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WO2013035525A1 - Corps stratifié moulé pour batterie entièrement solide, batterie entièrement solide et procédé de fabrication de celle-ci - Google Patents

Corps stratifié moulé pour batterie entièrement solide, batterie entièrement solide et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2013035525A1
WO2013035525A1 PCT/JP2012/071136 JP2012071136W WO2013035525A1 WO 2013035525 A1 WO2013035525 A1 WO 2013035525A1 JP 2012071136 W JP2012071136 W JP 2012071136W WO 2013035525 A1 WO2013035525 A1 WO 2013035525A1
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WIPO (PCT)
Prior art keywords
solid
molded body
laminated
polymer material
solid electrolyte
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PCT/JP2012/071136
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English (en)
Japanese (ja)
Inventor
剛司 林
充 吉岡
倍太 尾内
Original Assignee
株式会社 村田製作所
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Application filed by 株式会社 村田製作所 filed Critical 株式会社 村田製作所
Priority to JP2013532525A priority Critical patent/JP5556969B2/ja
Publication of WO2013035525A1 publication Critical patent/WO2013035525A1/fr

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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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 battery laminated molded body, an all-solid battery, and a method for producing the same.
  • the battery having the above configuration has a risk of leakage of the electrolyte.
  • the organic solvent etc. which are used for electrolyte solution are combustible substances. For this reason, it is required to further increase the safety of the battery.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2007-5279 proposes a method for manufacturing an all-solid battery.
  • an active material containing a phosphoric acid compound and a solid electrolyte are dispersed in a solution containing a binder and a plasticizer, respectively, to prepare a slurry,
  • An active material green sheet and a solid electrolyte green sheet obtained by molding these slurries are laminated and heat-treated to produce an all-solid battery laminate.
  • an object of the present invention is to suppress burning of the conductive agent contained in a green sheet, a film or the like before firing the electrode layer, and to form a green sheet, a film or the like before firing the solid electrolyte layer.
  • An object of the present invention is to provide a laminate for an all-solid battery capable of removing the contained binder, an all-solid battery, and a production method thereof.
  • an electrode layer having different binder species contained therein and a molded body before firing of the electrode layer and a molded body before firing of the solid electrolyte layer were used. It has been found that it is possible to suppress the burning of the conductive agent contained in the compact before firing the layer and to remove the binder contained in the compact before firing the solid electrolyte layer. Based on such knowledge of the inventors, the present invention has the following features.
  • An all-solid battery laminate molded body includes a first molded body including an electrode active material of either a positive electrode active material or a negative electrode active material and a first polymer material, and a first molded body. And a second molded body including a solid electrolyte and a second polymer material. The decomposition temperature of the first polymer material is higher than the decomposition temperature of the second polymer material.
  • the first and second polymer materials preferably have a molecular weight of 10,000 or more.
  • the molded body may be in one form selected from the group consisting of a green sheet and a film.
  • the manufacturing method of an all solid state battery according to one aspect of the present invention includes the following steps and features.
  • the decomposition temperature of the first polymer material is higher than the decomposition temperature of the second polymer material.
  • the manufacturing method of an all-solid battery according to another aspect of the present invention includes the following steps and features.
  • (E) A step of producing a first solid-liquid mixture containing either the positive electrode active material or the negative electrode active material and the first polymer material.
  • the decomposition temperature of the first polymer material is higher than the decomposition temperature of the second polymer material.
  • the step (G) of forming the first molded body includes applying the first solid-liquid mixture to the solid electrolyte layer and then solid electrolyte layer. Forming a laminated body of the first molded body and firing the first molded body to form an electrode layer (I) firing the laminated body of the solid electrolyte layer and the first molded body. And forming a laminated fired body composed of a solid electrolyte layer and an electrode layer.
  • the step (G) of forming the first molded body applies the first solid-liquid mixture to the second molded body.
  • the step (J) of forming a solid electrolyte layer by firing the substrate may include firing the laminated molded body to form a laminated fired body including the solid electrolyte layer and the electrode layer.
  • the manufacturing method of an all solid state battery according to another aspect of the present invention includes the following steps and features.
