WO2018123479A1 - Pile au ion-lithium, et son procédé de fabrication - Google Patents

Pile au ion-lithium, et son procédé de fabrication Download PDF

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Publication number
WO2018123479A1
WO2018123479A1 PCT/JP2017/043748 JP2017043748W WO2018123479A1 WO 2018123479 A1 WO2018123479 A1 WO 2018123479A1 JP 2017043748 W JP2017043748 W JP 2017043748W WO 2018123479 A1 WO2018123479 A1 WO 2018123479A1
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solid electrolyte
layer
lithium ion
electrode layer
positive electrode
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PCT/JP2017/043748
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English (en)
Japanese (ja)
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吉田　俊広
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日本碍子株式会社
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Priority to JP2018558965A priority Critical patent/JP7009390B2/ja
Publication of WO2018123479A1 publication Critical patent/WO2018123479A1/fr

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    • 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
    • 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
    • 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 a lithium ion battery and a method for manufacturing the same.
  • the lithium ion battery includes a positive electrode layer including a positive electrode active material, a negative electrode layer including a negative electrode active material, and a solid electrolyte layer including an ion conductor.
  • Patent Document 1 it is proposed to use a solid electrolyte layer material containing an ion conductor with a controlled particle size ratio and a sintering aid in order to lower the firing temperature to 700 ° C.
  • the content of the sintering aid relative to the ionic conductor is suppressed to 3.5 wt% or less. ing.
  • Patent Document 1 attempts to improve the ionic conductivity by increasing the content of the ionic conductor in the solid electrolyte layer.
  • the internal resistance is reduced.
  • new knowledge was obtained that it is more advantageous to expand the ion-conducting region by lowering the porosity of the solid electrolyte layer, rather than increasing the content of the ionic conductor.
  • the present invention has been made based on the above-described knowledge, and an object thereof is to provide a lithium ion battery capable of reducing internal resistance and a method for manufacturing the lithium ion battery.
  • the lithium ion battery according to the present invention includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer.
  • the solid electrolyte layer contains a first solid electrolyte that is a main component and a second solid electrolyte that is a subcomponent.
  • the average porosity of the solid electrolyte layer is 9% or less.
  • the present invention it is possible to provide a lithium ion battery capable of reducing internal resistance and a manufacturing method thereof.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of the lithium ion battery 100.
  • the chip-type lithium ion battery 100 configured in a plate shape is a secondary battery (rechargeable battery) that can be repeatedly used by charging and discharging.
  • the lithium ion battery 100 includes a positive electrode side current collecting layer 101, a negative electrode side current collecting layer 102, exterior materials 103 and 104, a current collecting connection layer 105, a positive electrode layer 106, a solid electrolyte layer 107, and a negative electrode layer 108.
  • the positive electrode side current collecting layer 101, the current collecting connection layer 105, the positive electrode layer 106, the solid electrolyte layer 107, the negative electrode layer 108, and the negative electrode side current collecting layer 102 are sequentially laminated in the laminating direction X.
  • the positive electrode part 110 is constituted by the positive electrode side current collecting layer 101, the current collecting connection layer 105 and the positive electrode layer 106.
  • the negative electrode side current collecting layer 102 and the negative electrode layer 108 constitute a negative electrode portion 120.
  • Positive electrode side current collecting layer 101 The positive electrode side current collecting layer 101 is disposed outside the positive electrode layer 106. The positive electrode side current collecting layer 101 is mechanically and electrically connected to the positive electrode layer 106 through the current collecting connection layer 105. The positive electrode side current collecting layer 101 functions as a positive electrode current collector.
  • the positive electrode side current collecting layer 101 can be made of metal.
  • the metal constituting the positive electrode side current collecting layer 101 include stainless steel, aluminum, copper, platinum, nickel and the like, and aluminum, nickel and stainless steel are particularly preferable.
  • the positive current collecting layer 101 can be formed in a plate shape or a foil shape, and a foil shape is particularly preferable. Therefore, it is particularly preferable to use an aluminum foil, a nickel foil, or a stainless steel foil as the positive electrode side current collecting layer 101.
  • the thickness of the positive electrode side current collecting layer 101 can be 1 ⁇ m or more and 30 ⁇ m or less, preferably 5 ⁇ m or more and 25 ⁇ m or less, and more preferably 10 ⁇ m or more and 20 ⁇ m or less.
  • Negative electrode side current collecting layer 102 The negative electrode side current collecting layer 102 is disposed outside the negative electrode layer 108. The negative electrode side current collecting layer 102 is mechanically and electrically connected to the negative electrode layer 108. The negative electrode side current collecting layer 102 functions as a negative electrode current collector.
  • the negative electrode side current collection layer 102 can be comprised with a metal.
  • the negative electrode side current collecting layer 102 can be made of the same material as that of the positive electrode side current collecting layer 101. Therefore, it is particularly preferable to use an aluminum foil, a nickel foil, or a stainless steel foil as the negative electrode side current collecting layer 102.
