WO2013038948A1 - Stratifié non fritté pour batterie entièrement solide, batterie entièrement solide et procédé pour sa production - Google Patents

Stratifié non fritté pour batterie entièrement solide, batterie entièrement solide et procédé pour sa production Download PDF

Info

Publication number
WO2013038948A1
WO2013038948A1 PCT/JP2012/072426 JP2012072426W WO2013038948A1 WO 2013038948 A1 WO2013038948 A1 WO 2013038948A1 JP 2012072426 W JP2012072426 W JP 2012072426W WO 2013038948 A1 WO2013038948 A1 WO 2013038948A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode layer
solid
unsintered
carbon material
layer
Prior art date
Application number
PCT/JP2012/072426
Other languages
English (en)
Japanese (ja)
Inventor
充 吉岡
倍太 尾内
剛司 林
武郎 石倉
彰佑 伊藤
Original Assignee
株式会社 村田製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社 村田製作所 filed Critical 株式会社 村田製作所
Priority to JP2013533617A priority Critical patent/JP5644951B2/ja
Publication of WO2013038948A1 publication Critical patent/WO2013038948A1/fr

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 unsintered laminate for an all-solid battery, an all-solid battery, and a method for producing the same.
  • the battery having the above configuration has a risk of leakage of the electrolyte.
  • the organic solvent etc. which are used for electrolyte solution are combustible substances. For this reason, it is required to further increase the safety of the battery.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2007-5279 discloses a method for producing an all-solid battery in which an active material containing a phosphoric acid compound and a solid electrolyte are respectively mixed with a solution containing a binder and a plasticizer.
  • the active material green sheet and solid electrolyte green sheet obtained by forming the slurry by dispersing in the slurry are laminated, and the binder and the plasticizer are thermally decomposed and removed, and then sintered. By doing so, it is described that a laminate of an all-solid-state battery is manufactured.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2007-258148 (hereinafter referred to as Patent Document 2), as an all-solid battery manufacturing method, an electrode paste prepared by mixing an electrode active material and acetylene black is used as a solid electrolyte. It is described that a laminated fired body in which an electrode layer and a solid electrolyte layer are fired and integrated is manufactured by screen printing on both surfaces of the body and then baking.
  • an object of the present invention is to suppress the burning of carbon as a conductive agent contained in an unsintered electrode layer and improve the capacity, an unsintered laminate for an all-solid battery, an all-solid battery, and its It is to provide a manufacturing method.
  • the use of a plurality of types of carbon materials having different combustion start temperatures as the conductive agent contained in the unsintered electrode layer, the unsintered electrode layer It has been found that combustion of the conductive agent contained in can be suppressed. That is, even if the carbon material having a low combustion start temperature burns with the removal of the organic material in the firing process, the carbon material having a combustion start temperature higher than that of the organic material to be removed is included in the electrode layer. It was revealed that the burning of the agent can be suppressed, and the capacity of the electrode active material can be sufficiently extracted as in the case of the battery using the organic electrolyte. Based on such knowledge of the inventors, the present invention has the following features.
  • the all solid state battery according to the present invention includes at least one of the positive electrode layer and the negative electrode layer and a solid electrolyte layer laminated on the electrode layer.
  • the electrode layer includes a first carbon material that starts burning at a first temperature, and a second carbon material that starts burning at a second temperature higher than the first temperature.
  • the electrode layer contains more second carbon material than first carbon material.
  • An unsintered laminate for an all-solid battery according to the present invention was laminated on an unsintered electrode layer that is an unsintered body of at least one of a positive electrode layer and a negative electrode layer, and an unsintered electrode layer.
  • An unsintered solid electrolyte layer that is an unsintered body of the solid electrolyte layer.
  • An unsintered electrode layer contains the 1st carbon material which starts combustion at the 1st temperature, and the 2nd carbon material which starts combustion at the 2nd temperature higher than the 1st temperature.
  • the unsintered electrode layer and the unsintered solid electrolyte layer may be in the form of a green sheet or a printed layer.
  • the manufacturing method of the all-solid-state battery according to the present invention includes the following steps.
  • the unsintered electrode layer includes a first carbon material that starts to burn at a first temperature and a second carbon material that starts to burn at a second temperature higher than the first temperature.
  • the first carbon material has a larger amount of burning than the second carbon material at the decomposition temperature of the organic material contained in the laminate.
  • the second carbon material is preferably carbon powder.
  • the first carbon material covers at least a part of the surface of the electrode active material particles contained in the unsintered electrode layer, or at least one of the electrode active material particles. It is preferably carried on the surface of the part.
  • the material forming at least one layer selected from the group consisting of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer is a solid electrolyte comprising a lithium-containing phosphate compound having a NASICON structure It is preferable to contain.
  • the material forming at least one layer selected from the group consisting of a positive electrode layer and a negative electrode layer contains an electrode active material composed of a lithium-containing phosphate compound.
  • a non-sintered electrode layer and a non-sintered solid electrolyte layer should just have the form of a green sheet or a printing layer.
  • the charge / discharge capacity can be increased.
  • an all-solid battery 10 is constituted by a single battery including a positive electrode layer 11, a solid electrolyte layer 12, and a negative electrode layer 13.
  • the positive electrode layer 11 is disposed on one surface of the solid electrolyte layer 12, and the negative electrode layer 13 is disposed on the other surface opposite to the one surface of the solid electrolyte layer 12.
  • the positive electrode layer 11 and the negative electrode layer 13 are provided at positions facing each other with the solid electrolyte layer 12 interposed therebetween.
  • Each of the positive electrode layer 11 and the negative electrode layer 13 includes a solid electrolyte and an electrode active material, and the solid electrolyte layer 12 includes a solid electrolyte.
  • Each of the positive electrode layer 11 and the negative electrode layer 13 includes a carbon material or the like as a conductive agent.
  • At least one of the positive electrode layer 11 and the negative electrode layer 13 includes a first carbon material that starts burning at a first temperature, and a first carbon material that is higher than the first temperature. And a second carbon material that starts burning at a temperature of 2.