  • (K) A step of producing a solid-liquid mixture for the positive electrode including the positive electrode active material and the first polymer material.
  • (M) A step of producing a solid-liquid mixture for a solid electrolyte containing the solid electrolyte and the second polymer material.
  • a solid-liquid mixture for electrodes is applied to a substrate to form a first laminated molded body composed of the substrate and one-electrode molded body.
  • (P) A step of applying a solid-liquid mixture for a solid electrolyte to the first laminated fired body to form a second laminated molded body comprising the first laminated fired body and the solid electrolyte molded body.
  • (Q) A step of firing the second laminated molded body to form a second laminated fired body composed of the base material, the one-electrode fired layer, and the solid electrolyte layer.
  • a solid-liquid mixture for positive electrode or a solid-liquid mixture for negative electrode, which is the other solid-liquid mixture for electrode, is applied to the second laminated fired body, and consists of the second laminated fired body and the other electrode molded body. Step of forming the third laminated molded body
  • (S) A step of firing the third laminated molded body to form a laminated fired body comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer.
  • the decomposition temperature of the first polymer material is higher than the decomposition temperature of the second polymer material.
  • the solid-liquid mixture may be in one form selected from the group consisting of slurry, paste, and colloid.
  • the molded body may be in one form selected from the group consisting of a green sheet and a film.
  • the difference between the decomposition temperature of the first polymer material and the decomposition temperature of the second polymer material is preferably 50 ° C. or more and 500 ° C. or less, preferably 50 ° C. or more. More preferably, it is 200 ° C. or lower.
  • the first polymer material and the second polymer material preferably contain at least one selected from the group consisting of polyvinyl acetal resin, cellulose, acrylic resin and urethane resin.
  • the weight content ratio of the first polymer material in the first molded body and the second polymer material in the second molded body is 5 parts by weight or more and 35 parts by weight with respect to 100 parts by weight of the inorganic material. The following is preferable.
  • the laminated fired body formed in the method for producing an all-solid battery of the present invention may include a laminated fired body having a single battery structure in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated.
  • the laminated fired body may include a laminated fired body obtained by laminating a plurality of laminated fired bodies having a single battery structure with a current collector layer interposed.
  • the material forming at least one layer selected from the group consisting of a positive electrode layer, a solid electrolyte layer and a negative electrode layer is a solid electrolyte comprising a lithium-containing phosphate compound having a NASICON structure It is preferable to contain.
  • the material forming at least one layer selected from the group consisting of a positive electrode layer and a negative electrode layer preferably contains an electrode active material made of a lithium-containing phosphate compound.
  • the first and second polymer materials preferably have a molecular weight of 10,000 or more.
  • the all solid state battery according to the present invention is manufactured by a manufacturing method having the above-described features.
  • a laminate 10 of an all-solid battery as one embodiment to which the manufacturing method of the present invention is applied is a single battery composed of a positive electrode layer 1, a solid electrolyte layer 2, and a negative electrode layer 3. Composed.
  • the positive electrode layer 1 is disposed on one surface of the solid electrolyte layer 2, and the negative electrode layer 3 is disposed on the other surface opposite to the one surface of the solid electrolyte layer 2.
  • the positive electrode layer 1 and the negative electrode layer 3 are provided at positions facing each other with the solid electrolyte layer 2 interposed therebetween.
  • an all-solid battery laminate 20 as another embodiment to which the manufacturing method of the present invention is applied includes a positive electrode layer 1, a solid electrolyte layer 2, and a negative electrode layer 3.
  • a plurality of, for example, two unit cells are connected in series via the current collector layer 4.
  • the current collector layer 4 disposed inside the laminate 20 of the all solid state battery is provided between the positive electrode layer 1 and the negative electrode layer 3.
  • each of the positive electrode layer 1 and the negative electrode layer 3 includes a solid electrolyte and an electrode active material, and the solid electrolyte layer 2 includes a solid electrolyte. At least one of the positive electrode layer 1 and the negative electrode layer 3 contains carbon or the like as a conductive agent.
  • the all-solid battery laminate molded body used for producing the all-solid battery laminates 10 and 20 configured as described above includes an electrode active material of either a positive electrode active material or a negative electrode active material and a first active material.
