WO2019031438A1 - 電極シート製造方法、全固体電池および全固体電池製造方法 - Google Patents

電極シート製造方法、全固体電池および全固体電池製造方法 Download PDF

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WO2019031438A1
WO2019031438A1 PCT/JP2018/029371 JP2018029371W WO2019031438A1 WO 2019031438 A1 WO2019031438 A1 WO 2019031438A1 JP 2018029371 W JP2018029371 W JP 2018029371W WO 2019031438 A1 WO2019031438 A1 WO 2019031438A1
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active material
solid electrolyte
material layer
layer
polymer
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PCT/JP2018/029371
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English (en)
French (fr)
Japanese (ja)
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東　昇
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倉敷紡績株式会社
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Priority to JP2019535641A priority Critical patent/JP7066719B2/ja
Priority to CN201880051227.5A priority patent/CN110998951A/zh
Publication of WO2019031438A1 publication Critical patent/WO2019031438A1/ja

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    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid electrode sheet using an inorganic solid electrolyte and a solid polymer electrolyte. Further, the present invention relates to an all solid film type battery using an inorganic solid electrolyte and a solid polymer electrolyte.
  • Inorganic solid electrolytes having excellent ion conductivity have recently been developed.
  • the form is in the form of particles, there is a problem that the internal resistance of the battery increases and the battery capacity decreases due to poor contact with the active material particles.
  • the polymer gel electrolyte is a gel solid electrolyte in which an organic solvent containing an electrolyte salt is held in a polymer network. It has been proposed to improve the contact state between the active material particles and the solid electrolyte by impregnating the polymer gel electrolyte between the active material particles constituting the electrode.
  • Patent Document 1 describes a polymer (gel-like) solid electrolyte battery in which a monomer composition is coated on the surface of a positive electrode active material layer, a portion thereof is impregnated into the positive electrode active material layer, and then thermally polymerized. ing.
  • the adhesiveness of the bonding interface between the solid electrolyte and the active material is favorably formed by impregnating the solid electrolyte solution in which the gel-like solid electrolyte is dissolved in the solvent on the active material layer.
  • Solid electrolyte batteries are described.
  • a lithium ion secondary battery using a laminate exterior material in which a resin film is bonded to both sides of a metal foil is used for a smartphone, a tablet terminal or the like.
  • Patent Document 3 in an electricity storage device in which a first metal foil layer, a positive electrode active material, a separator of a porous film, a negative electrode active material layer, and a second metal foil layer are laminated, the outer periphery of the positive and negative electrode active material layers is The first metal foil layer, the separator end, and the second metal foil layer are joined via the peripheral sealing layer containing the heat fusible resin to surround, and the separator of the first metal foil layer and the second metal foil layer
  • a thin power storage device is described in which an insulating resin film is laminated in a mode in which metal exposed portions are left on the surface opposite to the surface on the side (FIG. 4).
  • the storage device can be made thinner without the need for
  • JP 7-326383 A JP 11-195433 A JP, 2016-042459, A
  • the solid electrolyte layer made of a polymer gel electrolyte has low strength. Therefore, particularly when used for a flexible film-like battery, it has been feared that the separator layer separating the two electrodes of the battery may be damaged by the deformation of the battery to cause an internal short circuit.
  • the content of the organic solvent is excessively increased in order to increase the mobility of the electrolyte salt in the polymer gel electrolyte, the problem of liquid leakage remains.
  • the method of impregnating the solution of the polymer gel electrolyte into the active material layer there are problems such that it takes time to impregnate the solution, and it is difficult to permeate the solution into the entire active material layer.
  • the solid polymer electrolyte is a solid electrolyte containing an electrolyte salt in a polymer.
  • the mobility of the electrolyte salt in the solid polymer is low. Therefore, if the separator layer is too thick, there is a problem that the internal resistance of the battery is increased and practical charge and discharge characteristics can not be obtained.
  • the separator layer is too thin, the polymer solid electrolyte still leaves concern about damage to the separator layer due to repeated bending deformation of the battery and the like and internal short circuit.
  • Patent Document 3 discloses a method of manufacturing a lithium ion battery using a non-aqueous electrolyte solution, there is no description of a specific manufacturing method regarding an all-solid battery that does not require tab lead wires.
  • the present invention has been made in consideration of the above, and can be used for a thin all-solid battery having a small internal resistance and less occurrence of an internal short circuit using a solid polymer electrolyte, a method for producing the same, and such an all-solid battery It is an object of the present invention to provide a method of producing an electrode sheet.
  • the method for producing an electrode sheet according to the present invention comprises the steps of preparing a metal foil having a heat fusible resin frame formed on one side, and active material particles on the metal foil and inside the heat fusible resin frame.
  • a step of forming an active material layer by applying an electrode mixture containing the above a step of forming an inorganic solid electrolyte layer containing inorganic solid electrolyte particles on the active material layer, and a polymer from above the inorganic solid electrolyte layer
  • a polymer solid electrolyte solution containing a compound and an alkali metal salt is supplied to make the active material layer and the inorganic solid electrolyte layer permeate, and the polymer compound is polymerized after the solution supply step.
  • the method further includes a curing step of integrally forming a solid polymer electrolyte between the active material particles and between the inorganic solid electrolyte particles.
  • the polymer solid electrolyte solution means a raw material solution for forming a polymer solid electrolyte
  • a polymer solid electrolyte is formed by polymerizing a polymer compound in the polymer solid electrolyte solution.
  • polymerizing the polymer compound includes crosslinking the polymer compound with a crosslinking agent.
  • the inorganic solid electrolyte particles and the solid polymer electrolyte filling the gap constitute a separator layer positioned between the inorganic solid electrolyte particles and the counter electrode at the time of battery preparation, the ion conductivity and strength of the separator layer can be compatible at a high level. Further, since the solid polymer electrolyte in the electrode and the solid polymer electrolyte in the separator layer are integrally formed, the interface resistance between the electrode and the separator layer can be further reduced.
  • Another electrode sheet manufacturing method of the present invention is to form a heat fusible resin later.
  • another electrode sheet manufacturing method of the present invention comprises the steps of: preparing a metal foil; and applying an electrode mixture containing active material particles on the metal foil to form an active material layer; A process of forming an inorganic solid electrolyte layer containing inorganic solid electrolyte particles on the active material layer, and a polymer solid electrolyte solution containing a polymer compound and an alkali metal salt, to supply the active material layer and the inorganic solid
  • a polymer solid electrolyte is integrally formed between the active material particles and between the inorganic solid electrolyte particles by polymerizing the polymer compound after the solution supply step of permeating the electrolyte layer and the solution supply step. Curing step and any one step after the active material layer forming step to after the curing step to form a heat-fusible resin frame on the metal foil and around the active material layer And a process.
