TW388138B - A polyvinylidene fluoride metal-adhesive composition and an electrode for a battery - Google Patents

Abstract

The present invention has the objective of offering a metal-adhesive polyvinylidene fluoride composition provided with the solvent resistance and the mechanical/thermal properties inherently possessed by polyvinylidene fluoride resin; and a method for the production thereof; and also, by employing this composition as an electrode binding agent for batteries, obtaining battery electrodes of enhanced adhesion between the electrode active material and the current collector. A polyvinylidene fluoride metal-adhesive composition where, in a composition composed of vinylidene fluoride homopolymer and vinylidene fluoride copolymer, one or both of these polymers has/have functional groups which show metal-adhesion, and the vinylidene fluoride copolymer content is from 0.5 to 50 wt% of the total; and an electrode where, in an electrode for a battery in which an electrode compositional material layer comprising at least electrode active material layer comprising at least electrode active material and binding agent is formed on the surface of a current collector, there is employed as the binding agent the aforesaid polyvinylidene fluoride metal-adhesive composition.

Description

A7 B7__ printed by the employee's consumer cooperative of the Central Standards Bureau of Didi Department V. Description of the invention (/) [0001] [Field of the Invention] The present invention relates to polyvinylidene fluoride composition, which has outstanding metal adhesion properties; a preparation The other method; and an electrode for a battery using the composition as a binder. [0002] [Previous technology]. Because it has outstanding weather resistance and chemical resistance, and can be melt-molded fluoropolymer, therefore, two types of resins, polyvinylidene fluoride and vinylidene fluoride copolymers, are used for coating Materials and electrical / electronic components, steel pipe linings, chemical plant components and weathering / fouling resistant membranes, etc. However, since they are not actually adhesive to other materials, they are constrained by their difficulty in modifying or combining with other substances. [0003] Therefore, various attempts have been made to impart hydrophilic properties. In order to enhance the adhesive properties and dyeing / dispersing properties, etc., and to introduce a cross-linking site, etc., such as by introducing a carboxylic acid group into a polyvinylidene fluoride resin. For example, as to the method of introducing a carboxylic acid group, it is known to combine vinylidene fluoride with a monomer having a carboxylic acid group, or a monomer which can be converted into another group, such as acrylic acid; } Or these esters, direct vr introduction method for copolymerization (Japanese Examined Patent Publication No. 2-604, etc.). [0004] However, in the case where such technology is used in the production of carboxylic acid group-containing polyvinylidene fluoride resins, there is still a problem, that is, in consideration of the China National Standard Net ((: NS) Λ4 Specification (210X297mm) — ^^ 1 ^^^ 1 n ^ n I nk ·. N ^ i I w (Please read the precautions on the back before filling this page) Order A7 B7 V. Description of the invention (k) Copolymerization characteristics of monomers' etc. Unless special carboxyl-containing monomers that require complicated manufacturing procedures are used, the polymerization reaction rate may be significantly reduced and only low molecular weight materials can be obtained. [0005] In the Japanese Unexamined Patent Publication No. 50-41791, a fluoro monomer grafted with a carboxylic acid group is disclosed at the same time. A method of irradiating with ionizing radiation. However, in addition to the industrial difficulty of using radiation, this method is also subject to the problems of the decomposition of the polymer main chain or the accompanying cross-linking reaction. Β, therefore, have been tried so far Related to fluoropolymers All of them have related difficulties when they are implemented in industry. [0006] Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back before filling this page) At this point, turn to lithium secondary batteries In recent years, it has been used in portable devices, such as mobile phones, video cameras, and notebook computers, etc., and those that can be used as negative electrode active materials are carbonaceous materials such as coke or graphite. , Which shows lithium ion doping and un-doping (Japanese Unexamined Patent Publication No. 62-90863). Regarding the positive electrode active material, transition metal oxides such as manganese oxide and pentoxide can be used Vanadium, transition metal oxides {as they are} such as iron sulfide and titanium sulfide 'and these lithium-compound compounds (such as lithium-cobalt composite oxide, lithium-cobalt-nickel composite oxide, and lithium-manganese oxide), etc. In other cases, a paste is produced by mixing a solvent and a mixture obtained by adding an appropriate amount of a binder to an electrode active material in a powder form, and then coating it on a current collector. 'Dry' followed by pressure bonding to obtain the electrode. _____5_________ This paper size is applicable to the Chinese national standard ((: NS) Λ4 specification (210X297 mm) B7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. [0007] The binders used in the electrodes of their secondary batteries need to have resistance to organic solvents used in the electrolytic solution and resistance to the stomach of the active substance generated by the electrode reaction. Furthermore, from the electrode manufacturing process From the point of view, it is also necessary to have solubility in a specified solvent. In most cases, a polyvinylidene fluoride (PVDF) resin meeting these requirements is used. However, PVDF resin inherently has poor adhesion to metals and, in the case of both the negative electrode and the positive electrode, after the active material is pressure-bonded to the current electrode, the adhesion between the current collector and the active material Insufficient strength. Therefore, there are problems that the active material tends to be separated from the current collector and the cycle characteristics of the battery are poor. [0008] Regarding the method for improving the adhesion between the current collector and the electrode active material, there have been proposals to roughen the surface of the current collector (Japanese Unexamined Patent Publication No. 5-6766), but in this method Its adhesion is still not sufficient and needs further improvement. Again, a copolymer of vinylidene fluoride and a carboxylic acid group-containing monomer has been proposed (Japanese Unexamined Patent Publication No. 6-Π2452), but in general, a fluoro monomer and another carboxylic acid group-containing monomer Co-polymerization is not easy, and it is difficult to increase the scale of manufacture. Therefore, this approach cannot be called practical. [0009] [Problems to be Solved by the Present Invention] The object of the present invention is to propose a metal-adhesive polyvinylidene fluoride composition, wherein the metal adhesive properties are imparted by a simple method without damaging the polyvinylidene fluoride. Solvent resistance or mechanical properties possessed by fluoroethylene resins / ______ ΰ ___ —--------- This paper is suitable for Sichuan national standard ((, milk) 8 4 size (2 丨 0 '乂297 public love) ----- ΙΊ I —r --- I · 一 (Please read the precautions on the back before filling this page)

