WO2013146454A1 - Matériau d'électrode, batterie rechargeable au lithium à électrolyte entièrement solide, et procédé de fabrication associé - Google Patents

Matériau d'électrode, batterie rechargeable au lithium à électrolyte entièrement solide, et procédé de fabrication associé Download PDF

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WO2013146454A1
WO2013146454A1 PCT/JP2013/057782 JP2013057782W WO2013146454A1 WO 2013146454 A1 WO2013146454 A1 WO 2013146454A1 JP 2013057782 W JP2013057782 W JP 2013057782W WO 2013146454 A1 WO2013146454 A1 WO 2013146454A1
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solid electrolyte
electrode
solid
active material
molded body
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PCT/JP2013/057782
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English (en)
Japanese (ja)
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真嶋　正利
細江　晃久
奥野　一樹
弘太郎 木村
健吾 後藤
英彰 境田
吉田　健太郎
和宏 後藤
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住友電気工業株式会社
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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
    • H01M4/13—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
    • H01M10/052—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
    • H01M4/139—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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • 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 electrode material used for an all-solid lithium secondary battery using a lithium ion conductive solid electrolyte, an all-solid lithium secondary battery using this electrode material, and a method for producing the same.
  • lithium ion secondary batteries are actively studied in various fields as batteries capable of obtaining a high energy density because lithium has a small atomic weight and a large ionization energy.
  • an organic electrolyte is used as the electrolyte.
  • this organic electrolyte exhibits high ionic conductivity, since the electrolyte is a flammable liquid, there is a risk of liquid leakage or ignition when used as a battery.
  • the metal negative electrode is passivated by the reaction with the electrolytic solution, the impedance increases, current concentration occurs in the low impedance part, dendrite is generated, and this dendrite penetrates the separator existing between the positive and negative electrodes, thereby Problems such as internal short circuit of the battery are likely to occur. For this reason, further improvement in safety and performance of lithium ion secondary batteries are technical issues.
  • lithium secondary batteries using an inorganic solid electrolyte with higher safety instead of organic electrolytes have been studied. Since inorganic solid electrolytes are generally nonflammable and have high heat resistance, development of all-solid lithium secondary batteries using inorganic solid electrolytes is desired.
  • Patent Document 1 a main component Li 2 S and P 2 S 5, having a composition of Li 2 S82.5 ⁇ 92.5, P 2 S 5 7.5 ⁇ 17.5 by mol%
  • the use of lithium ion conductive sulfide ceramics as an electrolyte for all solid state batteries is described.
  • Patent Document 2 discloses a chemical formula M a XM b Y (M: alkali metal, X, Y: SO 4 , BO 3 , PO 4 , GeO 4 , WO 4 , MoO 4 , SiO 4 , NO 3 , BS 3. , PS 4 , SiS 4 , GeS 4 , a: the valence of the X anion, b: the valence of the Y anion) is used as the solid electrolyte. It is described to do.
  • Patent Document 3 discloses a positive electrode containing a compound selected from the group consisting of transition metal oxides and transition metal sulfides as a positive electrode active material, a lithium ion conductive glass solid electrolyte containing Li 2 S, and an alloy of lithium and alloy And a negative electrode containing a metal to be converted as an active material, and an all solid lithium secondary battery in which at least one of a positive electrode active material and a negative electrode metal active material contains lithium is described.
  • Patent Document 4 improves the flexibility and mechanical strength of the electrode material layer in the all-solid-state battery, suppresses missing or cracking of the electrode material, and peeling from the current collector.
  • an inorganic solid electrolyte is applied to the pores of the porous metal sheet having a three-dimensional network structure as the electrode material used in the all-solid lithium secondary battery. It is described that an electrode material sheet inserted is used.
  • Patent Document 5 the surface of a synthetic resin having a three-dimensional network structure is subjected to a primary conductive treatment by electroless plating, CVD, PVD, metal or graphite coating, and then metallization is performed by electroplating. It describes that the metal porous body obtained by making it into an electrical power collector.
  • Aluminum is preferred as the material for the current collector of the positive electrode for general-purpose lithium secondary batteries. Since aluminum has a lower standard electrode potential than hydrogen, in an aqueous solution, water is electrolyzed before plating, so that aluminum plating in an aqueous solution is difficult. Patent Document 6 describes that an aluminum porous body obtained by forming an aluminum film on the surface of a polyurethane foam by molten salt plating and then removing the polyurethane is used as a current collector for a battery.
