WO2012060349A1 - Batterie à l'état solide - Google Patents

Batterie à l'état solide Download PDF

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Publication number
WO2012060349A1
WO2012060349A1 PCT/JP2011/075137 JP2011075137W WO2012060349A1 WO 2012060349 A1 WO2012060349 A1 WO 2012060349A1 JP 2011075137 W JP2011075137 W JP 2011075137W WO 2012060349 A1 WO2012060349 A1 WO 2012060349A1
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solid
electrode layer
negative electrode
positive electrode
battery
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PCT/JP2011/075137
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English (en)
Japanese (ja)
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倍太 尾内
充 吉岡
剛司 林
邦雄 西田
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株式会社 村田製作所
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Publication of WO2012060349A1 publication Critical patent/WO2012060349A1/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
    • H01M10/056—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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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.
  • 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 an all-solid lithium secondary battery in which all components are made of solid using a nonflammable solid electrolyte.
  • an object of the present invention is to provide an all-solid-state battery capable of suppressing deterioration of characteristics due to overcharge or overdischarge.
  • An all solid state battery according to the present invention is an all solid state battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, wherein at least one of the positive electrode layer and the negative electrode layer has two or more electrodes having different oxidation-reduction potentials. Contains active material.
  • the electrode active material contained in the negative electrode layer contains two or more types of titanium oxide selected from the group consisting of rutile type titanium oxide, anatase type titanium oxide, and brookite type titanium oxide. Is preferred.
  • the electrode active material contained in the positive electrode layer contains two or more phosphate compounds having different oxidation-reduction potentials.
  • the phosphate compound is a lithium-containing phosphate compound of at least one of a NASICON structure and an olivine structure.
  • the solid electrolyte layer includes a solid electrolyte made of a lithium-containing phosphate compound having a NASICON type structure.
  • At least one of the positive electrode layer or the negative electrode layer contains a solid electrolyte made of a lithium-containing phosphate compound having a NASICON structure.
  • the all solid state battery of the present invention it is preferable that at least one of the positive electrode layer or the negative electrode layer and the solid electrolyte layer are joined by baking.
  • At least one of the positive electrode layer or the negative electrode layer and the solid electrolyte layer are joined by firing a laminate formed by laminating a plurality of green sheets.
  • At least one of the positive electrode layer or the negative electrode layer contains two or more electrode active materials having different oxidation-reduction potentials, so that even when the all solid state battery is overcharged or overdischarged, Among the electrode active materials contained in the layer or the negative electrode layer, the electrode active material having a high (low) redox potential is oxidized (reduced) in preference to a material or member such as a solid electrolyte layer constituting an all-solid battery. .
  • FIG. 1 is a perspective view schematically showing an all-solid battery as one embodiment of the present invention. It is a perspective view which shows typically an all-solid-state battery as another embodiment of this invention. It is sectional drawing which shows typically the cross-section of the laminated body which comprises the positive electrode half cell produced in the Example of this invention. It is sectional drawing which shows typically the cross-section of the laminated body which comprises the negative electrode half battery produced in the Example of this invention. It is sectional drawing which shows typically the cross-section of the laminated body which comprises the all-solid-state battery produced in the Example of this invention.
  • the all-solid battery stack 10 of the present invention includes a positive electrode layer 11, a solid electrolyte layer 13, and a negative electrode layer 12.
  • the all-solid battery stack 10 is formed in a rectangular parallelepiped shape, and is configured by a stack including a plurality of flat layers having a rectangular plane.
  • the all-solid-state battery stack 10 is formed in a cylindrical shape and is formed of a stack made of a plurality of disk-shaped layers.
  • 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.
  • Each of the positive electrode layer 11 and the negative electrode layer 12 may contain carbon, a metal, etc. as an electronically conductive material.
  • At least one of the positive electrode layer 11 or the negative electrode layer 12 includes two or more electrode active materials having different oxidation-reduction potentials.
  • the positive electrode layer 11 or the negative electrode layer 12 includes two or more electrode active materials having different oxidation-reduction potentials, even when the all solid state battery is overcharged or overdischarged, the positive electrode layer 11 or Among the electrode active materials contained in the negative electrode layer 12, the electrode active material having a high (low) oxidation (reduction) potential is oxidized in preference to a material or member such as the solid electrolyte layer 13 constituting the all-solid battery stack 10. (Reduced).
  • the material or members such as the solid electrolyte layer 13 which comprises the all-solid-state battery laminated body 10, are oxidized (reduced), and the characteristic of an all-solid-state battery, for example, a charge / discharge characteristic, deteriorates. .
