WO2014042083A1 - Batterie entièrement monolithique, stratifié vert de batterie entièrement monolithique et procédé de production de batterie entièrement monolithique - Google Patents

Batterie entièrement monolithique, stratifié vert de batterie entièrement monolithique et procédé de production de batterie entièrement monolithique Download PDF

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WO2014042083A1
WO2014042083A1 PCT/JP2013/074040 JP2013074040W WO2014042083A1 WO 2014042083 A1 WO2014042083 A1 WO 2014042083A1 JP 2013074040 W JP2013074040 W JP 2013074040W WO 2014042083 A1 WO2014042083 A1 WO 2014042083A1
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layer
electrode layer
solid
current collector
solid electrolyte
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PCT/JP2013/074040
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English (en)
Japanese (ja)
Inventor
充 吉岡
倍太 尾内
剛司 林
武郎 石倉
彰佑 伊藤
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株式会社 村田製作所
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Priority to JP2014535524A priority Critical patent/JP5804208B2/ja
Publication of WO2014042083A1 publication Critical patent/WO2014042083A1/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
    • 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
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/664—Ceramic materials
    • 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, an unfired laminate for an all-solid battery, and a method for producing an all-solid battery.
  • 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 JP-A-8-138671 (hereinafter referred to as Patent Document 1), a metal foil is used as a current collector layer in order to obtain a current collecting effect. Is commonly used.
  • Patent Document 1 When a metal foil as disclosed in Patent Document 1 is used as a current collector layer of an all-solid battery, the metal foil is easily oxidized when the laminate is fired to produce an all-solid battery. However, there is a problem that the current collecting performance is remarkably lowered and the battery capacity is lowered. In addition, since the metal foil is easily oxidized when the laminate is fired, there is a problem that the laminated structure constituting the all-solid battery is easily destroyed.
  • an object of the present invention is to provide an all-solid battery, an unfired laminate for an all-solid battery, and a method for producing an all-solid battery that can improve the battery capacity by improving the current collecting performance. is there.
  • the present invention has the following features.
  • An all-solid battery includes an electrode layer of at least one of a positive electrode layer and a negative electrode layer, a solid electrolyte layer laminated on one side of the electrode layer, and a current collector laminated on the other side of the electrode layer.
  • the conductive body preferably has a fiber shape or a flat shape.
  • the conductive material preferably contains carbon.
  • At least one layer constituting the electrode layer and the current collector layer includes another conductive body having a shape different from that of the conductive body. It is preferable that another electroconductive body of a different shape is a particle shape.
  • At least one of the electrode layer and the current collector layer contains ceramics.
  • the above ceramic contains a lithium-containing phosphate compound.
  • the lithium-containing phosphate compound is a lithium-containing phosphate compound having at least one of a nasicon type structure and an olivine type structure.
  • the electrode layer and the current collector layer contain a solid electrolyte material constituting the solid electrolyte layer.
  • the solid electrolyte material is a lithium-containing phosphate compound having at least one of a NASICON structure and an olivine structure.
  • the above-mentioned solid electrolyte material may be a glass phase in which a crystalline phase of a lithium-containing phosphate compound having at least one of a nasicon type structure and an olivine type structure is deposited by firing.
  • the all solid state battery according to the present invention comprises a positive electrode layer as an electrode layer laminated on one side of a solid electrolyte layer, and a positive electrode as a current collector layer laminated on the positive electrode layer on the side opposite to the solid electrolyte layer side.
  • a current collector layer, a negative electrode layer as an electrode layer laminated on the other side of the solid electrolyte layer, and a negative electrode current collector layer as a current collector layer laminated on the negative electrode layer on the side opposite to the solid electrolyte layer side It is preferable to have a single cell structure.
  • the all solid state battery of the present invention may have a structure in which at least two unit cell structures are connected in series or in parallel.
  • the unfired laminate for an all-solid battery according to the present invention is laminated on an unfired electrode layer that is an unfired body of at least one of the positive electrode layer and the negative electrode layer, and one side of the unfired electrode layer.
  • An unsintered solid electrolyte layer that is an unsintered body of the solid electrolyte layer, and an unsintered current collector layer that is laminated on the other side of the unsintered electrode layer and is an unsintered body of the current collector layer.
  • At least one layer constituting the green electrode layer and the green current collector layer includes a plurality of conductive bodies. Each of the plurality of conductive bodies has a major axis and a minor axis. In most of the plurality of conductive bodies, the direction in which the major axis extends is oriented substantially perpendicular to the stacking direction.