1T Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed A7 —_ B7 V. Description of the invention (^) Thermal properties; and a method of manufacturing them; and, by using this composition as a binder for electrodes used in batteries , To enhance the adhesion between the electrode active material and the current collector to the battery electrode. [Means for Solving the Problem] The inventors of the present case have found that if a mixture of vinylidene fluoride homopolymer and vinylidene fluoride copolymer is used, at least one of these components has a function of exhibiting metal adhesion. At base time, outstanding metal adhesion properties can be exhibited. Furthermore, they also found that by using such a composition as a binder for a battery electrode, the adhesion between the electrode active material and the current collector can be significantly improved. These findings are the basis on which the present invention is based. [0011] In particular, the present invention relates to a polyvinylidene fluoride metal adhesive composition. Among the vinylidene fluoride homopolymers and vinylidene fluoride, In the composition composed of the copolymer, one or both of these polymers have a functional group that exhibits metal adhesion, and the content of the vinylidene fluoride copolymer is 0 to 5 to 50% by weight of the total. [0012] The vinylidene fluoride homopolymer used in the present invention is obtained by polymerization using a vinylidene fluoride monomer in a suspension polymerization method or an emulsion polymerization method, and more preferably it has a temperature of 230 ° C. And a melt flow rate (MFR) of 0.01 to 30 g / 10 minutes at a load of 2.16 kg to 300 g / 10 minutes, and more preferably 0.01 to 30 g / 10 minutes. [0013] This paper is suitable for China National Standards (CNS) Λ4 specifications (------ (Please read the notes on the back before filling this page) ----------- i- ------ Installation ------ Order ------ X—— km m —l · — Seal A7 B7, Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (Γ) In addition, the vinylidene fluoride copolymer is a copolymer of a vinylidene fluoride monomer and another monomer copolymerizable therewith. The content of the vinylidene fluoride component in the copolymer is 50 to 95 as appropriate. % By weight and more preferably from 75 to 95% by weight »As regards another copolymerizable monomer referred to herein, a fluorine monomer such as tetrafluoroethylene, hexafluoropropylene, trifluoroethylene or trifluoro- Vinyl chloride, and one of these monomers, or two or more of them can be used. Such a resin can also be obtained by polymerizing by the suspension polymerization method or emulsion polymerization method using the aforementioned monomers, And the preferred one has a melt flow rate (MFR) of 0.005 to 300 g / 10 minutes under a load of 230 ° C and a weight of 2.16 kg, and more preferably 0.001 to 30 g / 10 minutes. ] In the present invention, The functional group having adhesion (adhesiveness or affinity) for the metal is not particularly limited, but examples that can be mentioned are carboxylic acid group or carboxylic anhydride group, epoxy group (epoxypropyl group), hydrogen thio group, Thioether group, oxazoline group, phenol group and ester group, etc. [0015] In the present invention, the content contained in the composition composed of vinylidene fluoride homopolymer and vinylidene fluoride copolymer The vinylidene fluoride copolymer is not more than 50% by weight of the total amount. 'Preferably 0.5 to 20% by weight and more preferably, 1 to 10 reset%. If the content of the vinylidene fluoride copolymer is too low , The improvement effect of the adhesion between the metal material and the PVDF composition will be insufficient, and if it is too large, it will impair the adhesion to the metal material by reducing the chemical resistance of the pVDF composition. In particular, when using PVDF composition as a binder for battery electrodes, the paper size in the electrolyte is subject to the Chinese National Standard (CNS) Λ4 Regulations -j "; ----- 1 I t '~ (Please read the notes on the back before filling in this page. Cooperative printed A7 _____B7 V. Expansion caused by organic solvents (ethyl carbonate, propyl carbonate, dimethyl carbonate, diethyl carbonate, etc.) used in the invention description ((;)) In all cases, they have an adverse effect on the properties of the electrode of the present invention or on the properties of the secondary battery. In particular, their effects are more significant at a temperature of 50 t or more. [0016] In the present invention, in the partial A method for introducing a functional group exhibiting a metal adhesive property into one or both of a difluoroethylene homopolymer and a vinylidene fluoride copolymer includes (a) adhering with a display metal under heating A method for treating {polymer} with a functional organic peroxide, (b) a method for performing heat treatment in the presence of a peroxide and an unsaturated organic compound having a functional group exhibiting metal adhesion, (c ) The method of grafting unsaturated or saturated P compounds having functional groups exhibiting metal adhesion using radiation is used. (Using unsaturated organic compounds having functional groups exhibiting metal adhesion as co- (E) using an organic peroxide compound having a functional group exhibiting metal adhesion as an initiator to polymerize vinylidene fluoride Method for vinyl monomer, or its additional fluorine monomer, and (f) unsaturated or saturated organic compounds having functional groups exhibiting metal adhesion in the polymerization of vinylidene fluoride or its additional fluorine monomer Method as a chain transfer agent. [0017] In the aforementioned method (a), the polyvinylidene fluoride is treated by using an organic peroxide compound having at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group under heating. Ethylene resin can smoothly introduce carboxylic acid group, carboxylic acid anhydride group or carboxylic acid ester group. -——----- 9 ________________ This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) (Please read the precautions on the back before filling this page).

