WO1999031750A1 - Adhesif pour elements, element l'utilisant et procede de fabrication d'elements - Google Patents

Adhesif pour elements, element l'utilisant et procede de fabrication d'elements Download PDF

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Publication number
WO1999031750A1
WO1999031750A1 PCT/JP1997/004677 JP9704677W WO9931750A1 WO 1999031750 A1 WO1999031750 A1 WO 1999031750A1 JP 9704677 W JP9704677 W JP 9704677W WO 9931750 A1 WO9931750 A1 WO 9931750A1
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WO
WIPO (PCT)
Prior art keywords
battery
adhesive
separator
electrode
polyvinyl alcohol
Prior art date
Application number
PCT/JP1997/004677
Other languages
English (en)
Japanese (ja)
Inventor
Michio Murai
Takayuki Inuzuka
Yasuhiro Yoshida
Shigeru Aihara
Daigo Takemura
Hisashi Shiota
Jun Aragane
Hiroaki Urushibata
Kouji Hamano
Original Assignee
Mitsubishi Denki Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Denki Kabushiki Kaisha filed Critical Mitsubishi Denki Kabushiki Kaisha
Priority to PCT/JP1997/004677 priority Critical patent/WO1999031750A1/fr
Publication of WO1999031750A1 publication Critical patent/WO1999031750A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a battery adhesive, a battery using the same, and a method for manufacturing a battery.
  • the present invention relates to a secondary battery used for portable electronic devices and the like. More specifically, the present invention relates to an adhesive capable of forming a high-performance battery in a thin shape, a battery using the same, and a method for manufacturing the battery. is there. Background art
  • Lithium-ion batteries are secondary batteries that are expected to achieve the highest voltage and highest energy density among batteries to date, and improvements are being actively pursued today.
  • a lithium ion battery has a positive electrode, a negative electrode, and an ion conductive layer sandwiched between them as main components.
  • a positive electrode is formed by applying a powder of lithium cobalt oxide or the like as an active material to a current collector to form a plate, and a negative electrode is similarly made of a carbon-based material as an active material. Is applied to a current collector and applied on a plate.
  • the ion conductive layer is filled with a non-aqueous electrolyte with a separator made of a porous film made of polyethylene and polypropylene interposed therebetween.
  • a layer of an ion-conductive solid electrolyte and a layer of an electrode material are heated with a thermoplastic resin binder.
  • a manufacturing method is shown in which a battery is integrated by binding.
  • the electrodes and the electrolyte are integrated to maintain electrical contact, they function as a battery without external pressure.
  • a battery using a polymer gel as an ionic conductor is known. By using vinylidene fluoride and hexafluoropropylene copolymer as the gel, the positive electrode, separator and negative electrode are integrated.
  • the conventional battery is configured as described above, in order to make the electrode layer and the electrolyte layer electrically contact sufficiently, use a strong outer can made of metal or the like that can apply pressure from the outside. As a result, the ratio of the outer case other than the power generation unit to the volume and weight of the battery has increased, and there has been a problem that it is disadvantageous to form a battery with a high energy density.
  • the electrode-electrolyte interface is covered with a solid binder.
  • This is disadvantageous compared to a battery that uses a liquid electrolyte and applies pressure from the outside with an outer can.
  • a binder having conductivity equal to or higher than that of the liquid electrolyte has not been generally found, and the same conductivity as that of a battery using the liquid electrolyte cannot be obtained.
  • a gel electrolyte having a conductivity equal to or higher than that of a liquid electrolyte has not been generally found, and it is possible to obtain the same charge / discharge characteristics as a battery using a liquid electrolyte. Can not.
  • the present invention has been made in order to solve the above-mentioned problems, and the electrode-electrolyte can be formed without using a strong outer can for applying pressure from the outside by joining the electrode layer and the electrolyte layer.
  • the first battery adhesive according to the present invention is an adhesive for bonding an active material layer bonded to a current collector to a separator for holding a battery electrolyte, and the adhesive is It consists of an organic solvent solution containing polyvinyl alcohol. This makes it possible to achieve high adhesiveness between each active material layer and the separator and high charge-discharge characteristics of the battery, and is a practical battery that is thin, has high reliability, and has high charge-discharge characteristics. Can be obtained at low cost.