  • the all-solid battery unsintered laminate used for producing the all-solid battery 10 includes a non-sintered electrode layer which is at least one of the positive electrode layer 11 and the negative electrode layer 13, and And a non-sintered solid electrolyte layer that is a non-sintered body of the solid electrolyte layer 12 laminated on the non-sintered electrode layer.
  • the fired laminate is sealed, for example, in a coin cell.
  • the sealing method is not particularly limited. For example, you may seal the laminated body after baking with resin.
  • an insulating paste having an insulating property such as Al 2 O 3 may be applied or dipped around the laminate, and the insulating paste may be heat-treated for sealing.
  • a conductive layer such as a metal layer may be formed on the positive electrode layer 11 and the negative electrode layer 13.
  • the method for forming the conductive layer include a sputtering method.
  • the metal paste may be applied or dipped and heat-treated.
  • the unsintered electrode layer includes a first carbon material that starts to burn at a first temperature and a second carbon material that starts to burn at a second temperature higher than the first temperature.
  • the unsintered electrode layer and the unsintered solid electrolyte layer have the form of a green sheet or a printed layer.
  • the unsintered electrode layer includes two or more carbon materials having different combustion start temperatures, even if the carbon material is burned out in the process of firing the laminate, One carbon material burns first. Accordingly, oxygen existing in the stack or oxygen supplied to the stack is preferentially consumed for the combustion of the first carbon material, so that the second carbon material having a high combustion start temperature burns. Can be prevented from being burned out. Thereby, since it can suppress that the effect of the carbon which provides electronic conductivity to an electrode layer becomes small, it can suppress that charging / discharging capacity
  • the electrode layer includes a first carbon material that starts burning at a first temperature and a second carbon material that starts burning at a second temperature higher than the first temperature.
  • the combustion start temperature can be measured as a temperature at which weight loss of carbon occurs by differential thermal and thermogravimetric simultaneous measurement (TG-DTA).
  • the carbon material may be crystalline carbon or carbon containing an amorphous part.
  • At least one of the positive electrode layer 11 and the negative electrode layer 13 contains more second carbon material than first carbon material.
  • the first carbon material has a larger amount of burning than the second carbon material at the decomposition temperature of the organic material contained in the laminate. That is, it is preferable that the first carbon material burns more easily than the second carbon material. In this case, even when the first carbon material (combustible carbon material) having a low combustion start temperature is burned out during firing of the laminate, the second carbon material (non-combustible carbon material) having a high combustion start temperature. Remains. Thereby, since it can suppress that the effect of the carbon which provides electronic conductivity to an electrode layer becomes small, it can suppress that charging / discharging capacity
  • the flame-retardant carbon material may be a carbon material that does not completely burn out at a temperature at which the laminate is fired to decompose the organic material. It does not have to be a carbon material that does not burn.
  • the flammable carbon material may be any carbon material that burns at the temperature at which the laminate is fired to decompose the organic matter, and does not need to be completely burned at the temperature at which the laminate is fired to decompose the organic matter. .
  • the second carbon material is preferably carbon powder.
  • the physical properties of the carbon powder are not particularly limited, but the specific surface area is preferably 10 to 80 m 2 / g, the particle size is preferably 10 nm to several ⁇ m, the specific surface area is 50 to 80 m 2 / g, and the particle size is 10 to 100 nm. It is particularly preferred.
  • the first carbon material covers at least a part of the surface of the electrode active material particles included in the unsintered electrode layer or is supported on at least a part of the surface of the electrode active material particles.
  • at least a part of the surface of the electrode active material particles can be coated with a carbon component using sugar or an organic acid, or a carbon component is applied to at least a part of the surface of the electrode active material particles using carbon black. Can be supported.
  • the thickness of the coating layer is preferably 10 nm or more.
  • a laminated body may be formed by laminating a plurality of laminated bodies having the above single cell structure with an unsintered 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 forming the green electrode layer and the green solid electrolyte layer is not particularly limited, but a doctor blade method, a die coater, a comma coater, or the like for forming a green sheet, or a printing layer is formed. Screen printing or the like can be used.
  • the method for laminating the above-mentioned unsintered electrode layer and unsintered solid electrolyte layer is not particularly limited, but the unsintered electrode using a hot isostatic press, a cold isostatic press, an isostatic press, etc.
  • the layer and the unsintered solid electrolyte layer can be laminated.
  • a slurry for forming a green sheet or printed layer is prepared by wet-mixing an organic vehicle in which an organic material is dissolved in a solvent, and a positive electrode active material, a negative electrode active material, a solid electrolyte, or a current collector material.
  • Media can be used in wet mixing, and specifically, a ball mill method, a viscomill method, or the like can be used.
  • a wet mixing method that does not use media may be used, and a sand mill method, a high-pressure homogenizer method, a kneader dispersion method, or the like can be used.
  • the slurry may contain a plasticizer.
  • plasticizer is not particularly limited, phthalic acid esters such as dioctyl phthalate and diisononyl phthalate may be used.
  • the atmosphere is not particularly limited, but it is preferably performed under conditions that do not change the valence of the transition metal contained in the electrode active material.
  • the type of the electrode active material contained in the positive electrode layer 11 or negative electrode layer 13 of the all-solid-state cell 10 producing method of the present invention is applied is not limited, as the positive electrode active material, Li 3 V 2 (PO 4 ) Lithium-containing phosphate compounds having a nasic structure such as 3, lithium-containing phosphate compounds having an olivine structure such as LiFePO 4 and LiMnPO 4 , LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2, etc.
  • a lithium-containing compound having a spinel structure such as LiMn 2 O 4 or LiNi 0.5 Mn 1.5 O 4 can be used.
  • MOx (M is at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb and Mo, and x is 0.9 ⁇ x ⁇ 2.0.
  • a compound having a composition represented by the following formula can be used.
  • a mixture obtained by mixing two or more active materials having a composition represented by MOx containing different elements M such as TiO 2 and SiO 2 may be used.