  • two or more kinds of the electrode active material having different redox potential of above is not limited, as the positive electrode active material, lithium-containing phosphate compound having a NASICON-type structure such as Li 3 V 2 (PO 4) 3 Lithium-containing phosphate compounds having an olivine structure such as LiFePO 4 and LiMnPO 4 , layered compounds such as LiCoO 2 and LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiMn 2 O 4 , LiNi 0.5 Mn 1.5
  • a lithium-containing compound having a spinel structure such as O 4 or Li 4 Ti 5 O 12 can be used.
  • MOx (M includes at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb and Mo, x is 0.9 ⁇ x ⁇ 2.0.
  • a compound having a composition represented by the following formula can be used.
  • a mixture in which 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, oxidations such as Li 3 V 2 (PO 4 ) 3 , Li 3 Fe 2 (PO 4 ) 3 , Li 4 Ti 5 O 12 Can be used.
  • a lithium-containing phosphate compound having a NASICON structure can be used as the solid electrolyte.
  • 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 Represents one or more elements selected from the group consisting of Ti, Ge, Al, Ga and Zr). In this case, part of P in the above chemical formula may be substituted with B, Si, or the like.
  • a compound having two or more different compositions of a lithium-containing phosphate compound having a NASICON type structure 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 mixed. You may use the mixture.
  • 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 mixed with lithium phosphate, and Li—Si—O such as Li 4 SiO 4
  • Li—Si—O such as Li 4 SiO 4
  • Examples thereof include a compound having a lobskite structure, a compound having a garnet structure having Li, La, and Zr.
  • the two or more electrode active materials having different redox potentials contained in the negative electrode layer 12 are composed of rutile titanium oxide, anatase titanium oxide, and brookite titanium oxide. Two or more types of titanium oxide selected from the group are preferred.
  • the electrode active material contained in the negative electrode layer 12 by using two or more kinds of titanium oxides having different redox potentials as the electrode active material contained in the negative electrode layer 12, at least one of the positive electrode layer 11 or the negative electrode layer 12 and the solid electrolyte layer 13 are baked. In the case of joining, the negative electrode layer 12 can be satisfactorily sintered.
  • the two or more electrode active materials having different oxidation-reduction potentials contained in the positive electrode layer 11 may be two or more phosphate compounds having different oxidation-reduction potentials. preferable. As described above, by using two or more phosphate compounds having different redox potentials as the electrode active material contained in the positive electrode layer 11, at least one of the positive electrode layer 11 or the negative electrode layer 12 and the solid electrolyte layer 13 are fired. In the case of bonding by the positive electrode layer 11, the positive electrode layer 11 can be satisfactorily sintered.
  • the phosphate compound is a lithium-containing phosphate compound of at least one of a NASICON structure and an olivine structure. That is, any of the two or more lithium-containing phosphate compounds having different oxidation-reduction potentials may have a NASICON type structure or an olivine type structure. Further, two or more lithium-containing phosphate compounds having different oxidation-reduction potentials may be a combination of those having a NASICON type structure and those having an olivine type structure.
  • the solid electrolyte layer 13 includes a solid electrolyte made of a lithium-containing phosphate compound having a NASICON structure.
  • At least one of the positive electrode layer 11 or the negative electrode layer 12 includes a solid electrolyte made of a lithium-containing phosphate compound having a NASICON structure.
  • a molded body of a positive electrode material including a solid electrolyte and an electrode active material is produced.
  • a molded body of a negative electrode material including a solid electrolyte and an electrode active material is produced.
  • a compact of a solid electrolyte material is produced.
  • each of the molded bodies can be produced in the form of a green sheet.
  • each molded object is laminated
  • the all-solid battery laminate 10 composed of the laminate of the positive electrode layer 11, the solid electrolyte layer 13, and the negative electrode layer 12 can be formed by integral firing.
  • the firing temperature is preferably 400 ° C. or higher and 1000 ° C. or lower.
  • the method for forming the green sheet is not particularly limited, but a die coater, a comma coater, screen printing, or the like can be used.
  • the method of laminating the green sheets is not particularly limited, but the green sheets can be laminated using a hot isostatic press (HIP), a cold isostatic press (CIP), a hydrostatic press (WIP), or the like. it can.
  • the atmosphere for firing the laminate of green sheets 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 all solid state battery laminate 10 of the present invention it is preferable that at least one of the positive electrode layer 11 or the negative electrode layer 12 and the solid electrolyte layer 13 are joined by baking.
  • At least one of the positive electrode layer 11 or the negative electrode layer 12 and the solid electrolyte layer 13 are joined by firing a laminate formed by laminating a plurality of green sheets.
  • Example shown below is an example and this invention is not limited to the following Example.
  • each slurry was produced as follows, and each slurry was used. Each green sheet was prepared.