'1T Ministry of Economic Affairs, Central Bureau of quasi-government, Shellfish Consumer Cooperative, India A7 B7 V. Description of the invention (7) [0018] It has at least one functional group selected from the group consisting of carboxylic acid group, carboxylic acid anhydride group and carboxylic acid ester group. Examples of the peroxide compound are disuccinate peroxide and tert-butylperoxymaleic acid 'and the like. The reaction mechanisms of heat-treated PVDF resins in the presence of their organic peroxides are not all clear. However, carboxylic acid groups, carboxylic acid anhydride groups, or carboxylic acid ester groups are indeed introduced into the resin. [0019] With regard to the reaction conditions in these cases, 0.5 to 100 parts by weight is used for 100 reset parts of polyvinylidene fluoride resin, and preferably 1 to 20 parts by weight has at least one selected from the group consisting of The organic peroxide of a functional group among a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group acts. [0020] In the method (b), heating is performed in the presence of a peroxide and an unsaturated organic compound having at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group. The treated polyvinylidene fluoride resin is grafted to introduce a carboxylic acid group or a carboxylic acid anhydride group. [0021] In their case 'for examples of unsaturated organic compounds having a carboxylic acid group or carboxylic anhydride group used are unsaturated carboxylic acids such as acrylic acid' methacrylic acid, crotonic acid, maleic acid 'transbutene Diacids' alkenyl succinic acid 'acrylic aminoglycolic acid and 1,2-cyclohexanedicarboxylic acid monoallyl ester' and the like; unsaturated carboxylic acid anhydrides such as maleic anhydride and alkenyl succinic anhydride, etc. ; And their derivatives. This paper size applies to Chinese national standard ((, NS) Λ4 specifications (2 丨 〇X297mm) (Please read the precautions on the back before filling out this page) • 彳, Packing. Order A7 _______B7_ V. Description of the invention (^ ) [00.22] Furthermore, the peroxide used in the method (b) is not particularly limited. Examples thereof are polyketals, alkyl hydroperoxides, dialkyl peroxides, and alkyl peroxyesters. 'Difluorenyl peroxide, peroxydicarbonate, and peroxyester, etc. [0023] In methods (a) and (b), PVDF heat treatment in the presence of peroxide can be in the molten state or in the It is carried out in a solvent, and any of the other methods can be carried out with β. For example, when carried out in a solvent, it is possible, for example, to dissolve or disperse PVDF resin and peroxide in a solvent and then carry out the reaction. Regardless of the reaction state used, all This treatment must be carried out under conditions that can sufficiently decompose the peroxide. Here, the conditions that can fully decompose the peroxide mean a temperature at least 10 hours and a half life temperature of the peroxide, and the reaction time is 1 Minutes to 10 hours, and preferably 10 minutes It is 5 to 5 hours. [0024] The solvent used in the methods (a) and (b) is not particularly limited and is selected from water and organic solvents having stability to peroxides. However, in order to make the reaction It can be carried out uniformly and efficiently. The reaction with the peroxide is preferably carried out with a binder resin in a dissolved state. Examples of the PVDF resin solvent used here are N-methylpyrrolidone, N , N-dimethylformamide 'dimethylacetamide, dimethyl arylene, tetramethylurea, propylamidine, methyl ethyl ketone and the like. After the reaction, if necessary, the polymer can be polymerized. The material is collected in the form of a precipitate, and then washed with a solvent such as an alcohol -U --- The paper size is suitable for China National Standard (CNS > Λ4 size (2 丨 0X297 male plating) III-...... . '· I 1 /. -----. ^' Please read the notes on the back before filling out this page and order B7 printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Finally, it is dried to obtain a desired binder resin having a carboxylic acid group. [0025] Even in a purification process, such as The solution is re-precipitated or the organic solvent is used for Soxhlet extraction. After that, the functional groups introduced through the above method will also remain in the resin to at least some fixed level. Therefore, they are considered to be fixed in some form of chemical bonding. To the PVDF resin. In this way, the carboxylic acid group, carboxylic acid anhydride group or carboxylic acid ester group of the polyvinylidene fluoride resin is fixed to (that is, cannot be removed by the purification procedure) via the method of the present invention at 0.002. To 2 milliequivalents, and more preferably 0.01 to 1 milliequivalent, per gram of dry resin. [Function] The polyvinylidene fluoride metal adhesive composition of the present invention can be used as a binder in a battery electrode, An electrode constituent material layer including at least an electrode active material and a binder is formed on the surface of the current collector. As a result, the adhesion between the electrode active material and the current collector can be improved, and not only can the electrode active material be prevented from falling off from the current collector during the manufacturing process of the battery, but also an improved cycle characteristic can be obtained. Battery Power ® 〇 \ [0027] For the current collector in the electrode, you can use metal foil, metal mesh or three-dimensional hole object, etc., but better, the metal used in the current collector is not easily A metal alloyed with lithium. In particular, it can be ^ _ 丨 " _ 丨 — 1〇—- The paper standard is common Chinese National Standard (CNS) Λ4 specification (2 丨 〇 > < 297 mm) Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Seal ^ V. Description of the Invention (σσ) The use of iron, 錬 'ming' copper, ming, Qin, hunger, network and fierce, their own or their alloys β [0028] in the electrode active material 'negative The electrode active material must be supplemented or depleted with available lithium ions. Examples of these materials are coke materials such as petroleum-based or carbon-based coke 'such as' acetylene black' or others such as carbon black, graphite, glassy carbon 'activated carbon' carbon fibers, and carbonaceous materials such as by placing organic high polymers in Burned organic polymer obtained by combustion in a non-oxidizing atmosphere. Furthermore, copper oxide may be added. [0029] Regarding the positive electrode active material, the active material commonly used in the foregoing can be used without particular limitation. In addition, a conductor may be added thereto. [0030] A mixture of the aforementioned polymer having a metal-adhesive functional group such as a carboxylic acid group or a carboxylic anhydride group and a polymer having no such functional group may also be used as a binder. In those cases, the content of the former is preferably at least 5 wt.% / ❶, and more preferably at least 10 wt.% Of the adhesive. [0031] In one embodiment of the electrode manufacturing process, a specified amount of electrode active material and the polyvinylidene fluoride metal adhesive composition of the present invention as a binder are kneaded together in the presence of a solvent. The obtained slurry was then coated on a current collector, followed by a drying step, followed by pressing as necessary to obtain an electrode. In this case, after coating the slurry, it should be between 60 and ___________ U- This paper size is generally in accordance with the Chinese standard. (C, NS> Λ4 specifications (2 丨 0X297 male thin) (please read the back first) Please note this page, please fill in this page) ♦ Order A7 B7 printed by Shelley Consumer Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs. 5. Description of invention (Π) 250 ° C 'Better 80 to 200 ° C for 1 minute to 10 hours' according to special requirements β. The strip electrode thus obtained can then be wound into a roll (spiral) together with the strip separator and used in the form of a wound electrode. [0032] Related The water used to obtain the slurry to be applied to the electrode current collector can be water, or an organic solution such as N-methylpyrrolidone, N, N · dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethyl Linn, hexamethyl {phospho} amine, tetramethylurea, acetone and methyl ethyl ketone, itself or a mixture of them. Among them, N-methylpyrrolidone is particularly suitable for users. Furthermore, A dispersant may be used when necessary. In those cases, a nonionic component is preferred. [0033] The amount of adhesive added to the electrode active material is preferably 1 to 30 parts of stomach and stomach, and more preferably 3 to 15 parts by weight, per 100 parts by weight of electrode active material. If this is added When the amount is too large, or if it is too small, no high-performance battery β will be obtained, and where necessary, a conductive agent and / or other additives (copper oxide, [0034] In the case of the polyvinylidene fluoride metal adhesive composition of the present invention, the case of being swollen by a carbonate solvent generally used in lithium batteries and the homopolymerization of unmodified vinylidene fluoride The thing happened is the same. In addition, in the observation with DSC, a peak can be seen near 17 ° C, which is unmodified {Jianxian first read the precautions on the back and then fill out this page} •- -I-·-The size of the paper is suitable for Sichuan China Store Standard (CNS) Λ4 specification (210X 297 mm) A7 _____B7_____ 5. The description of the invention (丨 二) The melting point of vinylidene fluoride homopolymer, so Obviously, there is no loss in heat resistance. Therefore, the present invention Genus as the non-adhesive composition having

