WO2018139657A1 - Stratifié d'électrode et pile au lithium entièrement solide - Google Patents

Stratifié d'électrode et pile au lithium entièrement solide Download PDF

Info

Publication number
WO2018139657A1
WO2018139657A1 PCT/JP2018/002795 JP2018002795W WO2018139657A1 WO 2018139657 A1 WO2018139657 A1 WO 2018139657A1 JP 2018002795 W JP2018002795 W JP 2018002795W WO 2018139657 A1 WO2018139657 A1 WO 2018139657A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
layer
electrode
laminate
solid electrolyte
Prior art date
Application number
PCT/JP2018/002795
Other languages
English (en)
Japanese (ja)
Inventor
亮太 江▲崎▼
努 西▲崎▼
田村　哲也
Original Assignee
セントラル硝子株式会社
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 セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Publication of WO2018139657A1 publication Critical patent/WO2018139657A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 electrode laminated body of an electrode layer containing an electrode active material and a separator layer containing a solid electrolyte, which is used for an all solid lithium battery.
  • Secondary batteries are used in portable devices such as mobile phones and laptop computers, transportation equipment such as automobiles and airplanes, and power storage devices for power leveling. Improvements in energy density are required in all applications. Yes.
  • the practical secondary battery with the highest energy density is a lithium ion battery, and research is being conducted to further increase the energy density while maintaining safety.
  • all-solid-state batteries batteries that use solid electrolytes instead of electrolytes, which is an improved technology for lithium-ion batteries, has been conducted.
  • the negative electrode, the electrolyte, and the positive electrode constituting the battery are all solid, and a separator layer is provided between the positive electrode and the negative electrode.
  • the separator layer has a function of insulating electrons and conducting ions between the positive electrode and the negative electrode of one cell.
  • An ion conductive solid electrolyte is mainly used as the separator layer.
  • the solid electrolyte layer between the positive electrode and the negative electrode is referred to as a separator layer instead of the solid electrolyte layer.
  • a current collector layer between adjacent cells has a function of conducting electrons and insulating ions between a positive electrode and a negative electrode of adjacent cells.
  • an all-oxide all-solid battery in which the negative electrode active material, the solid electrolyte, and the positive electrode active material are oxides can be expected to have an effect on safety and high-temperature durability in addition to improving energy density.
  • lithium titanate Li 4 Ti 5 O 12 (also referred to as LTO) having a spinel crystal structure described in Patent Document 1 or Ramsdelite (described in Patent Document 2)
  • LTO lithium titanate
  • Patent Document 2 Ramsdelite
  • a composite oxide of lithium and titanium such as lithium titanate (also called Li 2 Ti 3 O 7 ) having a crystal structure (also called ramsdellite) is known.
  • LAGP Li 1 + x Al x Ge 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 1) containing Li, Al, Ge, and P described in Patent Document 4 is used.
  • Patent Document 10 a solid composite separator containing an electronic insulating inorganic powder dispersed in an amorphous ion conductive inorganic metal oxide, a sulfide solid electrolyte, and a metal sulfate hydrate
  • Patent Document 11 An all-solid-state battery (Patent Document 11) including a separator layer containing benzene has been proposed.
  • a positive electrode active material, and a negative electrode active material are sequentially laminated to form a laminate, and then the adhesion at the interface of each layer is improved. Therefore, sintering by heat treatment may be performed.
  • both the electrode layer and the separator layer are made of an oxide-based material, it is necessary to heat at least 600 ° C., preferably 800 ° C. or higher, in order to obtain a dense sintered body.
  • the electrode active material constituting the electrode layer and the solid electrolyte constituting the separator layer are side-reacted with each other at the interface between the electrode layer and the separator layer, and charge and discharge are performed.
  • a side reaction product which is a material that does not contribute to the conduction of lithium ions or has a small contribution, is generated.
  • the adhesion at the interface between the electrode layer and the separator layer is not good.
  • Patent Document 12 formation of the impurity phase at the time of sintering is suppressed by using a specific material as an electrode active material and a solid electrolyte.
  • a specific material as an electrode active material
  • LiMPO 4 (M is (i) Mn, (ii) Fe, (iii) Co, (iv) Ni, (v) Co and Ni, or (vi) Mn and Fe).
  • Li 1 + X M III X Ti IV 2-X (PO 4 ) 3 (M III is an Al ion and 0 ⁇ x ⁇ 0.6) is used as the solid electrolyte.
  • a solid electrolyte and an electrode active material are made to react intentionally at the time of sintering, and the intermediate layer containing the substance which functions as an active material or a solid electrolyte is formed in the interface of an electrode layer and a solid electrolyte layer. This strengthens the interface bonding.
  • LiMnO 4 is used as the positive electrode active material
  • Li 3.5 Si 0.5 P 0.5 O 4 is used as the solid electrolyte
  • Li 4 Ti 5 O 12 is used as the negative electrode active material
  • the solid electrolyte is subjected to firing.
  • the produced LiO 2 reacts with the electrode active material to produce LiMnO 2 , Li 2 MnO 3, etc. at the interface between the positive electrode layer and the solid electrolyte layer, and LiTiO 2 or Li 2 TiO 3 at the interface between the negative electrode layer and the solid electrolyte layer.
  • JP 2012-104280 A Japanese Patent Laid-Open No. 11-283624 Japanese Translation of PCT International Publication No. 2010-534383 (Patent No. 5634865) JP 2016-177964 A JP 2010-272344 A JP 2016-110792 A Japanese Unexamined Patent Publication No. 2016-117644 JP-T-2014-534592 JP2015-144061A Special table 2015-513768 gazette Japanese Unexamined Patent Publication No. 2016-39128 JP 2007-005279 A International Publication No. 2008/143027
  • Li 4 Ti 5 O 12 is used as the negative electrode active material to strengthen the interface bonding.
  • LiTiO 2 and Li 2 TiO 3 produced at the interface between the negative electrode layer and the solid electrolyte layer have low lithium ion conductivity
  • the presence of the intermediate layer in Patent Document 13 is due to a decrease in the amount of the electrode active material.
  • the battery characteristics of the all-solid-state battery are deteriorated, such as a decrease in battery capacity and a decrease in charge / discharge rate due to inhibition of movement of lithium ions between the negative electrode layer and the positive electrode layer.
  • the precursor laminate of the electrode layer and the separator layer may be sintered at 600 ° C. or higher.
  • An object of the present invention is to provide an electrode laminate in which an electrode active material and a solid electrolyte do not undergo side reactions at the interface during sintering, and no by-product is contained in the interface between the electrode layer and the separator layer.
  • the present inventors have found that lithium phosphate, lithium niobate, and lithium silicate are less likely to side-react with the lithium-titanium composite oxide even at a high temperature of 600 ° C. or higher, and are used as electrode active materials.
  • the electrode active material and the solid electrolyte do not side-react at the interface even if the electrode layer and the separator layer are laminated and sintered.
  • the inventors have found that an electrode laminate in which the layer and the separator layer are in close contact with each other can be obtained, and the present invention has been completed. Specifically, the present invention provides the following.
  • an electrode laminate comprising an electrode layer containing an electrode active material and a separator layer containing a solid electrolyte laminated in this order, the electrode layer containing a composite oxide of lithium and titanium,
  • An electrode laminate including a lithium phosphate, a lithium niobate, or a lithium silicate is provided.
  • the electrode active material and the solid electrolyte are at the interface during sintering.
  • An electrode laminate in which deterioration of battery performance due to side reaction products at the interface between the electrode layer and the separator layer is prevented without causing side reactions can be obtained.
  • the side reaction in the present invention means a reaction that generates a side reaction product.
  • the side reaction product is Li / M (M: Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, lithium excess due to Li supplied from the separator layer on the electrode layer side of the interface. On the separator layer side of the interface, the ratio of any one or more transition metals among copper is more than 1, or on the separator layer side of the interface, lithium is no longer contained. Means a compound.
  • Examples of the side reaction product include Li 2 TiO 3 in the electrode layer, La 2 O 3 and LaNbO 4 in the separator layer, and the like.
  • the present inventors have found that lithium phosphate, lithium niobate and lithium silicate hardly undergo side reactions with perovskite oxides containing lithium even at a high temperature of 600 ° C. or higher.
  • the perovskite oxide is changed to a non-perovskite oxide such as Li 2 TiO 3 by a side reaction, lithium ion conductivity is greatly reduced. Therefore, the present invention provides a composite oxidation of lithium and titanium as an electrode active material. This is highly effective when an electrode composite is used that includes a perovskite oxide as a solid electrolyte.
  • the schematic sectional drawing of the electrode laminated body of this invention The flowchart of the 1st manufacturing method of a precursor.
  • the flowchart of the 2nd manufacturing method of a precursor The flowchart of the 3rd manufacturing method of a precursor.
  • the flowchart of the 4th manufacturing method of a precursor (A), (b), (c) The schematic sectional drawing of the all-solid-state lithium battery of this invention.