  • the second battery adhesive according to the present invention is the resin according to the first battery adhesive, wherein the resin is incompatible with polyvinyl alcohol in an organic solvent solution and swells or dissolves in a battery electrolyte. Are further mixed. Thereby, the ion conductivity of the interface layer between each active material layer formed by the adhesive and the separation layer can be made higher.
  • a third battery adhesive according to the present invention is the above-mentioned first battery adhesive, wherein the degree of saponification of polyvinyl alcohol is 95% or more.
  • a fourth battery adhesive according to the present invention is the first battery adhesive, wherein the degree of polymerization of polyvinyl alcohol is 100 or more. Thereby, a battery having high bonding strength and more preferable characteristics can be obtained.
  • the active material layers of the positive electrode and the negative electrode each having the active material layer adhered to the current collector are separated from the active material layer for holding the battery electrolyte, and the organic solvent contains polyvinyl alcohol. It has an electrode laminate bonded with a battery adhesive. As a result, it is possible to achieve high adhesion between each active material layer and the separator and high charge / discharge characteristics of the battery, and realize a thin, reliable, and practical battery with high charge / discharge characteristics. It can be obtained at low cost.
  • the second battery according to the present invention is the battery according to the first battery, wherein the battery adhesive is further incompatible with polyvinyl alcohol and further swells or dissolves in the battery electrolyte. It becomes. Thereby, the ionic conductivity of the interface layer between each active material layer formed by the adhesive and the separation layer can be made higher.
  • a third battery according to the present invention is the same as the first battery, except that the third battery includes a plurality of layers of the electrode laminate.
  • a fourth battery according to the present invention is a battery according to the third battery, wherein a plurality of layers of the electrode laminate are formed by alternately arranging a plurality of layers of the positive electrode and the negative electrode separated from each other. is there.
  • a plurality of layers of the electrode laminate are formed by alternately arranging the positive electrode and the negative electrode between the wound separators.
  • a plurality of layers of the electrode laminate are formed by alternately arranging a positive electrode and a negative electrode in a folded separator.
  • the adhesive strength and high ionic conductivity can be ensured, a strong outer can is required even in a configuration having a plurality of layers of the electrode laminate.
  • a compact, high-performance, large-capacity stacked electrode battery can be obtained.
  • the first method for producing a battery according to the present invention comprises the steps of:
  • the method includes a step of integrating the above-mentioned electrode and the separator by removing at least a part of the organic solvent.
  • the method for producing a second battery according to the present invention is the method for producing a battery according to the first battery, wherein the adhesive for a battery is applied to the surface of the separator, and then the adhesive for the battery is applied to the application surface of the separator.
  • the method further comprises a step of gelling the battery adhesive by adding a second solvent capable of gelling the adhesive solution. Thereby, the ionic conductivity of the interface layer between each active material layer formed by the adhesive and the separator can be further increased.
  • a third method for producing a battery according to the present invention is the method for producing a battery according to the first method, wherein the battery adhesive is incompatible with polyvinyl alcohol in the organic solvent solution and swells in the battery electrolyte.
  • the saponification degree of polyvinyl alcohol is 95% or more in the first method for producing a battery.
  • a fifth method for producing a battery according to the present invention is the method for producing a battery according to the first method, wherein the degree of polymerization of polyvinyl alcohol is 100 or more. You.
  • FIG. 1 is a schematic cross-sectional view of a main part of an embodiment of a battery according to the present invention.
  • FIGS. 2, 3, and 4 show other embodiments of the battery according to the present invention. It is a principal part cross-section schematic diagram demonstrated. BEST MODE FOR CARRYING OUT THE INVENTION
  • the present inventors have conducted intensive studies on a preferred method of bonding the active material layer surfaces of a pair of electrodes having the active material layer bonded to the current collector to the separator, and have reached the present invention.
  • the present invention provides a positive electrode 1 in which a positive electrode active material layer 3 is bonded to a positive electrode current collector 2, and a negative electrode 4 in which a negative electrode active material layer 6 is bonded to a negative electrode current collector 5.
  • the present invention relates to a battery having an electrode laminate 9 in which a separator 7 holding an electrolytic solution between a positive electrode 1 and a negative electrode 4 is joined by an adhesive layer 8.
  • a feature of the present invention resides in the composition of the battery adhesive forming the adhesive layer 8 that joins the electrodes (positive and negative electrodes) 1 and 4 and the separator.