  • the all-solid lithium secondary battery using the above three-dimensional network structure as a current collector has a problem that the internal resistance increases as charging and discharging are repeated.
  • An object of the present invention is to provide an all-solid lithium secondary battery that does not increase in internal resistance even when charging and discharging are repeated.
  • the present inventors have intensively studied, and as a result, the electrode material is filled with metal by plating in the pore portion of a solid powder molded body composed of at least an active material and a solid electrolyte.
  • the present invention was completed with the knowledge that it could be solved. That is, the present invention relates to an electrode material for an all-solid lithium secondary battery as described below.
  • An electrode material in an all-solid lithium secondary battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode, the electrode material comprising at least an active material and a solid
  • the solid electrolyte is a lithium ion conductive solid electrolyte containing lithium, phosphorus and sulfur as main components, and constitutes the solid electrolyte layer. Any one of (1) to (5) The electrode material according to claim 1.
  • An all-solid lithium secondary battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode, wherein the positive electrode and the negative electrode are as defined in (1) to (6)
  • An all-solid lithium secondary battery comprising the electrode material according to any one of the above.
  • (11) forming a solid electrolyte layer by applying a solid electrolyte slurry on one surface of a porous powder molded body for a first electrode containing at least an active material and a solid electrolyte; and A step of laminating a porous powder molded body for a second electrode containing an active material and a solid electrolyte to obtain a laminated body, and a porous powder molded body for the first electrode and the second electrode A method for producing an all-solid-state lithium secondary battery, wherein a metal coating is formed on the surfaces of the active material and the solid electrolyte by plating a porous powder compact.
  • the all-solid-state lithium secondary battery of the present invention has a high output, and has an effect of improving cycle characteristics because the internal resistance does not increase due to repeated charge and discharge.
  • FIG. 1 is a longitudinal sectional view of an all-solid lithium secondary battery 10.
  • the all solid lithium secondary battery 10 includes a positive electrode 1, a negative electrode 2, and a solid electrolyte layer (SE layer) 3 disposed between both electrodes.
  • the positive electrode 1 includes a positive electrode layer (positive electrode body) 4 and a positive electrode current collector 65, and the negative electrode 2 includes a negative electrode layer 6 and a negative electrode current collector 7.
  • the positive electrode is filled with a positive electrode active material and a lithium ion conductive solid electrolyte in the pores of the metal porous body
  • the negative electrode is a three-dimensional network metal porous body.
  • the pores are filled with a negative electrode active material powder and a lithium ion conductive solid electrolyte. Since the current collector has a three-dimensional network structure, the contact area with the active material increases, so that the battery internal resistance can be reduced and the battery efficiency is improved. Furthermore, the distribution of the electrolyte can be improved, current concentration can be prevented, battery reliability can be improved, heat generation can be suppressed, and battery output can be increased.
  • the unevenness of the skeleton surface improves the holding power of the active material, and can prevent the active material from falling off. Furthermore, the irregularity of the skeleton surface increases the specific surface area, improves the utilization efficiency of the active material, and allows the battery to have a higher capacity.
  • a three-dimensional reticulated metal porous body can be obtained by, for example, using urethane foam as a base material and forming a metal film on the surface and then removing the base material.
  • the cell diameter is usually 400 to 500 ⁇ m. Accordingly, the cell diameter formed by the porous metal skeleton obtained by forming a metal film on the surface of the urethane foam is about 400 to 500 ⁇ m.
  • the active material filled in the metal porous cell has a particle size of 5 to 10 ⁇ m, and the particle size of the solid charge charged in the cell together with the active material is 0.1 to 0 for the primary particles. 0.5 ⁇ m, secondary particles are 5-20 ⁇ m. For this reason, many active materials and solid electrolytes are filled in one cell, and since the distance between the active material and solid electrolyte near the center of the cell and the skeleton of the cell is long, the internal resistance becomes high, Battery output does not improve. Although the internal resistance can be reduced by allowing a conductive aid such as acetylene black to be present in the cell together with the active material, the effect is not sufficient.
  • the electrode material of the present invention solves the above-mentioned problems without using a three-dimensional network metal porous body.