  • the decomposition temperature of the first polymer material is higher than the decomposition temperature of the second polymer material.
  • an electrode active material of either the positive electrode active material or the negative electrode active material and the first A first molded body including the polymer material and a second molded body including the solid electrolyte and the second polymer material are manufactured (molded body manufacturing step).
  • the first molded body and the second molded body are laminated to form a laminated molded body (laminated molded body forming step).
  • the obtained laminated molded body is fired to form a laminated fired body including an electrode layer and a solid electrolyte layer (laminated fired body forming step).
  • a molded body is formed from the solid-liquid mixture, the molded body of the positive electrode layer 1, the solid electrolyte layer 2 and the negative electrode layer 3 is laminated to form a laminated molded body, and this laminated molded body is fired.
  • a laminated fired body of the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 may be formed.
  • the laminated bodies 10 and 20 of the all-solid-state battery comprised as mentioned above, in another aspect of this invention, first, either the electrode active material of a positive electrode active material or a negative electrode active material and A first solid-liquid mixture containing the first polymer material is prepared. Next, a second solid-liquid mixture containing the solid electrolyte and the second polymer material is prepared. And a 1st molded object is formed from the obtained 1st solid-liquid mixture. A second molded body is formed from the obtained second solid-liquid mixture. Furthermore, the obtained 1st molded object is baked and the electrode layer, ie, the positive electrode layer 1, and the negative electrode layer 3, is formed. The obtained 2nd molded object is baked and the solid electrolyte layer 2 is formed. Thus, you may form each sintered compact of the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 by forming a molded object from a solid-liquid mixture and baking the obtained molded object.
  • the molded body may be in one form selected from the group consisting of a green sheet and a film.
  • the solid-liquid mixture may be in one form selected from the group consisting of slurry, paste and colloid.
  • the step of forming the first molded body includes the step of applying the first solid-liquid mixture to the solid electrolyte layer and the first step. Forming the electrode body by firing the first compact, and firing the solid electrolyte layer and the first compact to form the solid electrolyte layer. You may make it include forming the laminated fired body which consists of an electrode layer.
  • a green sheet of a solid electrolyte material as a second molded body is formed from the second solid-liquid mixture.
  • the green sheet of the solid electrolyte material is fired to produce the solid electrolyte layer 2.
  • a slurry or paste of the positive electrode material as the first solid-liquid mixture is applied to one surface of the solid electrolyte layer 2, and the slurry of the negative electrode material as the first solid-liquid mixture is applied to the other surface opposite to the one surface.
  • the paste is applied to form a positive electrode coating film as a first molded body and a laminate of the negative electrode coating film and the solid electrolyte layer 2.
  • the laminate may be fired to form a laminated fired body including the positive electrode layer 1, the solid electrolyte layer 2, and the electrode layer 3.
  • the step of forming the first molded body includes the first solid-liquid mixture applied to the second molded body.
  • Forming a laminated molded body composed of the molded body and the second molded body, firing the first molded body to form an electrode layer, firing the second molded body, and solid electrolyte The step of forming a layer may include firing the laminated molded body to form a laminated fired body including a solid electrolyte layer and an electrode layer.
  • a green sheet of a solid electrolyte material as a second molded body is formed from the second solid-liquid mixture.
  • the positive electrode material slurry or paste as the first solid-liquid mixture is applied to one surface of the green sheet of the solid electrolyte material, and the negative electrode material as the first solid-liquid mixture is applied to the other surface opposite to the one surface.
  • the slurry or paste is applied to form a positive electrode coating film as a first molded body and a laminated molded body of a negative electrode coating film and a solid electrolyte green sheet as a second molded body.
  • the multilayer molded body may be fired to form a multilayer fired body including the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3.
  • a positive electrode material slurry or paste as a first solid-liquid mixture is applied to one surface of a solid electrolyte material green sheet, and a positive electrode coating film as a first molded body and a second molded body as A laminated molded body with a solid electrolyte green sheet is formed. And this laminated molded body may be fired to form a laminated fired body comprising the positive electrode layer 1 and the solid electrolyte layer 2.