  • the present inventor has conducted various studies on a secondary battery that has been studied as to how thin and reliable the battery is, and how to increase the charge / discharge efficiency.
  • the inventors have found that a thin and reliable secondary battery with high charge / discharge efficiency can be manufactured by using, and the present invention has been completed.
  • the battery adhesive for the adhesive layer 8 for example, “Poval” (Koichi Nagano et al. Polymer Publishing Association Showa 45 First Edition
  • the adhesive develops a strong adhesive force, and the battery can be integrated with a small amount of adhesive.
  • the adhesive strength obtained can be obtained, and the adhesive layer 8 is made porous by drying and removing the solvent in the adhesive, or the adhesive layer 8 is gelated by partially distilling off the solvent. 8, the ionic conductivity can be increased, and the charge / discharge characteristics can be improved.
  • a mixture of polyvinyl alcohol and another resin can be used.
  • the adhesive layer 8 is incompatible with polyvinyl alcohol and a phase exhibiting an adhesive function.
  • a battery having particularly excellent performance can be obtained by having a resin electrolyte and a resin that dissolves or swells in the battery electrolyte and has two phases, ie, a phase that exhibits ionic conduction.
  • the degree of saponification of polyvinyl alcohol is preferably 95% or more, and the degree of polymerization of polyvinyl alcohol is preferably 100 or more.
  • the active material layer of the pair of electrodes having the active material layer bonded to the current collector is applied to the coating surface of the separator.
  • at least a part of the organic solvent is distilled off to integrate the electrode and the separator to produce a single electrode laminate 9 shown in FIG.
  • a part of the adhesive layer 8 is gelled when the electrolytic solution is injected, and the ionic conductivity of the adhesive layer 8 is increased, and the charge / discharge characteristics are excellent. A battery is obtained.
  • FIG. 1 shows a single-electrode battery composed of a single electrode stack 9; As shown in FIGS. 3 and 4, a stacked electrode battery having a structure having a plurality of electrode stacks 9 can be manufactured. This manufacturing method will be described in detail in the following examples.
  • a second solvent capable of gelling the battery adhesive solution is added to the coating surface of the separator, thereby forming the battery.
  • the adhesive for use is gelled, the ionic conductivity of the adhesive layer 8 is increased, and the battery performance can be improved.
  • any solvent that does not dissolve polyvinyl alcohol can be used.
  • hydrocarbons, ketone compounds, ester compounds, ether compounds, alcohols and the like and mixed solvents thereof can be used.
  • the adhesive layer 8 has two phases of a phase exhibiting an adhesive function and a phase exhibiting ionic conduction, and a battery having particularly excellent performance can be obtained.
  • Examples of the resin that is incompatible with the polyvinyl alcohol and that dissolves or swells in the battery electrolyte include polystyrene, polyacrylate, polyacrylonitrile, polyvinyl acetate, polyacetal, and mixtures or copolymers thereof. it can.
  • a solution in which a lithium salt is dissolved in a non-protonic organic solvent can be used.
  • the lithium salt L i C 10 4, L iBF 4, L iAs F 6, L i CF 3 S0 3, L i PF 6, L il, L iB r, L i S CN, L i 2 B 10 C l 10 , Li CF 3 C ⁇ 2 and the like.
  • aprotic organic solvents propylene glycol, butyl lactone, ethylene glycol, tetrahydrofuran, 2-tetrahydrofuran Drofuran, 1,3-dioxolan, 4,4-dimethyl-1,3-dioxolan, getylcapone, dimethylcapone, sulfolane, 3-methylsulfolane, tert-butylether, iso-butylether, 1 , 2-Dimethoxetane, 1,2-ethoxymethoxetane, and the like, and a mixed solvent obtained by combining them can be used.
  • organic solvent constituting the adhesive N-methyl-2-pyrrolidone, dimethylsulfoxide, acetoamide, arptyrolactone, and the like, and a mixed solvent obtained by combining these can be used.
  • a filler such as an inorganic oxide can be added to the battery adhesive.
  • the adhesive layer 8 becomes porous by adding the filler, it is expected that the ionic conductivity of the adhesive layer 8 is improved and the battery characteristics are improved.
  • any material having sufficient strength such as a porous film made of an electrically insulating material, a net, and a nonwoven fabric, can be used.