  • ⁇ Preparation of slurry> ⁇ Preparation of Solid Electrolyte Slurry> First, a glass powder having a composition of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 as a main material, a binder and a solvent are made to have a mass ratio of 100: 15: 140. A solid electrolyte slurry was prepared by weighing and mixing.
  • Electrode Active Material Slurry 1 A powder having a crystal phase of NASICON structure having a composition of Li 3 V 2 (PO 4 ) 3 and a carbon powder as an electronic conductive material is in a mass ratio of 80:20.
  • the electrode active material slurry 1 was produced using the powder mixed in the above as the main material.
  • Electrode Active Material Slurry 2 In the same manner as in the production process of the electrode active material slurry 1 described above, a powder having an anatase-type titanium oxide crystal phase and a carbon powder as an electronic conductive material were mixed with 80:20. An electrode active material slurry 2 was prepared using a powder mixed at a mass ratio of 1 as a main material.
  • Electrode Active Material Slurry 3 In the same manner as in the production process of electrode active material slurry 1 described above, a powder having a rutile-type titanium oxide crystal phase and a carbon powder as an electronic conductive material were mixed with 80:20. The electrode active material slurry 3 was produced using the powder mixed at a mass ratio of 1 as the main material.
  • Electrode Active Material Slurry 4 In the same manner as in the preparation process of the electrode active material slurry 1, a powder having an olivine type crystal phase having a composition of LiFePO 4 and a carbon powder as an electronic conductive material are prepared. Electrode active material slurry 4 was produced using powder mixed at a mass ratio of 80:20 as a main material.
  • Electrode Active Material Slurry 5 In the same manner as the production process of the electrode active material slurry 1, the powder having an olivine structure crystal phase having a composition of LiFe 0.5 Mn 0.5 PO 4 and an electronic conductive material An electrode active material slurry 5 was prepared using as a main material a powder obtained by mixing the above carbon powder at a mass ratio of 80:20.
  • Electrode Slurry 1 The solid electrolyte slurry prepared above and the electrode active material slurry 1 were mixed at a mass ratio of 50:50 to prepare an electrode slurry 1.
  • Electrode Slurry 2 The solid electrolyte slurry prepared above, the electrode active material slurry 2 and the electrode active material slurry 3 were mixed at a mass ratio of 50:40:10 to prepare an electrode slurry 2.
  • Electrode Slurry 3 The solid electrolyte slurry prepared above and the electrode active material slurry 2 were mixed at a mass ratio of 50:50 to prepare an electrode slurry 3.
  • Electrode Slurry 4 The solid electrolyte slurry prepared above, the electrode active material slurry 4 and the electrode active material slurry 5 were mixed at a mass ratio of 50:25:25 to prepare an electrode slurry 4.
  • Electrode Slurry 5 The solid electrolyte slurry prepared above and the electrode active material slurry 4 were mixed at a mass ratio of 50:50 to prepare an electrode slurry 5.
  • Electrode Green Sheet 1 ⁇ Preparation of Electrode Green Sheet 1>
  • the electrode slurry 1 prepared as described above is applied onto a PET film, and the electrode green sheet 1 has a thickness of 40 ⁇ m. Was made.
  • Electrode Green Sheet 2 ⁇ Preparation of Electrode Green Sheet 2>
  • the electrode slurry 2 prepared above is applied onto a PET film, and the electrode green sheet 2 is formed to have a thickness of 14 ⁇ m. Was made.
  • Electrode Green Sheet 3 ⁇ Preparation of Electrode Green Sheet 3> In the same manner as the solid electrolyte green sheet preparation process, the electrode slurry 3 prepared above is applied onto a PET film, and the electrode green sheet 3 has a thickness of 14 ⁇ m. Was made.
  • Electrode Green Sheet 4 ⁇ Preparation of Electrode Green Sheet 4> In the same manner as the above-described solid electrolyte green sheet preparation process, the electrode slurry 4 prepared above is applied onto a PET film, and the electrode green sheet 4 is formed to have a thickness of 22 ⁇ m. Was made.
  • Electrode Green Sheet 5 ⁇ Preparation of Electrode Green Sheet 5>
  • the electrode slurry 5 prepared above is applied onto a PET film, and the electrode green sheet 5 is formed to have a thickness of 22 ⁇ m. Was made.
  • Example 1 ⁇ Preparation of Sintered Body 1 as Positive Electrode Layer>
  • Ten electrode green sheets 1 peeled from the PET film were stacked and pressed at a temperature of 60 ° C. for pressure bonding.
  • the obtained green sheet laminate was cut to a size of 10 mm ⁇ 10 mm, sandwiched between two porous ceramic plates, and baked at a temperature of 500 ° C. in an air atmosphere to remove the binder, and then nitrogen.