  • graphite-lithium compounds, lithium alloys such as Li-Al, oxidation of Li 3 V 2 (PO 4 ) 3 , Li 3 Fe 2 (PO 4 ) 3 , Li 4 Ti 5 O 12, etc. A thing etc. can be used.
  • the type of solid electrolyte contained in the positive electrode layer 11, the negative electrode layer 13, or the solid electrolyte layer 12 of the all-solid battery 10 to which the manufacturing method of the present invention is applied is not limited.
  • a lithium-containing phosphoric acid compound having the following can be used.
  • part of P in the above chemical formula may be substituted with B, Si, or the like.
  • a mixture obtained by mixing two or more Nasicon-type lithium-containing phosphate compounds having different compositions such as Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 and Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 is used. It may be used.
  • the lithium-containing phosphate compound having a NASICON structure used in the solid electrolyte is a compound containing a crystal phase of a lithium-containing phosphate compound having a NASICON structure or a lithium-containing phosphate having a NASICON structure by heat treatment. You may use the glass which precipitates the crystal phase of a phosphoric acid compound.
  • a material used for said solid electrolyte it is possible to use the material which has ion conductivity and is so small that electronic conductivity can be disregarded other than the lithium-containing phosphate compound which has a NASICON structure.
  • examples of such a material include lithium halide, lithium nitride, lithium oxyacid salt, and derivatives thereof.
  • Li—PO compounds such as lithium phosphate (Li 3 PO 4 ), LIPON (LiPO 4 ⁇ x N x ) in which nitrogen is introduced into lithium phosphate, Li—Si— such as Li 4 SiO 4 O-based compounds, Li-P-Si-O based compounds, Li-V-Si-O based compounds, La 0.51 Li 0.35 TiO 2.94 , La 0.55 Li 0.35 TiO 3 , Li 3x La 2 / 3-x TiO 3, etc.
  • Li—PO compounds such as lithium phosphate (Li 3 PO 4 ), LIPON (LiPO 4 ⁇ x N x ) in which nitrogen is introduced into lithium phosphate
  • Li—Si— such as Li 4 SiO 4 O-based compounds, Li-P-Si-O based compounds, Li-V-Si-O based compounds, La 0.51 Li 0.35 TiO 2.94 , La 0.55 Li 0.35 TiO 3 , Li 3x La 2 / 3-x TiO 3, etc.
  • Examples thereof include compounds having
  • the material forming at least one of the positive electrode layer 11, the solid electrolyte layer 12, or the negative electrode layer 13 of the all-solid battery 10 to which the manufacturing method of the present invention is applied is composed of a lithium-containing phosphate compound having a NASICON structure. It preferably contains a solid electrolyte. In this case, high ion conductivity that is essential for battery operation of an all-solid battery can be obtained.
  • glass or glass ceramics having a composition of a lithium-containing phosphate compound having a NASICON type structure is used as a solid electrolyte, a denser sintered body can be easily obtained due to the viscous flow of the glass phase in the firing step. It is particularly preferred to prepare the solid electrolyte starting material in the form of glass or glass ceramic.
  • the material forming at least one of the positive electrode layer 11 or the negative electrode layer 13 of the all solid state battery 10 to which the manufacturing method of the present invention is applied includes an electrode active material made of a lithium-containing phosphate compound.
  • the phase change of the electrode active material in the firing step or the reaction of the electrode active material with the solid electrolyte can be easily suppressed by the high temperature stability of the phosphoric acid skeleton. The capacity can be increased.
  • an electrode active material composed of a lithium-containing phosphate compound and a solid electrolyte composed of a lithium-containing phosphate compound having a NASICON structure are used in combination, the reaction between the electrode active material and the solid electrolyte is suppressed in the firing step. It is particularly preferable to use a combination of the electrode active material and the solid electrolyte material as described above, since both of them can be obtained and good contact can be obtained.
  • Example shown below is an example and this invention is not limited to the following Example.
  • Example 1 Preparation of electrode active material> A powder containing a lithium-containing vanadium phosphate compound Li 3 V 2 (PO 4 ) 3 (hereinafter referred to as “LVP”) as an electrode active material was produced as follows.
  • LVP lithium-containing vanadium phosphate compound Li 3 V 2 (PO 4 ) 3
  • Lithium carbonate (Li 2 CO 3 ), vanadium oxide (V 2 O 3 ), and diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) were used as starting materials. These raw materials are weighed so as to have a molar ratio of 27.3% -Li 2 CO 3 , 18.2% -V 2 O 3 , 54.5%-(NH 4 ) 2 HPO 4 and sealed in a container. The container was rotated at 150 rpm for 6 hours to obtain a mixed powder of starting materials.
  • the obtained mixed powder was fired in an air atmosphere at a temperature of 600 ° C. for 6 hours to remove volatile components, thereby obtaining a fired powder.
  • the fired powder was pulverized by adding water and a small amount of sucrose, enclosing it in a 500 ml polyethylene container together with a cobblestone having a diameter of 5 mm, and rotating the container at a rotation speed of 150 rpm for 24 hours. Thereafter, the powder was dried on a hot plate having a temperature of 120 ° C. to obtain a pulverized powder.
  • the obtained pulverized powder was fired in a nitrogen gas atmosphere at a temperature of 900 ° C. for 20 hours, so that the surfaces of the particles were coated with carbon remaining after pyrolysis of sucrose (hereinafter referred to as “carbon material 1”).
  • carbon material 1 carbon remaining after pyrolysis of sucrose
  • the electrode active material powder obtained above was mixed in a binder solution in which polyvinyl alcohol (hereinafter referred to as “organic material 1”) serving as a binder was dissolved in an organic solvent to prepare an electrode active material slurry.
  • organic material 1 polyvinyl alcohol
  • the mixing ratio of the electrode active material powder and the organic material 1 was 80:20 by weight.
  • LAGP Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3
  • the above glass powder of LAGP was mixed in a binder solution obtained by dissolving the organic material 1 serving as a binder in an organic solvent to prepare a solid electrolyte slurry.
  • the mixing ratio of the glass powder of LAGP and the organic material 1 was 80:20 by weight.
  • Acetylene black (hereinafter referred to as “AB”) powder (hereinafter referred to as “carbon material 2”) was mixed in a binder solution in which the organic material 1 serving as a binder was dissolved in an organic solvent to prepare a conductive agent slurry.
  • the mixing ratio of the carbon material 2 and the organic material 1 was 80:20 by weight.
  • the electrode active material slurry, the solid electrolyte slurry, and the conductive agent slurry prepared above are mixed so that the mixing ratio of the electrode active material powder, the glass powder of LAGP, and the carbon material 2 is 45:45:10 by weight. Mixing was performed to prepare an electrode slurry.
  • Each of the obtained electrode slurry and solid electrolyte slurry was molded by a doctor blade method to produce a molded body of an electrode sheet and a solid electrolyte sheet.
  • the thickness of the molded body was 50 ⁇ m.
