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WO1999034470A1 - Procede de fabrication d'une pile secondaire a ions de lithium - Google Patents

Procede de fabrication d'une pile secondaire a ions de lithium Download PDF

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Publication number
WO1999034470A1
WO1999034470A1 PCT/JP1997/004854 JP9704854W WO9934470A1 WO 1999034470 A1 WO1999034470 A1 WO 1999034470A1 JP 9704854 W JP9704854 W JP 9704854W WO 9934470 A1 WO9934470 A1 WO 9934470A1
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WO
WIPO (PCT)
Prior art keywords
separator
ion secondary
lithium ion
electrode
binder
Prior art date
Application number
PCT/JP1997/004854
Other languages
English (en)
Japanese (ja)
Inventor
Takayuki Inuzuka
Michio Murai
Yasuhiro Yoshida
Kouji Hamano
Hiroaki Urushibata
Jun Aragane
Hisashi Shiota
Shigeru Aihara
Daigo Takemura
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/JP1997/004854 priority Critical patent/WO1999034470A1/fr
Publication of WO1999034470A1 publication Critical patent/WO1999034470A1/fr

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Classifications

    • 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
    • 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
    • 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 method for manufacturing a lithium ion secondary battery. More specifically, the present invention relates to a method for manufacturing a lithium ion secondary battery that can be made thinner and lighter in an arbitrary shape.
  • Lithium-ion secondary batteries are the ones that are expected to have the highest voltage and high energy density among the batteries so far, and improvements are being actively pursued even today.
  • a lithium ion secondary battery has a positive electrode and a negative electrode as its main components, and an ion conductive layer sandwiched between the positive electrode and the negative electrode.
  • the positive electrode is a plate formed by applying an active material powder such as lithium monocondole oxide, an electron conductor powder, and a resin for binding these to a current collector
  • the negative electrode is a carbon-based material.
  • An active material powder and a binder resin are applied to a current collector to form a plate.
  • a separator made of a porous film such as polyethylene or polypropylene and filled with a non-aqueous electrolyte is used as the ion conductive layer.
  • a positive electrode, a separator, and a negative electrode are swirled.
  • the electrode body In order to maintain the electrical connection of the wound electrode body, the electrode body is placed in a strong outer can made of stainless steel or the like, and pressure is applied from the outside of the electrode body. Have maintained.
  • prismatic batteries a method has been used in which rectangular electrodes are bundled and placed in a rectangular outer can to apply force from the outside to hold them down.
  • Japanese Patent Application Laid-Open No. 5-159802 discloses a manufacturing method in which an ion-conductive solid electrolyte layer and a positive electrode and a negative electrode are integrally bonded by heating with a thermoplastic resin binder. It is shown.
  • the electrodes are brought into close contact by integrating the positive electrode and the negative electrode with the solid electrolyte, the electrical connection between the positive electrode, the negative electrode and the solid electrolyte is maintained without applying external pressure. Therefore, it operates as a battery.
  • conventional lithium-ion secondary batteries must use strong external cans made of metal, etc., to which external pressure can be applied.
  • the ratio of the volume and weight of the outer can to the entire battery becomes large, which is disadvantageous for obtaining a battery with high energy density.
  • the present invention has been made in order to solve the above problems, and in a battery using an electrolyte having excellent ionic conductivity, a positive electrode and a negative electrode can be used without adversely affecting the electrode active material and, consequently, the battery performance.
  • a positive electrode and a negative electrode can be used without adversely affecting the electrode active material and, consequently, the battery performance.
  • the separator By bonding the separator to the separator, the electrical connection between the electrodes is maintained without using a strong outer can for applying external pressure, and the outer can is not used. It is an object of the present invention to provide a method for manufacturing a lithium ion secondary battery which is thin and lightweight and can have any shape. Disclosure of the invention
  • the first method for manufacturing a lithium ion secondary battery according to the present invention is directed to a lithium ion secondary battery having a structure in which an electrode and a separator are bonded with a binder resin containing a fluorine-based resin or polyvinyl alcohol as a main component.
  • a binder resin containing a fluorine-based resin or polyvinyl alcohol as a main component.
  • Apply the binder-resin solution obtained by dissolving the binder-resin in the solvent over the separator and leave it until the fluidity decreases. Then, place the separator-coating surface and the electrode facing each other. Bonding is performed by laminating and drying.
