WO2013161982A1 - Solid-state battery, and method for producing same - Google Patents

Solid-state battery, and method for producing same 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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positive electrode
lithium
electrode layer
solid
solid electrolyte
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PCT/JP2013/062337
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French (fr)
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/en

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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

Provided is a low-resistance solid-state battery. This solid-state battery has a positive-electrode layer, a solid-electrolyte layer, and a negative electrode layer layered on one another, and is characterized in that the positive-electrode layer contains a lithium-phosphorus complex oxide having a polyanion structure, a lithium-sulfur compound, and lithium phosphate. As a result, it is possible to provide a low-resistance solid-state battery which uses the lithium-phosphorus complex oxide having the polyanion structure as a positive-electrode active material.

Description

固体電池およびその製造方法Solid battery and manufacturing method thereof
　本発明は、固体電池に関するものである。特に正極層がポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物を含む固体電池に関するものである。 The present invention relates to a solid state battery. In particular, 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.
　近年、携帯電話、ノートパソコン、ハイブリッド電気自動車等の市場拡大に伴い、二次電池の需要が大きくなっている。その中でも、エネルギー密度が高く、充放電可能なリチウムイオン二次電池の開発が盛んに行われている。 In recent years, with the expansion of the market for mobile phones, notebook computers, hybrid electric vehicles, etc., the demand for secondary batteries has increased. Among them, development of lithium ion secondary batteries that have high energy density and can be charged and discharged has been actively conducted.
　リチウムイオン二次電池では、正極活物質としてコバルト酸リチウム等の金属酸化物、負極活物質として、黒鉛等の炭素材料、電解質として六フッ化リン酸リチウムを有機溶媒に溶解させたもの、すなわち、有機溶媒系電解液が一般に使用されている。このような構成の電池において、活物質量を増加させることにより内部エネルギーを増加させ、さらにエネルギー密度を高くし、出力電流を向上させる試みがなされている。また、電池を大型化すること、電池を車両に安全に搭載することも要求されている。 In a lithium ion secondary battery, 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. In the battery having such a configuration, an attempt has been made to increase the internal energy by increasing the amount of the active material, further increase the energy density, and improve the output current. In addition, it is required to increase the size of the battery and to safely mount the battery in the vehicle.
　しかし、上記の構成のリチウムイオン二次電池では、電解質に用いられる有機溶媒は可燃性物質であるため、電池が発火する等の危険性がある。このため、電池の安全性をさらに高めることが求められている。 However, in the lithium ion secondary battery having the above configuration, since 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.
　そこで、リチウムイオン二次電池の安全性を高めるための一つの対策として、有機溶媒系電解液に代えて固体電解質を用いることが検討されている。固体電解質として、高分子、ゲル等の有機材料、ガラス、セラミックス等の無機材料を適用することが検討され、中でも、不燃性のガラスまたはセラミックスを主成分とする無機材料を固体電解質として用いる全固体二次電池が注目されている。 Therefore, as one countermeasure for improving the safety of the lithium ion secondary battery, use of a solid electrolyte in place of the organic solvent-based electrolyte has been studied. The application of organic materials such as polymers and gels, and inorganic materials such as glass and ceramics as solid electrolytes has been studied. Among them, all solids using non-flammable glass or ceramics as the main component are used as solid electrolytes. Secondary batteries are attracting attention.
　例えば、特許文献１に、固体電解質に、メカニカルミリング処理により合成されるリチウムイオン導電性のＬｉ2Ｓ－ＳｉＳ2－Ｐ2Ｓ5を用いた固体電池が記載されている。特許文献１では、正極活物質にＬｉＣｏＯ2、負極活物質に金属リチウムを用いている。特許文献１には、ＬｉＣｏＯ2は電気化学容量が大きく、粉砕条件により粒度の調整が比較的容易であるため特に好ましいことが記載されている。 For example, 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. In Patent Document 1, LiCoO 2 is used as the positive electrode active material, and 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.
特開２００５－３２７５２８号公報JP 2005-327528 A
　しかしながら、コバルト酸リチウムは、電気化学容量が大きい反面、コバルト資源の希少でかつ偏在していることから原料コスト高を招いており、低コスト化のための安価な正極活物質の開発が求められている。 However, while 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.