  • a laminate in which a positive electrode layer and a solid electrolyte layer were laminated was produced. Specifically, an electrode sheet cut into a circular shape with a diameter of 12 mm is laminated on one side of a solid electrolyte sheet cut into a circular shape with a diameter of 12 mm, and a pressure of 1 ton is applied at a temperature of 80 ° C. Thermocompression bonding was performed.
  • this laminate was fired under the following conditions.
  • the organic material 1 was removed by baking at a temperature of 500 ° C. in a nitrogen gas atmosphere containing a small amount of oxygen.
  • the positive electrode layer and the solid electrolyte layer were joined by baking at a temperature of 600 ° C. in a nitrogen gas atmosphere.
  • moisture content was removed by drying the laminated body after baking at the temperature of 100 degreeC.
  • a laminate and a metal lithium plate as a counter electrode were laminated.
  • a polymethyl methacrylate resin (hereinafter referred to as “PMMA”) gel compound was applied on a metal lithium plate prepared as a negative electrode.
  • PMMA polymethyl methacrylate resin
  • the laminated body and the metal lithium plate were laminated
  • Example 1 The electrode active material slurry and the solid electrolyte slurry prepared in Example 1 were mixed so that the mixing ratio of the electrode active material powder and the glass powder of LAGP was 50:50 by weight to prepare an electrode slurry. Except for this, an all-solid battery was produced in the same manner as in Example 1.
  • the obtained all solid state battery was subjected to constant current and constant voltage charge and discharge in the same manner as in Example 1.
  • the obtained charge / discharge curve (broken line) is shown in FIG. It was confirmed that charging / discharging was performed at an initial discharge capacity of about 20 mAh / g.
  • the positive electrode layer includes the carbon component (carbon material 1) covering the surface of the electrode active material particles and the AB powder (carbon material 2). For this reason, even if the carbon material 1 whose combustion start temperature is lower than that of the organic material 1 is burned off when the organic material 1 is removed, the carbon material 2 whose combustion start temperature is higher than that of the organic material 1 remains. It can be seen that the all solid state battery No. 1 shows a high capacity. On the other hand, in Comparative Example 1, since the positive electrode layer includes the carbon material 1 but does not include the carbon material 2, the carbon material 1 having a lower combustion start temperature than the organic material 1 is burned out when the organic material 1 is removed. It can be seen that the all solid state battery of Example 1 exhibits a low capacity.
  • Example 2 An all-solid battery was produced in the same manner as in Example 1 except that the electrode active material powder was produced as follows.
  • Example 2 Water was added to the fired powder produced in Example 1, sealed in a 500 ml polyethylene container together with a cobblestone having a diameter of 5 mm, and the fired powder was pulverized by rotating the container at a rotation speed of 150 rpm for 24 hours. Thereafter, the powder was dried on a hot plate having a temperature of 120 ° C. to obtain a pulverized powder.
  • pulverized powder and conductive carbon black (trade name: Super-P, registered trademark: sp, hereinafter referred to as “sp”) manufactured by Timcal Corporation were weighed so as to have a weight ratio of 100: 20. By mixing in a mortar, mixed pulverized powder was obtained.
  • the obtained mixed and pulverized powder is fired in a nitrogen gas atmosphere at a temperature of 900 ° C. for 20 hours to produce an electrode active material powder in which sp (hereinafter referred to as “carbon material 3”) is supported on the surface of the particles. did.
  • the obtained all solid state battery was subjected to constant current and constant voltage charge and discharge in the same manner as in Example 1.
  • the obtained charge / discharge curve (solid line) is shown in FIG. It was confirmed that charging / discharging was possible at a discharge capacity of about 130 mAh / g. Further, it was confirmed that a flat region was exhibited in the voltage range of 3.4 to 4.0 V during discharge.
  • Example 2 The electrode active material slurry and the solid electrolyte slurry prepared in Example 2 were mixed so that the preparation ratio of the electrode active material powder and the glass powder of LAGP was 50:50 by weight to prepare an electrode slurry. Except for this, an all-solid battery was fabricated in the same manner as in Example 2.
  • the obtained all solid state battery was subjected to constant current and constant voltage charge and discharge in the same manner as in Example 1.
  • the obtained charge / discharge curve (broken line) is shown in FIG. It was confirmed that charging / discharging was performed at an initial discharge capacity of about 60 mAh / g.
  • Example 2 sp (carbon material 3) supported on the surface of the electrode active material particles and AB powder (carbon material 2) are included in the positive electrode layer. For this reason, even if the carbon material 3 having the same combustion start temperature as the organic material 1 is burned off when the organic material 1 is removed, the carbon material 2 having a higher combustion start temperature than the organic material 1 remains. It can be seen that the all-solid-state battery of Example 2 shows a high capacity. On the other hand, in Comparative Example 2, since the positive electrode layer includes the carbon material 3 but does not include the carbon material 2, the carbon material 1 having a combustion start temperature similar to that of the organic material 1 is burned off when the organic material 1 is removed. It can be seen that the all solid state battery of Comparative Example 2 exhibits a low capacity.
  • Example 3 A powder containing a lithium-containing iron manganese phosphate compound LiMn 0.75 Fe 0.25 (PO 4 ) (hereinafter referred to as “LFMP”) as an electrode active material was produced as follows.
  • LFMP lithium-containing iron manganese phosphate compound LiMn 0.75 Fe 0.25
  • Lithium carbonate (Li 2 CO 3 ), manganese oxide (MnCO 3 ), iron oxide (Fe 2 O 3 ), and diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) were used as starting materials. Mole ratio of these raw materials to 21.1% -Li 2 CO 3 , 31.6% -MnCO 3 , 5.3% -Fe 2 O 3 , 42.1%-(NH 4 ) 2 HPO 4 The mixture was sealed in a container, and the container was rotated at 150 rpm for 6 hours to obtain a mixed powder of starting materials.
  • the obtained mixed powder was fired in an air atmosphere at a temperature of 500 ° C. for 6 hours to remove volatile components, thereby obtaining a fired powder.
  • the water was added to the fired powder, sealed in a 500 ml polyethylene container together with a cobblestone having a diameter of 5 mm, and the fired powder was pulverized by rotating the container at a rotation speed of 150 rpm for 24 hours. Thereafter, the powder was dried on a hot plate having a temperature of 120 ° C. to obtain a pulverized powder.
  • the obtained pulverized powder and a highly conductive carbon black (trade name: Ketjen Black, registered trademark: KB, hereinafter referred to as “KB”) manufactured by Lion Co., Ltd. are weighed so as to have a weight ratio of 100: 20. And mixed in a mortar to obtain a mixed and pulverized powder.
  • the obtained mixed and pulverized powder is fired in a nitrogen gas atmosphere at a temperature of 700 ° C. for 20 hours to produce an electrode active material powder in which KB (hereinafter referred to as “carbon material 4”) is supported on the surface of the particles. did.