  • the thickness of the negative electrode side current collecting layer 102 can be 1 ⁇ m or more and 30 ⁇ m or less, preferably 5 ⁇ m or more and 25 ⁇ m or less, and more preferably 10 ⁇ m or more and 20 ⁇ m or less.
  • Exterior material 103, 104 The exterior materials 103 and 104 seal a gap between the positive electrode side current collecting layer 101 and the negative electrode side current collecting layer 102.
  • the packaging materials 103 and 104 surround the side of the unit cell constituted by the positive electrode layer 106, the solid electrolyte layer 107, and the negative electrode layer 108.
  • the exterior materials 103 and 104 suppress moisture intrusion into the lithium ion battery 100.
  • the resistivity of the exterior materials 103 and 104 is preferably 1 ⁇ 10 6 ⁇ cm or more, and preferably 1 ⁇ 10 7 ⁇ cm or more in order to ensure electrical insulation between the positive electrode side current collection layer 101 and the negative electrode side current collection layer 102. Is more preferably 1 ⁇ 10 8 ⁇ cm or more.
  • Such exterior material 103,104 can be comprised with an electrically insulating sealing material.
  • As the sealing material a resin-based sealing material containing a resin can be used. By using the resin-based sealing material, the exterior materials 103 and 104 can be formed at a relatively low temperature (for example, 400 ° C. or lower), so that the destruction and deterioration of the lithium ion battery 100 due to heating can be suppressed.
  • the exterior materials 103 and 104 can be formed by laminating resin films or dispensing liquid resin.
  • the current collecting connection layer 105 is disposed between the positive electrode layer 106 and the positive electrode side current collecting layer 101.
  • the current collecting connection layer 105 mechanically bonds the positive electrode layer 106 to the positive electrode side current collecting layer 101 and electrically bonds the positive electrode layer 106 to the positive electrode side current collecting layer 101.
  • the current collecting connection layer 105 includes a conductive material and an adhesive.
  • conductive material conductive carbon or the like can be used.
  • adhesive an epoxy-based resin material can be used.
  • the thickness of the current collector connection layer 105 is not particularly limited, but can be 5 ⁇ m or more and 100 ⁇ m or less, and preferably 10 ⁇ m or more and 50 ⁇ m or less.
  • the current collecting connection layer 105 may not contain an adhesive.
  • an electrical connection between the current collector connection layer 105 and the positive electrode layer 106 can be obtained by directly forming the current collector connection layer 105 (eg, gold or aluminum) on the back surface of the positive electrode layer 106.
  • Positive electrode layer 106 The positive electrode layer 106 is formed into a plate shape.
  • the positive electrode layer 106 has a solid electrolyte side surface 106a and a current collecting connection layer side surface 106b.
  • the positive electrode layer 106 is connected to the solid electrolyte layer 107 on the solid electrolyte side surface 106a.
  • the positive electrode layer 106 is connected to the current collector connection layer 105 on the current collector connection layer side surface 106b.
  • Each of the solid electrolyte side surface 106 a and the current collecting connection layer side surface 106 b is a “plate surface” of the positive electrode layer 106.
  • the solid electrolyte side surface 106a is a line obtained by linearly approximating the interface between the positive electrode layer 106 and the solid electrolyte layer 107 by the least square method when a cross section of the positive electrode layer 106 is observed with a scanning electron microscope (SEM). It is prescribed by.
  • the current collecting connection layer side surface 106b is defined by a line obtained by linear approximation of the interface between the positive electrode layer 106 and the current collecting connection layer 105 by the least square method when the cross section of the positive electrode layer 106 is observed by SEM.
  • the thickness of the positive electrode layer 106 is not particularly limited, but is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, and further preferably 30 ⁇ m or more. In particular, by setting the thickness of the positive electrode layer 106 to 50 ⁇ m or more, the active material capacity per unit area can be sufficiently secured and the energy density of the lithium ion battery 100 can be increased.
  • the upper limit value of the thickness of the positive electrode layer 106 is not particularly limited, but is preferably less than 200 ⁇ m and more preferably 150 ⁇ m or less in consideration of suppression of deterioration of battery characteristics (particularly increase in resistance value) due to repeated charge / discharge. 120 ⁇ m or less is more preferable, and 100 ⁇ m or less is particularly preferable.
  • the expansion / contraction rate in a direction parallel to the plate surface of the positive electrode layer 106 is preferably suppressed to 0.7% or less.
  • plate surface direction The expansion / contraction rate in a direction parallel to the plate surface of the positive electrode layer 106.
  • the positive electrode layer 106 is preferably a sintered plate configured by combining a plurality of positive electrode active material crystal grains (primary particles).
  • the thickness can be increased as compared with the film formed by the vapor phase method, the capacity and energy density of the lithium ion battery 100 can be improved.