  • the electrode material of the present invention can be produced by performing a plating treatment using at least a powder molded body including an active material powder and a solid electrolyte powder as a base material, and filling the pores of the powder molded body with a metal. Since the metal filled in the pores of the powder molded body functions as a conductive path and increases the conductive path of the powder molded body, the internal resistance of the battery can be reduced. In addition, the pores of the powder compact are filled with metal by plating, and the time for the plating process is lengthened to form a metal film with a predetermined thickness on the surface of the powder compact, thereby collecting the metal film. It can function as a body. Since the electrode material of the present invention does not use a three-dimensional network metal porous body, the material cost can be reduced, and the current collector can be integrated with the electrode, thereby reducing the cost of battery assembly. Can do.
  • the positive electrode active material a material capable of removing and inserting lithium can be used.
  • the active material is used in combination with a conductive additive and a binder.
  • transition metal oxides such as olivine compounds which are conventional lithium iron phosphate and its compounds (LiFePO 4 , LiFe 0.5 Mn0.5PO 4 ). Further, the transition metal element contained in these materials may be partially substituted with another transition metal element.
  • Still other positive electrode active materials include, for example, TiS 2 , V 2 S 3 , FeS, FeS 2 , LiMSx (M is a transition metal element such as Mo, Ti, Cu, Ni, Fe, or Sb, Sn, Pb) ) And other metal oxides such as TiO 2 , Cr 3 O 8 , V 2 O 5 , and MnO 2 . Depending on the type of active material, it is necessary to appropriately select a plating solvent.
  • a material capable of inserting and extracting lithium ions can be used.
  • examples of such a negative electrode active material include graphite and lithium titanate (Li 4 Ti 5 O 12 ).
  • lithium titanate (Li 4 Ti 5 O 12 ) is used as the negative electrode active material, aluminum can be used as the plating metal for the negative electrode.
  • an alloy combined with a metal itself such as metallic lithium, metallic indium, metallic aluminum, metallic silicon, metallic tin, metallic magnesium, metallic calcium, or another element or compound can be used as the negative electrode active material.
  • These negative electrode active materials can be used individually by 1 type or in combination of 2 or more types. Depending on the type of active material, it is necessary to appropriately select a plating solvent.
  • Solid electrolyte Solid electrolyte
  • a solid electrolyte that is stable under the conditions of the plating treatment for example, an oxide-based solid electrolyte is selected.
  • a sulfide-based solid electrolyte having a high lithium ion conductivity is used as the solid electrolyte, but this material cannot be used because it reacts in water-based plating.
  • known ones can be used as the solid electrolyte.
  • lithium silicophosphate Li 3.5 Si 0.5 P 0.5 O 4
  • lithium titanium phosphate LiTi 2 (PO 4 ) 2
  • Lithium germanium phosphate LiGe 2 (PO 4 ) 3
  • Li 2 O—SiO 2 Li 2 O—V 2 O 5 —SiO 2
  • Li 2 O—P 2 O 5 —B 2 O 3 Li 2 O
  • Li 2 O At least one selected from the group consisting of —GeO 2 can be used.
  • a sulfide-based solid electrolyte having a high lithium ion conductivity as the solid electrolyte layer used by being sandwiched between the positive electrode and the negative electrode, and as such a sulfide-based solid electrolyte, lithium, phosphorus, And a sulfide-based solid electrolyte containing sulfur.
  • the sulfide solid electrolyte may further contain an element such as O, Al, B, Si, and Ge.
  • Such a sulfide-based solid electrolyte can be obtained by a known method.
  • lithium sulfide (Li 2 S) and diphosphorus pentasulfide (P 2 S 5 ) are prepared as starting materials, and the ratio of Li 2 S and P 2 S 5 is about 50:50 to 80:20 in molar ratio.
  • a method of melting and quenching the mixture melting and quenching method
  • a method of mechanically milling the mixture nocical milling method.
  • the sulfide-based solid electrolyte obtained by the above method is amorphous. Although it can be used in this amorphous state, it may be heat-treated to obtain a crystalline sulfide solid electrolyte. Crystallization can be expected to improve lithium ion conductivity.
  • a solid electrolyte layer is formed from the above-mentioned solid electrolyte powder.
  • the formation method is as follows. (1) A method of obtaining a solid electrolyte film by pulverizing a solid electrolyte and then pressing it to form a solid electrolyte film (2) Applying a slurry of the solid electrolyte to the surface of an electrode material obtained by plating a powder compact for an electrode and drying how to. In this case, a binder may be added to the slurry, but it may not be added. Moreover, the solid electrolyte layer may be formed on either one of the positive electrode material and the negative electrode material, or both.