  • the electrode laminate 1 of the present invention is formed by laminating an electrode layer 3 containing an electrode active material and a separator layer 5 containing a solid electrolyte in this order.
  • the electrode layer includes a composite oxide of lithium and titanium as an electrode active material, and the composite oxide includes lithium titanate having a spinel crystal structure (a spinel oxide including titanium and lithium), and In addition, lithium titanate having a ramsdelite type crystal structure (ramsdelite type oxide containing titanium and lithium) or a mixture thereof is preferable.
  • the lithium titanate having a spinel crystal structure is, for example, Li 4 Ti 5 O 12 .
  • Part of the elements constituting lithium titanate may be replaced with another element, or another element may be doped.
  • Another element Mg, Cr, Zn, Co , Fe, Ni, Mn, Al, Zr, Nb, Sn, Mo, W and the like, specifically, LiMg 1/2 Ti 3/2 O 4 , LiCo 1/2 Ti 3/2 O 4, LiZn 1/2 Ti 3/2 O 4, LiCrTiO 4, etc. LiFeTiO 4 and the like.
  • Lithium titanate having a ramsdelite type crystal structure is, for example, Li 2 Ti 3 O 7 .
  • Part of the elements constituting lithium titanate may be replaced with another element, or another element may be doped.
  • Examples of the lithium titanate having a Rams Delight type crystal structure, in addition to Li 2 Ti 3 O 7, LiTi 2 O 4 or the like, and a large number of substances are known, solid solutions thereof, for example, Li 2 Ti 3 O 7 A solid solution of LiTi 2 O 4 is also known.
  • Lithium titanate is often used as a negative electrode active material for lithium ion secondary batteries, but a counter electrode (such as lithium metal or lithium alloy) that has a relatively low charge / discharge potential relative to lithium titanate ( If used in a negative electrode), it can be used as a positive electrode active material. Therefore, the electrode layer 3 may be used as a negative electrode layer or a positive electrode layer.
  • the electrode layer 3 is preferably an electrode composite layer containing an electrode active material and a solid electrolyte.
  • the solid electrolyte contained in the electrode composite layer is preferably a perovskite oxide containing lithium.
  • the perovskite oxide is an oxide represented by ABO 3 having a perovskite crystal structure, and the A site is at least one element selected from the group consisting of La, Sr, Ba, Na, Ca and Nd. It is preferable that the B site contains at least one element selected from the group consisting of Ti, Ta, Cr, Fe, Co, Ga, and Nb.
  • the perovskite oxide particularly preferably contains lithium, lanthanum, and titanium.
  • Part of the elements constituting lithium lanthanum titanate may be replaced with another element, or another element may be doped.
  • Other elements include Na, K, Rb, Ag, Tl, Mg, Sr, Ca, Ba, Nb, Ta, W, Ru, Cr, Mn, Fe, Co, Al, Ga, Si, Ge, Zr, Hf, Pr, Nd, Sm, Gd, Dy, Y, Eu, and Tb can be mentioned.
  • La (2/3) ⁇ x Sr x Li x TiO 3 Li x La 2/3 Ti 1 ⁇ x Al x O 3 and the like.
  • the solid electrolyte network contributes to lithium ion conduction, and a lithium ion conduction path to the electrode active material is established through the solid electrolyte network. Can be charged and discharged. Therefore, in the all-solid-state cell using the electrode composite layer processed to a thickness of 10 ⁇ m or more and 150 ⁇ m or less as a negative electrode or a positive electrode and using a solid electrolyte, a charge / discharge test at a temperature of 60 ° C. and a rate of 0.02 mA / cm 2.
  • the initial charge capacity and / or initial discharge capacity of the electrode composite layer when subjected to the treatment is preferably 10 mAh / g or more, more preferably 20 mAh / g or more, and further preferably 30 mAh / g or more. preferable.
  • the capacity means a capacity per unit mass of the electrode composite layer obtained by dividing the capacity of the all-solid-type cell by the mass of the electrode composite layer.
  • the all-solid type cell is an all-solid type cell using a predetermined counter electrode and a solid electrolyte, with the electrode composite layer processed to a thickness of 10 ⁇ m or more and 150 ⁇ m or less as a negative electrode or a positive electrode.
  • the predetermined counter electrode is as described above.
  • the upper limit of the initial charge capacity and / or the initial discharge capacity is not particularly limited, and may be, for example, 336 mAh / g or less, or 250 mAh / g or less.
  • the electrode layer 3 may contain a conductive agent having electronic conductivity.
  • the conductive agent include metals such as gold, silver, copper, and nickel, oxides such as tin oxide, zinc oxide, titanium oxide, and indium tin oxide, and materials such as carbon, particles, fibers, It can be used in the form of a rod, tube or the like.
  • the carbon-based conductive agent carbon fiber, carbon black, carbon nanotube, carbon nanofiber, graphene, graphite or the like can be used.
  • the separator layer 5 contains at least one selected from the group consisting of lithium phosphate, lithium niobate and lithium silicate. Not only these materials can be used alone, but also a mixture of these materials or a solid solution containing another element in addition to these materials can be used.
  • lithium phosphate contained in the separator layer 5 examples include compounds represented by Li 3-x PO 4-y (0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 4), particularly phosphorus having the chemical formula of Li 3 PO 4.
  • Lithium acid can be used.
  • Li / P ⁇ 3 a part of the elements constituting the lithium phosphate may be replaced with another element, or another element may be doped.
  • elements that substitute or dope P include S, B, C, Si, and Se.
  • lithium phosphate a compound represented by Li 3-x PO 4-y N z can be given.
  • x preferably satisfies 0 ⁇ x ⁇ 3
  • y preferably satisfies 0 ⁇ y ⁇ 4
  • z preferably satisfies 0 ⁇ y ⁇ 4. It can be obtained by nitriding other lithium phosphates.
  • Examples of a method for synthesizing a lithium phosphate containing nitrogen include a method in which a compound before nitriding (raw material compound) and urea as a nitriding agent are mixed and heat-treated. In this case, the degree of nitriding can be adjusted by the amount of the nitriding agent. Furthermore, the Li 2 CO 3 and (NH 4) H 2 PO 4 were mixed at a predetermined amount, by performing mechanical milling, may be synthesized compounds having near composition of Li 3 PO 4.
  • the temperature of the heat treatment is usually a temperature equal to or higher than the temperature at which the nitriding agent decomposes, and is preferably in the range of 100 ° C. to 800 ° C., for example.
  • the heat treatment time is preferably in the range of 10 minutes to 5 hours, for example.
  • the atmosphere at the time of firing is not particularly limited, and examples thereof include an air atmosphere; an inert gas atmosphere such as a nitrogen atmosphere and an argon atmosphere; a reducing atmosphere such as an ammonia atmosphere and a hydrogen atmosphere; a vacuum and the like.
  • an inert gas atmosphere, a reducing atmosphere, and a vacuum are preferable, and a reducing atmosphere is particularly preferable. This is because oxidative degradation of the resulting compound can be prevented.
  • the lithium phosphate containing nitrogen is not a material in which N is simply adsorbed to the raw material compound, but is present in the phosphate group-containing Li ion conductor in a state where N is chemically bonded.
  • lithium niobate contained in the separator layer 5 examples include compounds represented by Li 1-x NbO 3-y (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 3), particularly lithium niobate having a chemical formula of LiNbO 3. Can be used. A part of Nb may be replaced with Ta or the like.
  • lithium silicate contained in the separator layer 5 a compound containing Li and Si and having a Li / Si molar ratio of Li / Si ⁇ 2 can be used. A part of Li can be replaced with a metal element, and a part of Si can be replaced with S, B, C, P, Se or the like. As the lithium silicate containing no metal element, Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 2 Si 3 O 7 , and the like can be used.
  • Li 4-xy M x SiO 4 (0 ⁇ x ⁇ 2, y is a valence of M 2 or 3, M: Mg, Zn, Ca, Mn, Ga, Co, Al, La, La Y, Nd, Sm, Gd, Dy, Ho, Er, Yb) or LiM′Si 2 O 6 (M ′: Al, Ga, Sc, Fe).
  • M Mg, Zn, Ca, Mn, Ga, Co, Al, La, La Y, Nd, Sm, Gd, Dy, Ho, Er, Yb
  • LiM′Si 2 O 6 M ′: Al, Ga, Sc, Fe
  • Li 2 SiO 3 , LiAlSiO 4 , LiAlSi 2 O 6 , Li 2 MgSiO 4 , or LiZnSiO 4 can be used as the lithium silicate.
  • the thickness of the electrode layer 3 is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more and 200 ⁇ m or less, and further preferably 10 ⁇ m or more and 150 ⁇ m or less in order to obtain a sufficient charge / discharge capacity. On the other hand, it is preferable that the thickness is 1 mm or less because the resistance hardly increases.
  • the thickness of the separator layer 5 is preferably 0.1 ⁇ m or more, more preferably 100 ⁇ m or less, and even more preferably 10 ⁇ m or less in order to prevent a short circuit between the positive electrode and the negative electrode. On the other hand, it is preferable that the thickness is 1 mm or less because the resistance hardly increases.
  • the electrode layer 3, the separator layer 5, and the electrode composite layer are all preferably sintered bodies, and are integrally sintered in a state where the electrode layer green sheet or the electrode composite layer green sheet and the separator layer green sheet are laminated.
  • a sintered body is preferred. It is preferable that no side reaction product is contained in the interface between the electrode layer and the separator layer, or the electrode composite layer and the separator layer.
  • the side reaction product is Li / M (M: titanium, vanadium, chromium, manganese, iron, cobalt, in which lithium is excessive due to Li supplied from the separator layer on the electrode layer or electrode composite side of the interface.
  • a compound having a ratio of one or more transition metals of nickel or copper) of 1 or more, or on the separator layer side of the interface, lithium is supplied to the electrode layer and contains lithium. It means a compound derived from a solid electrolyte that is no longer present.