  • a metal foil such as an alloy may be fixed as the negative electrode layer 3 on the other surface opposite to the one surface of the solid electrolyte layer 2.
  • a solid-liquid mixture for a positive electrode including a positive electrode active material and a first polymer material is prepared.
  • a solid-liquid mixture for negative electrode containing a negative electrode active material and a first polymer material is prepared.
  • a solid-liquid mixture for solid electrolyte containing the solid electrolyte and the second polymer material is prepared.
  • Either the obtained solid-liquid mixture for positive electrode or solid-liquid mixture for negative electrode is applied to the base material to form a first laminated molded body composed of the base material and the one-electrode molded body.
  • the first laminated molded body is fired to form a first laminated fired body including a base material and one electrode fired layer.
  • a solid-liquid mixture for solid electrolyte is applied to the first laminated fired body to form a second laminated molded body composed of the first laminated fired body and the solid electrolyte molded body. Further, the second laminated molded body is fired to form a second laminated fired body composed of the base material, the one electrode fired layer, and the solid electrolyte layer. Then, either the obtained solid-liquid mixture for positive electrode or solid-liquid mixture for negative electrode is applied to the second laminated fired body, and the second laminated fired body, the other electrode molded body, A third laminated molded body is formed. Finally, the third laminated molded body is fired to form a laminated fired body including a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. In this way, the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 may be formed by sequentially coating, firing, and laminating.
  • a positive electrode material paste is applied on a base material such as polyethylene terephthalate (PET) and fired to form the positive electrode layer 1.
  • the solid electrolyte layer 2 is formed by applying a paste of a solid electrolyte material on the obtained positive electrode layer 1 and baking it.
  • a negative electrode material paste is applied on the obtained solid electrolyte layer 2 and baked to form the negative electrode layer 3.
  • a laminated fired body composed of the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 may be formed. In this case, you may form the negative electrode layer 3 previously on a base material.
  • a solid-liquid mixture for a positive electrode including a positive electrode active material and a first polymer material is prepared.
  • a solid-liquid mixture for negative electrode containing a negative electrode active material and a first polymer material is prepared.
  • a solid-liquid mixture for solid electrolyte containing the solid electrolyte and the second polymer material is prepared.
  • the solid electrolyte layer 2 is formed by shaping and firing the obtained solid-liquid mixture for solid electrolyte.
  • One electrode molded body is formed by molding any one of the obtained solid-liquid mixture for positive electrode or solid-liquid mixture for negative electrode.
  • an electrode compact is laminated on one surface of the solid electrolyte layer to form a laminate.
  • a laminated fired body comprising a solid electrolyte layer and one electrode fired layer is formed.
  • the other electrode molded body is formed by molding either the obtained solid-liquid mixture for positive electrode or solid-liquid mixture for negative electrode, which is the other solid-liquid mixture for electrode.
  • the other electrode molded body is laminated on the other surface opposite to the one surface of the solid electrolyte layer to form a laminate.
  • a laminate fired body composed of the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 may be formed. In this way, a laminated fired body may be formed by sequentially laminating and firing the compacts of the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 before firing.
  • the multilayer molded body for an all-solid battery of the present invention has a structure in which molded bodies of the positive electrode layer 1, the solid electrolyte layer 2, and the negative electrode layer 3 are fired.
  • the kind of the first polymer material contained in the molded body before firing of at least one of the positive electrode layer 1 and the negative electrode layer 3, and the second polymer material contained in the molded body before firing of the solid electrolyte layer 2 The type is different.
  • the decomposition temperature of the first polymer material is higher than the decomposition temperature of the second polymer material.
  • the solid electrolyte layer 2 it is possible to suppress the residue of the polymer material that inhibits ion conductivity, the voids after the removal of the polymer material, and the like, and to form a dense solid electrolyte layer, Furthermore, an internal short circuit due to a residue of the polymer material can be suppressed. Therefore, when the all-solid battery laminate molded body of the present invention is fired to produce an all-solid battery, battery characteristics such as discharge capacity can be improved.