  • the drying time for removing the solvent after bonding can be shortened, and the binder-resin solution is concentrated to lower the fluidity, so that the binder-resin solution can permeate into the electrode after bonding. Since it is lost, the function of the electrode active material is not impaired. Therefore, the electrode and the separator can be effectively bonded without lowering the battery performance.
  • the second method for manufacturing a lithium ion secondary battery according to the present invention is directed to a lithium ion secondary battery having a structure in which an electrode and a separator are bonded with a binder resin containing a fluorine-based resin or polyvinyl alcohol as a main component.
  • the above binder resin is replaced with N-methylpyrrolidone or dimethyl
  • Bonding is performed by bonding and drying.
  • the third method of manufacturing a lithium ion secondary battery according to the present invention is directed to a lithium ion secondary battery having a structure in which an electrode and a separator are bonded with a binder resin containing a fluorine-based resin or polyvinyl alcohol as a main component.
  • a binder resin containing a fluorine-based resin or polyvinyl alcohol as a main component.
  • 3 to 25 parts by weight, preferably 5 to: L, of the above binder resin is used in a solvent containing either N-methylpyrrolidone, dimethylacetamide, or dimethylformamide.
  • the electrode and the separator can be bonded with a necessary and sufficient bonding strength.
  • the fourth method for manufacturing a lithium ion secondary battery according to the present invention is directed to a lithium ion secondary battery having a structure in which an electrode and a separator are bonded with a binder resin containing a fluorine-based resin or polyvinyl alcohol as a main component.
  • the binder resin is dissolved in a solvent containing N-methylpyrrolidone, dimethylacetamide, or dimethylformamide, and a solvent having a boiling point lower than that of the solvent is not more than 50 parts by weight.
  • Bonding is performed by applying the added binder-resin solution all over the separator and letting it stand until the fluidity decreases, and then bonding and drying with the separator-coated surface facing the electrode. . According to this, the time until the fluidity of the binder-resin solution decreases and the drying time can be shortened.
  • a fifth method for manufacturing a lithium ion secondary battery according to the present invention the positive electrode and the negative electrode are separated by a binder-resin layer containing a fluorine-based resin or polyvinyl alcohol as a main component in a separator holding an electrolytic solution.
  • a binder resin solution obtained by dissolving the binder resin in a solvent is applied to the separator and left until the fluidity is reduced. Adhesion is performed by laminating and drying the coated surface and the positive electrode or the negative electrode facing each other.
  • the adhesive strength and high ionic conductivity can be ensured, and a stacked electrode type battery that is compact, has high performance, and has a large battery capacity can be obtained without requiring a strong outer can. .
  • the positive electrode and the negative electrode are separated by a binder-resin layer containing a fluorine-based resin or polyvinyl alcohol as a main component in a separator holding an electrolytic solution.
  • a lithium ion secondary battery comprising a plurality of electrode laminates joined together by bonding the positive electrode and the negative electrode alternately in a plurality of separated separators.
  • a compact, high-performance, large-capacity multi-layer battery can be obtained that can secure adhesive strength and high ionic conductivity.
  • the positive electrode and the negative electrode are separated by a binder-resin layer containing a fluorine-based resin or polyvinyl alcohol as a main component in a separation holding an electrolytic solution.
  • Laminated electrode A lithium ion secondary battery comprising a plurality of layers, wherein the plurality of layers of the electrode laminate are formed by alternately disposing a positive electrode and a negative electrode in a rolled-up separator overnight.
  • a binder-resin solution prepared by dissolving the binder-resin in a solvent is applied over the separator and left until the fluidity decreases, then the separator-coated surface and the positive electrode or the negative electrode are opposed to each other and dried. By doing so, the bonding is performed.
  • the positive electrode and the negative electrode are separated by a binder-resin layer containing a fluorine-based resin or polyvinyl alcohol as a main component in a separation holding an electrolytic solution.
  • a lithium ion secondary battery including a plurality of electrode laminates joined by bonding, wherein the plurality of layers of the electrode laminates are formed by alternately arranging a positive electrode and a negative electrode in a folded separator.
  • a binder-resin solution prepared by dissolving the binder-resin in a solvent is applied to the separator and left until the fluidity decreases, and then the separator-coated surface is opposed to the positive electrode or the negative electrode. And bonding and drying.
  • FIG. 1 is a cross-sectional view showing a main part of a lithium ion secondary battery obtained by the manufacturing method of the present invention
  • FIG. 2 is a multilayer lithium ion secondary battery obtained by the manufacturing method of the present invention
  • FIG. 3 and FIG. 4 are cross-sectional views showing the main parts of a wound lithium ion secondary battery obtained by the manufacturing method of the present invention.