  • Whether or not a side reaction product is generated can be determined by pulverizing the electrode laminate and performing powder X-ray diffraction measurement. Specifically, in the diffraction pattern, when the strongest line intensity of the compound having a Li / M ratio of more than 1 is 10% or less with respect to the strongest line intensity of the composite oxide of titanium and lithium, or When the strongest line strength of a compound derived from a solid electrolyte that no longer contains lithium is 10% or less with respect to the strongest line strength of lithium phosphate, lithium niobate or lithium silicate, Judged not to contain side reaction products. The ratio of these strongest line intensities is preferably 5% or less, more preferably 1% or less. When a side reaction product is not included in the electrode laminate, a side reaction product is not included in the interface between the electrode layer and the separator layer or the electrode composite layer and the separator layer.
  • the electrode laminate 1 does not contain a side reaction product at the interface between the electrode layer 3 and the separator layer 5 or between the electrode composite layer and the separator layer 5, the electrode laminate 1 is between the electrode layer 3 or the electrode composite layer and the separator layer 5.
  • the movement of lithium ions is not hindered by the side reaction product, and the amount of the electrode active material can be prevented from decreasing due to the side reaction.
  • the laminate of the present invention is formed by laminating a layer containing a composite oxide of lithium and titanium or a precursor thereof and a layer containing lithium phosphate, lithium niobate, lithium silicate or a precursor thereof. It can be obtained by heat-treating the precursor laminate.
  • the precursor of a composite oxide of lithium and titanium is a material that becomes a composite oxide of lithium and titanium by heating such as firing and sintering.
  • Lithium phosphate precursor, lithium niobate precursor and lithium silicate precursor are converted into lithium phosphate, lithium niobate and lithium silicate by heating such as firing and sintering. It is a material.
  • a layer containing a composite oxide of lithium and titanium or a precursor thereof (hereinafter referred to as an electrode layer green sheet) and lithium phosphate, lithium niobate, lithium silicate or a precursor thereof
  • a green sheet laminate is formed by laminating layers (hereinafter referred to as separator layer green sheets).
  • a slurry or paste containing a composite oxide of lithium and titanium or a precursor thereof is applied and dried on a substrate to form an electrode layer green sheet, and further, Applying and drying slurry or paste containing lithium phosphate, lithium niobate, lithium silicate or their precursors to form a separator layer green sheet, peeling the substrate, and then removing the binder by heating And the method (sequential coating method) which shape
  • the separator layer green sheet and the electrode layer green sheet are prepared separately, and at least one of them is peeled off and bonded to the other, and pressure and / or heat is applied to bring them into close contact with each other to form a green sheet.
  • compression bonding method for obtaining a laminate.
  • the slurry or paste may contain a binder such as acrylic resin, PVA (polyvinyl alcohol), PVB (polyvinyl butyral).
  • the laminate of the electrode layer green sheet and the separator layer green sheet is heated to form an electrode layer containing a composite oxide of lithium and titanium, and a separator layer containing lithium phosphate, lithium niobate or lithium silicate.
  • a laminate is obtained.
  • the temperature of the heat treatment is preferably from 600 ° C. to 1300 ° C., preferably from 700 ° C. to 1250 ° C., more preferably from 800 ° C. to 1200 ° C., and from 850 to 1150 ° C. More preferably it is.
  • the electrode layer is an electrode composite containing lithium lanthanum titanate as a solid electrolyte
  • the crystal growth of lithium lanthanum titanate is 700 ° C. or higher.
  • the adhesion at the interface of the solid electrolyte of the layer can be increased and the resistance can be reduced.
  • the atmosphere during heating any of an air atmosphere, an inert atmosphere such as nitrogen, a highly oxidizing atmosphere such as oxygen, and a reducing atmosphere such as hydrogen can be used.
  • the temperature holding time can be appropriately changed according to the temperature or the like, but in practice it is preferably 24 hours or less.
  • the temperature holding time may be as short as 1 hour or less, and the holding time may be set to 0 minutes, and heating may be stopped immediately after reaching the target temperature.
  • the cooling method is not particularly limited, but may be naturally cooled (cooled in the furnace), may be cooled more rapidly than naturally cooled, or may be held at a certain temperature during cooling.
  • the lithium phosphate precursor may be a compound containing lithium and phosphorus, or a mixture of a lithium source and a phosphorus source.
  • Lithium halides, carbonates, hydroxides, and the like can be used as the lithium source, and phosphoric acid, phosphorous acid, ammonium phosphate, and the like can be used as the phosphorus source.
  • the lithium niobate precursor may be a compound containing lithium and niobium, or may be a mixture of a lithium source and a niobium source.
  • Lithium halides, carbonates, hydroxides, and the like can be used as the lithium source, and niobium oxides, halides, carboxylates, alkoxides, and the like can be used as the niobium source.
  • the lithium silicate precursor may be a compound containing lithium and silicon, or a mixture of a lithium source and a silicon source.
  • the precursor may be a compound containing lithium, silicon, and a metal element, or a mixture of a lithium source, a silicon source, and a metal element source. It may be.
  • the lithium source lithium halides, carbonates, hydroxides, etc. can be used.
  • silicon source or metal element source silicon or metal element oxides, halides, carboxylates, alkoxides, etc. Can be used.
  • a precursor of a composite oxide of lithium and titanium a compound containing lithium and titanium may be used, or a mixture of a lithium source and a titanium source may be used.
  • a lithium source lithium halides, carbonates, hydroxides, and the like can be used.
  • titanium sources titanium oxides, halides, carbonates, hydroxides, and the like can be used.
  • a precursor of a composite oxide of lithium and titanium can be obtained by solvothermal treatment of a mixture containing a lithium source, a titanium source and a solvent.
  • a laminate using an electrode composite layer instead of an electrode layer is a layer containing a composite oxide of lithium and titanium or a precursor thereof and a solid electrolyte or a precursor thereof (hereinafter referred to as an electrode composite layer green sheet). ) And a separator sheet green sheet can be obtained by heat treatment.
  • the electrode composite layer contains lithium titanate and lithium lanthanum titanate, it is preferably obtained by the following method.
  • the electrode composite layer green sheet may include a mixture of precursors that become lithium titanate or lithium lanthanum titanate by heating, or a mixture of lithium titanate and lithium lanthanum titanate. it can.
  • the mixture of precursors not only means that the precursor of lithium titanate and the precursor of lithium lanthanum titanate are separate particles, but also titanium, lanthanum, and lithium are integrated. It also means the case where lithium titanate and lithium lanthanum titanate are produced from solid substances by heating. Further, the precursor may contain lithium titanate or lithium lanthanum titanate crystals.
  • the mixing method of lithium titanate and lithium lanthanum titanate can be obtained by mixing with a ball mill or the like.
  • the lithium titanate powder and the lithium lanthanum titanate powder are mixed in a solvent such as water or alcohol for several minutes to several tens of hours, preferably 10 minutes or more. It is preferable to achieve
  • the crystal phase changes from the precursor and / or the crystallinity is improved.
  • the change in crystal phase and / or improvement in crystallinity can be confirmed by powder X-ray diffraction. Changes in the crystal phase are reflected in the X-ray diffraction pattern as changes in the diffraction pattern, and improvements in crystallinity are reflected in the diffraction line width as a decrease.
  • lithium titanate having a perovskite crystal structure Lanthanum such as Li 3x La 2 / 3-x TiO 3 (0 ⁇ x ⁇ 1/6) [ICDD numbers 01-074-4217, 00-046-0467, 01-087-0935, 00-046-0466 etc.] Produces.
  • the mixture of the lithium titanate precursor and the lithium lanthanum titanate precursor is preferably obtained by using the first to fourth precursor manufacturing methods using the solvothermal method described below.
  • the precursor production method requires at least a solvothermal treatment of a mixture containing a Ti element source, a Li element source, and a solvent.
  • the compound of the La element source can be added later as in the second precursor production method to be described later, but a mixture containing the La element source, the Ti element source, the Li element source and the solvent is solvothermal.
  • a precursor production method including a step of heating by a treatment method can also be used. This manufacturing method corresponds to the superordinate concept of the manufacturing method of the first precursor, the modification of the manufacturing method of the second precursor, the manufacturing method of the third precursor, and the manufacturing method of the fourth precursor.
  • a solvothermal treatment step a mixture of a lithium titanate precursor and a lithium lanthanum titanate precursor is obtained.
  • an aqueous solution preparation step of preparing an aqueous solution containing La cation and Ti cation, an aqueous solution obtained in the aqueous solution preparation step, and a basic aqueous solution To obtain a precipitate containing an oxide and / or hydroxide of La element and an oxide and / or hydroxide of Ti element, and obtained in the simultaneous precipitation process step.