  • Sintered body 1 as a positive electrode layer for X-ray diffraction measurement was produced by sintering at a temperature of 450 ° C. in a gas atmosphere.
  • the sintered body 2 as a negative electrode layer for X-ray diffraction measurement is prepared in the same manner as the above-described manufacturing process of the sintered body 1. did.
  • the XRD pattern of the sintered body 1 as the positive electrode layer is a JCPDS (Joint Committee on Powder Diffraction Standards) card of Li 3 Fe 2 (PO 4 ) 3 having the same NASICON type structure as Li 3 V 2 (PO 4 ) 3 ( Card number 80-1517), and a JCPDS card of LiGe 2 (PO 4 ) 3 (card number 80-1923).
  • JCPDS Joint Committee on Powder Diffraction Standards
  • the XRD pattern of the sintered body 2 as the negative electrode layer includes an anatase-type titanium oxide JCPDS card (card number 21-1272), a rutile-type titanium oxide JCPDS card (card number 21-1276), and LiGe 2 (PO 4 ) Matched 3 JCPDS cards (card number 80-1923).
  • ⁇ Preparation of sintered body 5 constituting all-solid-state battery 1> Four solid electrolyte green sheets peeled from the PET film are laminated, and pressed and pressed at a temperature of 60 ° C. to obtain a solid electrolyte green sheet laminate. Formed. One electrode green sheet 1 peeled from the PET film was laminated on one surface of the solid electrolyte green sheet laminate, and pressed and pressed at a temperature of 60 ° C. to form a positive electrode green sheet layer. One electrode green sheet 2 peeled from the PET film was laminated on the other surface of the solid electrolyte green sheet laminate on which the positive electrode green sheet layer was not formed, and pressed to form a negative electrode green sheet layer.
  • the obtained green sheet laminate is cut in the same manner as in the production process of the sintered body 1, the binder is removed, and then sintered, so that the positive electrode layer and the solid constituting the all-solid battery 1 are sintered.
  • a sintered body 5 composed of an electrolyte layer and a negative electrode layer was produced.
  • ⁇ Preparation of Positive Electrode Half Battery 1> Using the sintered body 3 produced as described above, in order to efficiently draw current from the positive electrode layer 11 as shown in FIG. After the platinum (Pt) layer as the electric layer 14 was formed, it was dried at a temperature of 100 ° C. to remove moisture. After that, a polymethyl methacrylate (PMMA) gel electrolyte 131 containing Li ions is applied on the metal lithium 15 as a counter electrode, and the metal lithium 15 is placed so that the surface of the solid electrolyte layer 13 is in contact with the gel electrolyte 131. By laminating, a positive electrode half-cell stack 110 was produced. The positive electrode half-cell stack 110 was sealed with a 2032 type coin cell to produce a positive electrode half-cell 1.
  • PMMA polymethyl methacrylate
  • the negative electrode half battery 1 is manufactured in the same manner as the positive electrode half battery 1 except that the sintered body 4 prepared above is used instead of the sintered body 3. Produced. As shown in FIG. 5, in order to efficiently draw current from the negative electrode layer 12, a platinum (Pt) layer as the current collecting layer 14 was formed on the negative electrode layer 12 by sputtering. The metal lithium 15 was laminated so that the surface of the solid electrolyte layer 13 was in contact with the PMMA gel electrolyte 131 to produce a negative electrode half-cell laminate 120. The negative electrode half battery stack 120 was sealed with a 2032 type coin cell to prepare the negative electrode half battery 1.
  • the negative electrode half-cell 1 was charged with a charging current of 10 ⁇ A and a lower limit voltage of 1.2 V (held at 1.2 V for 3 hours after reaching 1.2 V) and discharged at a discharge current of 10 ⁇ A and an upper limit voltage of 3 V .
  • the charge / discharge curve of the second cycle is shown in FIG.
  • a decrease in voltage due to insertion of lithium into titanium oxide used as the negative electrode active material is defined as charging
  • a rise in voltage due to lithium desorption from titanium oxide is defined as discharge.
  • the charge capacity of the negative electrode half-cell 1 was 310 ⁇ Ah, of which the charge capacity of anatase-type titanium oxide was 230 ⁇ Ah and the charge capacity of rutile-type titanium oxide was 80 ⁇ Ah.
  • the positive electrode half-cell 1 was charged at a charging current of 10 ⁇ A and an upper limit voltage of 4.5 V (held at 4.5 V for 3 hours after reaching 4.5 V), and discharged at a discharge current of 10 ⁇ A and a lower limit voltage of 3 V. .
  • charging is performed when the voltage rises due to lithium desorption from Li 3 V 2 (PO 4 ) 3 used as the positive electrode active material, and the voltage is increased by inserting lithium into Li 3 V 2 (PO 4 ) 3 .