I All properties required for the binder of electrodes used in water-based lithium batteries, not just the adhesive properties to the current collector. [0035] Hereinafter, the present invention will be explained using examples, but the present invention is not limited by these examples in any way. [Examples] [1 Example 1] 100 parts by weight of polyvinylidene fluoride (manufactured by Elf Atochem; Kynar 301F, 230 ° C, 2.16 kg load MFR = 0.03 g / (10 points) and 2 parts by weight of succinic acid peroxide were dissolved in 1000 parts by weight of N-methylpyrrolidone, and the resulting solution was heat-treated at 120 ° C for 30 minutes. The reaction liquid was then poured into methanol to precipitate the polymer. This polymer was subjected to Soxhlet extraction under reflux for 24 hours with methanol to remove unreacted peroxides and decomposition products of peroxides remaining in the polymer. From the IR spectrum measured from the film made with this polymer, the size of the absorption peak due to carbonyl group in the vicinity of 1700-1800 cnT1 and the size derived from PVDF at 881 cnT1, according to the additional use of polyvinylidene fluoride and two A calibration curve composed of a mixture of butyric acid peroxides was found to have a carbonyl content of 0.085 meq / g. [0037] 1 g of the polymer thus obtained and 0.1 parts by weight of vinylidene fluoride ____15-this paper is the standard of the state of China, suitable for jujube dates ((: NS> Λ4 specifications (2 丨 OX 297 mm) Ministry of Economic Affairs) A7 printed by the Central Bureau of Work and Consumer Cooperatives __; __B7_ V. Description of the invention (^) · ^ / Hexafluoropropylene copolymer (Hexafluoropropylene content is 10 weight. / ;; Elf)