  • the material is not particularly limited, but a single porous film or a laminated porous film of polyethylene or polypropylene is preferable from the viewpoint of battery performance.
  • the adhesive strength of the battery was 180 degrees of the test piece (20 mm XI 00 mm X 0.2 mm) in which the positive electrode 1, the negative electrode 4 and the separator 7 were bonded together with an adhesive.
  • the peel strength was measured.
  • UTM11-20 manufactured by Toyo Baldwin Co., Ltd. was used as a test device, and the measurement was performed at a tensile speed of 10 mm / min and a measurement temperature of 25 ° C.
  • the battery charge / discharge characteristics were measured under the following conditions, for example, using the method described in the Battery Handbook (Battery Handbook Editing Committee, published by Maruzen Publishing Co., Ltd. in 1990). did.
  • a negative electrode active material paste adjusted to 95% by weight of mesophase microbeads (Osaka Gas) and 5% by weight of polyvinylidene fluoride is applied by a doctor blade method while adjusting the thickness to 300 mm.
  • An active material thin film was formed.
  • a 20-m-thick strip-shaped copper net serving as a negative-electrode current collector was placed on the upper portion, and a negative-electrode active material paste was applied thereon by adjusting the thickness to 300-m by a doctor blade method. This was left in a dryer at 60 ° C. for 60 minutes to make it semi-dry.
  • a negative electrode was produced by rolling the produced laminate to 400 zm.
  • NMP N-methyl-2-pyrrolidone
  • Porous polypropylene sheet (to text, trade name Celgard # 2400) used as a separator evening the adhesive 3mg applied per separator Isseki 1 cm 2 to, there to be brought into close contact with the positive and negative electrodes becomes a predetermined thickness Then, it was heated at 80 ° C for 1 hour and then cut into a predetermined size.
  • Porous polypropylene sheet (to text, trade name Celgard # 2400) used as separator Isseki adhesive separator evening 1 cm 2 per then 3mg coated according to claim 1 or later on both sides of where adhesion to the positive electrode and the negative electrode Then, after laminating so as to have a predetermined thickness, it was heated and breathed under a vacuum of 80 ° C for 1 hour to obtain an electrode laminate.
  • Example 2 Instead of the adhesive in Example 1, 3 g of polyvinyl alcohol having a polymerization degree of 1000 and a saponification degree of 98 mol% was added to 97 g of N_methyl-1-piperidone, heated to 80 ° C. and stirred. The solution that was used while the solution was used.
  • Example 3 Instead of the adhesive in Example 1, 3 g of polyvinyl alcohol having a polymerization degree of 2400 and a saponification degree of 98 mol% was added to 97 g of N-methyl-2-piperone, heated to 80 ° C. and stirred. The solution that was used while the solution was used.
  • an adhesive was prepared in the following manner, and a test piece for an adhesive strength test and a battery were prepared.
  • the above adhesive was applied to a porous polypropylene sheet (made by Hext, product name Celgard # 2400) used as a separator overnight, 3 mg per cm 2 of the separator, and isopropyl alcohol was sprayed on the application surface. Thereafter, the positive electrode and the negative electrode were brought into close contact with each other so as to be bonded to a predetermined thickness, heated and pressed at 80 ° C. for 1 hour, and then cut into a predetermined size.
  • a porous polypropylene sheet made by Hext, product name Celgard # 2400
  • Example 4 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a polymerization degree of 1000 and a saponification degree of 98 mol% was added to 97 g of N-methyl-2-vinylidone, and the mixture was heated to 80 ° C. and stirred. The solution was used as it was.
  • Example 4 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a polymerization degree of 2400 and a saponification degree of 98 mol% was added to 97 g of N-methyl-2-pyrrolidone, and the mixture was heated to 80 ° C. and stirred. The solution was used.
  • Example 8 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a polymerization degree of 300 and a saponification degree of 87 mo 1% was added to 97 g of N-methyl-2-pyrrolidone, and the mixture was heated to 80 ° C. and stirred. A solution was used.
  • Example 8
  • Example 4 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a degree of polymerization of 1000 and a degree of saponification of 87 mol% was added to 97 g of N-methyl-12-piperidine, heated to 80 ° C. and stirred. The solution that was used while the solution was used.