  • the descending is defined as discharge.
  • the charge capacity of the positive electrode half battery 1 determined from the charge curve at the second cycle was 320 ⁇ Ah.
  • the all-solid-state battery 1 was charged with a charging current of 10 ⁇ A and an upper limit voltage of 3.3 V (held at 3.3 V for 3 hours after reaching 3.3 V), and discharged with a discharge current of 10 ⁇ A and a lower limit voltage of 0 V. .
  • the charge capacity of the positive electrode layer is 320 ⁇ Ah
  • the charge capacity of the negative electrode layer is 230 ⁇ Ah when charged to anatase-type titanium oxide and 310 ⁇ Ah when charged to rutile-type titanium oxide.
  • the negative electrode layer is overcharged with a charge capacity of 230 ⁇ Ah or more, and the rutile titanium oxide is charged.
  • the charge / discharge curve of the second cycle is shown in FIG.
  • the charge capacity of the all-solid battery 1 is 300 ⁇ Ah, and the discharge curve of the all-solid battery 1 has a good shape with a gentle slope despite the negative electrode layer being overcharged.
  • the discharge capacity of the all-solid-state battery 1 is 275 ⁇ Ah, 92% of the capacity is discharged with respect to the charge capacity.
  • the all-solid-state battery 1 is provided with a negative electrode layer containing two electrode active materials having different oxidation-reduction potentials, so that even when the all-solid-state battery 1 is overcharged, the charge / discharge characteristics of the all-solid-state battery 1 are improved. It was confirmed that there was no significant deterioration.
  • Example 2 ⁇ Preparation of Sintered Body 6 as Positive Electrode Layer> After the binder was removed by firing the green sheet laminate in an air atmosphere at a temperature of 500 ° C., the temperature was 700 ° C. in a nitrogen gas atmosphere. A sintered body 6 was produced as a positive electrode layer for X-ray diffraction measurement in the same manner as the production process of the sintered body 1 except that the sintered body 1 was sintered.
  • Sintered Body 7 as Negative Electrode Layer Sintered body as a negative electrode layer for X-ray diffraction measurement in the same manner as the sintered body 6 except that the electrode green sheet 3 was used. 7 was produced.
  • the XRD pattern of the sintered body 6 as the positive electrode layer is as follows: Li 3 Fe 2 (PO 4 ) 3 (card number 80-1517) and LiGe 2 (PO 4 ) 3 JCPDS card (card number 80-1923)
  • the sintered body 6 contained crystals of Li 3 V 2 (PO 4 ) 3 and LiGe 2 (PO 4 ) 3 . That is, the sintered body 6 was confirmed to contain the same crystals as the sintered body 1 although the sintering temperature was higher by 50 ° C. than the sintered body 1.
  • the XRD pattern of the sintered body 7 as the negative electrode layer is as follows. JCPDS card of anatase type titanium oxide (card number 21-1272), JCPDS card of rutile type titanium oxide (card number 21-1276), and LiGe 2 (PO 4 ) Matched 3 JCPDS cards (card number 80-1923). It is considered that a part of the anatase-type titanium oxide changed into rutile-type titanium oxide during sintering.
  • Negative electrode half-cell in the same manner as sintered body 8 except that electrode green sheet 3 prepared above was used instead of electrode green sheet 1.
  • a sintered body 9 comprising a solid electrolyte layer and a negative electrode layer constituting 2 was produced.
  • ⁇ Preparation of sintered body 10 constituting all-solid-state battery 2> Four solid electrolyte green sheets peeled from the PET film are laminated, and pressed and pressed at a temperature of 60 ° C. to obtain a solid electrolyte green sheet laminate. Formed.
  • One electrode green sheet 1 peeled from the PET film was laminated on one surface of the solid electrolyte green sheet laminate, and pressed and pressed at a temperature of 60 ° C. to form a positive electrode green sheet layer.
  • One electrode green sheet 3 peeled from the PET film was laminated on the other surface of the solid electrolyte green sheet laminate on which the positive electrode green sheet layer was not formed, and pressed to form a negative electrode green sheet layer.
  • the obtained green sheet laminate is cut in the same manner as in the production process of the sintered body 6, the binder is removed, and then sintered, so that the positive electrode layer and the solid constituting the all-solid battery 2 are sintered.
  • a sintered body 10 composed of an electrolyte layer and a negative electrode layer was produced.
  • the positive electrode half battery 2 was prepared in the same manner as the positive electrode half battery 1 except that the sintered body 8 prepared above was used instead of the sintered body 3. Produced.
  • the negative electrode half battery 2 was prepared in the same manner as the negative electrode half battery 1 except that the sintered body 9 prepared above was used instead of the sintered body 4. Produced.