  • the metal foil has a heat resistant resin layer on the side opposite to the side on which the active material layer is formed. Since the metal foil is thereby protected by the heat resistant resin layer, the current collector sheet can be used as it is as an exterior material of the battery.
  • the electrode mixture further includes the inorganic solid electrolyte particles.
  • the mobility of the charge moving through the gaps between the active material particles is improved, and the internal resistance of the electrode is further reduced.
  • the electrode mixture is applied by screen printing.
  • the active material layer can be coated only at a predetermined range such as the inner side of the heat fusible resin frame at low cost.
  • the solution supply step is a step of supplying the solid polymer electrolyte solution from the inorganic solid electrolyte layer by a non-contact coating method.
  • the non-contact coating method refers to a method of supplying a solution without bringing a member such as a roll or a nozzle into contact with the surface of the inorganic solid electrolyte layer.
  • the solid polymer electrolyte solution can be supplied without damaging the inorganic solid electrolyte layer and the active material layer.
  • the all-solid-state battery of the present invention comprises: a first electrode including a first metal foil, a first active material particle, and a solid polymer electrolyte in a first electrode filling the gap between the first active material particle, and inorganic solid electrolyte particles And a separator layer containing a solid polymer electrolyte in the separator layer filling the gaps between the inorganic solid electrolyte particles, and a gap between the second active material particles and the second active material particles having polarity opposite to that of the first electrode
  • a second electrode including a solid polymer electrolyte in a second electrode filling the second electrode and a second metal foil are laminated in this order.
  • At least one of the first in-electrode polymer solid electrolyte and the second in-electrode polymer solid electrolyte is integrally formed with the in-separator polymer solid electrolyte in a portion in contact with the first or second electrode. ing. And it has the heat fusible resin wall which encloses the outer periphery of the said 1st electrode, the said separator layer, and the said 2nd electrode, and couple
  • the contact state between the active material particles and the solid polymer electrolyte is improved, the ion conductivity and strength of the separator layer can be compatible at a high level, and the interface resistance between the electrode and the separator layer can be further reduced. Further, by exchanging electricity through the metal foil, tab lead wires derived from the electrodes become unnecessary.
  • the first metal foil has a first heat-resistant resin layer on the side opposite to the first electrode, and / or the second metal foil is secondly on the side opposite to the second electrode. It has a heat resistant resin layer.
  • the polymer solid electrolyte in the first electrode, the polymer solid electrolyte in the separator layer, and the polymer solid electrolyte in the second electrode are integrally formed. This makes it possible to lower the internal resistance of the battery.
  • the step of manufacturing the first electrode sheet by any one of the above methods, and the polarity opposite to the first electrode sheet by any of the above methods Manufacturing the second electrode sheet, and laminating the first electrode sheet and the second electrode sheet so that the respective heat sealable resin frames are joined together, the first electrode sheet, and And a sealing step of thermally fusing the thermally fusible resin frames of the second electrode sheet to form the thermally fusible resin wall.
  • Another all-solid-state battery manufacturing method for manufacturing the above-mentioned all-solid-state battery will be described later as an embodiment.
  • the all solid battery or the all solid battery manufacturing method of the present invention since the electrolyte of the all solid battery is composed of the inorganic solid electrolyte and the solid polymer electrolyte, there is no fear of liquid leakage.
  • the polymer solid electrolyte solution of low viscosity is made to permeate into gaps of the active material particles and into gaps of the inorganic solid electrolyte particles and then polymerized to form a polymer solid electrolyte
  • the polymer solid electrolyte solution is made into an active material layer. And it is easy to penetrate into a wide range of the inorganic solid electrolyte layer.
  • the solid polymer electrolyte fills in the gaps between the active material particles, so that the contact between the solid polymer electrolyte and the active material particles is good, and a battery with low internal resistance can be obtained.
  • the solid polymer electrolyte in at least one electrode is integrally formed with the solid polymer electrolyte in the separator layer, the interface resistance between the electrode and the separator layer is suppressed, and a battery with low internal resistance can be obtained.
  • the separator layer can contain an inorganic solid electrolyte having a higher mobility of the electrolyte salt and a lithium ion transport number than the polymer solid electrolyte, the internal resistance of the battery can be lowered to improve the charge / discharge characteristics. Furthermore, since the separator layer contains inorganic solid electrolyte particles having a hardness higher than that of the solid polymer electrolyte, the separator layer is less likely to be damaged even by repeated bending deformation of the battery and the like, so that internal short circuit does not easily occur. And since the separator layer can be formed thin, the internal resistance of the battery can be lowered and the charge / discharge characteristics can be improved. Thereby, the ion conductivity and strength of the separator layer can be compatible at a high level.
  • FIGS. 1 to 3 As a first embodiment of the present invention, a method of manufacturing an electrode sheet for an all solid lithium ion battery will be described based on FIGS. 1 to 3.
  • an electrode sheet 10 manufactured in the present embodiment is configured by laminating a metal foil 12, an electrode 16 and a separator layer 19 in this order.
  • the electrode is a positive electrode or a negative electrode.
  • the electrode sheet 10 is a positive electrode sheet, and when the electrode 16 is a negative electrode, the electrode sheet 10 is a negative electrode sheet.
  • the heat-fusing resin frame 13 is formed on the peripheral portion on one side of the metal foil 12, the heat-resistant resin layer 14 is provided on the opposite surface, and the metal foil is exposed on part of the heat-resistant resin layer An exposed portion 15 is formed.
  • the electrode 16 and the separator layer 19 are formed on the inner side of the heat sealable resin frame.
  • the electrode 16 is composed of an active material particle 17 and a solid polymer electrolyte 18 in the electrode filling the gap.
  • the separator layer 19 is composed of the inorganic solid electrolyte particles 20 and the polymer solid electrolyte 21 in the separator layer filling the gap therebetween. Details of each component will be described in the description of the manufacturing method.
  • the electrode sheet manufacturing method S10 of the present embodiment is described with reference to FIG. (S11) preparing a metal foil 12 having a heat-fusible resin frame 13 formed on one side thereof; (S12) forming an active material layer on the metal foil; (S13) forming an inorganic solid electrolyte layer on the active material layer; (S14) a solution supplying step of supplying a polymer solid electrolyte solution from above the inorganic solid electrolyte layer to permeate the active material layer and the inorganic solid electrolyte layer; (S15) A curing step of polymerizing the polymer compound.
  • step S ⁇ b> 11 of preparing the metal foil 12 the heat sealable resin frame 13 is formed on the peripheral portion on one side of the metal foil 12. Further, the heat resistant resin layer 14 is laminated on the surface of the metal foil opposite to the heat sealable resin frame, and the exposed portion 15 where the metal foil is exposed is formed on a part of the heat resistant resin layer. .