  • aqueous solution preparation process In the aqueous solution preparation step, an aqueous solution containing La cation and Ti cation is prepared.
  • La 3+ is exemplified as the La cation
  • Ti 4+ is exemplified as the Ti cation.
  • Each of the La cation and the Ti cation may form a complex with water, ammonia, oxide ions, hydroxide ions, counter anions described later, and the like as ligands.
  • the counter anion of La cation and Ti cation include, in addition to oxide ions and hydroxide ions, chlorine-containing anions such as chloride ions, nitrate anions, and the like. Said counter anion may be used independently or may use 2 or more types together.
  • the aqueous solution is prepared, for example, by dissolving a lanthanum compound that generates La cations by dissolution and a titanium compound that generates Ti cations by dissolution in water or an acidic aqueous solution.
  • these lanthanum compounds and titanium compounds include chlorides, oxychlorides, hydroxides, oxides, nitrates, and the like, and chlorides or oxychlorides are easily available or inexpensive. Is preferred.
  • nitrate is preferable from the viewpoint of easy dissolution. It does not specifically limit as said lanthanum compound and a form of a titanium compound, For example, solids, such as a powder, liquids, such as aqueous solution, etc. are mentioned.
  • Each of the above lanthanum compounds and titanium compounds may be used alone or in combination of two or more.
  • the aqueous solution prepared in the aqueous solution preparation step preferably has a pH of less than 7, that is, acidic.
  • La cations show a high aqueous solution in the region from strong acidity to weak acidity, while Ti cations show high water solubility only in the strong acidity region. Therefore, the aqueous solution prepared in the aqueous solution preparation step is preferably strongly acidic (for example, pH 3 or less) from the viewpoint of stability.
  • the precipitate containing lanthanum oxide and / or hydroxide and titanium oxide and / or hydroxide is mixed by mixing the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution.
  • the method of mixing the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution is not particularly limited, and examples thereof include a method of dropping or spraying the aqueous solution obtained in the aqueous solution preparation step onto the basic aqueous solution.
  • the pH of the basic aqueous solution is preferably 8 or more from the viewpoint of the precipitation rate. It does not specifically limit as basic aqueous solution, For example, ammonia water and lithium hydroxide aqueous solution are mentioned. Ammonia water is preferred because it is easily available and inexpensive. From the viewpoint of preventing contamination to the solid electrolyte, an aqueous lithium hydroxide solution in which the alkali cation is a lithium ion, that is, a cation constituting the solid electrolyte is preferable.
  • the molar equivalent of the base of the basic aqueous solution used in the simultaneous precipitation treatment step is the molar equivalent of the counter anion of La cation and Ti cation (excluding oxide ions and hydroxide ions) in the aqueous solution obtained in the aqueous solution preparation step. It is preferable that the amount is larger than that, and a large excess (for example, about twice or more) is more preferable.
  • the molar equivalent of the base in the basic aqueous solution is larger than the molar equivalent of the counter anion, the basicity of the mixed solution can be sufficiently maintained even after the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution are mixed.
  • the precipitate obtained in the simultaneous precipitation treatment step is appropriately separated and washed.
  • the separation method is not particularly limited, and examples thereof include centrifugation, decantation, and filtration. Moreover, it does not specifically limit as a solvent used for washing
  • the precipitate obtained in the simultaneous precipitation treatment step can prevent a large decrease in mass due to detachment of organic ligands during sintering, which occurs by a sol-gel method.
  • the lithium element source compound is not particularly limited, and examples thereof include lithium carbonate, lithium chloride, lithium fluoride, lithium hydroxide, lithium nitrate, lithium acetate, and hydrates thereof. These lithium compounds may be used alone or in combination of two or more. Moreover, the form of the lithium compound may be a solid such as a powder or an aqueous solution, and is not particularly limited.
  • the content ratio of La element to Ti element in the mixture before performing the solvothermal treatment step is La / Ti ⁇ 0.66.
  • La / Ti ⁇ 0.66 more La than required by the electrode composite containing the target mixed composition lithium titanate and lithium lanthanum titanate is unlikely to remain after firing. Therefore, by firing, other than LTO or LLTO Impurity phases such as La (OH) 3 , La 2 O 3 and La 2 Ti 2 O 7 are hardly generated.
  • hydrothermal treatment using water as a solvent is mainly performed as solvothermal treatment.
  • Hydrothermal treatment refers to a compound synthesis method or crystal growth method performed in the presence of hot water of high temperature and high pressure, and a chemical reaction that does not occur in an aqueous solution at normal temperature and pressure may proceed.
  • an aqueous solution containing lithium element is added to a solid or solution containing La cation and Ti cation, and a high temperature and high pressure treatment is performed, so that lithium element that is water-soluble at room temperature and normal pressure is replaced with titanium element.
  • Complex chloride can be incorporated into the complex salt, and the precursor is obtained by separating the complex salt from the solvent.
  • water is used as a solvent, but the same effect can be expected by a method (solvothermal method) using a solvent other than water (for example, an organic solvent).
  • the absolute pressure is higher than atmospheric pressure and lower than 8.7 MPa
  • the temperature is in an environment of 60 ° C. or higher and 300 ° C. or lower, more preferably, the absolute pressure is 0.15 MPa or higher and 4.0 MPa or lower.
  • the temperature is preferably about 1 hour to 100 hours in an environment of 60 ° C. to 250 ° C.
  • the Ti element source fine particles (solid matter) containing an oxide and / or hydroxide of Ti element can be used.
  • Method for synthesizing Ti-containing fine particles (solid matter) As a method for synthesizing the fine particles (solid matter) containing the oxide and / or hydroxide of the Ti element, titanium tetrachloride is vapor-phase oxidized, and the hydrous titanium oxide is first treated with sodium hydroxide and then with hydrochloric acid. And a method using a precipitation reaction. As an example, a method using a precipitation reaction is shown below. In this method, fine particles containing an oxide and / or hydroxide of Ti element are synthesized by mixing an aqueous solution containing Ti cations and a basic aqueous solution.
  • aqueous solution preparation process In the aqueous solution preparation step, an aqueous solution containing Ti cations is prepared.
  • the aqueous solution preparation step of the second precursor production method can be performed in the same manner as the aqueous solution preparation step of the first precursor production method, except that the lanthanum compound is not added.
  • a precipitate containing titanium oxide and / or hydroxide is obtained by mixing the aqueous solution containing the Ti cation obtained in the aqueous solution preparation step and the basic aqueous solution.
  • the precipitation treatment step of the second precursor production method can be performed in the same manner as the precipitation treatment step of the first precursor production method.
  • solvothermal treatment step a Ti element source that is a solid matter containing a Ti cation such as a precipitate obtained in the precipitation treatment step, a compound of a lithium element source, and a solvent are mixed, and the pressure is higher than atmospheric pressure. Under heating, a composite salt of Li and Ti is obtained.
  • the solvothermal treatment step of the second precursor production method can be performed in the same manner as the solvothermal treatment step of the first precursor production method.
  • the La element source is added following the solvothermal treatment step.
  • the La element source addition step may be performed before the composite salt after the solvothermal treatment is separated from the solvent or after it is separated from the solvent.
  • the form of the La element source may be, for example, a solid such as a powder or an aqueous solution, and is not particularly limited, and is dissolved in water or an acidic aqueous solution when the complex salt is added before separation from the solvent.
  • These lanthanum compounds include, for example, chlorides, oxychlorides, hydroxides, oxides, and nitrates. From the viewpoint of easy availability and low cost, chlorides or lanthanum compounds can be used. Oxychloride is preferred.
  • lanthanum compound in the case of adding after isolate
  • the above lanthanum compounds may be used alone or in combination of two or more.
  • the La element source may be simply mixed with the composite salt.
  • a solid substance can also be formed by a thermal treatment method.
  • the solvothermal treatment process for forming a composite salt of Li and Ti is a first solvothermal treatment process
  • the process for forming a solid substance is a second solvothermal treatment process.
  • the molar ratio (Li / Ti) with respect to the titanium in the reaction container which performs a 1st solvothermal treatment process is 0.5 or more and 3.5 or less. Preferably, it is 0.8 or more and 3.0 or less, more preferably 1.0 or more and 2.5 or less.
  • La element source lanthanum compounds that dissolve in water or acidic aqueous solutions can be used.
  • these lanthanum compounds include chlorides, oxychlorides, hydroxides, oxides, and nitrates, which are easily available. From the viewpoint of being inexpensive and inexpensive, chloride or oxychloride is preferred. Moreover, nitrate is preferable from the viewpoint of easy dissolution. It does not specifically limit as a form of said La element source, For example, solid, such as powder, aqueous solution etc. are mentioned.
