WO2013161982A1 - Batterie à électrolyte solide, et son procédé de production - Google Patents

Batterie à électrolyte solide, et son procédé de production Download PDF

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Publication number
WO2013161982A1
WO2013161982A1 PCT/JP2013/062337 JP2013062337W WO2013161982A1 WO 2013161982 A1 WO2013161982 A1 WO 2013161982A1 JP 2013062337 W JP2013062337 W JP 2013062337W WO 2013161982 A1 WO2013161982 A1 WO 2013161982A1
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WIPO (PCT)
Prior art keywords
positive electrode
lithium
electrode layer
solid
solid electrolyte
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PCT/JP2013/062337
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English (en)
Japanese (ja)
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忠朗 松村
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株式会社村田製作所
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Publication of WO2013161982A1 publication Critical patent/WO2013161982A1/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
    • H01M4/36—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • 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
    • 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 a solid state battery.
  • the present invention relates to a solid battery in which a positive electrode layer includes a lithium phosphorus composite oxide having a polyanion structure and a lithium sulfur compound.
  • a metal oxide such as lithium cobaltate as a positive electrode active material, a carbon material such as graphite as a negative electrode active material, and a lithium hexafluorophosphate dissolved in an organic solvent as an electrolyte that is, Organic solvent electrolytes are generally used.
  • a metal oxide such as lithium cobaltate as a positive electrode active material
  • a carbon material such as graphite as a negative electrode active material
  • a lithium hexafluorophosphate dissolved in an organic solvent as an electrolyte that is, Organic solvent electrolytes
  • the organic solvent used for the electrolyte is a flammable substance, there is a risk that the battery may ignite. For this reason, it is required to further increase the safety of the battery.
  • Patent Document 1 describes a solid battery using lithium ion conductive Li 2 S—SiS 2 —P 2 S 5 synthesized by mechanical milling as a solid electrolyte.
  • LiCoO 2 is used as the positive electrode active material
  • metallic lithium is used as the negative electrode active material.
  • Patent Document 1 describes that LiCoO 2 is particularly preferable because it has a large electrochemical capacity and is relatively easy to adjust the particle size depending on the grinding conditions.
  • lithium cobaltate has a large electrochemical capacity, it has a high raw material cost due to the scarcity and uneven distribution of cobalt resources, and the development of an inexpensive positive electrode active material for cost reduction is required. ing.
  • the present invention provides a solid battery having a low discharge resistance using a lithium phosphorus composite oxide having a polyanion structure as a positive electrode active material.
  • the present invention is a solid battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated, wherein the positive electrode layer includes a lithium-phosphorus composite oxide having a polyanion structure, a lithium-sulfur compound, and lithium phosphate. It is said.
  • the lithium phosphorus composite oxide has a general formula Li a M m XO b F c (M is at least one transition metal, X is B, Al, Si, P, S, Cl, Ti, One or more elements selected from V, Cr, Mo, W are preferably compounds represented by 0 ⁇ a ⁇ 3, 0 ⁇ m ⁇ 2, 2 ⁇ b ⁇ 4, 0 ⁇ c ⁇ 1). .
  • the lithium phosphorus composite oxide is at least one of lithium iron phosphate and lithium manganese phosphate. Thereby, material cost can be held down cheaply.
  • the lithium sulfur compound contained in the positive electrode layer is preferably THIO-LISICON.
  • the solid electrolyte layer of the present invention contains a sulfide solid electrolyte.
  • the solid electrolyte layer can have high ionic conductivity even at room temperature.
  • the lithium sulfur compound has a softer property than the oxide, the sulfide solid electrolyte particles are crushed and the interface area between the particles can be increased. With these effects, battery resistance can be lowered.
  • the method for producing a solid battery of the present invention comprises a positive electrode mixture preparation step of preparing a positive electrode mixture by mixing a lithium phosphorus composite oxide having a polyanion structure and a lithium sulfur compound, and heating the positive electrode mixture, A positive electrode layer manufacturing step of manufacturing a positive electrode layer; and a step of stacking the positive electrode layer and the negative electrode layer through a solid electrolyte layer to manufacture a solid battery, wherein the positive electrode layer is a lithium phosphate having a polyanion structure. It is characterized by containing a complex oxide, a lithium sulfur compound, and lithium phosphate.
  • the method for producing a solid battery of the present invention comprises a positive electrode mixture preparation step of preparing a positive electrode mixture by mixing a lithium phosphorus composite oxide having a polyanion structure and a lithium sulfur compound, and the positive electrode mixture and the solid electrolyte layer.