  • FIG. 1 is a cross-sectional configuration diagram showing a main part of a lithium ion secondary battery obtained by a manufacturing method of the present invention.
  • FIG. 2 to FIG. 4 are cross-sectional configuration diagrams showing main parts of a stacked lithium ion secondary battery and a wound lithium ion secondary battery obtained by the production method of the present invention, respectively.
  • reference numeral 1 denotes a positive electrode, which is formed by forming a positive electrode active material layer 3 on a positive electrode current collector 2 made of a metal such as an aluminum foil.
  • Reference numeral 4 denotes a negative electrode, which is formed by forming a negative electrode active material layer 6 on a negative electrode current collector 5 made of a metal such as copper.
  • Reference numeral 7 denotes a separator holding a liquid electrolyte containing lithium ions
  • 8 denotes a binder resin layer that joins the separator 7 and the positive electrode 1 and the separator resin and the negative electrode 4, and the binder resin layer 8 It has micropores, and these micropores hold the electrolyte.
  • the positive electrode active material layer 3, the negative electrode active material layer 6, and the separator 7 serving as the ion conductive layer are bonded via the binder resin layer 8 having micropores, so that the bonding strength between the electrode and the separator is secured.
  • the electrode and the separator communicate with each other through the fine holes in the binder-resin layer 8, and the fine holes hold the electrolytic solution. Conductivity can be ensured. Therefore, the electrical connection between the electrodes can be maintained without applying an external force, and the battery has the same battery characteristics as a battery using a conventional outer can.
  • the ion conductivity of the resin layer 8 can be adjusted by changing the porosity occupied by the micropores present in the resin layer 8 and the thickness of the resin layer 8. Specifically, the type of binder-resin used when forming the binder resin layer 8, the concentration of the binder-resin solution and the amount of coating Therefore, it can be controlled. By controlling these and making the ion conductivity of the binder resin layer 8 equal to or higher than the ion conductivity of Separator 7, the binder resin layer 8 reduces the load factor characteristics of the battery ⁇ charge / discharge characteristics, etc. It can be eliminated.
  • the adhesive strength between the positive electrode active material layer 3 and the separator 7 is equal to or higher than the adhesive strength between the positive electrode active material layer 3 and the positive electrode current collector 2, and the negative electrode active material
  • the adhesive strength between the layer 6 and the separator can be made equal to or greater than the adhesive strength between the negative electrode active material layer 6 and the negative electrode current collector 5, and an external force or a force that deforms the formed battery.
  • any metal that is stable in a lithium ion secondary battery can be used, and aluminum is preferably used as the positive electrode current collector 2, and copper is preferably used as the negative electrode current collector 5.
  • Can be The current collectors 2 and 5 can be in any shape such as foil, mesh, or expanded metal, but those having a large surface area such as mesh or expanded metal can be used as the active material layer 3 or 5. It is preferable to obtain an adhesive strength with 6, and to facilitate impregnation of the electrolyte solution after bonding.
  • the active material contained in the positive electrode active material layer 3 includes, for example, a composite oxide of lithium and a transition metal such as cobalt, manganese, or nickel, a composite oxide of lithium and a chalcogen compound, or a transition metal of this composite oxide.
  • Composite oxides containing, and those having various trace addition elements in these composite oxides are used, and are not particularly limited.
  • a carbonaceous material is preferably used, but in the battery of the present invention, it can be used irrespective of chemical characteristics, shape and the like.
  • the material used for Separation 7 can be used as long as it is capable of impregnating the electrolyte with an insulating porous membrane, mesh, non-woven fabric, etc. and has sufficient strength.
  • Polymer membrane made of polypropylene, polyethylene, etc. Is preferred from the viewpoint of ensuring adhesiveness and safety.
  • the binder-resin layer 8 is made of a material that does not dissolve in the electrolytic solution and does not cause an electrochemical reaction inside the battery to form a porous film, for example, a fluorine-based resin or a mixture containing a fluorine-based resin as a main component, or a polyvinyl resin. A mixture mainly composed of alcohol or polyvinyl alcohol is used.
  • a polymer or copolymer having a fluorine atom in its molecular structure such as vinylidene fluoride or 4-fluoroethylene, a polymer or copolymer having vinyl alcohol in its molecular skeleton, or Mixtures of these polymers or copolymers with polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polychloride vinylidene, polychloride vinyl, polyacrylonitrile, polyethylene oxide, etc. can be used. is there.