  • the green electrode layer, the green solid electrolyte layer, and the green current collector layer may have the form of a green sheet or a printed layer.
  • the manufacturing method of the all-solid-state battery according to the present invention includes the following steps.
  • an unsintered electrode layer that is an unsintered body of at least one of a positive electrode layer and a negative electrode layer, an unsintered solid electrolyte layer that is an unsintered body of a solid electrolyte layer, and an unsintered body of a current collector layer
  • the at least one layer constituting the green electrode layer and the green current collector layer includes a plurality of conductive bodies.
  • Each of the plurality of conductive bodies has a major axis and a minor axis. In most of the plurality of conductive bodies, the direction in which the major axis extends is oriented substantially perpendicular to the stacking direction.
  • most of the plurality of conductive bodies are oriented so that the direction in which the major axis extends is substantially perpendicular to the stacking direction.
  • an all-solid battery stack 10 is configured by a single cell including a positive electrode layer 11, a solid electrolyte layer 13, a negative electrode layer 12, and a current collector layer 14. Is done.
  • the positive electrode layer 11 is disposed on one surface of the solid electrolyte layer 13, and the negative electrode layer 12 is disposed on the other surface opposite to the one surface of the solid electrolyte layer 13.
  • the positive electrode layer 11 and the negative electrode layer 12 are provided at positions facing each other with the solid electrolyte layer 13 interposed therebetween.
  • the current collector layer 14 is disposed on the surface of the positive electrode layer 11 that does not contact the solid electrolyte layer 13, and the current collector layer 14 is disposed on the surface of the negative electrode layer 12 that does not contact the solid electrolyte layer 13.
  • a plurality of unit cells each composed of a positive electrode layer 11, a solid electrolyte layer 13, and a negative electrode layer 12, for example, Two of them are connected in series via the current collector layer 14.
  • the current collector layer 14 disposed inside the all-solid battery stack 20 is provided between the positive electrode layer 11 and the negative electrode layer 12.
  • a current collector layer 14 is disposed on the outer surface of the all-solid battery stack 20 on the surface of the positive electrode layer 11 located on the outermost layer and not in contact with the solid electrolyte layer 13, and the negative electrode layer 12 located on the outermost layer.
  • the current collector layer 14 is disposed on the surface not contacting the solid electrolyte layer 13.
  • a positive electrode terminal is connected to the current collector layer 14 in contact with the outermost positive electrode layer 11, and a negative electrode terminal is connected to the current collector layer 14 in contact with the outermost negative electrode layer 12.
  • a plurality of unit cells each composed of a positive electrode layer 11, a solid electrolyte layer 13, and a negative electrode layer 12, for example, 2 are connected in parallel via the current collector layer 14.
  • the current collector layer 14 disposed inside the all-solid battery stack 30 is provided between the negative electrode layer 12 and the negative electrode layer 12 (or between the positive electrode layer 11 and the positive electrode layer 11). Outside the all-solid-state battery stack 30, the current collector layer 14 is disposed on the surface of the positive electrode layer 11 (or the surface of the negative electrode layer 12) located in the outermost layer and not in contact with the solid electrolyte layer 13. Yes.
  • a current collector layer 14 in contact with the outermost positive electrode layer 11 (or negative electrode layer 12) is connected to a positive electrode terminal (or negative electrode terminal), and the current collector layer 14 in contact with the internal negative electrode layer 12 (or positive electrode layer 11).
  • a negative terminal (or a positive terminal) is connected to.
  • each of the positive electrode layer 11 and the negative electrode layer 12 includes a solid electrolyte and an electrode active material
  • the solid electrolyte layer 13 includes a solid electrolyte
  • the all-solid battery stack 10, 20, 30 as an embodiment of the present invention configured as described above is stacked on at least one electrode layer of the positive electrode layer 11 or the negative electrode layer 12 and on one side of the electrode layer.
  • At least one of the electrode layer and the current collector layer 14 includes a plurality of conductive bodies.
  • Each of the plurality of conductive bodies has a major axis and a minor axis. In most of the plurality of conductive bodies, the direction in which the major axis extends is oriented substantially perpendicular to the stacking direction. In the present invention, the “major axis” is the longest side of the conductive body, and the “short axis” is the shortest side of the conductive body.