  • metal foil 12 Various metal materials having electron conductivity can be used for the metal foil 12.
  • metal foil for positive electrodes foil of aluminum, titanium, and stainless steel can be used, for example, Preferably foil of aluminum which is excellent in oxidation resistance is used.
  • the thickness of the aluminum foil is preferably 5 to 25 ⁇ m.
  • metal foil for negative electrodes foil of copper, nickel, aluminum, and iron can be used, for example, Preferably copper foil which is stable in a reduction field and is excellent in conductivity is used.
  • the thickness of the copper foil is preferably 5 to 15 ⁇ m.
  • the heat sealable resin frame 13 various heat sealable resins such as polyethylene and polypropylene can be used.
  • the heat sealable resin frame is preferably made of an unstretched film. It is because it is excellent in heat sealability, moisture resistance, and flexibility.
  • the thickness (dimension in the vertical direction in FIG. 1) of the heat-fusible resin frame is 100 to 120 when the total thickness of the electrode 16 and the separator layer 19 to be formed in a later step is 100. preferable. This is because, at the time of battery preparation, it can be reliably fused with the heat-fusible resin frame of the opposing metal foil.
  • the thickness of the heat-fusible resin frame is preferably 20 to 24 ⁇ m.
  • the width of the frame portion of the heat-fusible resin frame (the width of the 13A surface in FIG. 1) is preferably 5 mm or more. If the width of the frame is too narrow, the sealing performance of the battery will be insufficient. On the other hand, the width of the frame portion of the heat-fusible resin frame is preferably 20 mm or less. This is because it is sufficient if there is a width necessary for securing the sealability, and even if the width of the frame is too wide, the battery becomes unnecessarily large.
  • the heat-fusible resin frame 13 can be formed into a frame shape by bonding the above-mentioned film to the metal foil 12 with an adhesive layer (not shown) and removing the central portion.
  • an adhesive layer not shown
  • a masking tape is attached in advance to the center of the metal foil, the heat fusible resin film is adhered to the entire surface of the metal foil from above the masking tape, and a cut is made with a cutter or a laser. And the heat fusible resin film can be removed.
  • the thermally fusible resin frame can be formed by inkjet printing, screen printing, or the like.
  • the heat resistant resin layer 14 is not an essential component of the present invention, but preferably the metal foil 12 comprises a heat resistant resin layer. It is because the metal foil 12 can be protected after battery manufacture.
  • the heat-resistant resin layer 14 is made of a material resistant to heating when the heat-fusible resin frame 13 is heat-fused, and for example, a polyamide film, a polyester film or the like can be used. Among them, it is preferable to use a biaxially stretched polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the heat resistant resin layer may be a single layer film, or a plurality of films may be laminated.
  • the thickness of the heat resistant resin layer is preferably 10 ⁇ m to 100 ⁇ m.
  • the heat resistant resin layer 14 can be laminated by adhering the above film to the metal foil 12 by an adhesive layer not shown.
  • a masking tape is previously attached to the relevant portion of the metal foil, and a film of heat resistant resin is adhered to the entire surface of the metal foil from above the masking tape and cut with a cutter or a laser. Then, the masking tape, the adhesive layer and the heat resistant resin film can be removed.
  • Step S12 of forming an active material layer is performed by applying an electrode mixture containing active material particles 17 on the metal foil 12 and inside the heat-fusible resin frame 13.
  • the electrode mixture is made into a paste by adding a conductive auxiliary agent, a binder, a filler and the like to the active material particles 17 as necessary, and adding an appropriate amount of solvent.
  • the positive electrode active material 17 known materials such as LiCoO 2 and LiNiO 2 that absorb and release Li ions can be used.
  • the conductive additive known electron conductive materials such as acetylene black, ketjen black, other carbon blacks, metal powders, conductive ceramic materials can be used. The addition amount of the conductive aid is typically several weight% with respect to the positive electrode active material.
  • the binder known materials such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF) can be used.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • a material having ionic conductivity can also be used as a binder.
  • a binder having ion conductivity for example, an ion conductive binder containing a polymer electrolyte composition obtained by graft polymerizing a skeleton of an ionic liquid to a fluoropolymer such as PVdF is disclosed in JP-A-2015-038870. It is disclosed in the official gazette. It is also possible to use, as a binder, other known lithium ion conductive polymer matrices in which an Li-based metal salt is held by an ether-based polymer such as polyethylene oxide or polyethylene oxide. The addition amount of the binder is typically several weight% with respect to the positive electrode active material.
  • the filler well-known materials such as olefin polymers such as polypropylene and zeolite can be used.
  • the addition amount of the filler is typically 0 to several weight% with respect to the positive electrode active material.
  • a known organic solvent such as N-methyl-2-pyrrolidone (NMP) can be used.
  • the negative electrode active material 17 known materials such as graphite and coke which absorb and release Li ions can be used.
  • the conductive additive, the binder, and the filler added to the negative electrode active material the same ones as those added to the positive electrode active material can be used.
  • the solvent a known organic solvent such as NMP can be used.
  • the coating method of the electrode mixture is applied only to the inside of the heat-fusible resin frame 13, it is impossible to adopt the die coating method or comma coating method generally used in the production of conventional lithium ion batteries.
  • the method of applying the electrode mixture is preferably performed by screen printing. This is because the area to be coated can be determined according to the shape of the battery. Moreover, even if it is a large area, it is because an electrode mixture paste can be coated to uniform thickness, suppressing cost increase.
  • primer coating may be performed on the metal foil surface in advance.
  • the electrode mixture is coated on a metal foil and then dried to remove the solvent, whereby an active material layer is formed.
  • the active material layer may be compressed by pressing after drying.
  • the thickness of the active material layer that is, the thickness of the electrode 16 is preferably 5 to 30 ⁇ m, more preferably 10 to 20 ⁇ m. If the electrode is too thin, sufficient battery capacity can not be obtained. On the other hand, if the electrode is too thick, it is difficult to infiltrate the solid polymer electrolyte solution homogeneously into the electrode, and voids tend to be generated inside the electrode. On the other hand, if the electrode is too thick, the migration distance of Li ions in the polymer solid electrolyte in the electrode will be long, and the charge / discharge rate of the battery will be lowered.
  • the screen is applied from above the heat fusible resin frame 13, and the inner surface of the heat fusible resin frame is filled completely within the heat fusible resin frame. It is not possible to coat the electrode mixture until near the end. However, this is not a problem in the present embodiment. The reason will be described later.
  • Step S13 of forming the inorganic solid electrolyte layer is performed by applying an electrolyte mixture containing the inorganic solid electrolyte particles 20 on the active material layer.