  • the all-solid battery 2 is prepared in the same manner as the above-described all-solid battery 1 except that the sintered body 10 prepared above is used instead of the sintered body 5. Produced.
  • a charging capacity of about 135 mAh / g with anatase-type titanium oxide was confirmed near 2.0 V, and a charging capacity of about 75 mAh / g with rutile-type titanium oxide was confirmed on the lower voltage side than 2.0 V. That is, in the negative electrode half-cell 2, since charging by insertion of lithium into the rutile type titanium oxide is preferentially performed after charging by insertion of lithium into the anatase type titanium oxide, the negative electrode layer was overcharged. Even in the case, it was confirmed that rutile titanium oxide absorbs the capacity due to overcharge. At this time, the charge capacity of the negative electrode half-cell 2 was 310 ⁇ Ah, of which the charge capacity of anatase-type titanium oxide was 200 ⁇ Ah and the charge capacity of rutile-type titanium oxide was 110 ⁇ Ah.
  • the all solid state battery 2 was charged and discharged in the same manner as the all solid state battery 1.
  • the charge / discharge curve of the second cycle is shown in FIG.
  • the charge capacity of the all solid state battery 2 is 300 ⁇ Ah, and the discharge curve of the all solid state battery 2 has a good shape with a gentle slope even though the negative electrode layer is overcharged. Further, since the discharge capacity of the all-solid-state battery 2 is 260 ⁇ Ah, 87% of the capacity is discharged with respect to the charge capacity.
  • Example 3 ⁇ Preparation of Sintered Body 12 as Negative Electrode Layer> After removing the binder by firing the laminate of green sheets at a temperature of 500 ° C. in a nitrogen gas atmosphere containing 0.1% by volume of hydrogen gas, Except for sintering at a temperature of 700 ° C. in a nitrogen gas atmosphere containing 0.1% by volume of hydrogen gas, as the negative electrode layer for X-ray diffraction measurement, in the same manner as the production process of the sintered body 7 A sintered body 12 was produced.
  • the XRD pattern of the sintered body 11 as the positive electrode layer is as follows: LiMnPO 4 JCPDS card (card number 74-0375), LiFePO 4 JCPDS card (card number 83-2092), and LiGe 2 (PO 4 ) 3 JCPDS. Matched the card (card number 80-1923).
  • the XRD pattern of the sintered body 12 as the negative electrode layer includes an anatase-type titanium oxide JCPDS card (card number 21-1272), a rutile-type titanium oxide JCPDS card (card number 21-1276), and LiGe 2 (PO 4). ) Matched 3 JCPDS cards (card number 80-1923). Similar to the sintered body 7, it is considered that a part of the anatase-type titanium oxide changed into a rutile-type titanium oxide during sintering.
  • Binder is removed by firing a laminate of green sheets at a temperature of 500 ° C. in a nitrogen gas atmosphere containing 0.1% by volume of hydrogen gas. After that, the negative electrode half-cell 3 was formed in the same manner as the above-described manufacturing process of the sintered body 9 except that sintering was performed at a temperature of 700 ° C. in a nitrogen gas atmosphere containing 0.1% by volume of hydrogen gas. A sintered body 14 composed of the solid electrolyte layer and the negative electrode layer to be formed was produced.
  • the positive electrode half battery 3 was prepared in the same manner as the positive electrode half battery 1 except that the sintered body 13 prepared above was used instead of the sintered body 3. Produced.
  • the negative electrode half battery 3 was prepared in the same manner as in the preparation process of the negative electrode half battery 1 except that the sintered body 14 prepared above was used instead of the sintered body 4. Produced.
  • the all-solid battery 3 is manufactured in the same manner as the above-described all-solid battery 1 except that the sintered body 15 prepared above is used instead of the sintered body 5. Produced.
  • the positive electrode half battery 3 was charged in the same manner as the positive electrode half battery 1, except that the upper limit voltage was 4.6 V (maintained at 4.6 V for 3 hours after reaching 4.6 V). Discharge was performed. Here, the voltage rises due to lithium desorption from LiFePO 4 and LiMn 0.5 Fe 0.5 PO 4 used as the active material of the positive electrode, and the voltage is increased by insertion of lithium into LiFePO 4 and LiMn 0.5 Fe 0.5 PO 4 . The descending is defined as discharge. The charge / discharge curve of the second cycle is shown in FIG. The horizontal axis of FIG.
  • FIG. 11 shows the capacity [mAh / g] per gram with respect to the total amount (mass) of LiFePO 4 and LiMn 0.5 Fe 0.5 PO 4 contained in the positive electrode layer.