　そこで、本発明は、正極活物質としてポリアニオン構造を有するリチウムリン複合酸化物を用いた放電抵抗が低い固体電池を提供する。 Therefore, 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.
　本発明は、正極層、固体電解質層、負極層が積層されている固体電池であって、正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含むことを特徴としている。 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.
　これにより、放電抵抗の低い固体電池を作製することが可能となる。 This makes it possible to produce a solid battery with a low discharge resistance.
　また、本発明において、リチウムリン複合酸化物が、一般式ＬｉaＭmＸＯbＦc（Ｍは少なくとも１種以上の遷移金属、ＸはＢ、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｃｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍｏ、Ｗから選ばれる１種以上の元素、０＜ａ≦３、０＜ｍ≦２、２≦ｂ≦４、０≦ｃ≦１）で表される化合物であることが好ましい。 In the present invention, 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). .
　さらに、前記リチウムリン複合酸化物が少なくともリン酸鉄リチウムおよびリン酸マンガンリチウムのどちらか一方であることがより好ましい。これにより、材料コストを安価に抑えることができる。 Furthermore, it is more preferable that 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.
　本発明において、正極層に含まれるリチウム硫黄化合物は、ＴＨＩＯ－ＬＩＳＩＣＯＮであることが好ましい。 In the present invention, the lithium sulfur compound contained in the positive electrode layer is preferably THIO-LISICON.
　また、本発明の固体電解質層が硫化物固体電解質を含むことが好ましい。これにより、固体電解質層は、室温でも高いイオン伝導度を有することができる。また、リチウム硫黄化合物は酸化物と比べ柔らかい性質を有するため、硫化物固体電解質粒子が潰れ、粒子間の界面面積を大きくすることができる。これらの効果により、電池抵抗を低くすることができる。 Moreover, it is preferable that the solid electrolyte layer of the present invention contains a sulfide solid electrolyte. Thereby, the solid electrolyte layer can have high ionic conductivity even at room temperature. Further, since 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.
　また、本発明の固体電池の製造方法は、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とを混合し正極合剤を作製する正極合剤作製工程と、前記正極合剤を加熱し、正極層を作製する正極層作製工程と、前記正極層と負極層とを固体電解質層を介して積層して固体電池を作製する工程とを有し、前記正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含むことを特徴としている。 Moreover, 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.
　さらに、本発明の固体電池の製造方法が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とを混合し正極合剤を作製する正極合剤作製工程と、前記正極合剤と固体電解質層を積層し、正極合剤と固体電解質層の積層体を作製する工程と、前記積層体を加熱し、正極層と固体電解質層の積層体を作製する工程と、前記正極層と固体電解質層の積層体に負極層とを積層して固体電池を作製する工程とを有し、前記正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含むことが好ましい。 Furthermore, 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. A step of producing a laminate of a positive electrode mixture and a solid electrolyte layer, a step of heating the laminate to produce a laminate of a positive electrode layer and a solid electrolyte layer, and a step of forming the positive electrode layer and the solid electrolyte layer. It is preferable that 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.
　正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含むことにより、放電抵抗の小さい固体電池を作製することができる。 When 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.
本発明の実施形態として固体電池の電池要素の断面構造を模式的に示す断面図である。It is sectional drawing which shows typically the cross-section of the battery element of a solid battery as embodiment of this invention. 本発明の一つの実施形態として固体電池の電池要素を模式的に示す斜視図である。1 is a perspective view schematically showing a battery element of a solid state battery as one embodiment of the present invention. 本発明のもう一つの実施形態として固体電池の電池要素を模式的に示す斜視図である。It is a perspective view which shows typically the battery element of a solid battery as another embodiment of this invention. 本発明の実施例と比較例で作製された正極層のＸ線回折強度特性を示す図である。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.
　以下において、本発明を実施するための形態について説明する。 Hereinafter, embodiments for carrying out the present invention will be described.