  • the electrolyte mixture is made into a paste by adding a binder, a filler and the like to the inorganic solid electrolyte particles 20 as necessary, and adding an appropriate amount of solvent.
  • a binder known materials such as PVdF can be used.
  • the solvent a known organic solvent such as NMP can be used.
  • La 2 / 3-x Li 3x TiO 3 (LLT), Li 1 + x Al y Ti 2-y (PO 4 ) 3 (LATP), Li 1 + x Al y Ge having high lithium ion conductivity Particles such as 2-y (PO 4 ) 3 (LAGP) can be used.
  • LAGP is used. This is because the structure is stable and reaction does not easily occur even when contacting with other materials when pasting at the time of electrode sheet production.
  • LAGP is used as the inorganic solid electrolyte
  • PVdF is used as the binder. Not only the performance of each is good, but according to this combination, PVdF does not react with the alkali salt to gel.
  • an ion conductive binder is used as the binder. This is because the mobility of lithium ions in the electrode is improved.
  • the particle size of the inorganic solid electrolyte particles 20 is preferably 0.1 ⁇ m to 1 ⁇ m. If the particle size is too small, the dispersibility at the time of paste formation will be poor, and it is likely to agglomerate to form large particles. When the particle diameter is too large, the flatness of the surface of the separator layer 19 is deteriorated, and the proportion of the solid polymer electrolyte 21 having low lithium ion mobility in the separator layer is increased, and lithium ions passing through the separator layer Mobility is easily lost.
  • the application of the electrolyte mixture is preferably carried out by screen printing. This is because the area to be coated can be determined according to the shape of the battery. Moreover, even if it is a large area, it is because the electrolyte mixture paste can be coated to uniform thickness, suppressing cost increase.
  • the electrolyte mixture is applied on the active material layer, it is dried and the solvent is removed to form an inorganic solid electrolyte layer.
  • the inorganic solid electrolyte layer is formed to cover the entire active material layer.
  • the preferred range of the thickness of the separator layer 19 differs depending on the method of manufacturing the all-solid battery described later.
  • the average thickness of the separator layer of the battery to be produced is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 6 ⁇ m or less. If the separator layer is too thick, the internal resistance of the battery will increase. Even if the separator layer is thin, short circuit is unlikely to occur due to the inclusion of the inorganic solid electrolyte particles 20 having high strength and hardness.
  • the thickness of the thinnest part of the separator layer of the battery is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more. If the separator layer is too thin, it is likely to be damaged and it becomes difficult to manufacture.
  • both positive and negative electrode sheets have separator layers.
  • the average thickness of the separator layer 19 of each electrode sheet is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less, and the thickness of the thinnest portion is preferably 0.5 ⁇ m The thickness is more preferably 1 ⁇ m or more.
  • the average thickness of the separator layer 19 of the electrode sheet is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, particularly preferably 6 ⁇ m or less, and the thickness of the thinnest portion is preferably 1 ⁇ m or more, more preferably 2 ⁇ m It is above.
  • the solution supply step S14 is performed by supplying the polymer solid electrolyte solution from the inorganic solid electrolyte layer and permeating the active material layer and the inorganic solid electrolyte layer.
  • the polymer solid electrolyte solution contains a polymer compound that becomes a skeleton of the polymer solid electrolyte after polymerization, and a lithium salt, and optionally contains a crosslinking agent and a polymerization initiator, and has an appropriate viscosity depending on the organic solvent. It is diluted.
  • the solid polymer electrolytes 18, 21 contain a lithium salt in the polymer.
  • the polymer polyethylene oxide (PEO), polypropylene oxide (PPO), copolymers of these, and the like can be used.
  • the polymer molecules are crosslinked, or other polymers or oligomers are graft polymerized on the main skeleton of the polymer. It is for suppressing that ion conductivity falls by crystallization of a polymer.
  • lithium perchlorate LiClO 4
  • LiPF 6 lithium hexafluorophosphate
  • LiN lithium bis (trifluoromethanesulfonyl) imide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • a dilution solvent a low boiling point organic solvent such as tetrahydrofuran (THF) or acetonitrile can be suitably used.
  • the viscosity of the solid polymer electrolyte solution is preferably 1 to 100 mPa ⁇ s, more preferably 5 to 10 mPa ⁇ s. If the viscosity is too high, it is difficult for the solution to penetrate into the active material layer and the inorganic solid electrolyte layer.
  • the solid polymer electrolyte solution may contain a plasticizer.
  • the solid polymer electrolytes 18 and 21 contain a plasticizer, and the ion conductivity is improved.
  • the content of the plasticizer in the solid polymer electrolyte is preferably 10% by weight or less, more preferably 5% by weight or less.
  • the solid polymer electrolyte does not contain a plasticizer.
  • the plasticizer known materials such as ethylene carbonate (EC), carbonates such as ethyl methyl carbonate (EMC), mixtures thereof, and the like can be used.
  • the method of supplying a solid polymer electrolyte solution is not particularly limited, it is preferably by a non-contact coating method.
  • the noncontact coating method refers to a method of supplying a solution without bringing a roll for transferring the solution, a nozzle for discharging the solution, etc. into contact with the inorganic solid electrolyte layer.
  • Examples of the non-contact coating method include a spray method, a dispenser using air pressure or electrostatic force, and various inkjet methods such as a piezo method. Above all, it is preferable to use a dispenser method using electrostatic force or an inkjet method.
  • the polymer solid electrolyte solution is filled in the entire spaces of the active material layer and the inorganic solid electrolyte layer, and the surface of the inorganic solid electrolyte layer is excellent because the quantitativeness and in-plane uniformity of the supply amount are excellent. It is possible to form a thin film of the solid polymer electrolyte solution.
  • the polymer solid electrolyte solution is preferably filled in the gaps between the active material particles and the inorganic solid electrolyte particles over the entire surface from the metal foil 12 surface to the inorganic solid electrolyte layer surface.
  • the solid polymer electrolyte solution thinly cover the entire surface of the inorganic solid electrolyte layer.
  • the high molecular solid electrolyte solution fills the region 10D immediately before the thermally fusible resin frame in which the active material particles and the inorganic solid electrolyte particles do not exist.
  • the polymer compound is polymerized in the curing step S15 to form the gaps between the active material particles 17 in the active material layer and the inorganic solid electrolyte in the inorganic solid electrolyte layer.
  • the solid polymer electrolytes 18 and 21 are formed in the gaps between the particles 20.
  • the polymer compound can be polymerized by either thermal curing, ultraviolet irradiation, electron beam irradiation, or a combination thereof.
  • the polymerization method of the polymer compound is preferably by ultraviolet irradiation. This is because the manufacturing equipment can be simplified.