  • the above lanthanum compounds may be used alone or in combination of two or more.
  • the second solvothermal treatment step may be performed in a state where an acid is added together with the La element source.
  • an acid an inorganic acid or an organic acid can be used, and hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid and the like can be used.
  • the amount of acid added was such that the difference from the molar ratio of acid to titanium (acid / Ti) from the molar ratio of lithium to titanium (Li / Ti) was 0.1 ⁇ [(Li / Ti)-(acid / Ti )] ⁇ 1.5, preferably 0.3 ⁇ [(Li / Ti)-(acid / Ti)] ⁇ 1.1.
  • the pH of the solution after addition of the acid is preferably 8 or more and 14 or less.
  • the same hydrothermal treatment method as that used in the first solvothermal treatment step can be used.
  • a complex salt is formed in order to supply a sufficient amount of lithium to the amount of titanium in the first solvothermal step.
  • the amount of Ti cations that have not been reduced can be reduced.
  • the impurity phase after firing can be reduced, and the sintering density can be increased when sintering is performed after molding.
  • a Li—Ti composite salt that becomes a precursor of LTO in the first solvothermal treatment step, a Li—Ti composite salt that becomes a precursor of LTO
  • a solid substance that becomes the precursor of LLTO is formed, so that a structure in which the periphery of LTO is covered with LLTO is formed in the lithium titanate composite product after firing. Is expected to do.
  • the aqueous solution preparation step, simultaneous precipitation treatment step, and first solvothermal treatment step of the third precursor production method are respectively the aqueous solution preparation step, simultaneous precipitation treatment step, and solvothermal of the first precursor production method.
  • the molar ratio (Li / Ti) of lithium to titanium in the reaction vessel in which the first solvothermal treatment step is performed is preferably 0.5 or more and 3.5 or less. It is more preferably 8 or more and 3.0 or less, and further preferably 1.0 or more and 2.5 or less.
  • an acid is added to the solid substance containing the Li—Ti composite salt and the La element source obtained in the first solvothermal treatment step, under a pressure higher than atmospheric pressure. Heat to obtain the precursor.
  • an inorganic acid or an organic acid can be used, and hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid and the like can be used.
  • the difference between the molar ratio of titanium (acid / Ti) and the molar ratio of lithium to titanium (Li / Ti) is 0.1 ⁇ [(Li / Ti)-(acid / Ti)]. It is preferable to satisfy ⁇ 1.5, and it is more preferable to satisfy 0.3 ⁇ [(Li / Ti)-(acid / Ti)] ⁇ 1.1.
  • the pH of the solution after addition of the acid is preferably 8 or more and 14 or less.
  • the same hydrothermal treatment method as that used in the first solvothermal treatment step can be used.
  • the amount of Ti cations that do not form a composite salt can be reduced.
  • the impurity phase after firing can be reduced, and the sintering density can be increased when sintering is performed after molding.
  • the precursor according to the present invention comprises a mixture containing a single salt of La element, a single salt of Ti element, a single salt of Li element and a solvent under a pressure higher than atmospheric pressure.
  • a complex salt of Li and Ti can also be obtained by a heating solvothermal treatment step. That is, a single salt of La element can be used as the La element source, and a single salt of Ti element can be used as the Ti element source.
  • a solvothermal process it can carry out by the method similar to the solvothermal process with respect to the precipitate obtained by the simultaneous precipitation method.
  • the elemental salt of La element is not particularly limited, and examples thereof include lanthanum oxide and / or hydroxide.
  • the single salt of Ti element is not particularly limited, and examples thereof include titanium oxide and / or hydroxide.
  • the Li element simple salt is not particularly limited, and examples thereof include lithium carbonate, lithium chloride, lithium fluoride, lithium hydroxide, lithium nitrate, lithium acetate, and hydrates thereof.
  • the average particle size of the single salt of Ti element is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. This is because when the Ti element single salt particles are within the above range, complex chlorination of Li and Ti easily proceeds during the solvothermal treatment.
  • the precursor obtained in the solvothermal treatment step may be dried.
  • conditions for the drying step include 60 ° C. or higher and 250 ° C. or lower and 1 hour or longer and 10 hours or shorter.
  • the all solid lithium battery of the present invention includes a negative electrode layer 13 having a negative electrode active material that absorbs and releases lithium, and a positive electrode layer 17 that has a positive electrode active material that absorbs and releases lithium.
  • a separator layer 15 interposed between the negative electrode layer 13 and the positive electrode layer 17 and conducting lithium ions.
  • the separator layer 15 contains lithium phosphate or lithium niobate, and the negative electrode layer 13 or the positive electrode
  • the layer 17 includes a composite oxide of lithium and titanium.
  • the negative electrode layer 13 or the positive electrode layer 17 may have the same structure as the electrode layer 3 of the electrode laminate 1 described above, and can be obtained by the same method.
  • the separator layer 15 may have the same structure as the separator layer 5 of the electrode laminate 1 described above, and can be obtained by the same method.
  • a composite oxide of lithium and titanium can be used as the negative electrode active material of the negative electrode layer 13.
  • Li x AMO 4 (0 ⁇ x ⁇ 2, A: lithium) is used as the positive electrode active material of the positive electrode layer 17.
  • the positive electrode layer 17 is preferably a positive electrode composite layer including a positive electrode active material and a solid electrolyte.
  • the all-solid-state lithium battery 21 in addition to the first separator layer 25 which is a layer containing lithium phosphate or lithium niobate.
  • the all-solid-state lithium battery 21 may be a laminate of the second separator layer 27 containing a lithium ion conductive solid electrolyte.
  • a lithium ion conductive solid electrolyte which is higher in lithium ion conductivity than lithium phosphate and lithium niobate but reacts with the negative electrode layer 13 during sintering.
  • the lithium ion conductivity between the negative electrode layer 13 and the positive electrode layer 17 can be increased.
  • the lithium ion conductive solid electrolyte may be a lithium ion conductive garnet oxide containing Li and La and one or more elements selected from the group consisting of Zr, Nb and Ta. When the garnet-type oxide is sintered in a state where it is in contact with the composite oxide of lithium and titanium, which is the negative electrode active material, the garnet-type oxide undergoes side reactions with each other.
  • a first separator layer 25 made of lithium phosphate or lithium niobate is interposed between the second separator layer 27 containing the garnet-type oxide and the negative electrode layer 13 containing a composite oxide of lithium and titanium. Thus, they can be integrally sintered together in a stacked state without reacting with each other.
  • the first separator layer 25 which is a layer containing lithium phosphate or lithium niobate is provided on the negative electrode layer 13 side, but lithium phosphate or lithium phosphate or lithium niobate is also provided on the positive electrode layer side.
  • a first separator layer 25 which is a layer containing lithium niobate may be provided.
  • the negative electrode layer 13, the positive electrode layer 17, the separator layer 15, the negative electrode composite layer, the positive electrode composite layer, the first separator layer 25, and the second separator layer 27 are all preferably sintered bodies.
  • a sintered body that is integrally sintered in a laminated state is preferable.
  • a side reaction product is not included in the interface between these layers.
  • the all-solid-state lithium battery 31 of this invention as shown in FIG.6 (c) may provide the collector layers 33 and 35 on the surface of the negative electrode layer 13 and the positive electrode layer 17.
  • FIG. The current collector layer is provided in an all-solid-state battery to exchange electricity with the outside during charging and discharging, and is an electron conductive material such as an oxide or a simple substance in which a metal, a carbon material, or a carbon material is dispersed. It is composed of an oxide exhibiting properties.
  • the metal constituting the current collector layer at least one metal selected from the group consisting of Ni, Cu, Ag, Au and the like can be used.
  • the current collector layer can be obtained by applying a metal paste and baking in an atmosphere containing a reducing gas containing hydrogen or the like.
  • a current collector layer may be provided on the surfaces of the negative electrode layer 23 and the positive electrode layer 29 of the all solid lithium battery 21.
  • the paste containing a metal, a carbon material, etc.
  • the metal constituting the current collector layer a metal having a melting point lower than the sintering temperature, such as Al, can also be used.
  • the all solid lithium battery of the present invention does not contain a side reaction product at the interface of each layer such as the negative electrode layer 13 and the separator layer 15 or the interface between the positive electrode layer 17 and the separator layer 15, the movement of lithium ions between the respective layers. Is not inhibited by the side reaction product, and the amount of the electrode active material due to the side reaction is not reduced, so that the battery capacity can be prevented from being reduced.
  • the all solid lithium battery of the present invention includes a negative electrode active material or a layer containing a precursor thereof, a lithium phosphate or a precursor thereof, or a layer containing a lithium niobate or a precursor thereof, a positive electrode active material or a precursor thereof. It can obtain by heat-processing the laminated body formed by laminating