  • polyvinylidene fluoride, a fluororesin is suitable.
  • N-methylpyrrolidone, dimethylacetamide, dimethylformamide, etc., which have excellent binder-resin solubility, are used. Highly polar solvents are preferred.
  • the concentration of the binder-resin in the binder-resin solution for example, in the case of the above polyvinylidene fluoride, the polyvinylidene fluoride is added to a solvent containing at least N-methylpyrrolidone, dimethylacetamide, or dimethylformamid. 3 to 25 parts by weight, desirably 5 to 10 parts by weight. If the amount of dissolution is less than 3 parts by weight, the adhesive strength is weak, and if it is more than 25 parts by weight, the solvent is difficult to dissolve, and the viscosity becomes high, so that it cannot be applied thinly.c. Bonding W
  • the drying time for removing the solvent after bonding can be reduced, and the fluidity is reduced by concentrating the binder resin solution, so that the binder-resin solution does not seep into the electrode after bonding.
  • the function of the electrode active material is not impaired, and the ability to hold the electrolytic solution inside the electrode is not reduced. Therefore, the electrode and the separator can be effectively bonded without lowering the battery performance.
  • the low boiling point solvent examples include ether solvents such as dimethoxymethane, dimethoxyethane, and dimethyl ether; ester solvents such as dimethyl carbonate and dimethyl carbonate; and alcohol solvents such as ethanol. Or it is possible to add a mixture.
  • the amount of these low-boiling solvents to be added is preferably not more than 50 parts by weight of the total solvent, and if added more than this, the solubility of the binder-resin decreases, and the solvent becomes evenly distributed over the separator. This is because it becomes difficult to apply the binder-resin solution.
  • the electrolyte solution dimethoxy E Tan, Jietokishetan, dimethyl ether, ether solvents such as Jefferies chill ether, ethylene carbonate, propylene emissions carbonate, Jimechiruka one Boneto, alone or as a mixture of S.
  • ether solvents such as Jefferies chill carbonate, LiPF 6 , LiAsF 6, LiCl 0 4, LiBF 6, LiCF 3 S0 3, L iN (CF 3 S0 2) 2, L i C (CF 3 S0 2) 3, LiN (C 2 F 5 S0 2) 2, L iN
  • an electrolyte such as (C 2 F 5 S 0 2 ) (CF 3 S 0 2 ) or LiN (C 4 F 9 S 0 2 ) (CF 3 S 0 2 ) is dissolved can be used.
  • the bond strength between the current collector and the active material layer, and between the electrode and the separator was measured by measuring the 180-degree peel strength of a test piece cut into a width of 20 mm and a length of 100 mm.
  • UT II-20 manufactured by Toyo Baldwin Co., Ltd. was used as the test apparatus, and the evaluation was performed at a stretching speed of 10 mm / min and a measurement temperature of 25 ° C.
  • Charge / discharge efficiency (%) Discharge electric capacity ⁇ Charge electric capacity X 100
  • LiCoO 2 87 parts by weight, 8 parts by weight of graphite powder, coating the positive electrode active material paste was prepared by dispersing polyvinylidene fluoride 5 parts by weight N- methylpyrrolidone, to a thickness of 30 at Doc evening one blade method As a result, a positive electrode active material thin film was formed.
  • a 30-zm-thick aluminum foil serving as the positive electrode current collector 2 was placed on the upper part, and a positive-electrode active material paste adjusted to a thickness of 300 m was again applied to the upper part by the dough-blade method. . This was left in a dryer at 60 ° C. for 60 minutes to be in a semi-dry state, and an aggregate of the positive electrode current collector 2 and the positive electrode active material was formed.
  • This laminate was rolled to 400 ⁇ m to produce a positive electrode 1 on which the positive electrode active material layer 3 was formed.
  • a negative electrode active material paste prepared by dispersing 5 parts by weight of vinylidene fluoride in N-methylpiperidone, was applied to a thickness of 300 ⁇ m by the Doc Yuichi blade method to form a negative electrode active material thin film.
  • a copper foil having a thickness of 20 m serving as a negative electrode current collector 5 was placed on the upper portion, and a negative electrode active material paste adjusted to a thickness of 300 zm was again applied on the upper portion by a doctor blade method. This was left in a dryer at 60 ° C. for 60 minutes to be in a semi-dry state, and an aggregate of the negative electrode current collector 5 and the negative electrode active material was formed.