  • the difference between the decomposition temperature of the first polymer material and the decomposition temperature of the second polymer material is preferably 50 ° C. or more and 500 ° C. or less, preferably 50 ° C. or more. More preferably, it is 200 ° C. or lower.
  • the difference between the decomposition temperature of the first polymer material and the decomposition temperature of the second polymer material is 50 ° C. or more and 500 ° C. or less, the above effect can be obtained more remarkably. More preferably, when the difference between the decomposition temperature of the first polymer material and the decomposition temperature of the second polymer material is 50 ° C. or higher and 200 ° C. or lower, the minimum necessary polymer material residue is used. Therefore, even in the positive electrode layer or the negative electrode layer containing a polymer material residue after firing, the densification of the positive electrode layer or the negative electrode layer is not hindered. Can increase the sex.
  • the first polymer material and the second polymer material are at least one selected from the group consisting of polyvinyl acetal resin, cellulose, acrylic resin, and urethane resin. It is preferable to include.
  • first and second polymer materials it is possible to achieve both dispersibility and viscosity in a slurry or paste for producing a molded body.
  • each weight content ratio of the 1st polymeric material in a 1st molded object and the 2nd polymeric material in a 2nd molded object is 100 weight of inorganic materials. It is preferably 5 parts by weight or more and 35 parts by weight or less with respect to parts.
  • the molecular weight of the first and second polymer materials is preferably 10,000 or more.
  • the laminated fired body may be a single battery structure laminated body 10 by laminating the positive electrode layer 1, the solid electrolyte layer 2 and the negative electrode layer 3, and the single battery structure laminated body with the current collector layer 4 interposed therebetween.
  • a laminated body 20 in which a plurality of bodies 10 are laminated may be used.
  • a plurality of laminates 10 having a single cell structure may be stacked electrically in series or in parallel.
  • the method for forming the molded body is not particularly limited, but a die coater, a comma coater, screen printing, or the like can be used.
  • the method of laminating the molded body is not particularly limited, but the molded body can be laminated using a hot isostatic press, a cold isostatic press, an isostatic press, or the like.
  • a solid-liquid mixture for forming a molded body may be prepared by wet-mixing an organic vehicle in which a polymer material is dissolved in a solvent and a positive electrode active material, a negative electrode active material, a solid electrolyte, or a current collector material. It can.
  • Media can be used in wet mixing, and specifically, a ball mill method, a viscomill method, or the like can be used.
  • a wet mixing method that does not use media may be used, and a sand mill method, a high-pressure homogenizer method, a kneader dispersion method, or the like can be used.
  • the solid-liquid mixture may contain a plasticizer.
  • a plasticizer is not particularly limited, phthalic acid esters such as dioctyl phthalate and diisononyl phthalate may be used.
  • the atmosphere is not particularly limited, but it is preferably performed under conditions that do not change the valence of the transition metal contained in the electrode active material.
  • the kind of electrode active material contained in the positive electrode layer 1 or the negative electrode layer 3 of the laminated bodies 10 and 20 of the all-solid-state battery to which the manufacturing method of the present invention is applied is not limited, as the positive electrode active material, Li 3 V 2 (PO 4 ) 3 and other lithium-containing phosphate compounds having NASICON type structure, LiFePO 4 and LiMnPO 4 and other lithium-containing phosphate compounds, LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1 A layered compound such as / 3 O 2 and a lithium-containing compound having a spinel structure such as LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4 can be used.
  • the positive electrode active material Li 3 V 2 (PO 4 ) 3 and other lithium-containing phosphate compounds having NASICON type structure, LiFePO 4 and LiMnPO 4 and other lithium-containing phosphate compounds, LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1 A layered compound such as / 3 O 2 and a lithium-containing compound having
  • MOx (M is at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb and Mo, and x is 0.9 ⁇ x ⁇ 2.0.
  • a compound having a composition represented by the following formula can be used.
  • a mixture obtained by mixing two or more active materials having a composition represented by MOx containing different elements M such as TiO 2 and SiO 2 may be used.
  • graphite-lithium compounds, lithium alloys such as Li-Al, oxidation of Li 3 V 2 (PO 4 ) 3 , Li 3 Fe 2 (PO 4 ) 3 , Li 4 Ti 5 O 12, etc. A thing etc. can be used.