  • a method in which a solid electrolyte slurry is formed by applying a solid electrolyte slurry to one surface of each of a positive electrode powder compact and a negative electrode powder compact before plating. Thereafter, two powder compacts are laminated through the surface on the side of the solid electrolyte layer to form a laminate of positive electrode powder compact / solid electrolyte layer / negative electrode powder compact, Apply plating.
  • a solid electrolyte slurry is applied to one surface of one of the positive electrode powder molded body and the negative electrode powder molded body, and then dried to form a solid electrolyte layer. The powder of the other electrode is formed on the solid electrolyte layer.
  • the molded body may be laminated to form a positive electrode material-solid electrolyte layer-negative electrode material laminate, and then the laminate may be subjected to a plating treatment.
  • the thickness of the solid electrolyte membrane is preferably 20 to 500 ⁇ m.
  • a conductive aid In the electrode material of the present invention, since the metal formed by plating exists between the active material and the solid electrolyte, it is not necessary to use a conductive aid, but a conductive aid may be added.
  • a conductive support agent is not specifically limited, A well-known or commercially available thing can be used. Examples thereof include carbon black such as acetylene black and ketjen black; activated carbon; graphite and the like. When graphite is used, the shape thereof may be any shape such as a spherical shape, a flake shape, a filament shape, and a fiber shape such as a carbon nanotube (CNT).
  • binder compact containing active material and solid electrolyte -Mixing mixture-
  • active material a conductive additive and a binder are added to the active material and the solid electrolyte (hereinafter referred to as “active material”) as necessary, and an organic solvent or water is added thereto.
  • the binder material include polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer in addition to the above-described fluororesins such as PVDF and PTFE.
  • thickeners such as water-soluble thickeners such as carboxymethylcellulose, xanthan gum, pectin agarose can also be used as the binder.
  • Organic solvents used in preparing the slurry include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl Examples thereof include ethylene carbonate, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, ethylene glycol, N-methyl- 2-pyrrolidone and the like.
  • surfactant when using water for a solvent, you may use surfactant in order to improve a filling property.
  • the binder may be mixed with a solvent when forming the molding mixture, but the binder may be dispersed or dissolved in the solvent in advance.
  • aqueous dispersion of a fluororesin in which a fluororesin is dispersed in water an aqueous binder such as an aqueous solution of carboxymethylcellulose; an NMP solution of PVDF ordinarily used when a metal foil is used as a current collector, etc. it can.
  • the content of each component in the molding mixture is not particularly limited, and may be appropriately determined according to the binder, solvent, and the like to be used.
  • a powder compact can be obtained also by the method of apply
  • the temperature of the heat treatment is 80 ° C. or higher, preferably 100 ° C. to 200 ° C.
  • the pressure at the time of heating may be normal pressure or may be reduced, but it is preferably performed under reduced pressure.
  • the pressure at which the pressure is reduced is, for example, 1000 Pa or less, preferably 1 to 500 Pa.
  • the heating time is appropriately determined according to the heating atmosphere, pressure, etc., but is usually 1 to 20 hours, preferably 5 to 15 hours.
  • the powder molded body obtained above is used as a base material, and a metal is filled in the pores of the powder molded body by plating.
  • a conductive film is formed by forming a metal film on the surface of the active material. Further, when the pores near the surface of the powder compact are filled with metal, the thickness of the metal coating formed on the surface of the powder compact increases, and the metal coating functions as a current collector. .
  • the plating treatment may be performed before the solid electrolyte layer is formed on the powder molded body, or may be performed after the solid electrolyte layer is formed.
  • a laminate of positive electrode powder compact / solid electrolyte layer / negative electrode powder compact may be formed, and the laminate may be plated.
  • a coating of a metal other than aluminum can be produced by a normal aqueous plating method, but aluminum is difficult to produce by an aqueous plating method, and is melted as described in International Publication No. 2011/118460.
  • An aluminum film can be formed by adopting a method of plating using a salt bath. However, depending on the active material, an aqueous plating solution may not be used.
  • molten salt plating A direct current is applied in molten salt using the powder compact as a cathode and aluminum having a purity of 99.0% as an anode.
  • the molten salt an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
  • the use of an organic molten salt bath that melts at a relatively low temperature is preferable because the binder resin contained in the powder molded body is not decomposed.
  • the organic halide imidazolium salt, pyridinium salt and the like can be used, and specifically, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable.
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • BPC butylpyridinium chloride
  • molten salt bath a molten salt bath containing nitrogen is preferable, and among them, an imidazolium salt bath is preferably used.
  • the imidazolium salt bath is preferable because it can be plated at a relatively low temperature.