  • This laminate was rolled so as to have a thickness of 400 ⁇ m, thereby producing a negative electrode 4 on which a negative electrode active material layer 6 was formed.
  • a binder resin solution was prepared by mixing 5 parts by weight of polyvinylidene fluoride and 95 parts by weight of N-methylpyrrolidone at a composition ratio and sufficiently stirring to obtain a uniform solution.
  • the binder-resin solution was dropped on the surface of a porous polypropylene sheet (Celgard # 2400, manufactured by Hext Co.) to be used as separator 7, and a filament having a diameter of 0.5 mm was immersed in a filament having a diameter of 1 cm.
  • the binder resin solution was uniformly applied over the entire surface of the separator by moving the barco overnight finely wound on the glass tube over the separator, and allowed to stand for 2 minutes.
  • the negative electrode one of the electrodes, is adhered to the coated surface of the polypropylene sheet, and the uncoated surface is also coated with a binder-resin solution using a barco overnight.
  • a binder-resin solution By making close contact with a certain positive electrode, a set of laminates was produced.
  • the laminated body was exposed to an air stream at 80 ° C. while being kept in contact with the laminate, and dried to evaporate and remove N-methylpyrrolidone as a solvent.
  • the binder resin becomes a porous film having continuous pores due to the evaporation of the N-methyl vinyl lidone.
  • the formed battery laminate is inserted into an aluminum laminate film bag, and ethylene-polycarbonate (manufactured by Kanto Chemical Co., Ltd.) and 1,2-dimethoxyethane are placed under reduced pressure.
  • Tan mixed solvent (1: 1 molar ratio) of (Wako Pure Chemical Industries, Ltd.) to the L i PF 6 (Tokyo reduction manufactured Narusha) was 1 O mo 1 / dm impregnated with an electrolytic solution obtained by dissolving at a concentration of 3.
  • a lithium ion secondary battery was manufactured by performing a sealing process with heat sealing.
  • N-methylpyrrolidone and dimethoxyethane (weight ratio 9: 1) was used in place of N-methylbipyridine, which is the solvent of the binder-resin solution in Example 1, and the other components were the same as in Example 1. Similarly, a lithium ion secondary battery was obtained.
  • a mixed solvent of N-methylpyrrolidone and ethanol (weight ratio 9: 1) was used in place of N-methylvirolidone as the solvent for the binder-resin solution in Example 1 above, and the other conditions were the same as in Example 1.
  • a lithium-ion secondary battery was obtained.
  • a lithium ion secondary battery was obtained in the same manner as in Example 1 except that dimethylacetamide was used in place of N-methyl vilolidone, which is a solvent for the binder-resin solution in Example 1 described above.
  • a mixed solvent of dimethylacetamide and dimethoxyethane (weight ratio 9: 1) was used in place of N-methyl vilolidone, which is the solvent for the binder-resin solution in Example 1, and the others were the same as in Example 1. Similarly, a lithium ion secondary battery was obtained.
  • a mixed solvent of dimethylacetamide and ethanol (weight) was used in place of N-methylvirolidone, which is the solvent for the binder-resin solution in Example 1 above.
  • a lithium ion secondary battery was obtained in the same manner as in Example 1 except for using the ratio 9: 1).
  • a lithium ion secondary battery was obtained in the same manner as in Example 1 except that dimethylformamide was used in place of N-methylvirolidone, which is the solvent for the binder-resin solution in Example 1, and the other conditions were used.
  • a mixed solvent of dimethylformamide and dimethoxetane (weight ratio 9: 1) was used in place of N-methylvirolidone, which is the solvent for the binder-resin solution in Example 1, and the other conditions were the same as in Example 1. Thus, a lithium ion secondary battery was obtained.
  • a mixed solvent of dimethylamide and ethanol (weight ratio 9: 1) was used in place of N-methylvirolidone, which is the solvent for the binder-resin solution in Example 1, and the lithium ion A secondary battery was obtained.
  • a lithium ion secondary battery was obtained in the same manner as in Example 1 above, except that the binder-resin solution was applied over the separator overnight and then immediately adhered to the electrode without leaving.
  • the adhesion strength of the lithium ion secondary batteries obtained in Examples 1 to 9 and Comparative Example 1 was measured, and the results were determined based on the following criteria of ⁇ , ⁇ , and X, and the results are shown in Table 1.
  • the adhesive strength between the electrode active material and the current collector in the positive electrode and the negative electrode used in Examples and Comparative Examples was 20 gf / cm and 1 Ogf / cm, respectively.