  • Example 10 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a polymerization degree of 2400 and a saponification degree of 87 mol% was added to 97 g of N-methyl-2-bilidone, and the mixture was heated to 80 ° C. and stirred. The solution was used.
  • Example 10
  • Example 4 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a degree of polymerization of 300 and a degree of saponification of 98% mo, and 3 g of polymethyl methacrylate were converted to 94 g of N-methyl-2-pyrrolidone. In addition, a solution which was heated to 80 ° C. and stirred while stirring was used.
  • Example 4 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a degree of polymerization of 100 and a saponification degree of 98%, and 3 g of polymethyl methacrylate were replaced with 94 g of N-methyl-2-pyrrolidone. In addition to 80. A solution which was heated to C while stirring was used.
  • Example 4 instead of the adhesive in Example 4, 3 g of polyvinyl alcohol having a degree of polymerization of 240 and a saponification degree of 98 mol%, and 3 g of polymethyl methacrylate were added to 94 g of N-methyl-2-pyrrolidone. The solution was heated to 80 ° C. and stirred to form a solution.
  • the preparation of the negative electrode and the positive electrode and the adjustment of the adhesive were performed in the same manner as in Example 1 above.
  • the adjusted adhesive was applied to one surface of each of the two separators, and the negative electrode was sandwiched between the coated surfaces.
  • the NMP was put in a hot air drier at 80 ° C. for 2 hours to evaporate NMP.
  • the separator with the negative electrode bonded in between was punched out to a predetermined size, the adhesive adjusted above was applied to one surface of the punched-out separator, and the positive electrode punched to a predetermined size was stuck, Further, the above-prepared adhesive was applied to one surface of another separator punched out to a predetermined size, and the coated surface of the separate separator was bonded to the surface of the positive electrode previously bonded. This step is repeated to form a battery body having a plurality of electrode laminates. The pond was dried while being pressurized to produce a flat-plate laminated battery as shown in FIG.
  • an adhesive was applied to the surface of the separator where the positive electrode was adhered and adhered in the same manner as described above, and the negative electrode was adhered to the coated surface.
  • the step of bonding another positive electrode with two positive electrodes bonded together during one separation may be repeated.
  • the preparation of the negative electrode and the positive electrode and the adjustment of the adhesive were performed in the same manner as in Example 1 described above.
  • the adjusted adhesive was applied to one surface of each of the two strip-shaped separators, and a belt-shaped adhesive was applied between the applied surfaces.
  • the adjusted adhesive was applied to one side of the strip-shaped separator with the positive electrode bonded between them, one end of the separator was bent by a certain amount, the negative electrode was sandwiched in the fold, and the laminate was passed through the laminator. . Subsequently, the adjusted adhesive is applied to the other side of the strip-shaped separator, and another negative electrode is attached to a position opposite to the negative electrode sandwiched between the folds, and the separator is rolled up in an oval shape. Further, the step of winding up the separator while attaching another negative electrode is repeated to form a battery body having a plurality of electrode laminates, and the battery body is dried while being pressed, and is then pressed as shown in FIG. A wound-type laminated structure battery body was produced. An electrolytic solution was poured into the plate-shaped wound laminated battery body in the same manner as in Example 1 described above, and the battery was sealed to obtain a lithium ion secondary battery.
  • an example is shown in which the negative electrode is adhered to the belt-shaped separator while the band-shaped positive electrode is joined and rolled up in the evening.
  • a method in which the positive electrode is bonded while the band-shaped negative electrode is joined is rolled up.
  • the method of winding up the separator is shown, but a method of bonding the positive electrode or the negative electrode while folding the band-shaped negative electrode or the positive electrode in the band-shaped separator may be used.
  • Preparation of the negative electrode and the positive electrode, and adjustment of the adhesive are performed in the same manner as in Example 1 above.
  • the strip-shaped positive electrode is placed between two strip-shaped separators, and the strip-shaped negative electrode is placed so as to protrude outside of one of the separators by a certain amount.
  • the adjusted adhesive is applied to the inner surface of each separator and the outer surface of the separator where the negative electrode is placed, and the positive electrode, the two separators and the negative electrode are overlapped and passed through the laminator.
  • the adjusted adhesive is applied to the outer surface of the other separator, and the protruding negative electrode is bent and adhered to this coated surface, and the laminated separator is wrapped inside so that the folded negative electrode is long. It is rolled up in a circular shape to form a battery body having a plurality of electrode laminates, and the battery body is dried while being pressurized to form a flat-plate wound type laminated structure battery body as shown in FIG. Made.