  • Most of the plurality of conductive bodies have a current distribution in a plane direction in the positive electrode layer 11, the negative electrode layer 12, or the current collector layer 14 because the direction in which the major axis extends is oriented substantially perpendicular to the stacking direction. Can be made uniform, and the current collecting effect can be enhanced.
  • the “most” in the present invention includes 50% or more of the plurality of conductive bodies, preferably 70% or more, more preferably 80% or more.
  • substantially vertical as used in the present invention includes 90 ° ⁇ 45 °, preferably includes 90 ° ⁇ 30 °, and more preferably includes 90 ° ⁇ 15 °.
  • the plurality of conductive bodies are prevented from shorting internally across the solid electrolyte layer 13 adjacent to the positive electrode layer 11 or the negative electrode layer 12. Accordingly, the electron conductivity in the surface direction can be increased inside the positive electrode layer 11, the negative electrode layer 12, or the current collector layer 14, and the battery capacity can be improved by improving the current collecting performance.
  • the conductive body may be any material having electronic conductivity such as carbon, metal, or oxide.
  • the conductive body has a fiber shape or a flat shape. Since the conductive material does not contribute to the charge / discharge capacity of the battery, or the contribution ratio is extremely small, the energy density per weight of the battery can be reduced by using a conductive material in a fiber shape or flat shape with a low bulk density. Can be high.
  • the conductive material preferably contains carbon.
  • carbon that does not substantially burn off at the temperature at which the unfired laminated body constituting the all-solid battery is fired to remove organic substances is used, carbon remains even after the laminated body is fired. It can suppress that an electric effect falls.
  • the carbon that does not substantially burn out may be carbon that does not burn out completely, and does not need to be carbon that does not burn at the temperature at which the laminate is fired to remove organic substances.
  • At least one layer constituting the positive electrode layer 11, the negative electrode layer 12, and the current collector layer 14 includes another conductive body having a shape different from that of the conductive body. It is preferable that another electroconductive body of a different shape is a particle shape. By doing in this way, since connection of said electroconductive bodies can be reinforced with another electroconductive body of particle shape, current collection performance can be improved.
  • the particle-shaped conductive body may be any material having electronic conductivity, such as carbon, metal, and oxide.
  • the ceramic contains a lithium-containing phosphate compound.
  • the lithium-containing phosphate compound is preferably a lithium-containing phosphate compound having at least one of a NASICON structure and an olivine structure.
  • the ceramics contained in the positive electrode layer 11, the negative electrode layer 12, and the current collector layer 14 and the lithium-containing phosphate compound contained in the solid electrolyte are preferably lithium-containing phosphate compounds containing a common component element. , They may not have the same composition.
  • the ceramic is not limited to a lithium-containing phosphate compound as long as it is a material that is sintered at a temperature at which the laminate is fired.
  • the positive electrode layer 11, the negative electrode layer 12, and the current collector layer 14 include a solid electrolyte material constituting the solid electrolyte layer 13.
  • the solid electrolyte material is preferably a lithium-containing phosphate compound having at least one of a NASICON structure and an olivine structure.
  • the solid electrolyte material may be a glass phase in which a crystal phase of a lithium-containing phosphate compound having at least one of a NASICON structure and an olivine structure is deposited by firing.
  • the solid electrolyte material contained in the positive electrode layer 11, the negative electrode layer 12, the current collector layer 14, and the solid electrolyte layer 13 is a lithium-containing phosphate compound containing a common component element, but may not have the same composition. .
  • the unsintered laminated body for an all-solid battery of the present invention includes an unsintered electrode layer that is an unsintered body of at least one of the positive electrode layer 11 and the negative electrode layer 12, and one side of the unsintered electrode layer.
  • At least one layer constituting the unfired electrode layer and the unfired current collector layer has a plurality of conductive bodies each having a major axis and a minor axis, and the ratio of the major axis to the minor axis is larger than 1. Including. In most of the plurality of conductive bodies, the direction in which the major axis extends is oriented substantially perpendicular to the stacking direction.
  • the green electrode layer, the green solid electrolyte layer, and the green current collector layer may have the form of a green sheet or a printed layer.
  • an unfired body that is an unfired body of at least one of the positive electrode layer 11 or the negative electrode layer 12 is used.
  • the green electrode layer, the green solid electrolyte layer, and the green current collector layer may have the form of a green sheet or a printed layer.