　図１に示すように、本発明の固体電池１０は、正極層１１と、負極層１２と、正極層１１と負極層１２との間に介在する固体電解質層１３とを備える。図２に示すように本発明の一つの実施形態として固体電池１０は直方体形状に形成され、矩形の平面を有する複数の平板状層からなる積層体で構成される。また、図３に示すように本発明のもう一つの実施形態として固体電池１０は円柱形状に形成され、複数の円板状層からなる積層体で構成される。なお、正極層１１と負極層１２のそれぞれは、固体電解質と電極活物質とを含み、固体電解質層１３は固体電解質を含む。 As shown in FIG. 1, 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. As shown in FIG. 2, as one embodiment of the present invention, 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. In addition, as shown in FIG. 3, as another embodiment of the present invention, 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, and the solid electrolyte layer 13 includes a solid electrolyte.
　上記のように構成された本発明の固体電池１０は、正極層１１が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含有することを特徴としている。 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.
　ポリアニオン構造を有するリチウムリン複合酸化物としては、一般式ＬｉaＭmＸＯbＦc（Ｍは少なくとも１種以上の遷移金属、ＸはＢ、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｃｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍｏ、Ｗから選ばれる１種以上の元素、０＜ａ≦３、０＜ｍ≦２、２≦ｂ≦４、０≦ｃ≦１）で表されるリチウム化合物が挙げられる。例えば、ＬｉＦｅＰＯ4、ＬｉＣｏＰＯ4、ＬｉＦｅ0.5Ｃｏ0.5ＰＯ4、ＬｉＭｎＰＯ4、ＬｉＣｒＰＯ4、ＬｉＦｅＶＯ4、ＬｉＦｅＳｉＯ4、ＬｉＦｅＳＯ4、ＬｉＴｉＰＯ4、ＬｉＦｅＢＯ3、Ｌｉ3Ｆｅ2ＰＯ4、ＬｉＦｅ0.9Ａｌ0.1ＰＯ4、ＬｉＦｅＰＯ3.9Ｆ0.1等がこれにあたる。また、電子電導性を改善する目的で上記元素の一部を他元素で置換したり、リチウムリン複合酸化物の表面を炭素などの導電性物質で被覆したり、粒子内部に導電性物質を内包させたものであっても、本発明の効果を阻害することなく好適に用いることができ、このようなものを用いた場合も本発明の範囲内である。正極活物質を構成する元素の組成比率は上述した比率に限定されず、化学量論からずれていてもよい。 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). For example, 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. In addition, for the purpose of improving the electronic conductivity, some of the above elements are replaced with other elements, 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. Even if it is made, it can be used suitably, without inhibiting the effect of this invention, and the case where such a thing is used is also within the scope of the present invention. The 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.
　リチウム硫黄化合物としては、ＴＨＩＯ－ＬＩＳＩＣＯＮを用いることができる。中でも、仕込み組成８０Ｌｉ2Ｓ-２０Ｐ2Ｓ5等の架橋Ｓを含まないＴＨＩＯ－ＬＩＳＩＣＯＮであることが好ましい。高温下における架橋Ｓに起因するリチウム硫黄化合物の分解や、抵抗相の生成を防ぐことができる。 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.
　負極層１２は、たとえば、負極活物質としての黒鉛、ハードカーボン等の炭素材料、合金系材料、硫黄、金属硫化物等を含む。さらに、リチウム硫黄化合物やイオン伝導性化合物であるＬｉ2ＳとＰ2Ｓ5の混合物等の固体電解質を含む。 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.
