance. One or both of the polymer compounds, or a polymer compound containing one or more of these polymer compounds as a repeat unit is denatured, and the denaturation method of the denatured substance is by radiation Or a method of generating free radicals by electron beam or light irradiation or heating or an initiator to form an active point of a denaturation reaction, and when the third adhesive is 100% by mass, the ratio of the denatured substance contained in the third adhesive is 2 ~ 50% by mass. 17. The method of synthesis according to item 16 of the scope of patent application, wherein the denaturation of the denaturing substance is to one or both of the polymer compounds contained in the first or second adhesive, or to contain (these ) After the polymer compound having any of the repeating units of the polymer compound is irradiated with radiation, the denatured substance is mixed with the irradiated substance, and then graft polymerization is performed. Printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs 1 8. The synthesis method according to item 16 of the scope of patent application, wherein the denaturation of the denatured substance is the polymer compound contained in the first or second adhesive. One or both of them, or a polymer compound containing the repeating unit of any one of these polymer compounds as a repeating unit is mixed with a denatured substance, and the mixture is irradiated with radiation and then subjected to graft polymerization. 19. The synthesis method according to item 16 of the scope of patent application, wherein one or both of the polymer compounds contained in the first or second adhesives, or any one of these polymer compounds The repeating unit is the repeating unit of the macromolecular compound. The radiation of the polymer compound is irradiated with r-rays to make the polymer size & Zhang scale applicable to the Chinese National Standard (CNS) A4 specifications (210X297 and 1-11567630 A8 B8 C8 D8 Six 2. The absorption linear amount of the compound in the patent application range 5 becomes 1 ~ 120kGy. 20. The synthesis method in item 18 of the patent application scope, wherein one or both of the polymer compounds contained in the first or the second adhesive, or The radiation irradiation of the polymer compound containing the polymer compound in any one of these repeating units as the repeating unit is to irradiate r rays so that the absorption line of the polymer compound becomes 1 to 120 kGy. 21 A method for synthesizing a polymer compound, such as the polymer contained in the third binder contained in the adhesion layer of the lithium ion polymer secondary battery in item 8 of the patent application scope The method for synthesizing a compound is characterized in that the fluorine-containing polymer compound is denatured by a denaturing substance. When the third binding agent after the synthesis is 100% by mass, the ratio of the denaturing substance contained in the third binding agent is 2 ~ 50% by mass. 22. The method of synthesis according to item 21 of the scope of patent application, wherein after the radiation is irradiated to the fluorine-containing polymer compound by the denaturation system of the denatured substance, the irradiated substance is mixed with the denatured substance, and then carried out. Graft polymerization 23. The synthesis method according to item 21 of the application, wherein the fluorine-containing polymer compound and the denatured substance are mixed by the denaturation system of the denatured substance, and then the mixture is irradiated with radiation and then subjected to graft polymerization. 24. The synthesis method of item 22 in the scope of patent application, wherein the radiation of the fluorine-containing polymer compound is irradiated with 7 rays so that the absorption line of the fluorine-containing polymer compound becomes 1 to 120 kGy. In the synthesis method, the radiation of the fluorine-containing polymer compound is irradiated with r-rays so that the amount of absorption rays of the fluorine-containing polymer compound becomes 1 to 120 kGy. Paper size applies Chinese National Standard (CNS) Α4 specification (210 X 297 mm)-(Please read the notes on the back of the department before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives -5- 567630 A8 B8 C8 D8 6. Scope of patent application 6 26. For the lithium ion polymer secondary battery of the scope of application for patent item 1, wherein the first conductive substance contained in the first adhesion layer and the second adhesion layer contain The second conductive substance contains a metal or a part of a metal oxide having a particle diameter of 0.1 to 20 μm, and a mass ratio of the third adhesive to the first conductive substance contained in the first adhesive layer (the third adhesive / The first conductive substance) and the mass ratio of the third adhesive to the second conductive substance contained in the second adhesive layer (the third adhesive / the second conductive substance) are 13/87 to 75/25, respectively. . 27. For example, the lithium ion polymer secondary battery of item 26 of the patent application scope, wherein the first and second conductive substances each contain a material selected from the group consisting of aluminum, copper, iron, nickel, cobalt, silver, gold, platinum, palladium, and One of these metals is a group or a mixture or alloy of two or more metals grouped by part of the oxidized metal oxide. 28. For example, a lithium ion polymer secondary battery with a scope of application for patent No. 26, wherein the first and second adhesion layers further contain an acidic polymer-based dispersant, an alkaline polymer-based dispersant or a neutral polymer-based dispersant. Dispersant. 29. The lithium ion polymer secondary battery according to item 8 of the scope of patent application, wherein the first conductive substance contained in the first adhesive layer and the second conductive substance contained in the second adhesive layer contain particle diameters. 0.1 ~ 20μm metal or partial metal oxide. The mass ratio of the third adhesive to the first conductive substance contained in the first adhesive layer (the third adhesive / the first conductive substance) and The mass ratio of the third adhesive and the second conductive substance contained in the second adhesive layer (the third adhesive / the second conductive substance) is 13/87 to 75/25, respectively. 30. The lithium-ion polymer secondary battery according to item 29 of the scope of patent application, wherein the first and second conductive substances each contain a material selected from the group consisting of aluminum, copper, iron, nickel, cobalt, silver, gold, platinum, and palladium. And some of these metals are oxidized. The paper size is applicable to China National Standard (CNS) Standard 4 (210 &gt; &lt; 297 mm) (please read the precautions on the back before filling this page). 567630 A8 B8 C8 D8 printed by the Consumers' Cooperative of the Property Bureau 夂 One or two or more mixtures or alloys of metal oxides grouped in the scope of patent application 7 points. (Please read the precautions on the back before filling out this page) 3 1 · If the lithium ion polymer secondary battery in the 29th scope of the patent application, the first and second adhesive layers further contain an acidic polymer dispersant , Basic polymer dispersant or neutral polymer dispersant. 3 2. An electrode for a secondary battery, which is an electrode for a secondary battery that is interposed between an adhesive layer containing a polymer binder and an active material layer on one or both sides of a current collector. A part of the polymer binder is in a particle state, and the volume average particle diameter of the particulate polymer binder is 1 to 100 μm. 33. The electrode for a secondary battery according to item 32 of the application, wherein the main component of the polymer binder is a fluorine-based resin. 34. The electrode for a secondary battery according to item 32 of the application, wherein the polymer binder is a compound obtained by graft polymerization of a monomer of acrylic acid or methacrylic acid and polyvinylidene fluoride. 35. For an electrode for a secondary battery, for example, in the scope of patent application No. 32, wherein the area density of the particulate polymer adhesive in the cross section in the adhesion layer parallel to the surface of the adhesion layer is 1 to 100 pieces / cm2 . Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 36. A secondary battery, which features electrodes for secondary batteries such as the 32nd in the scope of patent application. This paper size applies to China National Standard (CNS) A4 (210X297 mm)