  • the solution supply process may be divided into a plurality of steps. For example, as shown in FIG. 17, after the step S12 of forming the active material layer, a step S14-1 of supplying a solid polymer electrolyte solution onto the active material layer to permeate the active material layer is provided to form the inorganic solid electrolyte layer. After the forming step S13, a step S14-2 may be provided in which the solid polymer electrolyte solution is supplied onto the inorganic solid electrolyte layer to permeate the inorganic solid electrolyte layer.
  • the solid polymer electrolyte 18 contained in the electrode 16 and the solid polymer electrolyte 21 contained in the separator layer 19 are integrally formed in the curing step S15.
  • the polymer solid electrolyte solution in the active material layer and the polymer solid electrolyte in the inorganic solid electrolyte layer are separately supplied in separate steps to supply the viscosity of the polymer solid electrolyte solution to each layer, or Since the permeability can be optimized, it becomes easy to improve the bondability of the solid-solid interface in each layer, and it becomes easy to allow the solid polymer electrolyte solution to surely penetrate to the bottom of the active material layer.
  • the thickness of the entire electrode sheet 10 is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the electrode sheet of this embodiment is particularly suitable for producing a thin film battery.
  • the electrode sheet 10 uses a polymer solid electrolyte instead of a liquid electrolyte solution or polymer gel electrolyte, there is no fear of liquid leakage. Furthermore, the present inventors focused on the fact that even if the polymer solid electrolyte is used, if the effective thickness is sufficiently thin, charge / discharge characteristics similar to those of a battery using an electrolytic solution or a polymer gel electrolyte can be obtained. . By diluting the solid polymer electrolyte with a solvent, it becomes possible to cover between the particles of the electrode layer made of active material particles and the surface layer thereof with a very thin electrolyte. On the other hand, when the polymer solid electrolyte is formed so thin, penetration resistance and strength to lithium dendrite etc.
  • the solid polymer electrolyte which has been polymerized can not be impregnated between the particles, according to the electrode sheet manufacturing method of the present embodiment, the gaps between the active material particles 17 fixed by the binder and the inorganic solid A polymer solid electrolyte is formed after the low viscosity polymer solid electrolyte solution is infiltrated into the gaps of the electrolyte particles 20. Therefore, it is easy to form the solid polymer electrolyte so as to fill the minute gaps among the particles in the inorganic solid electrolyte layer, the interface between the inorganic solid electrolyte layer and the active material layer, and the entire area in the active material layer.
  • the region 10D in which the active material particles 17 and the inorganic solid electrolyte particles 20 do not exist in the immediate vicinity of the heat sealable resin frame 13 can be formed.
  • the region 10D is occupied by the hard solid polymer electrolyte, and the region 10D does not become void.
  • the electrode 16 and the separator layer 19 adjacent to the region 10D do not collapse during use of the battery, and the battery structure is not broken.
  • the electrode mixture to be coated further includes inorganic solid electrolyte particles.
  • the electrode 26 of the electrode sheet 25 manufactured is a polymer solid which fills the gaps between the active material particles 17, the inorganic solid electrolyte particles 27, the active material particles 17 and the inorganic solid electrolyte particles 27. And an electrolyte 18.
  • the inorganic solid electrolyte 27 contained in the electrode 26 particles of LLT, LATP, LAGP, etc. can be used as in the inorganic solid electrolyte 20 contained in the separator layer 19.
  • the inorganic solid electrolyte 27 and the inorganic solid electrolyte 20 use the same compound.
  • the heat-fusible resin frame 13 may be formed after the active material layer is formed.
  • the electrode sheet manufacturing method S10B is described with reference to FIG. (S11B) preparing a metal foil 12 not having a heat sealable resin frame; (S12) forming an active material layer on the metal foil; (S13) forming an inorganic solid electrolyte layer on the active material layer; (S14) a solution supplying step of supplying a polymer solid electrolyte solution from above the inorganic solid electrolyte layer to permeate the active material layer and the inorganic solid electrolyte layer; (S15) a curing step of polymerizing a polymer compound, (S11C) forming a thermally fusible resin frame 13 around the active material layer on the metal foil; Have.
  • the step of forming the heat fusible resin frame S11C can be performed after the active solid material layer forming step S12, after the inorganic solid electrolyte layer forming step S13, after the solution supply step S14, or after the curing step S15.
  • the heat-fusible resin frame 13 is preferably formed by inkjet printing or screen printing. It is because it is hard to damage the active material layer etc. which were already formed.
  • FIG. 5 An all solid lithium ion battery according to a second embodiment of the present invention and a method of manufacturing the same will be described with reference to FIGS. 5 and 6.
  • FIG. 5 An all solid lithium ion battery according to a second embodiment of the present invention and a method of manufacturing the same will be described with reference to FIGS. 5 and 6.
  • FIG. 5 An all solid lithium ion battery according to a second embodiment of the present invention and a method of manufacturing the same will be described with reference to FIGS. 5 and 6.
  • the positive electrode sheet 30 manufactured by the method of the first embodiment and the negative electrode sheet 40 manufactured by the method of the first embodiment , 49 are in contact with each other.
  • the separator layer 109 of the all solid battery is composed of the separator layer 39 of the positive electrode sheet and the separator layer 49 of the negative electrode sheet.
  • the thermally fusible resin frame 33 of the positive electrode sheet and the thermally fusible resin frame 43 of the negative electrode sheet are thermally fused at the broken line portion (33A) of FIG. 5 to form the thermally fusible resin wall 103 There is.
  • the heat fusible resin wall 103 encloses and seals the outer periphery of the positive electrode 36, the separator layer 109 and the negative electrode 46.
  • the heat fusible resin frame 33 of the positive electrode sheet 30 and the heat fusible resin frame 43 of the negative electrode sheet 40 are formed to have the same shape and the same size so that the whole can be superimposed. Since the positive electrode sheet 30 is manufactured by the method of the first embodiment, the solid polymer electrolyte in the positive electrode 36 is integrally formed with the solid polymer electrolyte in the portion of the separator layer 109 in contact with the positive electrode. In addition, since the negative electrode sheet 40 is manufactured by the method of the first embodiment, the solid polymer electrolyte in the negative electrode 46 is integrally formed with the solid polymer electrolyte in the portion of the separator layer 109 in contact with the negative electrode. .
  • the positive electrode sheet 30 and the negative electrode sheet 40 are overlapped such that the respective separator layers 39 and 49 are in contact with each other, that is, the respective heat sealable resin frames 33 and 43 are joined.
  • the surface layer of either or both of the separator layer 39 of the positive electrode sheet 30 and the separator layer 49 of the negative electrode sheet 40 for example, a region within 1 ⁇ m from the surface is softened with a plasticizer, and then the positive electrode sheet and the negative electrode sheet are bonded. .