　正極層１１と負極層１２との間に挟まれた固体電解質層１３は、たとえば、固体電解質としてイオン伝導性化合物を含む。なかでも、硫化物固体電解質が好ましく、Ｌｉ2ＳとＰ2Ｓ5の混合物等を含む。なお、固体電解質は、構成元素としてリチウムと硫黄とを少なくとも含有すればよく、このような化合物として、Ｌｉ2ＳとＰ2Ｓ5の混合物、Ｌｉ2ＳとＢ2Ｓ3の混合物等をあげることができる。また、固体電解質は、構成元素としてリチウムと硫黄に加えて、好ましくはリンをさらに含有すればよく、このような化合物として、Ｌｉ2ＳとＰ2Ｓ5の混合物、Ｌｉ7Ｐ3Ｓ11、Ｌｉ3ＰＳ4、ＰＳ4やこれらのアニオンの一部が酸素置換されたもの等をあげることができる。中でも、仕込み組成８０Ｌｉ2Ｓ-２０Ｐ2Ｓ5等の架橋Ｓを含まないＴＨＩＯ－ＬＩＳＩＣＯＮであることが好ましい。固体電解質を構成する元素の組成比率は上述した比率に限定されるものではない。 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. Among these, 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. In addition to lithium and sulfur as constituent elements, the solid electrolyte preferably further contains phosphorus. As such a compound, a mixture of Li 2 S and P 2 S 5 , Li 7 P 3 S 11 , Examples thereof include Li 3 PS 4 , PS 4, and those in which some of these anions are substituted with oxygen. Among these, 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.
　なお、本発明の固体電池１０は、図１～図３に示される電池要素を、たとえば、セラミックス製の容器に装入された形態で用いられてもよく、図１～図３に示される形態のままで自立した形態で用いられてもよい。 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.
　また、上記実施の形態では、コイン型二次電池について説明したが、電池形状は特に限定されるものでないのはいうまでもなく、円筒型、角型、シート型等にも適用できる。また、外装方法も特に限定されず、金属ケースや、モールド樹脂、アルミラミネートフイルム等を使用してもよい。 In the above embodiment, the coin-type secondary battery has been described. However, it is needless to say that the battery shape is not particularly limited, and can be applied to a cylindrical type, a square type, a sheet type, and the like. Also, the exterior method is not particularly limited, and a metal case, mold resin, aluminum laminate film, or the like may be used.
　本発明の固体電池の製造方法は、正極層は原材料を圧縮成形することにより作製することができる。この場合、正極層となる原材料を圧縮成形し、加熱し正極層を作製する。その後、正極層と負極層とを固体電解質層を介在させて積層し積層体を作製することができる。 In the method for producing a solid state battery of the present invention, the positive electrode layer can be produced by compression molding a raw material. In this case, the raw material to be the positive electrode layer is compression molded and heated to produce the positive electrode layer. Thereafter, the positive electrode layer and the negative electrode layer can be laminated with a solid electrolyte layer interposed therebetween to produce a laminate.
　また、スラリーを作製し各層を作製することもできる。この場合、まず、正極層、負極層、固体電解質層となるスラリーを作製する（スラリー作製工程）。作製したスラリーを用いて各層を作製する。そして、得られた各層を積層し積層体作製する（積層体作製工程）。なお、積層体を、たとえばコインセル内に封止してもよい。封止方法は特に限定されない。たとえば、積層体を樹脂で封止してもよい。また、Ａｌ2Ｏ3等の絶縁性を有する絶縁体ペーストを積層体の周囲に塗布またはディップして、この絶縁ペーストを熱処理することにより封止してもよい。 Moreover, a slurry can be produced to produce each layer. In this case, first, 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. And each obtained layer is laminated | stacked and a laminated body is produced (laminated body production process). In addition, you may seal a laminated body, for example in a coin cell. The sealing method is not particularly limited. For example, the laminate may be sealed with a 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.
　なお、正極層と負極層から効率的に電流を引き出すため、正極層と負極層の上に炭素層、金属層、酸化物層等の集電体層を形成してもよい。集電体層の形成方法は、たとえば、スパッタリング法が挙げられる。また、金属ペーストを塗布またはディップして、この金属ペーストを熱処理してもよい。また、カーボンシートを積層してもよい。 In order to efficiently draw current from the positive electrode layer and the negative electrode layer, 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. Examples of the method for forming the current collector layer include a sputtering method. Alternatively, the metal paste may be applied or dipped and heat-treated. Carbon sheets may be laminated.