  • the composition of the positive electrode layer 106 can be adjusted by weighing the raw materials, the composition can be controlled with higher accuracy than a film formed by a vapor phase method.
  • the positive electrode active material crystal grains are mainly formed in a plate shape, but may include those formed in a rectangular parallelepiped shape, a cubic shape, a spherical shape, or the like.
  • the positive electrode active material crystal grains are composed of a lithium composite oxide.
  • the lithium composite oxide is Li x MO 2 (0.05 ⁇ x ⁇ 1.10, M is at least one transition metal, and M is typically one of Co, Ni, and Mn. Including the above.)
  • the lithium composite oxide has a layered rock salt structure.
  • the layered rock salt structure is a crystal structure in which lithium layers and transition metal layers other than lithium are alternately stacked with oxygen layers in between, that is, the transition metal ion layers and lithium single layers are alternately arranged via oxide ions. (Typically an ⁇ -NaFeO 2 type structure, ie, a structure in which transition metals and lithium are regularly arranged in the [111] axis direction of a cubic rock salt type structure).
  • lithium composite oxide examples include Li x CoO 2 (lithium cobaltate), Li x NiO 2 (lithium nickelate), Li x MnO 2 (lithium manganate), and Li x NiMnO 2 (nickel / lithium manganate).
  • the lithium composite oxide includes Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te. , Ba, Bi, W, etc. may contain one or more elements.
  • the positive electrode active material crystal grains are preferably oriented in the lithium ion conduction direction.
  • the (003) plane of the positive electrode active material crystal grains is preferably oriented in the stacking direction X.
  • Solid electrolyte layer 107 contains a first solid electrolyte that is a main component and a second solid electrolyte that is a subcomponent.
  • the first solid electrolyte may be a base material
  • the second solid electrolyte may be an additive.
  • the first solid electrolyte is an oxide ceramic material having lithium ion conductivity.
  • the oxide ceramic material as the first solid electrolyte is at least one selected from the group consisting of garnet ceramic materials, nitride ceramic materials, perovskite ceramic materials, phosphate ceramic materials, and zeolite materials. be able to.
  • garnet-based ceramic materials include Li—La—Zr—O materials (specifically, Li 7 La 3 Zr 2 O 12 and the like) and Li—La—Ta—O materials (specifically, Li 7 La 3 Ta 2 O 12 etc.).
  • nitride-based ceramic materials include Li 3 N and LiPON (specifically, Li x PO y N z (2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5, 0.1 ⁇ z ⁇ 0.9)) ) And the like.
  • perovskite ceramic materials examples include Li—La—Ti—O materials (specifically, LiLa 1-x Ti x O 3 (0.04 ⁇ x ⁇ 0.14)).
  • Examples of phosphoric acid-based ceramic materials include Li—Al—Ti—P—O materials (specifically, Li (Al, Ti) 2 (PO 4 ) 3 ), Li—Al—Ge—PO materials. (Specifically, Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 etc.), and Li—Al—Ti—Si—P—O materials (specifically, Li 1 + x + y Al x Ti 2-x Si y P 3-y O 12 (0 ⁇ x ⁇ 0.4,0 ⁇ y ⁇ 0.6) , and the like).
  • the average content of the first solid electrolyte in the solid electrolyte layer 107 can be 70 wt% or more and 96 wt% or less.
  • the average content of the first solid electrolyte is determined by measuring the content of the first solid electrolyte at four locations in the cross section of the solid electrolyte layer 107 that equally divide the solid electrolyte layer 107 into five in the thickness direction (same as the stacking direction X). Is obtained by arithmetically averaging it.
  • the content rate of the first solid electrolyte in each location is measured by elemental analysis using an energy dispersive X-ray spectrometer (EDS).
  • EDS energy dispersive X-ray spectrometer
  • the second solid electrolyte is an oxide-based ceramic material, a plastic material, or a combination thereof.
  • the second solid electrolyte may have lithium ion conductivity or may not have lithium ion conductivity.
  • the lithium ion conductivity of the second solid electrolyte may be lower than the lithium ion conductivity of the first solid electrolyte.
  • the oxide-based ceramic material as the second solid electrolyte includes a general formula Li x AO y (where A is B, C, Cl, Al, Si, P, S, Ti, Zr, Nb) , Mo, Ta, or W, and x and y are positive integers).
  • Examples include at least one selected from the group consisting of TiO 3 , Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , Li 2 ZrO 3 , LiNbO 3 , Li 2 MoO 4 , and Li 2 WO 4 .
  • the solid electrolyte layer 107 can be produced by a sintering method.
  • the second solid electrolyte functions as a sintering aid that promotes liquid phase sintering of the first solid electrolyte.
  • the melting point of the oxide-based ceramic material that is the second solid electrolyte is preferably 600 ° C. or lower.