  • a charging capacity of about 125 mAh / g with LiFePO 4 was found near 3.5 V, and a charging capacity of about 35 mAh / g with LiFe 0.5 Mn 0.5 PO 4 was found on the higher voltage side than 3.5 V.
  • the positive electrode half-cell 3 is preferentially charged by the desorption of lithium from LiFe 0.5 Mn 0.5 PO 4 after the charge due to the desorption of lithium from LiFePO 4 is completed.
  • LiFe 0.5 Mn 0.5 PO 4 absorbs the capacity due to overcharge.
  • the charge capacity of the positive electrode half-cell 3 was 315 ⁇ Ah, of which the charge capacity of LiFePO 4 was 245 ⁇ Ah and the charge capacity of LiFeMnPO 4 was 70 ⁇ Ah.
  • the negative electrode half battery 3 was charged and discharged in the same manner as the negative electrode half battery 1.
  • the charge capacity of the negative electrode half battery 3 obtained from the charge curve in the second cycle is 310 ⁇ Ah, which is the same as that of the negative electrode half battery 2, of which the charge capacity of anatase-type titanium oxide is 200 ⁇ Ah and the charge capacity of rutile-type titanium oxide is 110 ⁇ Ah there were.
  • the all solid state battery 3 was charged in the same manner as the all solid state battery 1 except that the upper limit voltage was 3.4 V (held at 3.4 V after reaching 3.4 V for 3 hours). Discharge was performed.
  • the charge / discharge curve of the second cycle is shown in FIG.
  • the charge capacity of the all-solid-state battery 3 is 295 ⁇ Ah, and the discharge curve of the all-solid-state battery 3 has a good shape with a gentle slope even though the positive electrode layer and the negative electrode layer are overcharged.
  • the discharge capacity of the all-solid-state battery 3 is 260 ⁇ Ah, 88% of the capacity is discharged with respect to the charge capacity.
  • the all-solid-state battery 3 is provided with a positive electrode layer and a negative electrode layer containing two electrode active materials having different oxidation-reduction potentials, so that even when the all-solid-state battery 3 is overcharged, It was confirmed that the discharge characteristics were not significantly deteriorated.
  • X-ray diffraction is performed in the same manner as the sintered body 16 except that the electrode green sheet 3 prepared above is used instead of the electrode green sheet 5.
  • a sintered body 17 as a negative electrode layer for measurement was produced.
  • the XRD pattern of the sintered body 16 as the positive electrode layer coincided with the LiFePO 4 JCPDS card (card number 83-2092) and the LiGe 2 (PO 4 ) 3 JCPDS card (card number 80-1923).
  • the XRD pattern of the sintered body 17 as the negative electrode layer coincided with the JCPDS card (card number 21-1272) of anatase type titanium oxide and the JCPDS card (card number 80-1923) of LiGe 2 (PO 4 ) 3 . . Since sintered body 17 has a lower firing temperature than sintered body 7 and sintered body 12, it is considered that the phase change from anatase-type titanium oxide to rutile-type titanium oxide was suppressed.
  • the positive electrode half battery 4 is manufactured in the same manner as the positive electrode half battery 1 except that the sintered body 18 prepared above is used instead of the sintered body 3. Produced.
  • the negative electrode half battery 4 was prepared in the same manner as the negative electrode half battery 1 except that the sintered body 19 prepared above was used instead of the sintered body 4. Produced.
  • the reason why a plurality of the solid electrolyte green sheets are laminated is to give sufficient mechanical strength to the sintered solid electrolyte layer and facilitate the handling of the solid electrolyte layer in the subsequent process. It is. There is no particular problem even if the solid electrolyte layer is formed with a single green sheet without laminating a plurality of solid electrolyte green sheets.
  • the number of electrode green sheets used to form the positive electrode layer and the number of electrode green sheets used to form the negative electrode layer, or the thickness of each of the positive electrode layer and the negative electrode layer are determined depending on the electrode active material used. It can change suitably according to material.
  • the laminate was prepared by cutting the green sheet laminate into predetermined dimensions
  • the laminate may be produced by laminating green sheets that have been cut into predetermined dimensions in advance.
  • the cutting method is not particularly limited, and a die or the like can be used.
  • the sintering temperature and atmosphere can be appropriately changed according to the type of binder, solid electrolyte, and electrode active material used.
  • the material for the current collecting layer is not particularly limited as long as it has electron conductivity, and the method for forming the current collecting layer is not particularly limited.
  • the material having electron conductivity metal, carbon, conductive oxide, or the like can be used.
  • a method for forming the current collecting layer in addition to vacuum vapor deposition and chemical vapor deposition (CVD), a slurry of an electron conductive material or the like was applied or dipped on the outer surface of each of the positive electrode layer and the negative electrode layer. Thereafter, it may be formed by heat treatment.