  • a plasticizer organic solvents, such as ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and these mixtures, can be used.
  • the thermally fusible resin frame 33 of the positive electrode sheet and the thermally fusible resin frame 43 of the negative electrode sheet are thermally fused at the broken line portion (33A) to form the thermally fusible resin wall 103.
  • the outer periphery of the positive electrode 36, the separator layer 109, and the negative electrode 46 is enclosed and sealed.
  • the electrode mixture to be coated may further include inorganic solid electrolyte particles.
  • the heat-fusible resin frames 33 and 43 may be formed after forming the active material layer and the inorganic solid electrolyte layer. That is, in FIG. 6, as a manufacturing process of a positive electrode sheet and / or a negative electrode sheet, step S10B shown in FIG. 4 may be adopted instead of step S10.
  • the all solid state battery 110 of this embodiment is manufactured in the same manner as in the first embodiment except for the positive electrode sheet 30 manufactured by the method of the first embodiment, but without providing the separator layer.
  • the negative electrode sheet 50 has a laminated structure in which the heat-fusible resin frames 33 and 53 are joined.
  • negative electrode sheet 50 has the same structure as the electrode sheet according to the first embodiment, but does not have a separator layer composed of inorganic solid electrolyte particles and a solid polymer electrolyte.
  • the negative electrode sheet 50 is configured by laminating the negative electrode metal foil 52 and the negative electrode 56 in this order.
  • the negative electrode metal foil has a heat sealable resin frame 53 formed on the periphery of one side thereof, and a heat resistant resin layer 54 laminated on the opposite side, and the metal foil 52 is formed on part of the heat resistant resin layer 54. An exposed portion 55 is formed.
  • the negative electrode 56 is formed on the inner side of the heat sealing resin frame 53.
  • the negative electrode 56 is composed of negative electrode active material particles 57 and a solid polymer electrolyte 58 in the negative electrode filling the gap.
  • the separator layer 119 of the all solid battery 110 is composed of the separator layer 39 of the positive electrode sheet 30.
  • the thermally fusible resin frame 33 of the positive electrode sheet and the thermally fusible resin frame 53 of the negative electrode sheet 50 are thermally fused at the broken line portion (33A) to form the thermally fusible resin wall 113.
  • the heat fusible resin wall 113 encloses and seals the outer periphery of the positive electrode 36, the separator layer 119 and the negative electrode 56.
  • the all-solid-state battery manufacturing method S110 of the present embodiment is described with reference to FIG. (S10) a step of manufacturing the positive electrode sheet 30 by the method of the first embodiment; (S50) A process of manufacturing the negative electrode sheet (second electrode sheet) 50, (S106) superposing the positive electrode sheet and the negative electrode sheet, (S108) A sealing step of heat-sealing the heat-fusible resin frames of the positive electrode sheet and the negative electrode sheet.
  • the solid polymer electrolyte in the positive electrode 36 is integrally formed with the solid polymer electrolyte in the portion of the separator layer 119 in contact with the positive electrode.
  • the step of preparing the metal foil 52 and the step of forming the negative electrode active material layer on the metal foil in the step S50 of manufacturing the negative electrode sheet 50 are the same as the steps S11 and S12 in the first embodiment, respectively.
  • the solution supply step S54 is the same as the solution supply step S14 in the first embodiment. However, while the polymer solid electrolyte solution is supplied from above the inorganic solid electrolyte layer in step S14 of the first embodiment, the inorganic solid electrolyte layer does not exist in step S54 of the present embodiment, so the negative electrode active material layer The difference is that the solid polymer electrolyte solution is supplied from above.
  • the polymer solid electrolyte solution is preferably filled in the gaps of the negative electrode active material particles 57 over the entire area from the surface of the metal foil 52 to the surface of the negative electrode active material layer, and the polymer solid electrolyte solution is heat-fused It is also the same as it is preferable to fill a region 50D immediately before the negative resin frame 53 where the negative electrode active material particles 57 do not exist.
  • the curing step S55 for polymerizing the polymer compound is also the same as the curing step S15 in the first embodiment.
  • the irradiation target has the inorganic solid electrolyte layer in the first embodiment, it differs in that the inorganic solid electrolyte layer is not present in step S55 of the present embodiment.
  • Step S106 of stacking the positive electrode sheet 30 and the negative electrode sheet 50, heat sealing resin frame 33 of the positive electrode sheet, and heat sealing resin frame 53 of the negative electrode sheet are heat sealed to form heat sealing resin wall 113
  • the sealing step S108 for enclosing and sealing the outer periphery of the positive electrode 36, the separator layer 119, and the negative electrode 56 is the same as that in the second embodiment.
  • the positive electrode sheet 30 is manufactured by the method of the first embodiment and joined to the negative electrode sheet 50 not having the separator layer
  • the negative electrode sheet is manufactured by the method of the first embodiment. You may manufacture and join with the positive electrode sheet which does not have a separator layer.
  • the electrode mixture to be coated may further include inorganic solid electrolyte particles.
  • the heat fusible resin frame 33 may be formed after forming the active material layer or the like. That is, in FIG. 9, step S10B shown in FIG. 4 may be adopted as the manufacturing step of the positive electrode sheet 30 instead of step S10.
  • the heat fusible resin frame 53 may be formed after forming the active material layer or the like. That is, in FIG. 9, as a manufacturing process of the negative electrode sheet 50, step S50B shown in FIG. 10 may be employed instead of step S50.
  • FIG. 11 An all solid lithium ion battery according to a fourth embodiment of the present invention and a method of manufacturing the same will be described based on FIGS. 11 and 12.
  • FIG. 11 An all solid lithium ion battery according to a fourth embodiment of the present invention and a method of manufacturing the same will be described based on FIGS. 11 and 12.
  • FIG. 11 An all solid lithium ion battery according to a fourth embodiment of the present invention and a method of manufacturing the same will be described based on FIGS. 11 and 12.
  • all-solid battery 120 of the present embodiment has the same structure as that of all-solid battery 100 of the second embodiment.
  • the all-solid battery 120 of the present embodiment differs from the all-solid battery 100 of the second embodiment in that the whole of the polymer solid electrolyte in the battery is integrally formed.
  • the second metal foil 72 and the second heat resistant resin layer 74 are laminated in this order.
  • the first electrode and the second electrode have opposite polarities.
  • the first electrode may be a positive electrode
  • the second electrode may be a negative electrode, or vice versa.
  • the heat fusible resin wall 123 surrounds the outer peripheries of the both electrodes 66 and 76 and the separator layer 129 to couple the first metal foil 62 and the second metal foil 72.
  • the solid polymer electrolytes in the first electrode 66, the separator layer 129, and the second electrode 76 are integrally formed.