  • the electrode active material powder obtained above was mixed in a binder solution in which polyvinyl alcohol (hereinafter referred to as “organic material 2”) serving as a binder was dissolved in an organic solvent to prepare an electrode active material slurry.
  • organic material 2 polyvinyl alcohol
  • the mixing ratio of the electrode active material powder and polyvinyl alcohol was 80:20 by weight.
  • VGCF vapor grown carbon fiber
  • carbon material 5 a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent (hereinafter referred to as “VGCF”) , Referred to as “carbon material 5”) to prepare a conductive agent slurry.
  • the mixing ratio of the carbon material 5 and the organic material 2 was 80:20 by weight.
  • the mixing ratio of the electrode active material powder, the glass powder of LAGP, and the carbon material 5 is 45 parts by weight of the electrode active material slurry and conductive agent slurry prepared above and the solid electrolyte slurry prepared in Example 1. : 45:10 was mixed to prepare an electrode slurry.
  • Each of the obtained electrode slurry and solid electrolyte slurry was molded by a doctor blade method to produce a molded body of an electrode sheet and a solid electrolyte sheet.
  • the thickness of the molded body was 50 ⁇ m.
  • an all-solid battery was produced in the same manner as in Example 1. However, firing was performed under the following conditions. First, the organic material 2 was removed by baking at a temperature of 400 ° C. in a nitrogen gas atmosphere containing a small amount of oxygen. Then, it baked at the temperature of 600 degreeC in nitrogen gas atmosphere.
  • Example 3 (Comparative Example 3) The electrode active material slurry and the solid electrolyte slurry prepared in Example 3 were mixed so that the preparation ratio of the electrode active material powder and the glass powder of LAGP was 50:50 by weight to prepare an electrode slurry. Except for this, an all-solid battery was produced in the same manner as in Example 3.
  • the obtained all solid state battery was subjected to constant current and constant voltage charge and discharge in the same manner as in Example 3.
  • the obtained charge / discharge curve (broken line) is shown in FIG. It was confirmed that charging / discharging was performed at an initial discharge capacity of about 30 mAh / g.
  • Example 3 KB (carbon material 4) supported on the surface of the electrode active material particles and VGCF (carbon material 5) are included in the positive electrode layer. For this reason, even if the carbon material 4 whose combustion start temperature is lower than that of the organic material 2 is burned off when the organic material 2 is removed, the carbon material 5 whose combustion start temperature is higher than that of the organic material 2 remains. It can be seen that the all-solid battery No. 3 shows a high capacity. On the other hand, in Comparative Example 3, since the positive electrode layer includes the carbon material 4 but does not include the carbon material 5, the carbon material 4 having a lower combustion start temperature than the organic material 2 is burned out when the organic material 2 is removed. It can be seen that the all solid state battery of Example 3 exhibits a low capacity.
  • Example 4 ⁇ Preparation of electrode active material> A powder containing a lithium-containing iron manganese phosphate compound LiMn (PO 4 ) (hereinafter referred to as “LMP”) as an electrode active material was produced as follows.
  • LMP lithium-containing iron manganese phosphate compound LiMn (PO 4 )
  • Lithium carbonate (Li 2 CO 3 ), manganese oxide (MnCO 3 ), and diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) were used as starting materials. These raw materials are weighed so as to be 20.0% -Li 2 CO 3 , 40.0% -MnCO 3 , 40.0%-(NH 4 ) 2 HPO 4 in a molar ratio, sealed in a container, The container was rotated at a rotational speed of 150 rpm for 6 hours to obtain a mixed powder of starting materials.
  • the obtained mixed powder was fired in an air atmosphere at a temperature of 500 ° C. for 6 hours to remove volatile components, thereby obtaining a fired powder.
  • the water was added to the fired powder, sealed in a 500 ml polyethylene container together with a cobblestone having a diameter of 5 mm, and the fired powder was pulverized by rotating the container at a rotation speed of 150 rpm for 24 hours. Thereafter, the powder was dried on a hot plate having a temperature of 120 ° C. to obtain a pulverized powder.
  • the obtained pulverized powder and AB powder were weighed so as to have a weight ratio of 100: 20, and mixed with a planetary ball mill to obtain a coated pulverized powder having particles coated with AB by a mechanical alloying method. Produced.
  • the obtained coated pulverized powder is fired in a nitrogen gas atmosphere at a temperature of 700 ° C. for 20 hours, whereby the surface of the particles is coated with AB (hereinafter referred to as “carbon material 6”) by a mechanical alloying method.
  • An active material powder was prepared.
  • the electrode active material powder obtained above was mixed in a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent to prepare an electrode active material slurry.
  • the mixing ratio of the electrode active material powder and the organic material 2 was 80:20 by weight.
  • the carbon material 4 used in Example 3 was mixed in a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent, thereby preparing a conductive agent slurry.
  • the mixing ratio of the carbon material 4 and the organic material 2 was 80:20 by weight.
  • the mixing ratio of the electrode active material powder, the glass powder of LAGP, and the carbon material 4 is 45 parts by weight of the electrode active material slurry and conductive agent slurry prepared above and the solid electrolyte slurry prepared in Example 1. : 45:10 was mixed to prepare an electrode slurry.
  • Each of the obtained electrode slurry and solid electrolyte slurry was molded by a doctor blade method to produce a molded body of an electrode sheet and a solid electrolyte sheet.
  • the thickness of the molded body was 50 ⁇ m.
  • an all-solid battery was produced in the same manner as in Example 1. However, firing was performed under the following conditions. First, the organic material 2 was removed by baking at a temperature of 400 ° C. in a nitrogen gas atmosphere containing a small amount of oxygen. Then, it baked at the temperature of 600 degreeC in nitrogen gas atmosphere.
  • the pulverized powder produced in Example 4 and the carbon material 4 were weighed so as to have a weight ratio of 100: 20, and mixed in a mortar to obtain a mixed pulverized powder.
  • the obtained mixed and pulverized powder was baked at a temperature of 700 ° C. for 20 hours in a nitrogen gas atmosphere to prepare an electrode active material powder in which the carbon material 4 was supported on the particle surfaces.
  • the electrode active material powder obtained above was mixed in a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent to prepare an electrode active material slurry.
  • the mixing ratio of the electrode active material powder and the organic material 2 was 80:20 by weight.
  • the electrode active material slurry prepared above and the solid electrolyte slurry prepared in Example 1 were mixed so that the mixing ratio of the electrode active material powder and the glass powder of LAGP was 50:50 by weight.
  • An electrode slurry was prepared.
  • the obtained all solid state battery was subjected to constant current and constant voltage charge and discharge in the same manner as in Example 4.