  • the average content of the second solid electrolyte in the solid electrolyte layer 107 is preferably 4 wt% or more, more preferably 10 wt% or more, and particularly preferably 15 wt% or more. Accordingly, the second solid electrolyte can be sufficiently filled in the gap between the liquid-phase sintered first solid electrolyte, so that the solid electrolyte layer 107 can be densified as described later.
  • the average content of the second solid electrolyte in the solid electrolyte layer 107 is preferably 30 wt% or less, more preferably 25 wt% or less, and particularly preferably 20 wt% or less. . Thereby, even if the lithium ion conductivity of the second solid electrolyte is low, the lithium ion conductivity of the solid electrolyte layer 107 as a whole can be maintained.
  • the average content of the oxide-based ceramic material as the second solid electrolyte in the solid electrolyte layer 107 is the oxide-based ceramic material at four locations where the solid electrolyte layer 107 is equally divided into five in the thickness direction in the cross section of the solid electrolyte layer 107. It is obtained by measuring the content of and averaging it. The content of the oxide-based ceramic material at each location is measured by elemental analysis using an energy dispersive X-ray spectrometer (EDS).
  • EDS energy dispersive X-ray spectrometer
  • plastic material As the plastic material as the second solid electrolyte, glass material, lithium aluminum hexafluoride (Li 3 AlF 6 ), NaI—LiBH 4 or the like can be used.
  • the glass material Bi 2 O 3 , B 2 O 3 , or a mixture thereof can be used.
  • the solid electrolyte layer 107 can be produced by heating a mixture of the first solid electrolyte and the second solid electrolyte to a temperature above the softening point of the second solid electrolyte.
  • the glass material that is the second solid electrolyte spreads in the gaps of the first solid electrolyte by plastic deformation.
  • the softening point of the second solid electrolyte is preferably 600 ° C. or lower. Thereby, it is possible to prevent the active material in the positive electrode layer 106 or the negative electrode layer 108 from reacting with the first or second solid electrolyte to form a high resistance layer.
  • Li 3 AlF 6 and / or NaI-LiBH 4 is used as the second solid electrolyte
  • a mixture of the first solid electrolyte and the second solid electrolyte is deposited using an electrophoretic deposition (EPD) method.
  • the solid electrolyte layer 107 can be produced by applying pressure.
  • Li 3 AlF 6 and NaI—LiBH 4 that are the second solid electrolytes spread in the gaps of the first solid electrolyte by plastic deformation. Since Li 3 AlF 6 and NaI—LiBH 4 have plasticity at 20 ° C. or higher, the solid electrolyte layer 107 can be formed without heating. Therefore, it can suppress that the active material in the positive electrode layer 106 or the negative electrode layer 108 and the 1st or 2nd solid electrolyte react, and a high resistance layer is formed.
  • the second solid electrolyte when the second solid electrolyte has deliquescence, it is effective to increase the atmospheric humidity when the mixture of the first solid electrolyte and the second solid electrolyte is pressurized. As a result, a good interface can be formed between the positive electrode layer 106 and the solid electrolyte layer 107.
  • the average content of the second solid electrolyte in the solid electrolyte layer 107 is preferably 4 wt% or more, more preferably 10 wt% or more, and particularly preferably 15 wt% or more. Thereby, the gap between the first solid electrolytes can be sufficiently filled with the second solid electrolyte, so that the solid electrolyte layer 107 can be densified.
  • the average content of the second solid electrolyte in the solid electrolyte layer 107 is preferably 30 wt% or less, more preferably 25 wt% or less, and particularly preferably 20 wt% or less.
  • the average content of the plastic material in the solid electrolyte layer 107 is obtained by measuring the content of the plastic material at four locations where the solid electrolyte layer 107 is equally divided into five in the thickness direction in the cross section of the solid electrolyte layer 107, and arithmetically averaging them. Can be obtained.
  • the content rate of the plastic material in each location is measured by elemental analysis using an energy dispersive X-ray spectrometer (EDS).
  • the average porosity of the solid electrolyte layer 107 is 9% or less. That is, the average density of the solid electrolyte layer 107 is 91% or more. In this way, the ionic conductivity of the solid electrolyte layer 107 can be improved more than increasing the content of the ionic conductor by widening the ion conductive region by sufficiently reducing the average porosity of the solid electrolyte layer 107. Therefore, the internal resistance of the lithium ion battery 100 can be reduced.
  • the average porosity of the solid electrolyte layer 107 is preferably 7% or less, and particularly preferably 5% or less.
  • the average porosity of the solid electrolyte layer 107 is obtained by measuring the porosity at four locations in the cross section of the solid electrolyte layer 107 that equally divide the solid electrolyte layer 107 into five in the thickness direction, and arithmetically averaging them.
  • the porosity is calculated by obtaining an SEM (electron microscope) image at 20000 magnification at each measurement location, and dividing the total area of the pores in the solid electrolyte layer 107 by the area of the entire solid electrolyte layer 107.