  • an unsintered solid electrolyte layer is laminated on one side of the unsintered electrode layer, and an unsintered current collector layer is laminated on the other side of the unsintered electrode layer to form a laminate (laminated body forming step). And the obtained laminated body is baked (baking process). The current collector layer 14 and the positive electrode layer 11 and / or the negative electrode layer 12 and the solid electrolyte layer 13 are joined by firing. Finally, the fired laminate is sealed, for example, in a coin cell.
  • the sealing method is not particularly limited. For example, you may seal the laminated body after baking with resin. Alternatively, an insulating paste having an insulating property such as Al 2 O 3 may be applied or dipped around the laminate, and the insulating paste may be heat-treated for sealing.
  • a conductive layer such as a metal layer may be formed on the current collector layer.
  • the method for forming the conductive layer include a sputtering method.
  • the metal paste may be applied or dipped and heat-treated.
  • the unfired bodies of the current collector layer 14, the positive electrode layer 11, the solid electrolyte layer 13, the negative electrode layer 12, and the current collector layer 14 are laminated to form a single cell structure. It is preferable to form a green laminate.
  • a plurality of laminated bodies having the single cell structure described above are laminated with the unfired body of the current collector layer 14 interposed therebetween. It may be formed. In this case, a plurality of laminates having a single battery structure may be laminated electrically in series or in parallel.
  • the method for forming the unfired electrode layer, the unfired solid electrolyte layer, and the unfired current collector layer is not particularly limited, but a doctor blade method, a die coater, a comma coater, or the like, or printing to form a green sheet Screen printing or the like can be used to form the layer.
  • the method for laminating the green electrode layer, the green solid electrolyte layer, and the green current collector layer is not particularly limited, but a hot isostatic press, a cold isostatic press, an isostatic press, or the like is used.
  • an unsintered electrode layer, an unsintered solid electrolyte layer, and an unsintered current collector layer can be laminated.
  • a slurry for forming a green sheet or printed layer is prepared by wet-mixing an organic vehicle in which an organic material is dissolved in a solvent and a positive electrode material, a negative electrode material, a solid electrolyte material, or a current collector material.
  • 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 organic material contained in the slurry is not particularly limited, and polyvinyl acetal resin, cellulose resin, acrylic resin, urethane resin, vinyl acetate resin, polyvinyl alcohol resin, and the like can be used.
  • the slurry may contain a plasticizer.
  • plasticizer is not particularly limited, phthalic acid esters such as dioctyl phthalate and diisononyl phthalate may be used.
  • most of the plurality of conductive bodies are oriented so that the direction in which the major axis extends is substantially perpendicular to the stacking direction, for example, the line of a comma coater It is possible by increasing the speed, i.e. by increasing the application speed of the slurry.
  • 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 type of the electrode active material contained in the positive electrode layer 11 or negative electrode layer 12 of the all-solid battery stack 10, 20, 30 of the present invention is not limited, as the positive electrode active material, Li 3 V 2 (PO 4 ) Lithium-containing phosphate compounds having a nasic structure such as 3; Lithium-containing phosphate compounds having an olivine structure such as LiFePO 4 and LiMnPO 4 , LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2, etc.
  • a lithium-containing compound having a spinel structure such as LiMn 2 O 4 or LiNi 0.5 Mn 1.5 O 4 can be used.
  • MOx 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 ⁇ 2.5.
  • a compound having a composition represented by the following formula can be used. For example, it may be used a mixture prepared by mixing two or more active material having a composition represented by MOx containing different element M of such TiO 2 and SiO 2.
  • the lithium containing phosphoric acid containing the common component element contained in the positive electrode layer 11, the negative electrode layer 12, the electrical power collector layer 14, and the solid electrolyte layer 13 of the all-solid-state battery laminated body 10, 20, 30 of this invention is not limited, a lithium-containing phosphate compound having a NASICON structure or an olivine 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.
  • lithium-containing phosphate compound having an olivine type structure formula Li x M y PO 4 (in the chemical formula, x 1 ⁇ x ⁇ 2, y is a number in the range of 1 ⁇ y ⁇ 2, M is It is one or more elements selected from the group consisting of Mg, Al and Zr).
  • a part of P may be substituted with B, Si or the like, and a part of O may be substituted with F.
  • lithium-containing phosphate compound having a NASICON type structure or an olivine type structure used in the above solid electrolyte
  • a glass in which a crystal phase of a lithium-containing phosphate compound having a NASICON structure or an olivine structure is precipitated by heat treatment may be used.