  • the obtained charge / discharge curve (broken line) is shown in FIG. It was confirmed that charging / discharging was performed at an initial discharge capacity of about 10 mAh / g.
  • Example 4 AB (carbon material 6) and KB (carbon material 4) covering the surface of the electrode active material particles by the mechanical alloying method are included in the positive electrode layer. For this reason, even if the carbon material 4 whose combustion start temperature is lower than that of the organic material 2 is burned off when the organic material 2 is removed, the carbon material 6 whose combustion start temperature is higher than that of the organic material 2 remains. It can be seen that the all-solid battery No. 4 shows a high capacity. On the other hand, in Comparative Example 4, since the positive electrode layer includes the carbon material 4 but does not include the carbon material 6, the carbon material 4 having a lower combustion start temperature than the organic material 2 is burned out when the organic material 2 is removed. It can be seen that the all solid state battery of Example 4 exhibits a low capacity.
  • Example 5 A powder containing a lithium-containing cobalt phosphate compound LiCo (PO 4 ) (hereinafter referred to as “LCP”) as an electrode active material was produced as follows.
  • LCP lithium-containing cobalt phosphate compound LiCo (PO 4 )
  • Lithium carbonate (Li 2 CO 3 ), cobalt phosphate octahydrate (Co 3 (PO 4 ) 2 8H 2 O), and diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) were used as starting materials. These raw materials are weighed so that the molar ratio is 42.9% -Li 2 CO 3 , 28.6% -Co 3 (PO 4 ) 2 8H 2 O, 28.6%-(NH 4 ) 2 HPO 4. The mixture was sealed in a container, and the container was rotated at 150 rpm for 6 hours to obtain a mixed powder of starting materials.
  • the obtained mixed powder was fired in an air atmosphere at a temperature of 500 ° C. for 6 hours to remove volatile components, thereby obtaining a fired powder.
  • the water was added to the fired powder, sealed in a 500 ml polyethylene container together with a cobblestone having a diameter of 5 mm, and the fired powder was pulverized by rotating the container at a rotation speed of 150 rpm for 24 hours. Thereafter, the powder was dried on a hot plate having a temperature of 120 ° C. to obtain a pulverized powder.
  • the obtained pulverized powder and AB powder were weighed so as to have a weight ratio of 100: 20, and mixed with a planetary ball mill to obtain a coated pulverized powder having particles coated with AB by a mechanical alloying method. Produced.
  • the obtained coated pulverized powder is fired in a nitrogen gas atmosphere at a temperature of 700 ° C. for 20 hours, whereby the surface of the particles is coated with AB (hereinafter referred to as “carbon material 6”) by a mechanical alloying method.
  • An active material powder was prepared.
  • the electrode active material powder obtained above was mixed in a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent to prepare an electrode active material slurry.
  • the mixing ratio of the electrode active material powder and the organic material 2 was 80:20 by weight.
  • the carbon material 4 used in Example 3 was mixed in a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent, thereby preparing a conductive agent slurry.
  • the mixing ratio of the carbon material 4 and the organic material 2 was 80:20 by weight.
  • the mixing ratio of the electrode active material powder, the glass powder of LAGP, and the carbon material 4 is 45 parts by weight of the electrode active material slurry and conductive agent slurry prepared above and the solid electrolyte slurry prepared in Example 1. : 45:10 was mixed to prepare an electrode slurry.
  • Each of the obtained electrode slurry and solid electrolyte slurry was molded by a doctor blade method to produce a molded body of an electrode sheet and a solid electrolyte sheet.
  • the thickness of the molded body was 50 ⁇ m.
  • an all-solid battery was produced in the same manner as in Example 1. However, firing was performed under the following conditions. First, the organic material 2 was removed by baking at a temperature of 400 ° C. in a nitrogen gas atmosphere containing a small amount of oxygen. Then, it baked at the temperature of 600 degreeC in nitrogen gas atmosphere.
  • the pulverized powder prepared in Example 5 and the carbon material 4 were weighed so as to have a weight ratio of 100: 20, and mixed in a mortar to obtain a mixed pulverized powder.
  • the obtained mixed and pulverized powder was baked at a temperature of 700 ° C. for 20 hours in a nitrogen gas atmosphere to prepare an electrode active material powder in which the carbon material 4 was supported on the particle surfaces.
  • the electrode active material powder obtained above was mixed in a binder solution obtained by dissolving the organic material 2 serving as a binder in an organic solvent to prepare an electrode active material slurry.
  • the mixing ratio of the electrode active material powder and the organic material 2 was 80:20 by weight.
  • the electrode active material slurry prepared above and the solid electrolyte slurry prepared in Example 1 were mixed so that the mixing ratio of the electrode active material powder and the glass powder of LAGP was 50:50 by weight.
  • An electrode slurry was prepared.
  • the obtained all solid state battery was subjected to constant current and constant voltage charge and discharge in the same manner as in Example 5.
  • the obtained charge / discharge curve (broken line) is shown in FIG. It was confirmed that charging / discharging was performed at an initial discharge capacity of about 10 mAh / g.
  • Example 5 AB (carbon material 6) for covering the surface of the electrode active material particles by the mechanical alloying method and KB (carbon material 4) are included in the positive electrode layer. For this reason, even if the carbon material 4 whose combustion start temperature is lower than that of the organic material 2 is burned off when the organic material 2 is removed, the carbon material 6 whose combustion start temperature is higher than that of the organic material 2 remains. It can be seen that the all-solid-state battery 5 shows a high capacity. On the other hand, in Comparative Example 5, since the positive electrode layer includes the carbon material 4 but does not include the carbon material 6, the carbon material 4 having a lower combustion start temperature than the organic material 2 is burned off when the organic material 2 is removed. It can be seen that the all solid state battery of Example 5 exhibits a low capacity.
  • the carbon powder is not limited to the AB powder, and the firing step is performed. If the combustion start temperature is higher than that of the organic material to be removed in step 1, the same effect can be obtained even if another carbon material is used.
  • carbon material in addition to AB, carbon nanofiber (CNF), carbon nanotube (CNT), or the like may be used.
  • the LAGP raw material powder is not limited to the amorphous body.
  • the same effect can be obtained by using a crystal.
  • the negative electrode includes a graphite-lithium compound, a lithium alloy such as Li-Al, Li 3 V 2 (PO 4 ) 3 , TiO 2. Similar effects can be obtained by using oxides such as 2 , MoO 2 and Nb 2 O 5 , and the all-solid-state battery of the present invention is not limited to those using metallic lithium as the negative electrode.
  • the present invention is particularly useful for the production of an all-solid secondary battery.