  • the binder-resin solution was When they were immediately brought into close contact, a battery having excellent bonding strength and charge / discharge characteristics could not be obtained despite the same amount of binder-resin solution applied.
  • polyvinyl alcohol a mixture of polyvinyl alcohol and polyvinylidene fluoride, a mixture of polyvinyl alcohol and polyacrylonitrile, and a mixture of polyvinyl alcohol and polyethylene oxide are used instead of polyvinylidene fluoride.
  • polyvinyl alcohol a mixture of polyvinyl alcohol and polyvinylidene fluoride, a mixture of polyvinyl alcohol and polyacrylonitrile, and a mixture of polyvinyl alcohol and polyethylene oxide are used instead of polyvinylidene fluoride.
  • N-methylidone was dissolved or mixed with N-methylidone to produce a viscous adhesive solution.
  • lithium ion secondary batteries were produced in the same manner as in Examples 1 to 9 above.
  • the adhesive strength between the positive electrode 1 and the separator 7 and between the negative electrode 4 and the separator 7 was large, and a battery with excellent charge-discharge characteristics was obtained.
  • the drying time could be shortened as compared with the example not using the solvent.
  • a negative electrode, a positive electrode, and a binder resin solution were prepared in the same manner as in Example 1, a binder-resin solution was applied to one surface of each of the two separators, and left for 2 minutes.
  • the positive electrode was brought into close contact between the solution application surfaces, and dried under the same conditions as in Example 1.
  • Example 1 the positive electrode with the separator was punched to a predetermined size, a binder-resin solution was applied to one of the separator surfaces, left for 2 minutes, and the negative electrode punched to a predetermined size was adhered thereon. Furthermore, a binder-resin solution was applied to one of the surfaces of the separator with a new separator and left for two minutes, and then adhered to the other surface of the previously bonded negative electrode. This process is repeated a predetermined number of times to form a laminate After that, drying was performed while applying pressure, and the positive electrode and the negative electrode were adhered to the separator to obtain a flat battery laminate as shown in FIG. An electrolytic solution was injected into the obtained battery laminate in the same manner as in Example 1, and the battery was sealed. Thus, a lithium ion secondary battery was obtained.
  • Example 1 2.
  • a negative electrode, a positive electrode, and a binder resin solution were prepared in the same manner as in Example 1, a binder-resin solution was applied to one surface of each of the two separators, allowed to stand for 2 minutes, and then a binder-resin solution of two separators was prepared.
  • the negative electrode was closely adhered between the application surfaces, and dried under the same conditions as in Example 1.
  • Example 13 the negative electrode with the separator was punched into a predetermined size, a binder-resin solution was applied to one of the separator surfaces, left for 2 minutes, and the positive electrode punched into the predetermined size was bonded thereon. Furthermore, a binder-resin solution was applied to one of the surfaces of the separator with a new separator and left for two minutes, and then bonded to the other surface of the previously bonded positive electrode. This process was repeated a predetermined number of times to form a laminate, which was then dried while applying pressure, and the positive electrode and the negative electrode were adhered to the separator to obtain a flat battery laminate as shown in FIG. An electrolytic solution was injected into the obtained battery stack in the same manner as in Example 1, and the battery was sealed. Thus, a lithium ion secondary battery was obtained.
  • Example 13 Example 13
  • a negative electrode, a positive electrode and a binder-resin solution were prepared in the same manner as in Example 1, a binder-resin solution was applied to one surface of each of the two separators, and left for 2 minutes.
  • the positive electrode was brought into close contact between the solution application surfaces, and dried under the same conditions as in Example 1.
  • a binder-resin solution was applied to one surface of the positive electrode with a strip-shaped separator and left for 2 minutes. After leaving it for 2 minutes, one end of the positive electrode with the separator was folded a certain amount, and the negative electrode was sandwiched at the fold. Subsequently, the negative electrode and the positive electrode with separation And then went to Lamine overnight. After that, the binder-resin solution was applied to the opposite side of the positive electrode with the separation resin from the surface on which the binder-resin solution was applied, left for 2 minutes, and rolled into an oval shape.
  • the rolled-up elliptical battery stack is dried while applying pressure, the positive electrode and the negative electrode are adhered to the separator, and the separated positive electrode is laminated so that the folded positive electrode is wrapped inside. This was rolled up to obtain a flat battery laminate as shown in FIG. An electrolytic solution was injected into the obtained battery laminate in the same manner as in Example 1, and then the container was sealed to obtain a lithium ion secondary battery.