　積層体作製工程では、正極層、固体電解質層、および、負極層を積層して単電池構造を形成することが好ましい。さらに、積層体形成工程において、集電体を介在させて、上記の単電池構造の積層体を複数個、積層して積層体を形成してもよい。この場合、単電池構造の積層体を複数個、電気的に直列、または並列に積層してもよい。 In the laminate manufacturing step, it is preferable to form a unit cell structure by laminating the positive electrode layer, the solid electrolyte layer, and the negative electrode layer. Furthermore, in the stacked body forming step, 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. In this case, a plurality of laminates having a single battery structure may be laminated electrically in series or in parallel.
　上記の各層を作製する方法は特に限定されないが、各層を形成するためにドクターブレード法、ダイコーター、コンマコーター等、または、印刷層を形成するためにスクリーン印刷等を使用することができる。また、各層を積層する方法は特に限定されないが、熱間等方圧プレス（ＨＩＰ）、冷間等方圧プレス（ＣＩＰ）、静水圧プレス（ＷＩＰ）等を使用して積層することができる。 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.
　スラリーは、有機材料を溶剤に溶解した有機ビヒクルと、（正極活物質および固体電解質、負極活物質および固体電解質、または、固体電解質）とを湿式混合することによって作製することができる。湿式混合ではメディアを用いることができ、具体的には、ボールミル法、ビスコミル法等を用いることができる。一方、メディアを用いない湿式混合方法を用いてもよく、サンドミル法、高圧ホモジナイザー法、ニーダー分散法等を用いることができる。スラリーに含まれる有機材料は特に限定されないが、硫化物と反応しないアクリル樹脂などを用いることができる。スラリーは可塑剤を含んでもよい。 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. On the other hand, 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.
　なお、リン酸リチウムを含有させる方法としては、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを混合し正極層を作製することができる。 In addition, as a method of containing lithium phosphate, 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.
　さらに、ポリアニオン構造を有するリチウムリン複合酸化物と混合し、加熱することによりリン酸リチウムを正極層に含有させてもよい。この場合、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とを混合し正極合剤を作製し、前記正極合剤を加熱して正極層を作製することができる。なお、正極合剤と固体電解質層を積層した後、積層体を加熱して作製してもよい。 Further, lithium phosphate may be incorporated into the positive electrode layer by mixing with a lithium phosphorus composite oxide having a polyanion structure and heating. In this case, 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. In addition, after laminating | stacking a positive mix and a solid electrolyte layer, a laminated body may be heated and produced.
　正極層を加熱する焼成温度、雰囲気などの焼成条件は特に限定されないが、固体電池の特性に悪影響を及ぼさない条件で行うことが好ましい。真空条件下、２５０℃以下で加熱することが好ましい。 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.
　なお、正極合剤に電池伝導性改善する目的で導電剤を含有させる場合、リチウムリン複合酸化物とリチウム硫黄化合物の反応を起こりやすくするため、リチウムリン複合酸化物とリチウム硫黄化合物が直接接するように、両材料を先に混合した後に導電剤を加えた方がよい。 When the positive electrode mixture contains a conductive agent for the purpose of improving battery conductivity, 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. In addition, it is better to add the conductive agent after mixing both materials first.
　次に、本発明の実施例を具体的に説明する。なお、以下に示す実施例は一例であり、本発明は下記の実施例に限定されるものではない。 Next, specific examples of the present invention will be described. In addition, the Example shown below is an example and this invention is not limited to the following Example.
（実施例１）
　＜リチウム硫黄化合物の作製＞
　硫化物であるＬｉ2Ｓ粉末とＰ2Ｓ5粉末とをメカニカルミリング処理することにより、リチウム硫黄化合物を作製した。 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.
　具体的には、アルゴンガス雰囲気中で、Ｌｉ2Ｓ粉末とＰ2Ｓ5粉末とを８：２のモル比になるように秤量し、アルミナ製の容器に入れた。直径が１０ｍｍのアルミナボールを入れて、容器を密閉した。容器をメカニカルミリング装置（フリッチュ製　遊星ボールミル、型番Ｐ-７）にセットして、３７０ｒｐｍの回転数で２０時間、メカニカルミリング処理した。その後、容器をアルゴンガス雰囲気中に開放し、容器にトルエンを２ｍｌ入れて、容器を密閉した。さらに、メカニカルミリング処理を２００ｒｐｍの回転数で２時間行った。このようにして得られたスラリー状の材料をアルゴンガス雰囲気中でろ過した後、真空乾燥した。得られた粉末を真空雰囲気中にて２００℃～３００℃の温度で加熱することにより、ガラスセラミック粉末を得た。このガラスセラミック粉末をリチウム硫黄化合物として用いた。 Specifically, 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.