Landscapes

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

Abstract

L'invention concerne : un stratifié non fritté destiné à une batterie entièrement solide, capable de limiter la combustion du carbone en tant qu'agent conducteur incorporé à une couche d'électrode non frittée et d'améliorer la capacité ; une batterie entièrement solide ; et un procédé pour sa production. La batterie entièrement solide (10) comporte : au moins une couche d'électrode constituant une couche (11) d'électrode positive ou une couche (13) d'électrode négative ; et une couche (12) d'électrolyte solide stratifiée sur la couche d'électrode. La couche d'électrode comprend : un premier matériau carboné qui commence à brûler à une première température ; et un deuxième matériau carboné qui commence à brûler à une deuxième température supérieure à la première température. Afin de produire la batterie entièrement solide (10) : la couche d'électrode non frittée, constituée d'un corps non fritté formé au moins de la couche (11) d'électrode positive ou de la couche (13) d'électrode négative, et une couche non frittée d'électrolyte solide, constituée d'un corps non fritté formé de la couche (12) d'électrolyte solide, sont préparées ; la couche d'électrode non frittée et la couche non frittée d'électrolyte solide sont stratifiées et un stratifié est formé ; puis le stratifié est cuit. La couche d'électrode non frittée comprend : le premier matériau carboné qui commence à brûler à la première température ; et le deuxième matériau carboné qui commence à brûler à la deuxième température supérieure à la première température.
PCT/JP2012/072426 2011-09-12 2012-09-04 Stratifié non fritté pour batterie entièrement solide, batterie entièrement solide et procédé pour sa production WO2013038948A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013533617A JP5644951B2 (ja) 2011-09-12 2012-09-04 全固体電池用未焼結積層体、全固体電池およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011197896 2011-09-12
JP2011-197896 2011-09-12

Publications (1)

Publication Number Publication Date
WO2013038948A1 true WO2013038948A1 (fr) 2013-03-21