  • the negative electrode layer is laminated on the laminate to produce a solid battery, and the positive electrode layer contains a lithium phosphorus composite oxide having a polyanion structure, a lithium sulfur compound, and lithium phosphate.
  • the positive electrode layer contains a lithium-phosphorus composite oxide having a polyanion structure, a lithium-sulfur compound, and lithium phosphate, a solid battery having a low discharge resistance can be produced.
  • FIG. 1 is a perspective view schematically showing a battery element of a solid state battery as one embodiment of the present invention. It is a perspective view which shows typically the battery element of a solid battery as another embodiment of this invention. It is a figure which shows the X-ray-diffraction intensity characteristic of the positive electrode layer produced by the Example and comparative example of this invention.
  • a solid battery 10 of the present invention includes a positive electrode layer 11, a negative electrode layer 12, and a solid electrolyte layer 13 interposed between the positive electrode layer 11 and the negative electrode layer 12.
  • the solid battery 10 is formed in a rectangular parallelepiped shape, and is configured by a stacked body including a plurality of flat layers having a rectangular plane.
  • the solid battery 10 is formed in a cylindrical shape, and is formed of a laminated body including a plurality of disk-like 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.
  • the solid battery 10 of the present invention configured as described above is characterized in that the positive electrode layer 11 contains a lithium phosphorus composite oxide having a polyanion structure, a lithium sulfur compound, and lithium phosphate.
  • the lithium phosphorus composite oxide having a polyanion structure has a general formula Li a M m XO b F c (M is at least one transition metal, X is B, Al, Si, P, S, Cl, Ti, V And one or more elements selected from Cr, Mo, and W, and lithium compounds represented by 0 ⁇ a ⁇ 3, 0 ⁇ m ⁇ 2, 2 ⁇ b ⁇ 4, and 0 ⁇ c ⁇ 1).
  • LiFePO 4 , LiCoPO 4 , LiFe 0.5 Co 0.5 PO 4 , LiMnPO 4 , LiCrPO 4 , LiFeVO 4 , LiFeSiO 4 , LiFeSO 4 , LiTiPO 4 , LiFeBO 3 , Li 3 Fe 2 PO 4 , LiFe 0.9 Al 0.1 PO 4 , LiFePO 3.9 F 0.1 etc. corresponds to this.
  • the surface of the lithium phosphorus composite oxide is covered with a conductive material such as carbon, or the conductive material is included inside the particles.
  • composition ratio of the elements constituting the positive electrode active material is not limited to the above-described ratio, and may deviate from the stoichiometry.
  • THIO-LISICON As the lithium sulfur compound, THIO-LISICON can be used. Among these, a THIO-LISICON containing no crosslinking S such as a charging composition 80Li 2 S-20P 2 S 5 is preferable. It is possible to prevent the decomposition of the lithium sulfur compound and the generation of the resistance phase due to the cross-linking S under high temperature.
  • the negative electrode layer 12 includes, for example, graphite as a negative electrode active material, carbon materials such as hard carbon, alloy materials, sulfur, metal sulfides, and the like. Further, it includes a solid electrolyte such as a mixture of Li 2 S and P 2 S 5 which are lithium sulfur compounds and ion conductive compounds.
  • the solid electrolyte layer 13 sandwiched between the positive electrode layer 11 and the negative electrode layer 12 includes, for example, an ion conductive compound as a solid electrolyte.
  • an ion conductive compound as a solid electrolyte.
  • a sulfide solid electrolyte is preferable, and includes a mixture of Li 2 S and P 2 S 5 and the like.
  • the solid electrolyte only needs to contain at least lithium and sulfur as constituent elements. Examples of such a compound include a mixture of Li 2 S and P 2 S 5, a mixture of Li 2 S and B 2 S 3 , and the like. be able to.
  • the solid electrolyte preferably further contains phosphorus.
  • a THIO-LISICON containing no crosslinking S such as a charging composition 80Li 2 S-20P 2 S 5 is preferable.
  • the composition ratio of the elements constituting the solid electrolyte is not limited to the above-described ratio.
  • the solid battery 10 of the present invention may be used in a form in which the battery element shown in FIGS. 1 to 3 is inserted into a ceramic container, for example, as shown in FIGS. It may be used in a self-supporting form.
  • the coin-type secondary battery has been described.
  • the battery shape is not particularly limited, and can be applied to a cylindrical type, a square type, a sheet type, and the like.
  • the exterior method is not particularly limited, and a metal case, mold resin, aluminum laminate film, or the like may be used.
  • the positive electrode layer can be produced by compression molding a raw material.