  • a negative electrode, a positive electrode, and a binder resin solution were prepared in the same manner as in Example 1, a binder resin solution was applied to one surface of each of the two separators, and left for 2 minutes. The negative electrode was closely adhered between the application surfaces, and dried under the same conditions as in Example 1.
  • a binder-resin solution was applied to one of the separation surfaces of the strip-shaped negative electrode and left for 2 minutes. After that, one end of the separated negative electrode was folded a certain amount, and the positive electrode was sandwiched between the folds. Subsequently, the positive electrode and the negative electrode with separator were stacked, and then passed through Lamine. After that, the binder-resin solution was applied to the opposite side of the negative electrode with the separator from the surface to which the binder-resin solution was applied, left for 2 minutes, and rolled into an oval shape. The rolled-up elliptical battery laminate was dried while applying pressure, and the positive electrode and the negative electrode were adhered to the separator to obtain a flat battery laminate. An electrolytic solution was injected into the obtained battery laminate in the same manner as in Example 1, and the battery was sealed. Thus, a lithium ion secondary battery was obtained.
  • a negative electrode, a positive electrode, and a binder resin solution were prepared in the same manner as in Example 1, and a strip-shaped 2
  • the separators are arranged on both sides of the strip-shaped positive electrode, and the strip-shaped negative electrode is arranged so as to protrude by a certain amount outside one of the separators.
  • the binder-resin solution is applied to both sides of the separator between the negative and positive electrodes, and the binder-resin solution is applied only to the side facing the positive electrode on the other separator, and left for 2 minutes.
  • one end of the protruding negative electrode was first passed through lamine overnight, and then the positive electrode, the separator, and the negative electrode were overlaid through laminating to obtain a strip-like laminate.
  • a negative electrode, a positive electrode, and a binder resin solution were prepared in the same manner as in Example 1, two strip-shaped separators were arranged on both sides of the strip-shaped negative electrode, and the strip-shaped positive electrode was fixed outside one of the separated separators. It is arranged to protrude by a certain amount.
  • the binder resin solution is applied to both sides of the separator located between the negative electrode and the positive electrode, and the binder resin solution is applied only to the side facing the negative electrode in the other separator, and left for 2 minutes Then, one end of the protruding positive electrode was first passed through the laminator, and then the positive electrode, the separator, and the negative electrode were overlapped with each other to obtain a strip-like laminate.
  • the binder-resin solution was applied to the separation surface of the band-shaped laminate and left for 2 minutes, and then the protruding positive electrode was folded and adhered to the application surface, and the folded positive electrode was laminated so as to wrap it inside. Separation evening was rolled up in an oval shape.
  • the rolled-up elliptical battery stack is dried while pressing, The positive electrode and the negative electrode were bonded to the separator to obtain a flat battery laminate.
  • An electrolytic solution was injected into the obtained battery laminate in the same manner as in Example 1, and the battery was sealed. Thus, a lithium ion secondary battery was obtained.
  • the lithium ion secondary battery according to the present invention is used as a secondary battery of a portable electronic device, and can be reduced in size and weight, and formed into an arbitrary shape while improving the performance of the battery.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

Dans une pile secondaire traditionnelle à ions de lithium qui utilise une solution électrolytique, on doit recourir à un boîtier rigide renforcé pour assurer la connexion électrique entre les électrodes, ce qui empêche d'effectuer la miniaturisation du dispositif. On peut résoudre ce problème grâce au procédé de l'invention et fabriquer une pile secondaire à ions de lithium mince, légère et possédant une forme arbitraire, qui se passe de boîtier renforcé. On crée la pile secondaire à ions de lithium en faisant adhérer une électrode et un séparateur grâce à l'utilisation d'une résine liante qui contient en tant que composant principal une résine à base de fluor ou d'alcool polyvinylique. On applique la solution de résine liante au séparateur et on la laisse reposer pendant un moment jusqu'à ce que sa fluidité baisse. On fait ensuite adhérer le séparateur à l'électrode par collage et par séchage. Ce procédé permet d'obtenir une pile possédant un pouvoir adhésif et une conductivité ionique élevés.