　　＜正極合剤の作製＞
　正極活物質として平均粒径０．５７μｍのリン酸鉄リチウムを使用した。 <Preparation of positive electrode mixture>
Lithium iron phosphate having an average particle diameter of 0.57 μm was used as the positive electrode active material.
　リン酸鉄リチウムと固体電解質の反応を起こりやすくするため、粒子表面のＣが少ないリン酸鉄リチウムを使用した。リン酸鉄リチウムに含まれるＣ成分はリン酸鉄リチウムに対し１ｗｔ％であった。 In order to facilitate the reaction between lithium iron phosphate and the solid electrolyte, 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.
　アルゴンガス雰囲気中で、上記で作製したリチウム硫黄化合物とリン酸鉄リチウムを重量比で５７：３３となるように秤量し、ロッキングミルで１時間混合した。得られた混合物と導電剤のＶＧＣＦ－Ｈ（昭和電工株式会社製）が９０：１０の重量比になるように秤量し、ロッキングミルで１時間混合し正極合材を作製した。なお、リン酸鉄リチウムとリチウム硫黄化合物が反応しやすいように、両材料を先に混合した後に導電剤を加えた。 In an argon gas atmosphere, 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. In addition, after mixing both materials previously, the electrically conductive agent was added so that lithium iron phosphate and a lithium sulfur compound might react easily.
　＜正極合材と固体電解質の積層体の作製＞
　上記で得られたリチウム硫黄化合物を固体電解質として用いた。固体電解質２５ｍｇ、正極合剤５ｍｇをこの順に直径７．５ｍｍの金型に入れて５ＭＰａの圧力でプレス成形して、成形体を作製した。 <Preparation of laminate of positive electrode mixture and solid electrolyte>
The lithium sulfur compound obtained above was used as a solid electrolyte. 25 mg of the solid electrolyte and 5 mg of the positive electrode mixture were put in this order in a mold having a diameter of 7.5 mm and press-molded at a pressure of 5 MPa to produce a molded body.
　作製した成形体をカーボンルツボ上に置き、真空状態で２５０℃で６時間、加熱し正極合剤と固体電解質の積層体を作製した。 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.
　　＜Ｘ線回折法による解析＞
　加熱後の正極層をＸ線回折法（θ－２θ法）によって解析した。 <Analysis by X-ray diffraction method>
The positive electrode layer after heating was analyzed by an X-ray diffraction method (θ-2θ method).
　　＜固体電池の作製＞
　作製した積層体の固体電解質層側にＩｎ－Ｌｉを配置し発電要素を作製した。発電要素をＳＵＳ板で挟みラミネート容器に封入し固体電池を作製した。なお、正極層とＳＵＳ板の間に集電体としてカーボンシートを介在させた。 <Production of solid battery>
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.
　　＜電池特性の評価＞
　上記の固体電池に対し、６Ｖまで、１０μＡで定電流充電し、１Ｖまで１０μＡで定電圧放電を行い、充放電できるか確認した。さらに、放電前の開回路電圧、放電後１０秒後の電圧を測定した。 <Evaluation of battery characteristics>
The solid battery was charged at a constant current of 10 μA up to 6 V, discharged at a constant voltage of 10 μA 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.
　また、放電抵抗を以下のようにして求めた。 Also, the discharge resistance was obtained as follows.
　放電抵抗 = （放電前開回路電圧 － 放電後１０秒後の電圧） / 定電流値
　なお、電池特性の評価には、東方技研のＰＳ－０８ ガルバノポテンショメーターを使用した。測定間隔は０．２ｓｅｃで行い、１０秒後の電圧は１０秒に一番近いポイントでの、電圧値を読み取った。 Discharge resistance = (open circuit voltage before discharge−voltage 10 seconds after discharge) / constant current value For evaluation of battery characteristics, 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.