  • a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
  • an aluminum chloride + 1-ethyl-3-methylimidazolium chloride (AlCl 3 + EMIC) molten salt is stable. Is most preferably used because it is high and difficult to decompose.
  • the temperature of the molten salt bath is 10 ° C to 60 ° C, preferably 25 ° C to 45 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to plate. If it exceeds 60 ° C., the binder resin in the powder molded body may be decomposed, so that it is preferably 60 ° C. or less.
  • Example 1 Manufacture of positive electrode 1 -Manufacture of powder compact for positive electrode- As an active material, a lithium cobaltate powder (positive electrode binder) having an average particle diameter of 5 ⁇ m is prepared. This lithium cobaltate powder, Li 2 S + P 2 S 5 (solid electrolyte), PVDF (binder), and acetylene black (Conductive auxiliary agent) was mixed at a mass ratio of 55: 35: 5: 5. N-methyl-2-pyrrolidone (organic solvent) was added dropwise to the mixture and mixed to prepare a powder mixture for a positive electrode powder compact. Next, this powder mixture was applied in a glass shape with a thickness of 700 ⁇ m, and then dried at 100 ° C. for 40 minutes to remove the organic solvent. It peeled from the glass and compressed with the roller press, and 5 cm x 5 cm x 0.05 cmt [Positive powder body 1 for positive electrodes] was obtained.
  • Li 2 S + P 2 S 5 solid electrolyte
  • PVDF bin
  • a DC current having a current density of 3.6 A / dm 2 was applied for 90 minutes, and only one side was plated to obtain [Positive electrode 1].
  • the plating bath was stirred with a stirrer using a Teflon (registered trademark) rotor.
  • the current density is a value calculated by the apparent area of the positive electrode powder compact 1.
  • the aluminum plate side of the counter electrode was coated with aluminum metal on the active material and the solid electrolyte surface, and an aluminum film having a thickness of 5 ⁇ m was formed on the outermost surface of the powder compact.
  • lithium titanate powder (negative electrode active material) having an average particle diameter of 5 ⁇ m is prepared.
  • This lithium titanate powder, Li 2 S + P 2 S 5 (solid electrolyte), PVDF (binder), and acetylene black ( Conductive aid) was mixed in a mass ratio of 50: 40: 5: 5.
  • N-methyl-2-pyrrolidone organic solvent
  • this powder mixture was applied in a glass shape with a thickness of 700 ⁇ m, and then dried at 100 ° C. for 40 minutes to remove the organic solvent. It peeled from the glass and compressed with the roller press, and 5 cm x 5 cm x 0.05 cmt [Powder compact 1 for negative electrodes] was obtained.
  • Example 2 [All-solid lithium secondary battery 2] was obtained in the same manner as in Example 1 except that the current density of molten salt plating in Example 1 was 7.2 A / dm 2 and the DC current application time was 45 minutes. . An evaluation test was performed on [All-solid lithium secondary battery 2] in the same manner as in Example 1, and the evaluation results are shown in Table 1.
  • the all-solid-state lithium secondary battery of the present invention does not decrease from the initial charge / discharge capacity even after 500 cycles, and the charge / discharge efficiency also changes at 100% and operates stably. It was. Further, no change in impedance was observed in the all solid lithium secondary battery of the present invention even after 100 hours. On the other hand, the all-solid lithium secondary battery of the comparative example had lower characteristics than the all-solid lithium secondary battery of the present invention.
  • the all-solid-state lithium secondary battery of the present invention can be suitably used as a power source for portable electric devices such as mobile phones and smartphones, electric vehicles using a motor as a power source, and hybrid electric vehicles.

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Abstract

La présente invention se rapporte à une batterie rechargeable au lithium à électrolyte entièrement solide qui ne subit pas une augmentation de la résistance interne même avec des opérations de charge et de décharge répétées. La présente invention se rapporte également à un matériau d'électrode pour une batterie rechargeable au lithium à électrolyte entièrement solide pourvue d'une électrode positive, d'une électrode négative, et d'une couche d'électrolyte solide agencée entre l'électrode positive et l'électrode négative. Ledit matériau d'électrode est obtenu par placage d'un substrat qui se compose d'un compact de poudre poreux qui contient, au moins, un matériau actif et un électrolyte solide et est caractérisé en ce qu'un revêtement métallique est formé sur la surface dudit matériau actif et dudit électrolyte solide.