  • CVD chemical vapor deposition
  • an all solid state secondary battery capable of suppressing deterioration of charge / discharge characteristics can be provided.

Abstract

La présente invention concerne une batterie à l'état solide, capable de supprimer la détérioration des caractéristiques dues à une surcharge ou à une décharge accélérée. Une pile de batteries à l'état solide (10) est munie d'une couche d'électrode positive (11), d'une couche d'électrolyte solide (13) et d'une couche d'électrode négative (12). La couche d'électrode positive (11) et/ou la couche d'électrode négative (12) contient deux matériaux d'électrode active ou plus qui ont des potentiels d'oxydo-réduction différents.
PCT/JP2011/075137 2010-11-02 2011-11-01 Batterie à l'état solide WO2012060349A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013190930A1 (fr) * 2012-06-20 2013-12-27 トヨタ自動車株式会社 Système de batterie, procédé de fabrication de système de batterie, et appareil de commande de batterie
JP2016039006A (ja) * 2014-08-06 2016-03-22 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． リチウムイオン二次電池
CN112751076A (zh) * 2019-10-30 2021-05-04 太阳诱电株式会社 全固体电池
US11764407B2 (en) 2017-11-21 2023-09-19 Samsung Electronics Co., Ltd. All-solid-state secondary battery including anode active material alloyable with lithium and method of charging the same
US11824155B2 (en) 2019-05-21 2023-11-21 Samsung Electronics Co., Ltd. All-solid lithium secondary battery and method of charging the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001307730A (ja) * 2000-04-25 2001-11-02 Sony Corp 正極及び非水電解質電池
JP2002216755A (ja) * 2001-01-22 2002-08-02 Denso Corp 非水電解質二次電池
WO2004095607A2 (fr) * 2003-04-03 2004-11-04 Valence Technology, Inc. Electrodes comportant des particules actives melangees
JP2006216336A (ja) * 2005-02-02 2006-08-17 Geomatec Co Ltd 薄膜固体二次電池
WO2008047898A1 (fr) * 2006-10-20 2008-04-24 Ishihara Sangyo Kaisha, Ltd. dispositif de stockage
JP2008226666A (ja) * 2007-03-13 2008-09-25 Ngk Insulators Ltd 全固体電池用の固体電解質構造体の製造方法、及び全固体電池の製造方法
JP2009093968A (ja) * 2007-10-10 2009-04-30 Seiko Epson Corp 全固体リチウム二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001307730A (ja) * 2000-04-25 2001-11-02 Sony Corp 正極及び非水電解質電池
JP2002216755A (ja) * 2001-01-22 2002-08-02 Denso Corp 非水電解質二次電池
WO2004095607A2 (fr) * 2003-04-03 2004-11-04 Valence Technology, Inc. Electrodes comportant des particules actives melangees
JP2006216336A (ja) * 2005-02-02 2006-08-17 Geomatec Co Ltd 薄膜固体二次電池
WO2008047898A1 (fr) * 2006-10-20 2008-04-24 Ishihara Sangyo Kaisha, Ltd. dispositif de stockage
JP2008226666A (ja) * 2007-03-13 2008-09-25 Ngk Insulators Ltd 全固体電池用の固体電解質構造体の製造方法、及び全固体電池の製造方法
JP2009093968A (ja) * 2007-10-10 2009-04-30 Seiko Epson Corp 全固体リチウム二次電池

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013190930A1 (fr) * 2012-06-20 2013-12-27 トヨタ自動車株式会社 Système de batterie, procédé de fabrication de système de batterie, et appareil de commande de batterie
JP2014002966A (ja) * 2012-06-20 2014-01-09 Toyota Motor Corp 電池システム、電池システムの製造方法、電池の制御装置
US9484596B2 (en) 2012-06-20 2016-11-01 Toyota Jidosha Kabushiki Kaisha Battery system, method for producing battery system, and battery control apparatus
JP2016039006A (ja) * 2014-08-06 2016-03-22 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． リチウムイオン二次電池
US11764407B2 (en) 2017-11-21 2023-09-19 Samsung Electronics Co., Ltd. All-solid-state secondary battery including anode active material alloyable with lithium and method of charging the same
US11929463B2 (en) 2017-11-21 2024-03-12 Samsung Electronics Co., Ltd. All-solid-state secondary battery and method of charging the same
US11824155B2 (en) 2019-05-21 2023-11-21 Samsung Electronics Co., Ltd. All-solid lithium secondary battery and method of charging the same
CN112751076A (zh) * 2019-10-30 2021-05-04 太阳诱电株式会社 全固体电池
CN112751076B (zh) * 2019-10-30 2024-04-26 太阳诱电株式会社 全固体电池

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