  • the solid electrolyte layer 107 does not substantially contain sulfur.
  • substantially containing no sulfur means that the average content of sulfur in the solid electrolyte layer 107 is 0.1 wt% or less. Accordingly, it is possible to suppress generation of toxic gas from the solid electrolyte layer 107 when moisture enters from the outside of the lithium ion battery 100.
  • the average content of sulfur in the solid electrolyte layer 107 is more preferably 0.01 wt% or less, and particularly preferably 0.001 wt% or less.
  • the average content of sulfur in the solid electrolyte layer 107 is obtained by measuring the sulfur content at four locations that divide the solid electrolyte layer 107 into 5 parts in the thickness direction in the cross section of the solid electrolyte layer 107 and arithmetically averaging them. can get.
  • the sulfur content in each location is measured by elemental analysis using an energy dispersive X-ray spectrometer (EDS).
  • EDS energy dispersive X-ray spectrometer
  • the thickness of the solid electrolyte layer 107 is preferably thin from the viewpoint of improving lithium ion conductivity, but is set as appropriate in consideration of reliability during charge / discharge (suppression of defects and cracks, function as a separator, etc.). can do.
  • the thickness of the solid electrolyte layer 107 can be, for example, 1 ⁇ m or more and 1000 ⁇ m or less.
  • the thickness of the solid electrolyte layer 107 is preferably 10 ⁇ m or more and 500 ⁇ m or less, and particularly preferably 20 ⁇ m or more and 200 ⁇ m or less.
  • Negative electrode layer 108 The negative electrode layer 108 is disposed on the solid electrolyte layer 107.
  • the negative electrode layer 108 contains a negative electrode active material.
  • the negative electrode active material may be any material that can occlude and release lithium ions.
  • As the negative electrode active material for example, a carbonaceous material or a lithium storage material can be used.
  • the carbonaceous material examples include graphite, pyrolytic carbons, cokes, glassy carbons, fired bodies of organic polymer compounds, mesocarbon microbeads, carbon fibers, and activated carbon.
  • a part of graphite may be replaced with a metal or an oxide that can be alloyed with lithium.
  • the thickness of the negative electrode layer 108 can be 10 ⁇ m or more and 500 ⁇ m or less.
  • the lithium storage material examples include metallic lithium, alloys containing metallic lithium and other elements (silicon, tin, indium, etc.), oxides such as silicon or tin that can be charged and discharged at a low potential close to lithium, Li 4 Ti 5 O
  • examples thereof include an oxide of lithium and titanium such as 12 (LTO), a nitride of lithium and cobalt such as Li 2.6 Co 0.4 N, and TiO 2 (titania).
  • the negative electrode layer 108 may be composed of sintered plate by a plurality of anode active material crystal grains (primary particles) binds.
  • the composition formula of the lithium occlusion material naturally changes according to the occlusion and release of lithium ions.
  • the thickness of the negative electrode layer 108 can be 10 ⁇ m or more and 500 ⁇ m or less.
  • the negative electrode layer 108 is preferably manufactured by the EPD method. As a result, the negative electrode layer 108 can be fabricated at a lower temperature than in the sputtering method, the CVD method, or the like. Therefore, the active material in the negative electrode layer 108 reacts with the first or second solid electrolyte in the solid electrolyte layer 107 to increase resistance. Formation of a layer can be suppressed.
  • the negative electrode layer 108 may be formed by a tape molding method, a printing method, a spin coating method, or the like depending on the material of the negative electrode layer 108.
  • a foil-like lithium storage member (such as Sn foil or Li foil) can be used for the negative electrode layer 108.
  • the negative electrode layer 108 can be produced by press-molding a foil-like lithium occlusion member on the solid electrolyte layer 107. Also in this case, it can be suppressed that the active material in the negative electrode layer 108 reacts with the first or second solid electrolyte in the solid electrolyte layer 107 to form a high resistance layer.
  • the positive electrode layer 106 (an example of the first electrode) is composed of the positive electrode active material crystal grains, but in addition to the positive electrode active material, the constituent material of the solid electrolyte layer 107 described above It is preferable to contain (first solid electrolyte and second solid electrolyte). As a result, the ion conductivity between the positive electrode layer 106 and the solid electrolyte layer 107 can be improved, so that the internal resistance of the lithium ion battery 100 can be reduced.
  • the total content of the first solid electrolyte and the second solid electrolyte in the positive electrode layer 106 is preferably 30 wt% or more, and the average content of the second solid electrolyte in the positive electrode layer 106 is preferably 4 wt% or more and 20 wt% or less.
  • the porosity of the positive electrode layer 106 can be 9% or less.
  • the total content of the first solid electrolyte and the second solid electrolyte in the positive electrode layer 106 is more preferably 40 wt% or more, and particularly preferably 50 wt% or more.