  • the raw material to be the positive electrode layer is compression molded and heated to produce the positive electrode layer.
  • the positive electrode layer and the negative electrode layer can be laminated with a solid electrolyte layer interposed therebetween to produce a laminate.
  • a slurry can be produced to produce each layer.
  • a slurry to be a positive electrode layer, a negative electrode layer, and a solid electrolyte layer is prepared (slurry manufacturing step).
  • a slurry to be a positive electrode layer, a negative electrode layer, and a solid electrolyte layer is prepared (slurry manufacturing step).
  • Each layer is produced using the produced slurry.
  • each obtained layer is laminated
  • the sealing method is not particularly limited.
  • the laminate may be sealed with a resin.
  • 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 current collector layer such as a carbon layer, a metal layer, or an oxide layer may be formed on the positive electrode layer and the negative electrode layer.
  • the method for forming the current collector layer include a sputtering method.
  • the metal paste may be applied or dipped and heat-treated. Carbon sheets may be laminated.
  • a stacked body may be formed by stacking a plurality of stacked bodies having the above single cell structure with a current collector interposed therebetween.
  • a plurality of laminates having a single battery structure may be laminated electrically in series or in parallel.
  • the method for producing each layer is not particularly limited, and a doctor blade method, a die coater, a comma coater, or the like can be used to form each layer, or screen printing or the like can be used to form a printing layer.
  • the method of laminating each layer is not particularly limited, but the layers can be laminated using a hot isostatic press (HIP), a cold isostatic press (CIP), a hydrostatic press (WIP), or the like.
  • HIP hot isostatic press
  • CIP cold isostatic press
  • WIP hydrostatic press
  • the slurry can be prepared by wet-mixing an organic vehicle in which an organic material is dissolved in a solvent and (a positive electrode active material and a solid electrolyte, a negative electrode active material and a solid electrolyte, or a solid electrolyte).
  • 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 an acrylic resin that does not react with sulfide can be used.
  • the slurry may contain a plasticizer.
  • a lithium phosphorus composite oxide having a polyanion structure a lithium sulfur compound, and lithium phosphate can be mixed to produce a positive electrode layer.
  • lithium phosphate may be incorporated into the positive electrode layer by mixing with a lithium phosphorus composite oxide having a polyanion structure and heating.
  • a lithium phosphorus composite oxide having a polyanion structure and a lithium sulfur compound can be mixed to prepare a positive electrode mixture, and the positive electrode mixture can be heated to prepare a positive electrode layer.
  • a laminated body may be heated and produced.
  • the firing conditions such as the firing temperature and atmosphere for heating the positive electrode layer are not particularly limited, but it is preferably performed under conditions that do not adversely affect the characteristics of the solid state battery. It is preferable to heat at 250 ° C. or lower under vacuum conditions.
  • the lithium phosphorus composite oxide and the lithium sulfur compound are in direct contact with each other in order to facilitate the reaction between the lithium phosphorus composite oxide and the lithium sulfur compound.
  • Example shown below is an example and this invention is not limited to the following Example.
  • Example 1 Preparation of lithium sulfur compound> A lithium-sulfur compound was prepared by mechanically milling Li 2 S powder and P 2 S 5 powder, which are sulfides.
  • Li 2 S powder and P 2 S 5 powder were weighed so as to have a molar ratio of 8: 2 in an argon gas atmosphere, and placed in an alumina container.
  • An alumina ball having a diameter of 10 mm was put and the container was sealed.
  • the container was set in a mechanical milling device (Planet Ball Mill, model No. P-7, manufactured by Fritsch) and subjected to mechanical milling at a rotation speed of 370 rpm for 20 hours. Thereafter, the container was opened in an argon gas atmosphere, and 2 ml of toluene was placed in the container to seal the container. Furthermore, the mechanical milling process was performed at 200 rpm for 2 hours.
  • the slurry-like material thus obtained was filtered in an argon gas atmosphere and then vacuum-dried.
  • the obtained powder was heated at a temperature of 200 ° C. to 300 ° C. in a vacuum atmosphere to obtain a glass ceramic powder.
  • This glass ceramic powder was used as a lithium sulfur compound.
  • Lithium iron phosphate having an average particle diameter of 0.57 ⁇ m was used as the positive electrode active material.
  • lithium iron phosphate with less C on the particle surface was used.
  • C component contained in lithium iron phosphate was 1 wt% with respect to lithium iron phosphate.
  • the lithium-sulfur compound prepared above and lithium iron phosphate were weighed so as to have a weight ratio of 57:33, and mixed with a rocking mill for 1 hour.