  • a lithium-containing phosphate compound having a NASICON structure can be used.
  • Lithium-containing phosphoric acid compound having a NASICON-type structure the chemical formula Li x M y (PO 4) 3 ( Formula, x 1 ⁇ x ⁇ 2, y is a number in the range of 1 ⁇ y ⁇ 2, M Is one or more elements selected from the group consisting of Ti, Ge, Al, Ga and Zr).
  • part of P in the above chemical formula may be substituted with B, Si, or the like.
  • a mixture obtained by mixing two or more Nasicon-type lithium-containing phosphate compounds having different compositions such as Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 and Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 is used. It may be used.
  • the lithium-containing phosphate compound having a NASICON structure used in the solid electrolyte is a compound containing a crystal phase of a lithium-containing phosphate compound having a NASICON structure or a lithium-containing phosphate having a NASICON structure by heat treatment. You may use the glass which precipitates the crystal phase of a phosphoric acid compound.
  • a material used for said solid electrolyte it is possible to use the material which has ion conductivity and is so small that electronic conductivity can be disregarded other than the lithium-containing phosphate compound which has a NASICON structure.
  • examples of such a material include lithium halide, lithium nitride, lithium oxyacid salt, and derivatives thereof.
  • Li—PO compounds such as lithium phosphate (Li 3 PO 4 ), LIPON (LiPO 4 ⁇ x N x ) in which nitrogen is introduced into lithium phosphate, Li—Si— such as Li 4 SiO 4 O-based compounds, Li-P-Si-O based compounds, Li-V-Si-O based compounds, La 0.51 Li 0.35 TiO 2.94 , La 0.55 Li 0.35 TiO 3 , Li 3x La 2 / 3-x TiO 3, etc.
  • Li—PO compounds such as lithium phosphate (Li 3 PO 4 ), LIPON (LiPO 4 ⁇ x N x ) in which nitrogen is introduced into lithium phosphate
  • Li—Si— such as Li 4 SiO 4 O-based compounds, Li-P-Si-O based compounds, Li-V-Si-O based compounds, La 0.51 Li 0.35 TiO 2.94 , La 0.55 Li 0.35 TiO 3 , Li 3x La 2 / 3-x TiO 3, etc.
  • Examples thereof include compounds having
  • the material forming at least one of the positive electrode layer 1, the solid electrolyte layer 2 or the negative electrode layer 3 of the laminates 10 and 20 of the all-solid-state battery to which the manufacturing method of the present invention is applied is a lithium-containing phosphoric acid having a NASICON structure. It is preferable to include a solid electrolyte made of a compound. In this case, high ion conductivity that is essential for battery operation of an all-solid battery can be obtained. In addition, when glass or glass ceramics having a composition of a lithium-containing phosphate compound having a NASICON type structure is used as a solid electrolyte, a denser sintered body can be easily obtained due to the viscous flow of the glass phase in the firing step. It is particularly preferred to prepare the solid electrolyte starting material in the form of glass or glass ceramic.
  • the material which forms at least 1 layer of the positive electrode layer 1 or the negative electrode layer 3 of the laminated bodies 10 and 20 of the all-solid-state battery to which the manufacturing method of this invention is applied is an electrode active material which consists of a lithium containing phosphate compound. It is preferable to include.
  • the phase change of the electrode active material in the firing step or the reaction of the electrode active material with the solid electrolyte can be easily suppressed by the high temperature stability of the phosphoric acid skeleton. The capacity can be increased.
  • an electrode active material composed of a lithium-containing phosphate compound and a solid electrolyte composed of a lithium-containing phosphate compound having a NASICON structure are used in combination, the reaction between the electrode active material and the solid electrolyte is suppressed in the firing step. It is particularly preferable to use a combination of the electrode active material and the solid electrolyte material as described above, since both of them can be obtained and good contact can be obtained.
  • the current collector layer 4 of the laminate 20 of the all-solid-state battery to which the manufacturing method of the present invention is applied contains an electron conductive material.
  • the electron conductive material preferably contains at least one selected from the group consisting of conductive oxides, metals and carbon materials.