Made by Atochem; Kynar 2801, MFR = 0.2 g / 10 min at 230 ° C, 2-16 kg load) dissolved in 10 g of N-methylpyrrolidone to form a solution, and this solution was coated to a thickness of 1 mm Copper and aluminum, and castor at 120 ° C for 1 hour, then dried under reduced pressure. [0038] When the surface of the obtained polymer coating was cut at a pitch of 1 mm and a cross-cut test (according to JIS K5400, 6.15) was performed, the percentage of the remaining adhesion PVDF coating layer was on the aluminum sheet and the copper sheet Both are 100%, and further, when the tape peeling test is performed, the residual adhesion percentage is 95% in the case of aluminum sheet and 100% in the case of copper sheet. Therefore, it was confirmed that there was good adhesion between the gold tincture and the carboxylic acid group-containing polyvinylidene fluoride. In addition, after peeling the polymer layer from the metal sheet and immersing it in ethylene carbonate at 60 ° C for 72 hours, the degree of solvent expansion was found to be 27%. This ratio is slightly higher than the unmodified Kynar 301F, but no major changes have been found. [0039] [Example 2] 90 parts by weight of polyvinylidene fluoride (Kynar 301F), 10 weight Parts of Kynar 2801 and 2 parts by weight of succinic acid peroxide are dissolved in

After 1000 weight parts of N-methylbiconone and the resulting solution was placed at 120 ° C for 30 minutes, the reaction liquid was poured into methanol to precipitate a polymer. This polymer was subjected to Soxhlet extraction with methanol under reflux for 24 hours and subjected to polymer purification. In the same manner as in Example 1, using the film made of this polymer, the carbonyl content calculated from the IR spectrum was 0.15 millimeters --- 16 --- --- This paper scale is applicable to China National Standards (CNS) ) Λ4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

1T A7 _B7___ 5. Description of the invention (, 屮 'one equivalent per gram. [0040] 1 gram of the resin composition thus obtained was dissolved in 10 gram of N-methyl quaglitazone to form a solution, and the solution was applied to the thickness respectively. 1 mm copper and nameplates, and placed at 120 ° C for 1 hour, and then dried under reduced pressure. "When the crossover test was performed as the adhesion test in the same manner as in Example 1, the residual adhesion PVDF coating was applied. The percentage of the layer is 100% for both the aluminum sheet and the copper sheet, and when the tape peeling test is performed, the residual adhesion percentage is 90% for the aluminum sheet and 98% for the copper sheet. Therefore, it can be determined that the Good adhesion to carboxylic acid group-containing polyvinylidene fluoride. In addition, the degree of swelling in the ethyl carbonate was measured in the same manner as in Example 1 using a resin peeled from a metal sheet, and was 26%. [Example 3] 95 parts by weight of polyvinylidene fluoride (made by Elf Atochem; Kynar 301F), 5 parts by weight of Kynar 2801, 10 parts by weight of maleic anhydride and 10 parts by weight Parts by weight of lauryl peroxide is dissolved in N-methylpyrrolidone and the resulting solvent is dissolved After the liquid was heat-treated at 100 ° C for 30 minutes, the reaction liquid was poured into methanol to precipitate the polymer. The polymer was subjected to Soxhlet extraction with methanol under reflux for 24 hours, and subjected to polymer purification. In the same manner as in Example 1, using the film made of this polymer, the carbonyl content calculated from the IR spectrum was 0.55 meq / g. [0042] 1 g of the thus obtained resin composition was dissolved in 10 g of N-methylpyrrole The size of this paper is suitable for the national standard (CNs) Λ4 specification (210X29k, t). (Please read the note on the back before filling this page)