PCT/JP2013/057782 2012-03-29 2013-03-19 Matériau d'électrode, batterie rechargeable au lithium à électrolyte entièrement solide, et procédé de fabrication associé WO2013146454A1 (fr)

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JP2012-076113 2012-03-29
JP2012076113A JP2013206790A (ja) 2012-03-29 2012-03-29 電極材料及び全固体リチウム二次電池、並びに製造方法

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* Cited by examiner, † Cited by third party
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US9780360B2 (en) 2014-09-10 2017-10-03 Toyota Jidosha Kabushiki Kaisha Cathode mixture, cathode, solid battery and method for producing cathode mixture, cathode and solid battery
CN109494398A (zh) * 2017-09-11 2019-03-19 现代自动车株式会社 全固态电池及其制造方法
WO2019116857A1 (fr) * 2017-12-12 2019-06-20 日本碍子株式会社 Batterie au lithium tout solide et son procédé de fabrication

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9608288B2 (en) 2014-07-17 2017-03-28 Samsung Electronics Co., Ltd. Positive electrode for lithium ion secondary battery and lithium ion secondary battery including the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006216565A (ja) * 2003-12-04 2006-08-17 Mitsui Mining & Smelting Co Ltd 二次電池用電極及びその製造方法並びに二次電池
JP2008135287A (ja) * 2006-11-28 2008-06-12 Idemitsu Kosan Co Ltd 全固体電池用部材、該部材の製造方法並びに全固体電池
JP2010040218A (ja) * 2008-07-31 2010-02-18 Idemitsu Kosan Co Ltd リチウム電池用電極材料シート、固体リチウム電池、及び、固体リチウム電池を備えた装置
JP2010097832A (ja) * 2008-10-17 2010-04-30 Mitsui Mining & Smelting Co Ltd 非水電解液二次電池用負極
JP2010192255A (ja) * 2009-02-18 2010-09-02 Nissan Motor Co Ltd 電極構造およびリチウムイオン二次電池
JP2011249260A (ja) * 2010-05-31 2011-12-08 Sumitomo Electric Ind Ltd 非水電解質電池用集電体、及び非水電解質電池用電極、並びに非水電解質電池
JP2011258388A (ja) * 2010-06-08 2011-12-22 Dainippon Printing Co Ltd 非水電解液二次電池用電極板、非水電解液二次電池用電極板の製造方法、および非水電解液二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006216565A (ja) * 2003-12-04 2006-08-17 Mitsui Mining & Smelting Co Ltd 二次電池用電極及びその製造方法並びに二次電池
JP2008135287A (ja) * 2006-11-28 2008-06-12 Idemitsu Kosan Co Ltd 全固体電池用部材、該部材の製造方法並びに全固体電池
JP2010040218A (ja) * 2008-07-31 2010-02-18 Idemitsu Kosan Co Ltd リチウム電池用電極材料シート、固体リチウム電池、及び、固体リチウム電池を備えた装置
JP2010097832A (ja) * 2008-10-17 2010-04-30 Mitsui Mining & Smelting Co Ltd 非水電解液二次電池用負極
JP2010192255A (ja) * 2009-02-18 2010-09-02 Nissan Motor Co Ltd 電極構造およびリチウムイオン二次電池
JP2011249260A (ja) * 2010-05-31 2011-12-08 Sumitomo Electric Ind Ltd 非水電解質電池用集電体、及び非水電解質電池用電極、並びに非水電解質電池
JP2011258388A (ja) * 2010-06-08 2011-12-22 Dainippon Printing Co Ltd 非水電解液二次電池用電極板、非水電解液二次電池用電極板の製造方法、および非水電解液二次電池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9780360B2 (en) 2014-09-10 2017-10-03 Toyota Jidosha Kabushiki Kaisha Cathode mixture, cathode, solid battery and method for producing cathode mixture, cathode and solid battery
CN109494398A (zh) * 2017-09-11 2019-03-19 现代自动车株式会社 全固态电池及其制造方法
WO2019116857A1 (fr) * 2017-12-12 2019-06-20 日本碍子株式会社 Batterie au lithium tout solide et son procédé de fabrication
JPWO2019116857A1 (ja) * 2017-12-12 2020-12-24 日本碍子株式会社 全固体リチウム電池及びその製造方法
US11404683B2 (en) 2017-12-12 2022-08-02 Ngk Insulators, Ltd. All-solid-state lithium battery and method for manufacturing same
JP7126518B2 (ja) 2017-12-12 2022-08-26 日本碍子株式会社 全固体リチウム電池及びその製造方法

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