  • Example shown below is an example and this invention is not limited to the following Example.
  • an organic vehicle was prepared by dissolving 20 parts by weight of various polymer materials having different decomposition temperatures shown in Table 1 below as binders in 100 parts by weight of a solvent.
  • the decomposition temperature of the polymer material was judged at a temperature at which the weight loss rate of the polymer material exceeded 95% using a differential thermothermal gravimetric simultaneous measurement device (model number: TG-DTA7200) manufactured by Seiko Instruments Inc. .
  • a urethane resin having a weight average molecular weight of 60,000 was used as urethane A
  • a urethane resin having a weight average molecular weight of 200,000 was used as urethane B.
  • LAGP Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3
  • Li 3 V 2 (PO 4 ) Li 3 V 2 (PO 4 ) as an electrode active material 45 parts by weight of a powder having a crystal phase of 3 , 5 parts by weight of carbon powder as a conductive agent, and 120 parts by weight of an organic vehicle prepared as described above so as to include the polymer material A shown in Table 2 below.
  • a spherical medium made of zirconia having a diameter of 1 mm was enclosed in a container and the container was rotated, and then the spherical medium was taken out to prepare an electrode slurry.
  • Each electrode slurry is coated on a polyethylene terephthalate (PET) film using a doctor blade method, formed into a sheet having a thickness of 50 ⁇ m, and punched into a disk having a diameter of 10 mm.
  • PET polyethylene terephthalate
  • the solid electrolyte slurry was coated on a PET film using a doctor blade method, formed into a sheet shape having a thickness of 30 ⁇ m, and punched into a disk shape having a diameter of 11 mm, thereby producing a solid electrolyte green sheet.
  • a single electrode green sheet peeled from the PET film was laminated on one side of the solid electrolyte layer obtained above, and pressed at a temperature of 60 ° C. for pressure bonding to form a positive electrode layer.
  • a negative electrode layer was formed by pressure-bonding two electrode sheets to the opposite surface of the solid electrolyte layer in the same manner.
  • the green sheet laminated body for all-solid-state batteries was produced.
  • the reason for the difference in the number of electrode sheets used in the positive electrode layer and the negative electrode layer is that when Li 3 V 2 (PO 4 ) 3 is used as the positive electrode active material and the negative electrode active material, This is because the capacity per unit weight (gram) of Li 3 V 2 (PO 4 ) 3 differs by about twice.
  • the thickness of a positive electrode layer and a negative electrode layer can be suitably changed according to the material of the electrode active material to be used.
  • the polymer material was removed by heat-treating the obtained laminate at a temperature of 500 ° C. in an air atmosphere (first firing step). Then, the all-solid-state battery was obtained by heat-processing in a nitrogen atmosphere at the temperature of 700 degreeC, and sintering the laminated body (2nd baking process).
  • the residue of the polymer material contained in the solid electrolyte layer was confirmed by observing the color of the solid electrolyte layer with an optical microscope on the fracture surface of the obtained all solid state battery. Moreover, the burning suppression effect of the electrically conductive agent contained in an electrode layer was confirmed by observing the color of an electrode layer with a scanning electron microscope. The results are shown in Table 3.
  • the obtained all solid state battery was sealed in a 2032 type coin type battery, a charge / discharge test was performed, and a discharge amount was measured.
  • the battery was charged until the voltage became 4.5 V with a charging current of 20 ⁇ A (the voltage was held for 3 hours at a voltage of 4.5 V after reaching the voltage of 4.5 V), and discharged until the voltage became 3 V with a discharging current of 20 ⁇ A. .
  • the sealing method for comprising a battery is not specifically limited, You may seal the laminated body of the all-solid-state battery obtained by sintering with resin etc.
  • a paste obtained by applying or dipping an insulating paste such as Al 2 O 3 around the laminate may be sealed by heat treatment.
  • a conductive layer such as a metal layer may be formed on the positive and negative electrode layers by sputtering or the like.
  • the conductive layer may be formed by applying or dipping a metal paste or the like on the positive and negative electrode layers, followed by heat treatment.