  • a strip-shaped positive electrode is arranged in a strip-shaped separator and a negative electrode is arranged outside one separator and rolled up, but conversely, a strip-shaped separator is formed in a strip-shaped separator.
  • a method in which a negative electrode is arranged, and a positive electrode is arranged outside one separator and wound up may be used.
  • Comparative Example 1 17 Instead of the adhesive in Example 4, 3 g of polyvinylidene fluoride was added to 97 g of N-methyl-2-pyrrolidone, and a solution was used while heating to 80 ° C. and stirring.
  • Example 4 In place of the adhesive in Example 4 above, 6 g of polyvinylidene fluoride was added to 94 g of N-methyl-2-pyrrolidone, and the mixture was dried. The solution which was heated to C and stirred while stirring was used.
  • Example 3 XXX Using the adhesive test pieces obtained in the above Examples and Comparative Examples, the adhesive strength of the adhesive was determined according to the following criteria (1) and (2). The results are shown in Table 1 above.
  • ⁇ The peel adhesion between the electrode and the separator was 40 gf / cm or more.
  • X The peel adhesion between the electrode and the separator was less than 40 gf / cm. Also, the batteries obtained in the above Examples and Comparative Examples were used. The charge-discharge was repeated for 100 cycles, and the charge and discharge characteristics at the first cycle and at the 100th cycle were determined based on the following criteria of X and X. The results are shown in Table 1 above.
  • the positive electrode 1-separator was used.
  • the bonding strength between the negative electrode 7 and the negative electrode 4 and the separator 7 was increased. This is because the adhesive solution gels and the amount absorbed into the porous electrode active material layer decreases, resulting in the amount of adhesive remaining at the electrode-separator interface and contributing to the development of adhesive strength. This is thought to be the result of the increase.
  • Comparative Example 2 when polyvinylidene fluoride was used as the adhesive and the concentration of the adhesive solution was increased to twice that of Examples 1 to 12, sufficient adhesive strength was obtained. However, the charge / discharge characteristics of the battery deteriorated.
  • It is used as a secondary battery in portable electronic devices such as mobile personal computers and mobile phones, and can be made smaller, lighter, and arbitrarily shaped as well as improving battery performance.

Abstract

Adhésif permettant de faire adhérer facilement une électrode et un séparateur, élément l'utilisant et procédé de fabrication d'éléments, de manière à obtenir des éléments d'accumulateurs avec une épaisseur réduite et d'excellentes caractéristiques charge/décharge. L'adhésif pour éléments permet de faire adhérer à un séparateur (7), qui contient une solution électrolytique pour l'élément, des couches de substance active (3,6) adhérant aux collecteurs (2,5). L'adhésif comprend une solution de solvant organique contenant un alcool polyvinylique. L'utilisation de cet adhésif rend possible la fabrication bon marché et de façon satisfaisante d'éléments d'accumulateurs d'épaisseur réduite, de bonne fiabilité, et à bon rendement de charge/décharge.