Printed by Shelley Consumer Cooperative, Central Standards Bureau of the Ministry of Economy The sheet and aluminum sheet were left at 120 ° C. for 1 hour, and then dried under reduced pressure. When the cross-section test was performed as an adhesion test in the same manner as in Example 1, the percentage of the residual adhesive PVDF coating layer on both the aluminum sheet and the copper sheet was 100%, and when the tape peeling test was performed, the residual adhesion percentage was on the aluminum sheet. It is 90% in the case and 95% in the case of the copper sheet. Therefore, it can be confirmed that there is good adhesion between the metal sheet and the polyvinylidene fluoride containing a carboxylic acid group. In addition, the degree of swelling in the ethylene carbonate was measured in the same manner as in Example 1 using the resin peeled from the metal sheet. [0043] [Example 4] Prepared in the same manner as in Example 2 Metal Adhesive Resin Composition 'The difference lies in the use of high MFR polyvinylidene fluoride (manufactured by Elf Atochem; Kynar 741, MFR = 0.3 g / 10 min at 230 eC, 2.16 kg load) instead of Example 2 Kynar 301F. The carbonyl content of the obtained resin composition was measured in the same manner as in Example 2 to be 0.04 meq / g, and it exhibited outstanding metal adhesion. Further, the degree of swelling of ethyl carbonate was measured in the same manner as in Example 1 and was 25%. [Example 4] {The original text}, using a coal mill honing coal pitch coke as a support for the negative electrode active material, with 100 parts by weight and 10 parts by weight of the carboxyl group obtained in Example 2 After the acid-based polyvinylidene fluoride resin is mixed, the mixture is dispersed in N-methylpyrrolidone to form a slurry (paste). Apply this slurry to a thickness of 20 __—- IS ------- This paper size is in accordance with the Chinese national standard (rNS) Λ4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Dingjing Jingdi Dibei Central Standards Bureau Shellfish Consumer Cooperatives Co., Ltd. Seal A7 _B7____ V. Description of the Invention (丨 k) Micro-movement, as one side of the aluminum foil as a current collector, and dried at 120 ° C for 20 minutes to make a thickness 110 micron and 20 mm wide negative electrode "[0045] When fixed to the electrode active layer on the surface of the electrode with tape, and using a tensile tester to measure the adhesion strength between the current collector and the electrode active layer It was measured to be 220 g / cm2. In addition, after peeling off, significant electrode active materials still remained on the current collector, so it was determined that there was a silly adhesion between the electrode active material and the current collector. In addition, when the electrode was wound on a 1 mm cylinder to form a roll for adhesion test, no separation of the electrode active layer was observed. Subsequently, the electrode was immersed in ethylene carbonate and placed at 60 ° C. After the next 3 days, no separation of the electrode active material layer occurred. [Example 4] {Original Text} In Example 3, 94 parts by weight of UC02 as a positive electrode active material, 6 parts by weight of graphite as a conductive agent, and 10 parts by weight of a binder were used. The measured PVDF resin composition containing carboxylic acid groups was mixed together ', and the mixture was dispersed in N-methylpyrrolidone to form a slurry (paste P. This slurry was applied to a thickness of 20 microns as a current collector A copper foil was placed on one side and dried at 12 ° C for 20 minutes to make a negative electrode with a thickness of 110 μm and a width of 20 mm. '[0047] When fixed to the electrode active layer on the surface of the electrode with tape' and Measure the adhesion between the current collector and the active layer of the electrode with a tension tester ------------_____ 12__ ________- This paper size applies to Chinese national standards (CNS > Λ4 specification (2 丨 OX297 mm) I ·- : 11. _ · II-* I—-r IC (Read the note f on the back before reading this page)