  • a material having ion conductivity and small enough to have negligible electronic conductivity is used as the material used for the solid electrolyte. Is possible. 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 11, the solid electrolyte layer 13, and the negative electrode layer 12 of the all-solid battery laminate 10, 20, 30 of the present invention is a lithium-containing phosphorus having a NASICON structure or an olivine structure. It is preferable to include a solid electrolyte made of an acid compound. In this case, high ion conductivity that is essential for battery operation of an all-solid battery can be obtained.
  • a glass or glass ceramic having a composition of a lithium-containing phosphate compound having a NASICON structure or an olivine structure is used as a solid electrolyte, a denser fired body can be easily formed due to the viscous flow of the glass phase in the firing process. Since it can be obtained, it is particularly preferable to prepare a starting material for the solid electrolyte in the form of glass or glass ceramics.
  • the material forming at least one of the positive electrode layer 11 and the negative electrode layer 12 of the all-solid battery stack 10, 20, 30 of the present invention includes an electrode active material made of a lithium-containing phosphate compound.
  • 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 14 of the all-solid battery stack 10, 20, 30 of the present invention includes an electron conductive material.
  • An electron conductive material may be comprised from said electroconductive body, and may be comprised from said electroconductive body and another electroconductive body.
  • Example shown below is an example and this invention is not limited to the following Example.
  • NASICON-type lithium-containing vanadium phosphate compound Li 3 V 2 (PO 4 ) 3 ) containing 5% by weight of acetylene black as a positive electrode active material, anatase-type titanium oxide (TiO 2 ) as a negative electrode active material, solid
  • glass powder of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 that precipitates a crystal phase of a lithium-containing phosphate compound having a NASICON type structure as an electrolyte and the carbon material shown in Table 1 as a conductive material
  • Table 1 also shows organic substances used as binders for preparing the slurry.
  • the major axis of fibrous carbon 1 (VGCF) shown in Table 1 is 150 nm
  • the minor axis is 8 nm
  • the major axis of carbon 2 (VGCF-H) is 150 nm
  • the minor axis is 6 nm
  • the major axis of carbon 3 (VGCF-X) Is 15 nm and the minor axis is 3 nm.
  • the ratio of the major axis to the minor axis is greater than 1.
  • the solid electrolyte was mixed in the binder solution to prepare a solid electrolyte slurry.
  • the mixing ratio of the solid electrolyte and polyvinyl alcohol was 80:20 by weight.
  • the positive electrode active material was mixed in the binder solution to prepare a positive electrode active material slurry.
  • the mixing ratio of the positive electrode active material and polyvinyl alcohol was 80:20 by weight.
  • the negative electrode active material was mixed in the binder solution to prepare a negative electrode active material slurry.
  • the mixing ratio of the negative electrode active material and polyvinyl alcohol was 80:20 by weight.
  • Each of carbon 1 to 4 was mixed in a binder solution to prepare a slurry of carbon 1 to 4.
  • the mixing ratio of each of carbon 1 to 4 and polyvinyl alcohol was 80:20 by weight.
  • the solid electrolyte slurry, the positive electrode active material slurry, the negative electrode active material slurry, and the carbon 1 to 4 slurry obtained above were mixed in the ratios shown in Tables 2 to 4 below. 1-5, negative electrode layer no. 1 to 5 and the current collector layer No. Slurries 1-7 were prepared.
  • the comma coater In the production of the solid electrolyte layer green sheet, the comma coater was formed to a thickness of 100 ⁇ m at a line speed of 100 cm / min. Positive electrode layer No. 1 to 5 and negative electrode layer no. In the production of 1 to 5 green sheets, the line speed of the comma coater was set to 100 cm / min and molded to a thickness of 50 ⁇ m. Current collector layer No. In the production of 1 to 6 green sheets, the line speed of the comma coater was set to 100 cm / min and molded to a thickness of 10 ⁇ m. Current collector layer No. In the production of the green sheet No. 7, the comma coater was formed to a thickness of 10 ⁇ m at a line speed of 50 cm / min.
  • Each green sheet punched into a disk shape having a diameter of 12 mm is laminated in the order of a current collector layer 14, a positive electrode layer 11, a solid electrolyte layer 13, a negative electrode layer 12, and a current collector layer 14 as shown in FIG.