  • the positive electrode layer or the negative electrode layer can suppress the burning of the conductive agent and can form a dense solid electrolyte layer. Since battery characteristics such as discharge capacity can be improved, the present invention is particularly useful for the production of all-solid secondary batteries.

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Abstract

L'invention fournit un corps stratifié moulé pour batterie entièrement solide, une batterie entièrement solide et le procédé de fabrication de celle-ci, tout en permettant d'inhiber la combustion d'un agent conducteur contenu dans un corps moulé avant cuisson d'une couche d'électrode, et de retirer un liant contenu dans le corps moulé avant cuisson d'une couche d'électrolyte solide. Le corps stratifié moulé pour batterie entièrement solide est équipé: d'un premier corps moulé qui contient une matière active d'électrode qui peut être une matière active d'électrode positive ou négative, et un premier matériau polymère, et qui consiste en un corps moulé avant cuisson d'une couche d'électrode positive (1) ou d'une couche d'électrode négative (3); et d'un second corps moulé qui est stratifié sur le premier corps moulé, qui contient un électrolyte solide et un second matériau polymère, et qui consiste en un corps moulé avant cuisson de la couche d'électrolyte solide (2). Afin de fabriquer un corps stratifié (10) de batterie entièrement solide constitué de la couche d'électrode positive (1), de la couche d'électrolyte solide (2), et de la couche d'électrode négative (3), le premier et le second corps moulé sont produits puis stratifiés, et cuits après formation du corps stratifié moulé. La température de dégradation du premier matériau polymère, est supérieure à celle du second matériau polymère.
PCT/JP2012/071136 2011-09-09 2012-08-22 Corps stratifié moulé pour batterie entièrement solide, batterie entièrement solide et procédé de fabrication de celle-ci WO2013035525A1 (fr)

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JP2015069843A (ja) * 2013-09-30 2015-04-13 Fdk株式会社 全固体電池及び全固体電池の製造方法
CN106688132A (zh) * 2014-07-22 2017-05-17 瑞克锐斯株式会社 硅二次电池
WO2017146105A1 (fr) * 2016-02-23 2017-08-31 凸版印刷株式会社 Feuille crue stratifiée et feuille crue stratifiée continue, leur procédé de fabrication, et procédé de fabrication de batterie secondaire entièrement solide
EP3425719A4 (fr) * 2016-02-29 2019-09-18 Hitachi Zosen Corporation Batterie rechargeable entièrement solide et son procédé de fabrication
JP2021064584A (ja) * 2019-10-17 2021-04-22 マクセルホールディングス株式会社 固体電解質電池

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JP2009187911A (ja) * 2008-02-08 2009-08-20 Ohara Inc 固体電池およびその電極の製造方法
JP2010244727A (ja) * 2009-04-01 2010-10-28 Namics Corp 電極材料とその製造方法、及び、リチウムイオン二次電池
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JP2009181877A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池およびその電極の製造方法
JP2009187911A (ja) * 2008-02-08 2009-08-20 Ohara Inc 固体電池およびその電極の製造方法
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Publication number Priority date Publication date Assignee Title
JP2015069843A (ja) * 2013-09-30 2015-04-13 Fdk株式会社 全固体電池及び全固体電池の製造方法
CN106688132A (zh) * 2014-07-22 2017-05-17 瑞克锐斯株式会社 硅二次电池
JP2017526150A (ja) * 2014-07-22 2017-09-07 リクリッス カンパニー リミテッド シリコン二次電池
CN106688132B (zh) * 2014-07-22 2020-09-04 瑞克锐斯株式会社 硅二次电池
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WO2017146105A1 (fr) * 2016-02-23 2017-08-31 凸版印刷株式会社 Feuille crue stratifiée et feuille crue stratifiée continue, leur procédé de fabrication, et procédé de fabrication de batterie secondaire entièrement solide
EP3425719A4 (fr) * 2016-02-29 2019-09-18 Hitachi Zosen Corporation Batterie rechargeable entièrement solide et son procédé de fabrication
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JP2021064584A (ja) * 2019-10-17 2021-04-22 マクセルホールディングス株式会社 固体電解質電池

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