　その結果、開回路電圧は、３．４１Ｖ、放電後１０秒後の電圧は１．６３Ｖであった。また、放電抵抗は１７８ｋΩであった。以上より、１０μＡでの可逆的な充放電が可能であり、放電抵抗も小さかった。 As a result, the open circuit voltage was 3.41 V, and the voltage 10 seconds after the discharge was 1.63 V. The discharge resistance was 178 kΩ. From the above, reversible charging / discharging at 10 μA was possible and the discharge resistance was small.
　（比較例１）
　正極合材と固体電解質の積層体の作製において、加熱した積層体を使用せずに成形体を使用したこと以外は、実施例１と同様にして固体電池を作製した。 (Comparative 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.
　＜電池特性の評価＞
　上記の固体電池に対し実施例１と同様に、１０μＡで充電したところ、抵抗が高く、充電が進行しなかった。そこで電流値を低くし、５．５Ｖまで、５μＡで定電流充電し、１.５Ｖまで１０μＡで定電圧放電を行った。さらに、放電前の開回路電圧、放電後１０秒後の電圧を測定した。 <Evaluation of battery characteristics>
When the solid battery was charged at 10 μA as in Example 1, the resistance was high and charging did not proceed. Therefore, the current value was lowered, constant current charging was performed at 5 μA up to 5.5 V, and constant voltage discharging was performed at 10 μA up to 1.5 V. Furthermore, the open circuit voltage before discharge and the voltage 10 seconds after discharge were measured.
　その結果、開回路電圧は、３．４０Ｖ、放電後１０秒後の電圧は２．１０Ｖであった。また、放電抵抗は２６０ｋΩであった。以上より、５μＡではなんとか充放電可能なものの、電池抵抗は非常に高い結果となった。 As a result, the open circuit voltage was 3.40 V, and the voltage 10 seconds after discharge was 2.10 V. The discharge resistance was 260 kΩ. From the above, although 5 μA could be charged / discharged somehow, the battery resistance was very high.
　以上の結果を表１に示す。 The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように。リン酸リチウムを含有しているものは、正極にリン酸鉄リチウムを用いても充放電が可能であり、さらに、放電抵抗が低い固体電池を得ることができる。 As shown in Table 1. Those containing lithium phosphate can be charged and discharged even when lithium iron phosphate is used for the positive electrode, and a solid battery having a low discharge resistance can be obtained.
　また、図４に本発明の実施例と比較例で作製された正極層のＸ線回折強度特性を示す。図４に示すように、実施例１では、リン酸鉄リチウム、加熱後のリチウム硫黄化合物、リン酸リチウムの混合物であることが分かる。比較例１ではリン酸リチウムのピークはみられない。 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.
　今回開示された実施の形態と実施例はすべての点で例示であって制限的なものではないと考慮されるべきである。本発明の範囲は以上の実施の形態と実施例ではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての修正と変形を含むものであることが意図される。 It should be considered that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is shown not by the above embodiments and examples but by the scope of claims, and is intended to include all modifications and variations within the meaning and scope equivalent to the scope of claims. .
　　本発明により、放電抵抗の低い固体電池を得ることができる。 According to the present invention, a solid battery having a low discharge resistance can be obtained.
　１０：固体電池、１１：正極層、１２：負極層、１３：固体電解質層。 10: solid battery, 11: positive electrode layer, 12: negative electrode layer, 13: solid electrolyte layer.

Claims (7)

  1. 　正極層、固体電解質層、負極層が積層されている固体電池であって、
    　前記正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含む、
    　固体電池。     A solid battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated,
    The positive electrode layer includes a lithium phosphorus composite oxide having a polyanion structure, a lithium sulfur compound, and lithium phosphate,
    Solid battery.
  2. 　前記リチウムリン複合酸化物が、一般式ＬｉaＭmＸＯbＦc（Ｍは少なくとも１種以上の遷移金属、ＸはＢ、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｃｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍｏ、Ｗから選ばれる１種以上の元素、０＜ａ≦３、０＜ｍ≦２、２≦ｂ≦４、０≦ｃ≦１）で表される、請求項１に記載の固体電池。 The lithium phosphorus composite oxide has the 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, Cr, Mo 1 or more elements selected from W, 0 <a ≦ 3, 0 <m ≦ 2, 2 ≦ b ≦ 4, 0 ≦ c ≦ 1).