  • the all-solid-state battery manufacturing method S120 of this embodiment is described with reference to FIG. (S60) a step of manufacturing the first sheet 60; (S60) a step of manufacturing the second sheet 70; (S126) superposing the positive electrode sheet and the negative electrode sheet, (S127) a curing step of polymerizing a polymer compound, (S128) A sealing step of thermally fusing the heat-fusible resin frames of the first sheet and the second sheet.
  • 1st sheet manufacturing process S60 and 2nd sheet manufacturing process S70 are the same as electrode sheet manufacturing process S10 of 1st Embodiment, they do not have the hardening process (process S15 of FIG. 2) which polymerizes a high molecular compound. It is different.
  • the polymer compound is polymerized after the first sheet 60 and the second sheet 70 both containing an unpolymerized polymer solid electrolyte solution are superposed in the superposition step S126 (S127).
  • the curing step S127 can be performed by thermal curing, electron beam irradiation, or a combination thereof.
  • the electron beam is irradiated from the side of the first metal foil 62 and the second metal foil 72, which is a metal foil made of a metal having a small atomic number.
  • the first metal foil is aluminum foil and the second metal foil is copper foil, electron beams are irradiated from the aluminum foil side. This is because the electron beam is easily transmitted.
  • the sealing step S128 can be performed in the same manner as the sealing step S108 of the second and third embodiments.
  • the sealing step may be performed simultaneously with the curing step S127, but is preferably performed after the curing step. This is because the inclusion of outgassing or the like generated in the polymerization process of the polymer compound can be prevented.
  • the first electrode 66 and / or the second electrode 76 may include inorganic solid electrolyte particles.
  • the first heat sealable resin frame 63 may be formed after forming the active material layer or the like. Specifically, in the first sheet manufacturing step S60 of FIG. 12, the metal foil 62 in which the heat fusible resin frame is not formed is prepared, and after the active material layer forming step S12 and the inorganic solid electrolyte layer forming step S13. Alternatively, after the solution supply step S14, the first heat-fusible resin frame 63 may be formed. The same applies to the formation of the second heat sealable resin frame 73 of the second sheet. Further, as in the third embodiment, either one of the first sheet 60 or the second sheet 70 may not have the inorganic solid electrolyte layer.
  • the entire solid polymer electrolyte in the all-solid battery 120 is integrally formed, so the internal resistance of the battery can be further lowered.
  • the all solid state battery 130 of the present embodiment has the same structure as the all solid state battery 120 of the fourth embodiment.
  • the first heat resistant resin layer 84, the first metal foil 82, the first electrode 86, the separator layer 89, the second electrode 92, the second metal foil 96, and the second heat resistant resin layer 98 are in this order It is stacked.
  • the first electrode and the second electrode have opposite polarities.
  • the first electrode may be a positive electrode, and the second electrode may be a negative electrode, or vice versa.
  • the heat fusible resin wall 133 surrounds the outer peripheries of the both electrodes 86 and 92 and the separator layer 89 to bond the first metal foil 82 and the second metal foil 96.
  • the solid polymer electrolytes in the first electrode 86, in the separator layer 89, and in the second electrode 92 are integrally formed.
  • the all-solid-state battery manufacturing method S130 of the present embodiment is described with reference to FIG. (S11) preparing a first metal foil 82 having a first heat sealable resin frame 83 formed on one side thereof; (S12) forming a first active material layer on the first metal foil; (S13) forming an inorganic solid electrolyte layer on the first active material layer; (S82) forming a second active material layer on the inorganic solid electrolyte layer; (S84) a solution supplying step of supplying a solid polymer electrolyte solution from above the second active material layer to permeate the first active material layer, the inorganic solid electrolyte layer, and the second active material layer; (S85) a curing step of polymerizing a polymer compound, (S136) overlapping the second metal foil 96 having the second heat sealable resin frame 97 formed on one side, (S138) A sealing step of heat-sealing the first heat-fusion resin frame 83 and the second heat-fusion resin frame 97
  • step S11, step S12 and step S13 in the first embodiment are the same as step S11, step S12 and step S13 in the first embodiment.
  • Step S82 of forming the second active material layer on the inorganic solid electrolyte layer can be performed in the same manner as step S12 of forming the first active material layer.
  • the solution supply step S84 is the same as the solution supply step S14 in the first embodiment. However, while the polymer solid electrolyte solution is supplied from above the inorganic solid electrolyte layer in step S14 in the first embodiment, the second active material layer formed on the inorganic solid electrolyte in step S84 of the present embodiment The difference is that the solid polymer electrolyte solution is supplied from above.
  • the polymer solid electrolyte solution is preferably filled over the entire surface from the surface of the metal foil 82 to the surface of the second active material layer, and the polymer solid electrolyte solution is the closest to the heat fusible resin frame 83, Similarly, it is preferable to fill the region 130D in which no active material particles / inorganic solid electrolyte particles are present.
  • the curing step S85 is also the same as the curing step S15 in the first embodiment.
  • the irradiation object has an active material layer and an inorganic solid electrolyte layer in step S15 of the first embodiment
  • the irradiation object further has a second active material layer in step S85 of the present embodiment. It is different.
  • the solid polymer electrolytes 88, 91, and 94 in the first electrode 86, the separator layer 89, and the second electrode 92 are integrally formed by this curing step.
  • a first electrode 86 including the first active material particles 87 and the solid polymer electrolyte in the first electrode 88 filling the gap, the inorganic solid electrolyte particles 90, and the solid polymer electrolyte 91 in the separator layer filling the gap The second electrode 92 including the separator layer 89 including the second active material particle 93 and the second solid polymer electrolyte 94 in the second electrode filling the gap is completed.
  • Step S136 of stacking the second metal foil is the same as that of the second embodiment.
  • the second metal foil is overlaid on the second electrode 92 so that the first heat fusion resin frame 83 and the second heat fusion resin frame 97 are joined.
  • the sealing step S138 is also the same as in the second embodiment.
  • the first thermally fusible resin frame 83 and the second thermally fusible resin frame 97 are thermally fused at the broken line portion (83A) of FIG. 13 to form a thermally fusible resin wall 133, The outer periphery of the first electrode 86, the separator layer 89, and the second electrode 92 is enclosed and sealed.
  • the first electrode and the second electrode may further include inorganic solid electrolyte particles.
  • the first heat sealable resin frame 83 may be formed after forming the active material layer and the like. Specifically, in FIG. 14, the first metal foil 82 in which the heat fusible resin frame is not formed is prepared, and any one of after the first active material layer forming step S12 to the overlapping step S136. The first heat sealable resin frame 83 may be formed at a stage.