  • the average content of the second solid electrolyte in the positive electrode layer 106 is more preferably 5 wt% or more and 15 wt% or less, and particularly preferably 7 wt% or more and 12 wt% or less.
  • the positive electrode layer 106 containing the constituent materials (the first solid electrolyte and the second solid electrolyte) of the solid electrolyte layer 107 can be produced in the same manner as the solid electrolyte layer 107.
  • the negative electrode layer 108 (an example of the first electrode) can be composed of a negative electrode active material such as a carbonaceous material or a lithium storage material.
  • the solid electrolyte described above is used. It is preferable that the constituent materials of the layer 107 (first solid electrolyte and second solid electrolyte) are contained. Thereby, since the ion conductivity between the negative electrode layer 108 and the solid electrolyte layer 107 can be improved, the internal resistance of the lithium ion battery 100 can be reduced.
  • the total content of the first solid electrolyte and the second solid electrolyte in the negative electrode layer 108 is preferably 30 wt% or more, and the average content of the second solid electrolyte in the negative electrode layer 108 is preferably 4 wt% or more and 20 wt% or less.
  • the porosity of the negative electrode layer 108 can be reduced to 9% or less.
  • the total content of the first solid electrolyte and the second solid electrolyte in the negative electrode layer 108 is more preferably 40 wt% or more, and particularly preferably 50 wt% or more.
  • the average content of the second solid electrolyte in the negative electrode layer 108 is particularly preferably 10 wt% or more and 15 wt% or less.
  • the negative electrode layer 108 containing the constituent materials (the first solid electrolyte and the second solid electrolyte) of the solid electrolyte layer 107 can be manufactured in the same manner as the solid electrolyte layer 107.
  • the positive electrode layer 106 and the solid electrolyte layer 107 are in direct contact with each other.
  • the present invention is not limited to this.
  • a solid electrolyte oxide-based ceramic material, plastic material, or a combination thereof
  • One intermediate layer may be interposed.
  • the solid electrolyte constituting the first intermediate layer may be different from the second solid electrolyte contained in the solid electrolyte layer 107 as a subcomponent, but is preferably the same.
  • the thickness of the first intermediate layer is not particularly limited, and can be, for example, 1 ⁇ m or more and 5 ⁇ m or less. By interposing such a first intermediate layer, the adhesion between the positive electrode layer 106 and the solid electrolyte layer 107 is improved, so that the resistance between the positive electrode layer 106 and the solid electrolyte layer 107 can be reduced. .
  • the negative electrode layer 108 and the solid electrolyte layer 107 are in direct contact with each other.
  • the present invention is not limited to this.
  • a solid electrolyte oxide-based ceramic material, plastic material, or a combination thereof
  • Two intermediate layers may be interposed.
  • the solid electrolyte constituting the second intermediate layer may be different from the second solid electrolyte contained in the solid electrolyte layer 107 as a subcomponent, but is preferably the same.
  • the thickness of the second intermediate layer is not particularly limited, and can be, for example, 1 ⁇ m or more and 5 ⁇ m or less.
  • a known organic electrolytic solution may be interposed between the positive electrode layer 106 and the solid electrolyte layer 107. Thereby, the bondability between the positive electrode layer 106 and the solid electrolyte layer 107 can be improved.
  • a known organic electrolyte solution may be interposed between the negative electrode layer 108 and the solid electrolyte layer 107. Thereby, the bondability between the negative electrode layer 108 and the solid electrolyte layer 107 can be improved.
  • At least one of the positive electrode layer 106, the solid electrolyte layer 107, and the negative electrode layer 108 may contain a known organic electrolytic solution. Thereby, it is possible to improve the bonding property between the particles constituting the layer containing the organic electrolyte.
  • the content rate of the organic electrolyte solution in the layer containing the organic electrolyte solution is not particularly limited, it is preferably 9% or less because the organic electrolyte solution can be disposed in the pores.
  • the content of the organic electrolyte in the layer containing the organic electrolyte is obtained by measuring the content of the organic electrolyte at four locations that divide each layer into 5 parts in the thickness direction in the cross section of each layer, and arithmetically averaging it. can get.
  • the content rate of the organic electrolyte is calculated by acquiring a SEM image at a magnification of 20000 at each measurement location and dividing the total area of the organic electrolyte in the SEM image by the area of the entire layer.
  • LiCoO 2 powder was pulverized to obtain plate-like LiCoO 2 particles (LCO template particles).
  • Co 3 O 4 (CoO) raw material powder manufactured by Shodo Chemical Industry Co., Ltd. was prepared as matrix particles.
  • the mixture was degassed by stirring under reduced pressure, and a slurry was prepared by adjusting the viscosity to 40960000 cP.
  • the green sheet peeled from the PET film was placed on a zirconia setter and subjected to primary firing to obtain a Co 3 O 4 sintered plate.