  3. 　前記リチウムリン複合酸化物が少なくともリン酸鉄リチウムおよびリン酸マンガンリチウムのどちらか一方である、請求項１または２に記載の固体電池。 The solid battery according to claim 1 or 2, wherein the lithium phosphorus composite oxide is at least one of lithium iron phosphate and lithium manganese phosphate.
  4. 　前記リチウム硫黄化合物が、ＴＨＩＯ－ＬＩＳＩＣＯＮである、請求項１～３のいずれか１項に記載の固体電池。 The solid state battery according to any one of claims 1 to 3, wherein the lithium sulfur compound is THIO-LISICON.
  5. 　前記固体電解質層が、硫化物固体電解質を含む、請求項１～４のいずれか１項に記載の固体電池。 The solid battery according to any one of claims 1 to 4, wherein the solid electrolyte layer includes a sulfide solid electrolyte.
  6. 　正極層、固体電解質層、負極層が積層されている固体電池の製造方法であって、
    　ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とを混合し正極合剤を作製する正極合剤作製工程と、
    　前記正極合剤を加熱し、正極層を作製する正極層作製工程と、
    　前記正極層と負極層とを固体電解質層を介して積層して固体電池を作製する工程とを有し、
    　前記正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含む、固体電池の製造方法。     A method for producing a solid battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated,
    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;
    A positive electrode layer preparation step of heating the positive electrode mixture and preparing a positive electrode layer;
    Laminating the positive electrode layer and the negative electrode layer through a solid electrolyte layer to produce a solid battery,
    The method for producing a solid battery, wherein the positive electrode layer includes a lithium phosphorus composite oxide having a polyanion structure, a lithium sulfur compound, and lithium phosphate.
  7. 　正極層、固体電解質層、負極層が積層されている固体電池の製造方法であって、
    　ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とを混合し正極合剤を作製する正極合剤作製工程と、
    　前記正極合剤と固体電解質層を積層し、正極合剤と固体電解質層の積層体を作製する工程と、
    　前記積層体を加熱し、正極層と固体電解質層の積層体を作製する工程と、
    　前記正極層と固体電解質層の積層体に負極層とを積層して固体電池を作製する工程とを有し、
    　前記正極層が、ポリアニオン構造を有するリチウムリン複合酸化物とリチウム硫黄化合物とリン酸リチウムを含む、固体電池の製造方法。     A method for producing a solid battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated,
    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;
    Laminating the positive electrode mixture and the solid electrolyte layer, and producing a laminate of the positive electrode mixture and the solid electrolyte layer;
    Heating the laminate to produce a laminate of a positive electrode layer and a solid electrolyte layer;
    A step of laminating a negative electrode layer on a laminate of the positive electrode layer and the solid electrolyte layer to produce a solid battery,
    The method for producing a solid battery, wherein the positive electrode layer includes a lithium phosphorus composite oxide having a polyanion structure, a lithium sulfur compound, and lithium phosphate.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010073539A (en) * 2008-09-19 2010-04-02 Toyota Motor Corp Electrode body, method of manufacturing the same, and lithium ion secondary battery
JP2011233246A (en) * 2010-04-23 2011-11-17 Toyota Motor Corp Composite cathode active material, all-solid battery and manufacturing method for the same
WO2012029641A1 (en) * 2010-09-01 2012-03-08 株式会社 村田製作所 Solid state battery and manufacturing method for same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010073539A (en) * 2008-09-19 2010-04-02 Toyota Motor Corp Electrode body, method of manufacturing the same, and lithium ion secondary battery
JP2011233246A (en) * 2010-04-23 2011-11-17 Toyota Motor Corp Composite cathode active material, all-solid battery and manufacturing method for the same
WO2012029641A1 (en) * 2010-09-01 2012-03-08 株式会社 村田製作所 Solid state battery and manufacturing method for same

Cited By (2)

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

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