  • the method for forming the laminate and the heating conditions can be the same as those for the laminate of the electrode layer and the separator layer of the present invention.
  • the electrode laminate 1 of the present invention when the electrode laminate 1 is a laminate of a negative electrode layer and a separator layer, a positive electrode layer as a counter electrode is laminated, and the electrode laminate 1 is a laminate of a positive electrode layer and a separator layer.
  • a negative electrode layer as a counter electrode can be laminated to form an all-solid lithium battery.
  • a layer containing a solid electrolyte or its precursor is sandwiched between a layer containing a positive electrode active material or its precursor and a layer containing a negative electrode active material or its precursor.
  • An all-solid lithium battery can also be obtained by forming an electrode laminate and sintering the laminate.
  • the shape of the all solid lithium battery of the present invention is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type.
  • Example 1 Preparation of negative electrode composite pre-fired particles] (Simultaneous precipitation process) A solution obtained by dissolving lanthanum chloride heptahydrate in water is mixed with an aqueous solution of titanium tetrachloride, and an aqueous solution having a La concentration of 0.50 mmol / g, a Ti concentration of 2.60 mmol / g, and a Cl concentration of 8.23 mmol / g. Prepared. At this time, the La / Ti ratio was 0.192 (molar ratio). This aqueous solution was transparent and did not produce a precipitate when left at room temperature. When 350 g of this aqueous solution was sprayed into 500 g of 28% by mass ammonia water, a precipitate was formed. The precipitate was separated, washed with water, dried at 200 ° C. and mechanically crushed.
  • the obtained negative electrode composite layer paste was applied onto a polyethylene terephthalate (PET) film by a doctor blade method and dried at 120 ° C. for 10 minutes to prepare a negative electrode composite layer green sheet.
  • PET polyethylene terephthalate
  • separator layer green sheet A separator layer green sheet was prepared in the same manner as in the preparation of the negative electrode composite layer green sheet, using the solid electrolyte temporary fired particles instead of the negative electrode composite temporarily fired particles.
  • the negative electrode composite layer green sheet and the separator layer green sheet prepared by the above method were cut into a disk shape having a diameter of 12 mm.
  • a separator layer green sheet cut and peeled off from the PET film is placed in this order, and the negative electrode composite layer green sheet with the PET film facing the upper surface is placed in this order.
  • the uppermost layer and the lowermost layer PET film were peeled off to prepare a green sheet laminate of a negative electrode composite layer-separator layer-negative electrode composite layer.
  • a sintered body was produced in the same manner as in Example 1 except that the above-described LiNbO 3 was used instead of Li 3 PO 4 as the solid electrolyte temporary fired body, and the main firing temperature was 850 ° C.
  • a sintered body was produced in the same manner as in Example 2 except that the above Li 2 SiO 3 was used as the solid electrolyte temporary fired body.
  • a sintered body was produced in the same manner as in Example 1 except that the above Li 4 SiO 4 was used instead of Li 3 PO 4 as the solid electrolyte temporary fired body, and the main firing temperature was 800 ° C.
  • Li 2 TiO 3 is a side reaction product produced by the reaction of LTO or LLTO with Li 4 SiO 4 during sintering, resulting in excess of lithium.
  • a laminated sintered body was produced in the same manner as in Example 1 except that the above-mentioned LAGP was used instead of Li 3 PO 4 as the solid electrolyte temporary fired body, and the main firing temperature was 800 ° C.
  • This suspension was dried at 120 ° C. to obtain a powder.
  • This powder was mixed and pulverized in isopropyl alcohol with a planetary ball mill (300 rpm / zirconia ball) for 3 hours. The powder was separated from the balls and isopropyl alcohol, dried, and then placed in an alumina firing boat and fired in a nitrogen atmosphere at 700 ° C. for 5 hours to obtain a solid electrolyte calcined body.
  • a sintered body was produced in the same manner as in Example 1 except that the above LLZO was used instead of Li 3 PO 4 as the solid electrolyte calcined body.
  • the sintered body was pulverized and subjected to powder X-ray diffraction measurement. As a result, La 2 Zr 2 O 7 [ICDD No. 01-0748764], LLTO [ICDD No. 00-046-0465], Li 2 TiO 3 [ICDD] No. 01-071-2348] was detected.
  • Example 4-2 [Production and evaluation of fired body] A sintered body was produced in the same manner as in Example 1, except that LLZO synthesized in Comparative Example 4-1 was used instead of Li 3 PO 4 as the solid electrolyte, and the main sintering temperature was 800 ° C.
  • the sintered body was pulverized and subjected to powder X-ray diffraction measurement.
  • La 2 Zr 2 O 7 [ICDD number 01-0748764], LLZO [ICDD number 01-080-4947], LLTO [ICDD number 00- 046-0465], diffraction lines compared with LTO [ICDD No. 00-049-0207] were detected.
  • the powder was separated from the balls and isopropyl alcohol, dried, and then placed in an alumina crucible, and calcined in the atmosphere at 950 ° C. for 24 hours to obtain a solid electrolyte calcined body.
  • a diffraction line compared with Li 5 La 3 Ta 2 O 12 [ICDD No. 01-075-3359] was detected.
  • the sintered body was prepared in the same manner as in Example 1 except that the above Li 5 La 3 Ta 2 O 12 was used instead of Li 3 PO 4 as the solid electrolyte temporary fired body, and the main firing temperature was 850 ° C. Produced.
  • the powder was separated from the balls and isopropyl alcohol, dried, and then placed in an alumina crucible and baked in the atmosphere at 950 ° C. for 24 hours to obtain a solid electrolyte calcined body.
  • a diffraction line compared with Li 5 La 3 Nb 2 O 12 [ICDD No. 00-045-0109] was detected.
  • the sintered body was prepared in the same manner as in Example 1 except that the above Li 5 La 3 Nb 2 O 12 was used instead of Li 3 PO 4 as the solid electrolyte temporary fired body, and the main firing temperature was 850 ° C. Produced.
  • Example 5 [Preparation of mixture of positive electrode active material and solid electrolyte] A mixture of a positive electrode active material and a solid electrolyte was obtained by kneading a reagent LiMn 2 O 4 and a reagent Li 3 PO 4 preliminarily fired at 700 ° C. using a mortar at a weight ratio of 8: 2.
  • a positive electrode composite layer green sheet was prepared in the same manner as in the preparation of the negative electrode composite layer green sheet, using a mixture of the positive electrode active material and the solid electrolyte instead of the negative electrode composite calcined particles.
  • a sintered body was produced by the same method as in Example 1 except that the green sheet laminate produced by the above method was used and the main firing temperature was 950 ° C.
  • a sintered body was produced by the same method as in Example 4 except that the green sheet laminate produced by the above method was used.
  • LiAlSiO 4 is a solid electrolyte having lithium ion conductivity, which is generated by changing LiAlSi 2 O 6 during firing.
  • a sintered body was produced by the same method as in Example 4 except that the green sheet laminate produced by the above method was used.
  • a sintered body was produced by the same method as in Example 4 except that the green sheet laminate produced by the above method was used.
  • a sintered body was produced by the same method as in Example 4 except that the green sheet laminate produced by the above method was used.
  • Example 10 [Production of green sheet laminate (including current collector layer)]
  • the negative electrode composite layer green sheet and separator layer green sheet produced by the method of Example 1 and the positive electrode composite layer green sheet produced in Example 4 were cut into a disk shape having a diameter of 12 mm. Each cut green sheet is peeled from the PET film, a separator layer green sheet and a positive electrode composite layer green sheet are placed in this order on the negative electrode composite green sheet, and Ni paste is applied to both surfaces (upper and lower surfaces). After sandwiching between the films and thermocompression bonding with a thermocompression bonding apparatus at 80 ° C. for 30 minutes, the uppermost layer and the lowermost PET film are peeled off to obtain a current collector layer—a negative electrode composite layer—a separator layer—a positive electrode composite layer— A green sheet laminate of the current collector layer was produced.
  • the green sheet laminate produced by the above method is sandwiched between alumina plates, polyvinyl butyral is removed by pre-baking at 500 ° C. for 4 hours in the atmosphere, and then N 2 containing 2 % by volume of hydrogen at 950 ° C. for 12 hours.
  • the sintered body was produced by firing in an atmosphere and then annealing in an N 2 atmosphere containing 1% by volume of oxygen at 600 ° C. for 24 hours.
  • An all-oxide-based all-solid lithium battery in which a layer and a current collector layer containing metallic Ni were laminated could be obtained.
  • Example 11 [Production of green sheet laminate (including current collector layer)] A green sheet laminate of the current collector layer-negative electrode composite layer-separator layer-positive electrode composite layer-current collector layer was prepared in the same manner as in Example 10 except that Cu paste was used as the current collector paste. Produced.
  • a sintered body was produced in the same manner as in Example 10 except that the green sheet laminate produced by the above method was used.
  • Electrode laminated body 3 Electrode layer 5 Separator layer 11 All solid lithium battery 13, 23 Negative electrode layer 15 Separator layer 17, 29 Positive electrode layer 21 All solid lithium battery 25 First separator layer 27 Second separator layer 31 All solid lithium battery 33, 35 Current collector layer