  • Thermocompression bonding was performed at a temperature of 80 ° C. and a pressure of 1 ton to produce an unfired all-solid battery stack 10.
  • the green sheets of Examples 1 to 5 and Comparative Examples 1 and 2 were produced by combining the green sheets 1 to 7, respectively.
  • the obtained all solid state battery laminate 10 was dried at a temperature of 100 ° C. to remove moisture. Then, the all-solid-state battery laminated body 10 was sealed with a 2032 type coin cell, and the all-solid-state battery was produced.
  • the current collector layer, the positive electrode layer, and the negative electrode layer contain only granular carbon 4 as a conductive material, the current collector layer, the positive electrode layer, and the negative electrode layer It is considered that the current distribution in the surface direction in the inside cannot be made uniform, so that the discharge capacity at a high current density is lowered and a low discharge capacity maintenance rate is exhibited.
  • the current collector layer No. formed with a comma coater line speed as low as 50 cm / min was used. Since the green sheet of No. 7 was used, the current collector layer, the positive electrode layer, and the negative electrode layer were all solid even though the ratio of the major axis to the minor axis contained fibrous carbon 2 larger than 1.
  • SEM scanning electron microscope
  • the present invention is particularly useful for the production of an all-solid secondary battery.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

La présente invention concerne : une batterie entièrement monolithique permettant d'augmenter la capacité de batterie en augmentant la performance de collecte de courant ; un stratifié vert de batterie entièrement monolithique et un procédé de production d'une batterie entièrement monolithique. Selon l'invention, un stratifié de batterie entièrement monolithique (10) est doté : d'une couche d'électrode qui est une couche de cathode (11) et/ou une couche d'anode (12) ; d'une couche d'électrolyte solide (13) stratifiée sur un côté de la couche d'électrode ; et d'une couche de collecteur (14) stratifiée sur l'autre côté de la couche d'électrode. Au moins une couche constituant la couche d'électrode et la couche de collecteur (14) comprend une pluralité de corps conducteurs. Les corps conducteurs de la pluralité de corps conducteurs ont tous un diamètre majeur et un diamètre mineur. La majeure partie des corps conducteurs de la pluralité des corps conducteurs est orientée dans la direction d'étendue du diamètre majeur, sensiblement perpendiculairement à la direction de stratification.
PCT/JP2013/074040 2012-09-11 2013-09-06 Batterie entièrement monolithique, stratifié vert de batterie entièrement monolithique et procédé de production de batterie entièrement monolithique WO2014042083A1 (fr)

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WO2018047946A1 (fr) * 2016-09-12 2018-03-15 富士フイルム株式会社 Matériau de couche d'électrode, feuille destinée à une électrode de batterie rechargeable entièrement solide, batterie rechargeable entièrement solide, feuille d'électrode destinée à une batterie rechargeable entièrement solide, et procédé de production d'une batterie rechargeable entièrement solide
JP2019175771A (ja) * 2018-03-29 2019-10-10 太陽誘電株式会社 全固体電池およびその製造方法
WO2019216216A1 (fr) * 2018-05-09 2019-11-14 積水化学工業株式会社 Couche collectrice pour batteries entièrement solides, batterie entièrement solide et matériau carboné
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CN113474926A (zh) * 2019-03-26 2021-10-01 株式会社村田制作所 固体电池
CN114556671A (zh) * 2019-10-11 2022-05-27 株式会社村田制作所 固体电池

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JP2016167356A (ja) * 2015-03-09 2016-09-15 Fdk株式会社 全固体電池の製造方法、及び全固体電池
WO2018047946A1 (fr) * 2016-09-12 2018-03-15 富士フイルム株式会社 Matériau de couche d'électrode, feuille destinée à une électrode de batterie rechargeable entièrement solide, batterie rechargeable entièrement solide, feuille d'électrode destinée à une batterie rechargeable entièrement solide, et procédé de production d'une batterie rechargeable entièrement solide
JPWO2018047946A1 (ja) * 2016-09-12 2019-06-24 富士フイルム株式会社 電極層材、全固体二次電池電極用シートおよび全固体二次電池ならびに全固体二次電池用電極シートおよび全固体二次電池の製造方法
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CN113474926A (zh) * 2019-03-26 2021-10-01 株式会社村田制作所 固体电池
CN114556671A (zh) * 2019-10-11 2022-05-27 株式会社村田制作所 固体电池

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