PCT/JP1997/004854 1997-12-25 1997-12-25 Procede de fabrication d'une pile secondaire a ions de lithium WO1999034470A1 (fr)

Priority Applications (1)

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PCT/JP1997/004854 WO1999034470A1 (fr) 1997-12-25 1997-12-25 Procede de fabrication d'une pile secondaire a ions de lithium

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Application Number Priority Date Filing Date Title
PCT/JP1997/004854 WO1999034470A1 (fr) 1997-12-25 1997-12-25 Procede de fabrication d'une pile secondaire a ions de lithium

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WO1999034470A1 true WO1999034470A1 (fr) 1999-07-08

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001028273A (ja) * 1999-07-15 2001-01-30 Mitsubishi Materials Corp リチウムイオンポリマー二次電池
KR20020000015A (ko) * 2000-06-20 2002-01-04 김순택 리튬 2차 전지 및 그 제조방법
JP2003031265A (ja) * 2001-07-12 2003-01-31 Japan Storage Battery Co Ltd 非水電解質二次電池
US7537682B2 (en) 2004-03-17 2009-05-26 California Institute Of Technology Methods for purifying carbon materials
US7563542B2 (en) 2005-10-05 2009-07-21 California Institute Of Technology Subfluorinated graphite fluorides as electrode materials
US8968921B2 (en) 2005-10-05 2015-03-03 California Institute Of Technology Fluoride ion electrochemical cell
CN105304907A (zh) * 2015-11-02 2016-02-03 多氟多（焦作）新能源科技有限公司 锂离子电池复合极片用粘结剂及其制备方法、复合极片、电芯、锂离子电池
CN108400274A (zh) * 2018-03-15 2018-08-14 重庆市紫建电子有限公司 一种具有隔膜制袋的电池
CN109148967A (zh) * 2018-07-26 2019-01-04 深圳吉阳智能科技有限公司 组合式叠片电芯及其叠片单元和叠片方法
US10283747B2 (en) * 2014-03-17 2019-05-07 Kabushiki Kaisha Toshiba Nonaqueous electrolyte secondary battery and battery pack
CN113497224A (zh) * 2020-04-01 2021-10-12 深圳格林德能源集团有限公司 一种锂离子电池硅碳负极极片
CN114323138A (zh) * 2021-12-29 2022-04-12 江苏天鹏电源有限公司 一种锂离子电池用负极粘结剂动力学性能的快速评测方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09293518A (ja) * 1996-04-26 1997-11-11 Asahi Chem Ind Co Ltd 薄膜状電解質および該電解質を用いた電池

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09293518A (ja) * 1996-04-26 1997-11-11 Asahi Chem Ind Co Ltd 薄膜状電解質および該電解質を用いた電池

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001028273A (ja) * 1999-07-15 2001-01-30 Mitsubishi Materials Corp リチウムイオンポリマー二次電池
KR20020000015A (ko) * 2000-06-20 2002-01-04 김순택 리튬 2차 전지 및 그 제조방법
JP2003031265A (ja) * 2001-07-12 2003-01-31 Japan Storage Battery Co Ltd 非水電解質二次電池
US7537682B2 (en) 2004-03-17 2009-05-26 California Institute Of Technology Methods for purifying carbon materials
US7563542B2 (en) 2005-10-05 2009-07-21 California Institute Of Technology Subfluorinated graphite fluorides as electrode materials
US8968921B2 (en) 2005-10-05 2015-03-03 California Institute Of Technology Fluoride ion electrochemical cell
US10283747B2 (en) * 2014-03-17 2019-05-07 Kabushiki Kaisha Toshiba Nonaqueous electrolyte secondary battery and battery pack
CN105304907A (zh) * 2015-11-02 2016-02-03 多氟多（焦作）新能源科技有限公司 锂离子电池复合极片用粘结剂及其制备方法、复合极片、电芯、锂离子电池
CN108400274A (zh) * 2018-03-15 2018-08-14 重庆市紫建电子有限公司 一种具有隔膜制袋的电池
CN109148967A (zh) * 2018-07-26 2019-01-04 深圳吉阳智能科技有限公司 组合式叠片电芯及其叠片单元和叠片方法
CN113497224A (zh) * 2020-04-01 2021-10-12 深圳格林德能源集团有限公司 一种锂离子电池硅碳负极极片
CN114323138A (zh) * 2021-12-29 2022-04-12 江苏天鹏电源有限公司 一种锂离子电池用负极粘结剂动力学性能的快速评测方法
CN114323138B (zh) * 2021-12-29 2023-12-26 江苏天鹏电源有限公司 一种锂离子电池用负极粘结剂动力学性能的快速评测方法

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