* 1T-Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives, 51 A7 ____B7 V. Description of Invention (纟 ^) When the strength is measured, its 値 is 190 g / cm. In addition, after peeling, significant electrode active materials still remain on the current collector, so it is determined that there is excellent adhesion between the electrode active material and the current collector. Furthermore, the electrode is wound in a 1 mm circle When the tube was rolled into a roll for adhesion test, no separation of the electrode active layer was observed. Subsequently, after the electrode was immersed in ethylene carbonate and placed at 60 ° C for 3 days, the electrode active material layer separation phenomenon did not occur at all. [Comparative Example 1] A solution formed by dissolving 1 g of polyvinylidene chloride (manufactured by Elf Atochem; Kynar 301F) in 10 g of N-methylpyrrolidone was heated at 90 eC for 6 hours, It was cooled to room temperature and the solution was coated on a copper sheet and an aluminum sheet each having a thickness of 1 mm. After leaving it at 12 ° C for 1 hour, it was dried under reduced pressure. When the crossover test was performed in the same manner as in Example 1 as the adhesion test of the polymer coating layer, the percentage of the remaining adhered PVDF coating layer was Both aluminum and copper sheets did not exceed 20%. All PVDF was peeled off during the tape peel test. In addition, the same method as in Example 1 was used to measure the ethyl carbonate in resin peeled from the metal sheet. [0049] [Comparative Example 2] '1 g of the carboxylic acid group-containing polyvinylidene fluoride resin obtained in Example 1 was dissolved in 10 g of N-methylpyrrolidone and The solution formed without the addition of Kynar 2801 was coated on copper and aluminum sheets with a thickness of 1 mm, respectively, and placed on-; --- ------------------------------------------------------------------------------------------------------------- Λ4 specification (210X297 mm) (Please read the precautions on the back before filling in this page)

388138 A7 B7 V. Description of the invention (f and) After 1 hour at 120 ° C, dry under reduced pressure. [0050] When the crossover test was performed in the same manner as in Example 1 as the adhesion test by the polymer coating layer, the percentage of the residual adhesion PVDF coating layer was 100% for both the aluminum sheet and the copper sheet. When performing the tape peeling test, the percentage of residual adhesive PVDF coating layer is 50% on aluminum sheet and at least 80% on copper sheet. Therefore, it was determined that the adhesion between the PVDF layer and the metal foil was inferior to that in Example 1. [0051] [Comparative Example 3] Coal pitch coke honed by a ball mill was used as a support for a negatively charged active material. 〇〇parts by weight and 10 replacement parts, polyvinylidene fluoride (Kynar 301F manufactured by Elf Atochem) as a binder-after mixing, the mixture is dispersed in N-methylpyrrolidone to form a slurry ( paste). This slurry was applied to one side of an aluminum foil having a thickness of 20 micrometers as a current collector, and was dried at 120 ° C for 20 minutes to prepare a negative electrode having a thickness of 120 micrometers and a width of 20 mm. [0052] When the tape was fixed on the electrode active layer on the surface of the electrode, and the adhesion strength between the current collector and the electrode active layer was measured with a tensile tester, a low chirp was measured, which was 40 grams. / Cm, and after peeling off, no sticking electrode active material remained on the current collector. Furthermore, when the electrode was wound on a 1 mm cylinder into a roll form, about 20% of the electrode active layer was separated. __________ 2J _—__ This paper size is applicable to the Chinese National Standard (rNS) λ4 specification (210 × 297 mm)-III _ · I —l) r: I HI I * (Please read the precautions on the back before filling this page) Order economy Printed by the Central Bureau of Standards, Shellfish Consumer Cooperatives, and printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumers Cooperatives of the Ministry of Economic Affairs " 388138 $ V. Description of Invention (1) [00.53] [Comparative Example 4]

I A ball mill-based honing coal-tar pitch coke was used as a support for a negatively charged active material, and the carboxylic acid group-containing polyisocyanate obtained in Example 1 with 100 parts by weight and 10 parts by weight as a binder was used. After the fluoroethylene resins are mixed together, the mixture is dispersed in N-methylpyrrolidone to form a slurry (paste). This slurry was applied to one side of an aluminum foil having a thickness of 20 micrometers as a current collector, and was dried at 120 ° C for 20 minutes to prepare a negative electrode having a thickness of 120 micrometers and a width of 20 mm. [0054] When the tape was fixed on the electrode active layer on the electrode surface, and the adhesion strength between the current collector and the electrode active layer was measured by a tensile tester, it was slightly improved that 80 g / cm, but after peeling off, no residual electrode active material was observed on the current collector. In addition, when the electrode is wound on a 1 mm cylinder into a roll form, some separation phenomenon occurs. [0055] [Inventive effect] According to the present invention, a metal adhesive poly-bias can be obtained through a simple method. Difluoroethylene composition without compromising the solvent resistance or mechanical / thermal properties inherently possessed by polyvinylidene fluoride resins. By using the metal-adhesive polyvinylidene fluoride composition of the present invention as a binder for electrodes used in batteries, an electrode having a high degree of adhesion between an electrode active material and a current collector can be produced. When their electrodes are used in secondary batteries, they can not only < .. ____ 22 ----- ^ paper size China National Materials ((, NS) Λ4 ^ (210X297 public envy) (please read the note on the back first) (Please fill in this page for matters) J ----- ΙΊ.