PCT/JP1997/004677 1997-12-18 1997-12-18 Adhesif pour elements, element l'utilisant et procede de fabrication d'elements WO1999031750A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
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WO2008093575A1 (fr) 2007-01-30 2008-08-07 Asahi Kasei E-Materials Corporation Membrane poreuse multicouche et son procédé de fabrication
WO2009025332A1 (fr) * 2007-08-22 2009-02-26 Japan Vilene Company, Ltd. Batterie secondaire lithium-ion
JP2010192248A (ja) * 2009-02-18 2010-09-02 Japan Vilene Co Ltd リチウムイオン二次電池
JP2011054502A (ja) * 2009-09-04 2011-03-17 Hitachi Maxell Ltd リチウム二次電池およびその製造方法
JP2011124074A (ja) * 2009-12-10 2011-06-23 Japan Vilene Co Ltd リチウムイオン二次電池用熱暴走抑制剤及びリチウムイオン二次電池
JP2011165501A (ja) * 2010-02-10 2011-08-25 Japan Vilene Co Ltd リチウムイオン二次電池用熱暴走抑制剤及びリチウムイオン二次電池
KR101143307B1 (ko) 2007-07-23 2012-05-08 주식회사 엘지화학 유화 중합으로 제조된 폴리비닐 아세테이트와 폴리비닐알코올의 이중충 바인더 및 이를 포함하고 있는 이차전지
WO2012128026A1 (fr) * 2011-03-18 2012-09-27 協立化学産業株式会社 Agent de traitement de surface métallique aqueux pour accumulateur lithium-ion
JP2014026986A (ja) * 2013-10-04 2014-02-06 Hitachi Maxell Ltd リチウム二次電池用セパレータ、並びにリチウム二次電池およびその製造方法
US9525189B2 (en) 2011-09-26 2016-12-20 Sumitomo Chemical Company, Limited Adhesive resin composition for secondary battery
US9843049B2 (en) 2011-09-26 2017-12-12 Sumitomo Chemical Company, Limited Adhesive resin composition for secondary battery
WO2020255802A1 (fr) * 2019-06-17 2020-12-24 株式会社クラレ Séparateur pour batterie secondaire à électrolyte non aqueux et son procédé de fabrication

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US9293752B2 (en) 2007-01-30 2016-03-22 Asahi Kasei E-Materials Corporation Multilayer porous membrane and production method thereof
KR101479822B1 (ko) * 2007-01-30 2015-01-06 아사히 가세이 이-매터리얼즈 가부시키가이샤 다층 다공막 및 그의 제조 방법
WO2008093575A1 (fr) 2007-01-30 2008-08-07 Asahi Kasei E-Materials Corporation Membrane poreuse multicouche et son procédé de fabrication
KR101143307B1 (ko) 2007-07-23 2012-05-08 주식회사 엘지화학 유화 중합으로 제조된 폴리비닐 아세테이트와 폴리비닐알코올의 이중충 바인더 및 이를 포함하고 있는 이차전지
JP2013258150A (ja) * 2007-08-22 2013-12-26 Japan Vilene Co Ltd リチウムイオン二次電池
US8546025B2 (en) 2007-08-22 2013-10-01 Japan Vilene Company, Ltd. Lithium ion secondary battery
EP2192648A4 (fr) * 2007-08-22 2011-01-19 Japan Vilene Co Ltd Batterie secondaire lithium-ion
WO2009025332A1 (fr) * 2007-08-22 2009-02-26 Japan Vilene Company, Ltd. Batterie secondaire lithium-ion
JP5458304B2 (ja) * 2007-08-22 2014-04-02 日本バイリーン株式会社 リチウムイオン二次電池
JP2010192248A (ja) * 2009-02-18 2010-09-02 Japan Vilene Co Ltd リチウムイオン二次電池
JP2011054502A (ja) * 2009-09-04 2011-03-17 Hitachi Maxell Ltd リチウム二次電池およびその製造方法
JP2011124074A (ja) * 2009-12-10 2011-06-23 Japan Vilene Co Ltd リチウムイオン二次電池用熱暴走抑制剤及びリチウムイオン二次電池
JP2011165501A (ja) * 2010-02-10 2011-08-25 Japan Vilene Co Ltd リチウムイオン二次電池用熱暴走抑制剤及びリチウムイオン二次電池
WO2012128026A1 (fr) * 2011-03-18 2012-09-27 協立化学産業株式会社 Agent de traitement de surface métallique aqueux pour accumulateur lithium-ion
JPWO2012128026A1 (ja) * 2011-03-18 2014-07-24 協立化学産業株式会社 水性のリチウムイオン２次電池用金属表面処理剤
JP5934695B2 (ja) * 2011-03-18 2016-06-15 協立化学産業株式会社 水性のリチウムイオン２次電池用金属表面処理剤
US9525189B2 (en) 2011-09-26 2016-12-20 Sumitomo Chemical Company, Limited Adhesive resin composition for secondary battery
US9843049B2 (en) 2011-09-26 2017-12-12 Sumitomo Chemical Company, Limited Adhesive resin composition for secondary battery
JP2014026986A (ja) * 2013-10-04 2014-02-06 Hitachi Maxell Ltd リチウム二次電池用セパレータ、並びにリチウム二次電池およびその製造方法
WO2020255802A1 (fr) * 2019-06-17 2020-12-24 株式会社クラレ Séparateur pour batterie secondaire à électrolyte non aqueux et son procédé de fabrication

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