Landscapes

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

Abstract

La présente invention concerne un procédé d'obtention d'un stratifié d'électrode d'une couche d'électrode et d'une couche de séparateur avec lequel, même lorsqu'un stratifié de la couche d'électrode qui contient un sel composite de lithium et de titane en tant que matériau actif d'électrode et que la couche de séparateur est frittée à 600 °C ou plus, une réaction latérale du matériau actif d'électrode et de l'électrolyte solide ne se produit pas pendant le frittage. Un stratifié d'électrode fabriqué par stratification de la couche d'électrode contenant le matériau actif d'électrode et de la couche de séparateur contenant un électrolyte solide dans cet ordre est utilisé, le stratifié d'électrode étant caractérisé en ce que le matériau actif d'électrode est un oxyde composite de lithium et de titane, et que l'électrolyte solide contient du phosphate de lithium et/ou du niobate de lithium. De plus, la couche d'électrode peut également être une couche composite d'électrode contenant : un matériau actif d'électrode, et un électrolyte solide qui est un oxyde de type pérovskite contenant du lithium.
PCT/JP2018/002795 2017-01-30 2018-01-29 Stratifié d'électrode et pile au lithium entièrement solide WO2018139657A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-013800 2017-01-30
JP2017013800 2017-01-30

Publications (1)

Publication Number Publication Date
WO2018139657A1 true WO2018139657A1 (fr) 2018-08-02

Family

ID=62978553

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/002795 WO2018139657A1 (fr) 2017-01-30 2018-01-29 Stratifié d'électrode et pile au lithium entièrement solide

Country Status (2)

Country Link
JP (1) JP2018125286A (fr)
WO (1) WO2018139657A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546152A (zh) * 2018-11-13 2019-03-29 南昌大学 一种全固态锂电池电极材料及其制备方法
WO2019221140A1 (fr) * 2018-05-17 2019-11-21 日本碍子株式会社 Batterie secondaire au lithium
CN110828756A (zh) * 2019-10-29 2020-02-21 东北大学 一种锂离子固体电解质隔膜及其制备和使用方法
JPWO2020188914A1 (fr) * 2019-03-15 2020-09-24
WO2020188913A1 (fr) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie l'utilisant
WO2020188915A1 (fr) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie l'utilisant
CN111995396A (zh) * 2020-07-20 2020-11-27 南昌航空大学 一种利用镁改性铌酸钠陶瓷氧离子电导性能的方法
US10938063B2 (en) 2019-01-31 2021-03-02 University Of Maryland, College Park Lithium silicate compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
US11056717B2 (en) 2019-01-31 2021-07-06 University Of Maryland, College Park Lithium phosphate derivative compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
CN113169327A (zh) * 2018-12-07 2021-07-23 住友化学株式会社 锂二次电池正极活性物质用前体、锂二次电池正极活性物质用前体的制造方法以及锂复合金属化合物的制造方法
US20220052333A1 (en) * 2019-04-30 2022-02-17 Innolith Technology AG Rechargeable battery cell
CN115133114A (zh) * 2022-07-29 2022-09-30 重庆太蓝新能源有限公司 一种固态电解质材料及其制备方法和电池
CN117276522A (zh) * 2023-11-22 2023-12-22 天津润光恒科技开发有限公司 纳米铌酸锂包覆的三元正极材料及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3796456B1 (fr) * 2018-05-17 2024-09-11 NGK Insulators, Ltd. Batterie secondaire au lithium
JP6966639B2 (ja) * 2018-05-17 2021-11-17 日本碍子株式会社 リチウム二次電池
DE102019210857A1 (de) * 2019-07-22 2021-01-28 Volkswagen Aktiengesellschaft Lithium-Ionen-Batteriezelle und Verfahren zu deren Herstellung
JP6982712B2 (ja) * 2019-12-27 2021-12-17 昭和電工株式会社 リチウムイオン伝導性酸化物焼結体およびその用途