Family

ID=47883179

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/072426 WO2013038948A1 (fr) 2011-09-12 2012-09-04 Stratifié non fritté pour batterie entièrement solide, batterie entièrement solide et procédé pour sa production

Country Status (2)

Country Link
JP (1) JP5644951B2 (fr)
WO (1) WO2013038948A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208133A1 (fr) * 2013-06-28 2014-12-31 太陽誘電株式会社 Accumulateur entièrement solide et son procédé de fabrication
JP2021515963A (ja) * 2018-03-15 2021-06-24 エスケー イノベーション カンパニー リミテッドＳｋ Ｉｎｎｏｖａｔｉｏｎ Ｃｏ．，Ｌｔｄ． 二次電池用電極およびその製造方法
US11075368B2 (en) 2017-11-02 2021-07-27 Taiyo Yuden Co., Ltd. All solid battery and manufacturing method of the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4123750A1 (fr) 2020-03-16 2023-01-25 Murata Manufacturing Co., Ltd. Batterie à semi-conducteur
CN115413378A (zh) 2020-05-25 2022-11-29 株式会社村田制作所 固体电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533373A (ja) * 2002-07-12 2005-11-04 イドロ−ケベック ハイブリッド導電性層で被覆された、非導電性コア又は半導電性コアを含む粒子とその製造方法、及び電気化学的デバイスにおけるその使用
JP2007227362A (ja) * 2006-01-27 2007-09-06 Matsushita Electric Ind Co Ltd 固体電池の製造方法
JP2011134617A (ja) * 2009-12-24 2011-07-07 Ohara Inc 全固体電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533373A (ja) * 2002-07-12 2005-11-04 イドロ−ケベック ハイブリッド導電性層で被覆された、非導電性コア又は半導電性コアを含む粒子とその製造方法、及び電気化学的デバイスにおけるその使用
JP2007227362A (ja) * 2006-01-27 2007-09-06 Matsushita Electric Ind Co Ltd 固体電池の製造方法
JP2011134617A (ja) * 2009-12-24 2011-07-07 Ohara Inc 全固体電池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208133A1 (fr) * 2013-06-28 2014-12-31 太陽誘電株式会社 Accumulateur entièrement solide et son procédé de fabrication
JP2015011864A (ja) * 2013-06-28 2015-01-19 太陽誘電株式会社 全固体二次電池およびその製造方法
US9865899B2 (en) 2013-06-28 2018-01-09 Taiyo Yuden Co., Ltd. All-solid-state secondary battery with solid electrolyte layer containing particulate precipitate of an olivine-type crystal structure
US10249905B2 (en) 2013-06-28 2019-04-02 Taiyo Yuden Co., Ltd. All-solid-state secondary battery and method for manufacturing same
US11075368B2 (en) 2017-11-02 2021-07-27 Taiyo Yuden Co., Ltd. All solid battery and manufacturing method of the same
JP2021515963A (ja) * 2018-03-15 2021-06-24 エスケー イノベーション カンパニー リミテッドＳｋ Ｉｎｎｏｖａｔｉｏｎ Ｃｏ．，Ｌｔｄ． 二次電池用電極およびその製造方法

Also Published As

Publication number Publication date
JP5644951B2 (ja) 2014-12-24
JPWO2013038948A1 (ja) 2015-03-26

Similar Documents

Publication Publication Date Title
WO2012008422A1 (fr) Batterie tout solide
WO2011132627A1 (fr) Pile rechargeable intégralement à base de semi-conducteurs, et procédé de production correspondant
KR101319376B1 (ko) 리튬 이차 전지용 양극 활물질, 및 이를 포함하는 양극 및 리튬 이차 전지
WO2013137224A1 (fr) Cellule entièrement électronique et son procédé de fabrication
JP2023080348A (ja) 全固体電池
JP5516749B2 (ja) 全固体電池およびその製造方法
JP5804208B2 (ja) 全固体電池、全固体電池用未焼成積層体、および全固体電池の製造方法
WO2013175991A1 (fr) Batterie entièrement à l'état solide et son procédé de fabrication
JP5796687B2 (ja) 正極材料、二次電池およびそれらの製造方法
JP5796798B2 (ja) 正極材料、全固体電池およびそれらの製造方法
JP5796686B2 (ja) 全固体電池およびその製造方法
JP5644951B2 (ja) 全固体電池用未焼結積層体、全固体電池およびその製造方法
JP5556969B2 (ja) 全固体電池用積層成形体、全固体電池およびその製造方法
WO2012060402A1 (fr) Accumulateur entièrement solide et son procédé de fabrication
US20200194829A1 (en) Solid electrolyte layer and all-solid-state battery
JP6587555B2 (ja) 固体電解質組成物、これを用いた全固体二次電池用シートおよび全固体二次電池ならびにこれらの製造方法
JP6030960B2 (ja) 全固体電池の製造方法
WO2019203334A1 (fr) Composition d'électrolyte solide, feuille de batterie secondaire tout solide, batterie secondaire tout solide, et procédé de fabrication d'une feuille de batterie secondaire tout solide ou d'une batterie secondaire tout solide
JP6623083B2 (ja) 固体電解質組成物、これを用いた全固体二次電池用シートおよび全固体二次電池ならびにこれらの製造方法
JP2020024780A (ja) 全固体電池およびその製造方法
WO2013161982A1 (fr) Batterie à électrolyte solide, et son procédé de production
JP6003982B2 (ja) 全固体電池
JPWO2013035526A1 (ja) 全固体電池用積層成形体、全固体電池およびその製造方法
WO2013161981A1 (fr) Procédé de production d'une batterie à électrolyte solide, et batterie à électrolyte solide
JP2021172545A (ja) 複合材料、その製造方法および全固体型リチウムイオン二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12831636

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013533617

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12831636

Country of ref document: EP

Kind code of ref document: A1