  • the obtained mixture and the conductive agent VGCF-H (manufactured by Showa Denko KK) were weighed so as to have a weight ratio of 90:10 and mixed with a rocking mill for 1 hour to prepare a positive electrode mixture.
  • the electrically conductive agent was added so that lithium iron phosphate and a lithium sulfur compound might react easily.
  • the produced molded body was placed on a carbon crucible and heated in a vacuum state at 250 ° C. for 6 hours to produce a laminate of a positive electrode mixture and a solid electrolyte.
  • a power generation element was produced by arranging In—Li on the solid electrolyte layer side of the produced laminate. The power generation element was sandwiched between SUS plates and enclosed in a laminate container to produce a solid battery. A carbon sheet was interposed as a current collector between the positive electrode layer and the SUS plate.
  • the solid battery was charged at a constant current of 10 ⁇ A up to 6 V, discharged at a constant voltage of 10 ⁇ A up to 1 V, and it was confirmed whether charging or discharging could be performed. Furthermore, the open circuit voltage before discharge and the voltage 10 seconds after discharge were measured.
  • Discharge resistance (open circuit voltage before discharge ⁇ voltage 10 seconds after discharge) / constant current value
  • PS-08 galvanopotentiometer manufactured by Toho Giken was used. The measurement interval was 0.2 sec, and the voltage after 10 seconds was read at the point closest to 10 seconds.
  • the open circuit voltage was 3.41 V
  • the voltage 10 seconds after the discharge was 1.63 V.
  • the discharge resistance was 178 k ⁇ . From the above, reversible charging / discharging at 10 ⁇ A was possible and the discharge resistance was small.
  • Example 1 A solid battery was produced in the same manner as in Example 1 except that in the production of the laminate of the positive electrode mixture and the solid electrolyte, the molded body was used without using the heated laminate.
  • the open circuit voltage was 3.40 V, and the voltage 10 seconds after discharge was 2.10 V.
  • the discharge resistance was 260 k ⁇ . From the above, although 5 ⁇ A could be charged / discharged somehow, the battery resistance was very high.
  • FIG. 4 shows the X-ray diffraction intensity characteristics of the positive electrode layers produced in Examples and Comparative Examples of the present invention. As shown in FIG. 4, in Example 1, it turns out that it is a mixture of lithium iron phosphate, the lithium sulfur compound after a heating, and lithium phosphate. In Comparative Example 1, no lithium phosphate peak is observed.
  • a solid battery having a low discharge resistance can be obtained.

Abstract

L'invention concerne une batterie à électrolyte solide à faible résistance. La présente batterie à électrolyte solide a une couche d'électrode positive, une couche d'électrolyte solide, et une couche d'électrode négative stratifiées les unes sur les autres, et est caractérisée en ce que la couche d'électrode positive contient un oxyde complexe lithium-phosphore ayant une structure de polyanion, un composé lithium-soufre, et un phosphate de lithium. Par conséquent, il est possible de produire une batterie à électrolyte solide à faible résistance qui utilise l'oxyde complexe lithium-phosphore ayant la structure de polyanion comme matériau actif d'électrode positive.
PCT/JP2013/062337 2012-04-27 2013-04-26 Batterie à électrolyte solide, et son procédé de production WO2013161982A1 (fr)

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JP2012-102977 2012-04-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017054634A (ja) * 2015-09-08 2017-03-16 トヨタ自動車株式会社 硫化物固体電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010073539A (ja) * 2008-09-19 2010-04-02 Toyota Motor Corp 電極体及びその製造方法、並びに、リチウムイオン二次電池
JP2011233246A (ja) * 2010-04-23 2011-11-17 Toyota Motor Corp 複合正極活物質、全固体電池、および、それらの製造方法
WO2012029641A1 (fr) * 2010-09-01 2012-03-08 株式会社 村田製作所 Batterie monolithique et procédé de fabrication de celle-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010073539A (ja) * 2008-09-19 2010-04-02 Toyota Motor Corp 電極体及びその製造方法、並びに、リチウムイオン二次電池
JP2011233246A (ja) * 2010-04-23 2011-11-17 Toyota Motor Corp 複合正極活物質、全固体電池、および、それらの製造方法
WO2012029641A1 (fr) * 2010-09-01 2012-03-08 株式会社 村田製作所 Batterie monolithique et procédé de fabrication de celle-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017054634A (ja) * 2015-09-08 2017-03-16 トヨタ自動車株式会社 硫化物固体電池
US10283812B2 (en) 2015-09-08 2019-05-07 Toyota Jidosha Kabushiki Kaisha Sulfide solid-state cell

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