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002357586A (ja) * 2001-06-04 2002-12-13 Tokuyama Corp 固体電解質成形体
JP2009181807A (ja) * 2008-01-30 2009-08-13 Sony Corp 固体電解質、および固体電解質電池、並びにリチウムイオン伝導体の製造方法、固体電解質の製造方法、および固体電解質電池の製造方法
JP2012248514A (ja) * 2011-05-31 2012-12-13 Kyocera Corp リチウム二次電池
WO2013161765A1 (fr) * 2012-04-25 2013-10-31 東邦チタニウム株式会社 Corps fritté à base d'oxyde de lithium, de lanthane et de titane, électrolyte solide contenant un oxyde, batterie lithium-air utilisant l'électrolyte solide et batterie au lithium à l'état solide
JP2015084321A (ja) * 2013-09-20 2015-04-30 株式会社東芝 電池用活物質材料及びその製造方法、非水電解質電池、並びに電池パック
JP2015088392A (ja) * 2013-10-31 2015-05-07 セイコーエプソン株式会社 固体電解質、固体電解質の製造方法およびリチウムイオン電池
JP2016001595A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002357586A (ja) * 2001-06-04 2002-12-13 Tokuyama Corp 固体電解質成形体
JP2009181807A (ja) * 2008-01-30 2009-08-13 Sony Corp 固体電解質、および固体電解質電池、並びにリチウムイオン伝導体の製造方法、固体電解質の製造方法、および固体電解質電池の製造方法
JP2012248514A (ja) * 2011-05-31 2012-12-13 Kyocera Corp リチウム二次電池
WO2013161765A1 (fr) * 2012-04-25 2013-10-31 東邦チタニウム株式会社 Corps fritté à base d'oxyde de lithium, de lanthane et de titane, électrolyte solide contenant un oxyde, batterie lithium-air utilisant l'électrolyte solide et batterie au lithium à l'état solide
JP2015084321A (ja) * 2013-09-20 2015-04-30 株式会社東芝 電池用活物質材料及びその製造方法、非水電解質電池、並びに電池パック
JP2015088392A (ja) * 2013-10-31 2015-05-07 セイコーエプソン株式会社 固体電解質、固体電解質の製造方法およびリチウムイオン電池
JP2016001595A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019221140A1 (fr) * 2018-05-17 2019-11-21 日本碍子株式会社 Batterie secondaire au lithium
JP6643528B1 (ja) * 2018-05-17 2020-02-12 日本碍子株式会社 リチウム二次電池
US12034145B2 (en) 2018-05-17 2024-07-09 Ngk Insulators, Ltd. Lithium secondary battery
CN109546152A (zh) * 2018-11-13 2019-03-29 南昌大学 一种全固态锂电池电极材料及其制备方法
CN113169327A (zh) * 2018-12-07 2021-07-23 住友化学株式会社 锂二次电池正极活性物质用前体、锂二次电池正极活性物质用前体的制造方法以及锂复合金属化合物的制造方法
US11705577B2 (en) 2019-01-31 2023-07-18 University Of Maryland, College Park Lithium phosphate derivative compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
US11784346B2 (en) 2019-01-31 2023-10-10 University Of Maryland, College Park Lithium phosphate derivative compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
US11056717B2 (en) 2019-01-31 2021-07-06 University Of Maryland, College Park Lithium phosphate derivative compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
US10938063B2 (en) 2019-01-31 2021-03-02 University Of Maryland, College Park Lithium silicate compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
JPWO2020188913A1 (fr) * 2019-03-15 2020-09-24
JP7535711B2 (ja) 2019-03-15 2024-08-19 パナソニックＩｐマネジメント株式会社 固体電解質材料およびこれを用いた電池
JPWO2020188915A1 (fr) * 2019-03-15 2020-09-24
WO2020188914A1 (fr) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie l'utilisant
JP7535712B2 (ja) 2019-03-15 2024-08-19 パナソニックＩｐマネジメント株式会社 固体電解質材料およびこれを用いた電池
WO2020188913A1 (fr) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie l'utilisant
CN113474910A (zh) * 2019-03-15 2021-10-01 松下知识产权经营株式会社 固体电解质材料及使用了该固体电解质材料的电池
WO2020188915A1 (fr) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie l'utilisant
JP7496509B2 (ja) 2019-03-15 2024-06-07 パナソニックＩｐマネジメント株式会社 固体電解質材料およびこれを用いた電池
JPWO2020188914A1 (fr) * 2019-03-15 2020-09-24
US20220052333A1 (en) * 2019-04-30 2022-02-17 Innolith Technology AG Rechargeable battery cell
CN110828756A (zh) * 2019-10-29 2020-02-21 东北大学 一种锂离子固体电解质隔膜及其制备和使用方法
CN110828756B (zh) * 2019-10-29 2021-07-23 东北大学 一种锂离子固体电解质隔膜及其制备和使用方法
CN111995396A (zh) * 2020-07-20 2020-11-27 南昌航空大学 一种利用镁改性铌酸钠陶瓷氧离子电导性能的方法
CN115133114A (zh) * 2022-07-29 2022-09-30 重庆太蓝新能源有限公司 一种固态电解质材料及其制备方法和电池
CN117276522A (zh) * 2023-11-22 2023-12-22 天津润光恒科技开发有限公司 纳米铌酸锂包覆的三元正极材料及其制备方法和应用
CN117276522B (zh) * 2023-11-22 2024-01-26 天津润光恒科技开发有限公司 纳米铌酸锂包覆的三元正极材料及其制备方法和应用

Also Published As

Publication number Publication date
JP2018125286A (ja) 2018-08-09

Similar Documents

Publication Publication Date Title
WO2018139657A1 (fr) Stratifié d'électrode et pile au lithium entièrement solide
JP7025620B2 (ja) 全固体リチウム電池用電極積層体の製造方法、全固体リチウム電池用電極複合体及びその製造方法
JP4797105B2 (ja) リチウムイオン二次電池、及び、その製造方法
KR101582394B1 (ko) 정극 활물질 입자, 그리고 그것을 사용한 정극 및 전고체 전지
JP6904423B2 (ja) 共焼成型全固体電池
US20160181657A1 (en) Solid electrolyte, all-solid-state battery including the same, and method for making solid electrolyte
TWI423508B (zh) A positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery
JP6109672B2 (ja) セラミック正極−固体電解質複合体
WO2017018488A1 (fr) Corps fritté contenant du titanate de lithium et titanate de lithium et de lanthane, procédé de production associé et batterie au lithium
JP2016171067A (ja) ガーネット型又はガーネット型類似の結晶構造を有するリチウムイオン伝導性酸化物セラミックス材料
JP2019164980A (ja) 複合体電極及び全固体リチウム電池
JP6109673B2 (ja) セラミック正極−固体電解質複合体
JP6099407B2 (ja) 全固体蓄電素子
WO2022009811A1 (fr) Électrode à corps fritté, élément de batterie, procédés de fabrication d'électrode à corps fritté et d'élément de batterie, solution de précurseur d'électrolyte solide, précurseur d'électrolyte solide et électrolyte solide
US20230402606A1 (en) Solid-state battery
JP2020071948A (ja) 電極積層体及び焼結体並びにそれらの製造方法
JP7115626B2 (ja) 固体電解質の前駆体組成物、二次電池の製造方法
CN114946049A (zh) 固体电池
JP6168690B2 (ja) セラミック正極−固体電解質複合体
JP2019077573A (ja) スピネル型チタン酸リチウムを含む焼結体の製造方法
JP2021012807A (ja) ニッケルマンガンコバルト含有複合水酸化物およびその製造方法、リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池
JPWO2018181576A1 (ja) 全固体電池
CN114122505B (zh) 固体电解质、固体电解质的制造方法及复合体
WO2022124348A1 (fr) Batterie à semi-conducteur
WO2024157640A1 (fr) Batterie à électrolyte solide

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: 18744468

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18744468

Country of ref document: EP

Kind code of ref document: A1