  • the order of the curing step and the superposition step may be switched. That is, referring to FIG. 15, after the solution supply step S84, the second metal foil 96 is superposed without carrying out the curing step, and thereafter the curing step S137 is carried out. At the stage where the second metal foils are superposed, the solid polymer electrolyte solution is unpolymerized.
  • the curing step S137 can be performed in the same manner as the curing step S127 of the fourth embodiment.
  • the manufactured all solid battery uses a polymer solid electrolyte instead of a liquid electrolyte solution or a polymer gel electrolyte, so there is no fear of liquid leakage.
  • the solid polymer electrolyte fills in the gaps between the active material particles, a battery in which the contact state between the solid polymer electrolyte and the active material particles is good and the internal resistance is low can be obtained.
  • the solid polymer electrolyte in either or both electrodes is integrally formed with the solid polymer electrolyte in at least a portion in contact with the electrode in the separator layer, the interfacial resistance between the electrode and the separator layer is suppressed. , A battery with low internal resistance is obtained.
  • the separator layer contains an inorganic solid electrolyte having higher ion conductivity and hardness than the solid polymer electrolyte, the ion conductivity and strength of the separator layer can be compatible at a high level.
  • the manufactured all-solid-state battery is a region in which no active material particles and inorganic solid electrolyte particles near the heat fusible resin frame are present. Is occupied by a solid polymer electrolyte, so the battery structure in use of the battery is unlikely to be broken.
  • a laminate comprising an electrode comprising active material particles and a solid polymer electrolyte and a separator layer comprising inorganic solid electrolyte particles and a solid polymer electrolyte functions as a battery.
  • Lithium cobaltate LiCoO 2 , Toshima Manufacturing Co., Ltd., part number: LiCoO 2 fine powder, average particle diameter 1 ⁇ m
  • LiCoO 2 fine powder, average particle diameter 1 ⁇ m LiCoO 2 fine powder, average particle diameter 1 ⁇ m
  • ketjen black KB
  • PVdF polyvinylidene fluoride
  • NMP N methyl pyrrolidone
  • This electrolyte mixture paste is applied by screen printing to a size of 56 mm ⁇ 56 mm on the positive electrode active material layer, dried at 80 ° C. for 20 minutes, and a 10 ⁇ m thick inorganic solid electrolyte layer on the positive electrode active material layer. Formed.
  • the polymer solid electrolyte solution was prepared by mixing polyethylene oxide (PEO) as a polymer compound, LiTFS as a photopolymerization initiator and a lithium salt, and adding NMP as a solvent to adjust the viscosity.
  • PEO polyethylene oxide
  • LiTFS LiTFS as a photopolymerization initiator
  • NMP NMP as a solvent to adjust the viscosity.
  • This polymer solid electrolyte solution is supplied to the surface of the inorganic solid electrolyte layer by the ink jet method, and allowed to stand to fill the entire void of the positive electrode active material layer and the inorganic solid electrolyte layer, and then ultraviolet rays are irradiated to crosslink the polymer compound. I did. Thereby, the separator layer was formed on the positive electrode and the positive electrode active material layer.
  • the thickness of the separator layer was 13 ⁇ m, that is, the region of the surface layer 3 ⁇ m did not contain the inorganic solid electrolyte particles but contained only the solid polymer electrolyte.
  • NMP was added so as to have a solid content ratio of 50% by weight to form a paste.
  • the negative electrode material mixture paste is applied by screen printing to a size of 50 mm ⁇ 50 mm on a copper foil having a thickness of 15 ⁇ m, and dried at 80 ° C. to 120 ° C. for 2 hours to form a negative electrode active material layer having a thickness of 15 ⁇ m. It formed.
  • the polymer solid electrolyte solution and the negative electrode active material layer were supplied by the inkjet method to the same surface as above, and the whole area of the negative electrode active material layer was filled, and then the polymer compound was crosslinked by irradiating ultraviolet rays. As a result, a solid polymer electrolyte phase was formed between the negative electrode active material particles, and a solid polymer electrolyte layer having a thickness of 5 ⁇ m was formed on the negative electrode active material layer. By the above, the negative electrode sheet which does not have a separator layer was produced.
  • a plasticizer was spread on the surface of the separator layer of the positive electrode sheet, and was then bonded to the negative electrode sheet to produce a battery of an experimental example.
  • Figure 16 shows the results of the charge / discharge test conducted under the conditions of 100 ⁇ A current, 4.2V constant current constant voltage charge, 60 minutes charge time, 100 ⁇ A current discharge, 1.0V constant voltage discharge. Show. It was confirmed from FIG. 16 that the battery of the experimental example stably operates in charge and discharge.
  • an inorganic solid electrolyte layer having polyvinylidene fluoride (PVdF) as a binding agent on an aluminum foil After forming an inorganic solid electrolyte layer having polyvinylidene fluoride (PVdF) as a binding agent on an aluminum foil, a polymer solid electrolyte solution is infiltrated into the inorganic solid electrolyte layer, and the counter electrode of the aluminum foil is placed on contact therewith. Then, the polymer in the polymer solid electrolyte solution was crosslinked and cured by a polymerization reaction to form an all solid electrolyte layer in which the polymer solid electrolyte permeated between the inorganic solid electrolyte particles, and its ion conductivity was evaluated.
  • PVdF polyvinylidene fluoride
  • Li 1 + x Al y Ge 2-y (PO 4 ) 3 (LAGP) having a particle diameter of about 1 ⁇ m is used as the inorganic solid electrolyte particles, and the solid polymer electrolyte solution is converted to a skeleton of the solid polymer electrolyte after polymerization. It contains a molecular compound, a lithium salt, a crosslinking agent, and a polymerization initiator, and is diluted with an organic solvent to an appropriate viscosity.
  • the lithium ion conductivity of the obtained all solid electrolyte layer at room temperature was measured using an alternating current impedance method.
  • the ion conductivity of the inorganic solid electrolyte layer before application of the solid polymer electrolyte solution was 2.0 ⁇ 10 ⁇ 7 S / cm, while polymerization was carried out after the solid polymer electrolyte solution was impregnated.
  • the ion conductivity of the all solid electrolyte layer obtained by curing was 2.7 ⁇ 10 ⁇ 5 S / cm. This is 5.4 ⁇ 10 ⁇ 2 S / 5 ⁇ m when converted to a thickness of 5 ⁇ m for the total solid electrolyte layer, and the polymer solid electrolyte is inorganic even if it is an all solid electrolyte layer not containing an electrolytic solution. It was confirmed that good lithium ion conductivity is exhibited by filling in the particles of the solid electrolyte.
  • the ionic conductivity of the solid polymer electrolyte used at this time was 6.4 ⁇ 10 ⁇ 5 S / cm.

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