  • the Co 3 O 4 sintered plate was placed on a zirconia setter while being sandwiched between upper and lower lithium sheets and subjected to secondary firing to obtain a LiCoO 2 (LCO) sintered plate as a positive electrode layer.
  • the thickness of the LCO sintered plate was 50 ⁇ m.
  • Example 8 LATP was used as the main component, and Li 3 BO 3 was used as the subcomponent.
  • the subcomponents of Examples 1 to 8 are oxide ceramic materials. The mixing ratio of the subcomponents was changed between 3 and 40 wt% as shown in Table 1.
  • a solid electrolyte layer and a negative electrode layer were formed by collectively firing a laminate of a positive electrode layer, a solid electrolyte layer compact, and a negative electrode layer compact.
  • the thickness of the positive electrode layer was 50 ⁇ m.
  • the thickness of the solid electrolyte layer was 20 ⁇ m.
  • Example 1 since the melting point of Li 4 SiO 4 —Li 3 BO 3 which is a subcomponent is 550 ° C., the firing temperature was set to 600 ° C. In Example 7, since the melting point of LiPO 3 as the accessory component was 660 ° C., the firing temperature was 700 ° C. In Example 8, since the melting point of Li 3 BO 3 , which is a subcomponent, is 715 ° C., the firing temperature was 750 ° C.
  • Example 9 The same as in Examples 1 to 6 except that the laminate of the positive electrode layer and the molded body of the solid electrolyte layer was fired to form the solid electrolyte layer, and then the foil-shaped negative electrode layer was press-molded on the solid electrolyte layer.
  • Lithium ion batteries according to Examples 9 and 10 were produced according to the process.
  • Example 9 Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) was used as the main component of the solid electrolyte layer, and Li 4 SiO 4 —Li 3 BO 3 was used as the subcomponent. .
  • the main component and the subcomponent were mixed at a ratio of 70 wt%: 30 wt%.
  • Li 7 La 3 Zr 2 O 12 (LLZ) was used as the main component of the solid electrolyte layer, and Li 3 ClO was used as the subcomponent.
  • the main component and the subcomponent were mixed at a ratio of 90 wt%: 10 wt%. Since the melting point of Li 3 ClO is 350 ° C., the firing temperature in Example 10 was set to 350 ° C.
  • Example 11 The lithium ion battery according to Example 11 was manufactured in the same manner as in Example 10 except that the negative electrode layer was formed by printing a mixture of the carbon powder and the main component and subcomponent of the solid electrolyte layer on the solid electrolyte layer. Produced. In the negative electrode layer of Example 11, LLZ which is the main component of the carbon powder and the solid electrolyte layer and Li 3 ClO which is the subcomponent were mixed at a ratio of 50 wt%: 40 wt%: 10 wt%.
  • Example 12 Except that the solid electrolyte layer and the negative electrode layer were formed by collectively uniaxially pressing the molded body of the positive electrode layer, the solid electrolyte layer and the negative electrode layer (room temperature, 200 MPa), and A lithium ion battery according to Example 12 was fabricated by the same process.
  • Example 12 LAGP was used as the main component of the solid electrolyte layer, and Li 3 AlF 6 was used as the subcomponent.
  • the main component and the subcomponent were mixed at a ratio of 90 wt%: 10 wt%.
  • the accessory component of Example 12 is a plastic material.
  • Example 12 a compact of the solid electrolyte layer was formed by depositing a mixture of LAGP and Li 3 AlF 6 on the positive electrode layer using the EPD method. Further, a mixture of LTO powder and LAGP and Li 3 AlF 6, by depositing with the EPD method on molded article of the solid electrolyte layer to form a molded body of the negative electrode layer.
  • Example 13 A lithium ion battery according to Example 13 was fabricated by the same process as in Example 9, except that Bi 2 O 3 —B 2 O 3 (90 wt%: 10 wt%) was used as a subcomponent of the solid electrolyte layer.
  • Bi 2 O 3 —B 2 O 3 used as an accessory component is a plastic material. Since the softening point of Bi 2 O 3 —B 2 O 3 is 389 ° C., the heating temperature was set to 400 ° C.
  • Example 14 to 18 The lithium ion batteries according to Examples 14 to 18 were manufactured in the same manner as in Example 12 except that LAGP was used as the main component of the solid electrolyte layer and NaI-LiBH 4 (99 wt%: 1 wt%) was used as the subcomponent. Produced. NaI—LiBH 4 used as an accessory component is a plastic material.
  • Examples 14 to 18 a mixture of LAGP and NaI-LiBH 4 was deposited on the positive electrode layer using the EPD method, thereby forming a solid electrolyte layer compact. Further, a mixture of LTO powder and LAGP and NaI-LiBH 4, by depositing with the EPD method on molded article of the solid electrolyte layer to form a molded body of the negative electrode layer.