• 1T 383138 A7 B7 V. Description of the invention (y °) In battery manufacturing, the separation between the electrode active material and the current collector is suppressed, and it can be shown that the secondary discharge does not damage the discharge capacitor under repeated charging and discharging. Battery β The present invention is particularly useful for non-aqueous secondary batteries such as lithium batteries β (please read the notes on the back before filling this page)-° Τ Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives * | Shizhou China National Standard Season (C: NS) Λ4 Specification (210X 297 cm)

Claims (1)

SSS138 ϋ g | __ VI. Scope of patent application 1 · A polyvinylidene fluoride metal adhesive composition, wherein, in a composition composed of vinylidene difluoride homopolymer and vinylidene fluoride copolymer One or both of the polymers have a functional group that exhibits metal adhesion and the vinylidene fluoride copolymer contains 0.5 to 50% by weight of the total 0 / 〇β 2 * as in the scope of application for item i The polyvinylidene fluoride metal adhesion composition 'wherein the vinylidene fluoride copolymer is a vinylidene fluoride military and at least one selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, trifluoroethylene or trifluoromonochloroethylene. A copolymer of monomers, and the proportion of the vinylidene fluoride component in the copolymer is 50 to 95% by weight. 3. The polyvinylidene fluoride metal adhesive composition according to item 1 or 2 of the patent application park, wherein it is applied to both the vinylidene fluoride homopolymer and the vinylidene fluoride copolymer through any of the following methods, or One or the other introduces a functional group exhibiting a metal adhesion property: (a) a method of treating {polymer} with an organic peroxide having a functional group exhibiting a metal adhesion property under heating 'or (b A method of performing a heat treatment in the presence of a peroxide and an unsaturated organic compound having a functional group exhibiting metal adhesion. Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Consumer Cooperatives (please read the precautions on the back, and then fill out this page) 4 · If you apply for a polyvinylidene fluoride metal adhesive composition in the scope of patent application item 1 or 2, where The functional group exhibiting a metal adhesive property is at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group. 5 * The polyvinylidene fluoride metal adhesive composition according to item 1 or 2 of the patent application scope, wherein the at least one is selected from the group consisting of a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group. The amount of functional groups fixed by the chemical bonding of the resin is 0.002 to 2 milliequivalents per gram of the composition. ____1____ This paper size is in accordance with China National Standard (CNS) A4 (210X297 mm). Central Bureau of Standards, Ministry of Economic Affairs A8 B8 C8 D8 printed by Beige Consumer Cooperative 6. Application scope 6. A method for preparing polyvinylidene fluoride metal adhesive composition, which comprises using at least one selected from carboxylic acid group, carboxylic acid anhydride group and carboxylic acid The functional organic peroxide compound in the ester group acts in a solution or in a molten state under heating. A mixture of vinylidene fluoride homopolymer and vinylidene fluoride copolymer. The content of the difluoroethylene copolymer is 0.5 to 50% by weight of the total. 7. A method for preparing a polyvinylidene fluoride gold tincture adhesive composition, comprising: 0.5 to 100 parts by weight of a vinylidene fluoride copolymer and 100 parts by weight, with at least one selected from a carboxylic acid group, The vinylidene fluoride homopolymer modified by the organic peroxide function of the functional group of the carboxylic acid anhydride group and the carboxylic acid ester group is mixed in a solution or in a molten state under heating. 8. A method for preparing a polyvinylidene fluoride gold tincture adhesive composition according to item 6 or 7 of the scope of patent application, wherein the vinylidene fluoride copolymer is a vinylidene fluoride monomer and at least one selected from tetrafluoroethylene, A copolymer of monomers among hexafluoropropylene, trifluoroethylene, or trifluoromonochloroethylene, and the proportion of the vinylidene fluoride component in the copolymer is 50 to 95% by weight. 9 ♦ A method for preparing a polyvinylidene fluoride metal adhesive composition according to item 6 or 7 of the scope of the patent application, wherein the 100 parts by weight of the polyvinylidene fluoride resin is used in the range of 0.5 to 100 weight. The organic peroxide having at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid anhydride group, and a carboxylic acid ester group acts. 10. A kind of electrode is used in batteries and is characterized in that an electrode constituent material layer including at least an electrode active material and a binder is formed on the surface of its current collector, wherein the binder is as applied Scope of patent 2 C (Please read the notes on the back before filling this page) Revision of the paper size Free use of China National Standards (CNS) Α4 specifications (210X297 mm) '~~' A8 B8 C8 08 388138 Apply for a patent The polyvinylidene fluoride metal adhesive composition described in the first item of the scope (please read the precautions on the back before filling out this page). Ordered by the Central Bureau of the Ministry of Economy Ladder standard (CNS) A4 specification (210X297 mm)