  • LTO powder, LAGP, which is the main component of the solid electrolyte layer, and NaI—LiBH 4 which is the subcomponent were mixed at a ratio of 50 wt%: 45 wt%: 5 wt%.
  • Example 19 A first intermediate layer (thickness 1 ⁇ m) composed of Li 4 SiO 4 —Li 3 BO 3 (30 wt%: 70 wt%), which is a subcomponent of the solid electrolyte layer, is interposed between the positive electrode layer and the solid electrolyte layer.
  • a lithium ion battery according to Example 19 was fabricated by the same process as in Example 2 except that it was inserted. However, in Example 19, an LTO sintered plate was used as the negative electrode layer.
  • Example 20 Between the positive electrode layer and the solid electrolyte layer, a first intermediate layer (thickness 2 ⁇ m) composed of Li 3 AlF 6 which is a subcomponent of the solid electrolyte layer is interposed, and between the negative electrode layer and the solid electrolyte layer, A lithium ion battery according to Example 20 was produced by the same process as Example 12 except that a second intermediate layer (thickness 2 ⁇ m) constituted by Li 3 AlF 6 which is a subcomponent of the solid electrolyte layer was interposed. . However, in Example 20, the main component and the subcomponent were mixed at a ratio of 70 wt%: 30 wt%, and the LTO sintered plate was used as the negative electrode layer.
  • Comparative Examples 1 and 2 Lithium ion batteries according to Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that no subcomponent was added to the solid electrolyte layer. However, in Comparative Example 1, the firing temperature was 500 ° C., and in Comparative Example 2, the firing temperature was 900 ° C.
  • the porosity was calculated by acquiring a SEM image at a magnification of 20000 at each measurement location and dividing the total area of the pores in the solid electrolyte layer by the total area.
  • the solid electrolyte layer was densified by firing at a temperature equal to or higher than the melting point of the second solid electrolyte (oxide-based ceramic material) contained in the solid electrolyte layer.
  • the average porosity of the solid electrolyte layer could be 9% or less.
  • the average porosity of the solid electrolyte layer was 9%. I was able to:
  • Examples 1 to 11 and 19 in which an oxide-based ceramic material is used for the second solid electrolyte of the solid electrolyte examples 1 to 6, 9 to 11 and 19 in which the firing temperature is 600 ° C. or less, and a plastic material
  • Examples 12 to 18 and 20 in which was used for the second solid electrolyte of the solid electrolyte the battery internal resistance could be further reduced. This is because the formation of the solid electrolyte layer by a low-temperature process can suppress the formation of the high resistance layer by reacting the active material of the positive electrode layer or the negative electrode layer with the solid electrolyte.
  • Examples 12 to 18 and 20 in which a plastic material is used for the second solid electrolyte of the solid electrolyte layer examples 12 to 16 and 20 in which the average content of the second solid electrolyte is 4 wt% or more and 30 wt% or less. Then, the average porosity of the solid electrolyte layer could be reduced to 7% or less.
  • Example 19 in which the first and second intermediate layers constituted by the second solid electrolyte of the solid electrolyte layer were provided, the battery internal resistance could be further reduced as compared with Example 2. This is because the adhesion between the positive electrode layer and the solid electrolyte layer can be improved by the first intermediate layer, and the adhesion between the negative electrode layer and the solid electrolyte layer can be improved by the second intermediate layer.
  • Example 21 was performed in the same manner as in Example 1 except that a molded body of the positive electrode layer was produced by molding a mixture of the LCO powder, the main component of the solid electrolyte layer, and the subcomponent of the solid electrolyte layer by a tape molding method. , 22 were produced.
  • Example 21 Li 1.5 Al 0.5 Ge 1.5 using (PO 4) 3 (LAGP) in the main component of the solid electrolyte layer, Li 4 SiO 4 -Li 3 to subcomponent BO 3 was used.
  • the main component and subcomponent of the LCO powder and the solid electrolyte layer were mixed at a ratio of 50 wt%: 46 wt%: 4 wt%.
  • the LCO powder, the main component and the subcomponent of the solid electrolyte layer were mixed at a ratio of 70 wt%: 10 wt%: 20 wt%.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were simultaneously formed by laminating and respectively firing the positive electrode layer, the solid electrolyte layer, and the negative electrode layer.
  • Example 23 to 27 Lithium ion batteries according to Examples 23 to 27 were fabricated by the same process as in Examples 21 and 22, except that an LTO sintered plate was used as the negative electrode layer.
  • the mixing ratio of the positive electrode active material and the solid electrolyte (main component and subcomponent) in the positive electrode layer was changed for each example.
  • Example 28 to 32 Lithium ion batteries according to Examples 28 to 32 were produced in the same manner as in Examples 21 and 22, except that an LCO sintered plate was used as the positive electrode layer.
  • the mixing ratio of the negative electrode active material and the solid electrolyte (main component and subcomponent) in the negative electrode layer was changed for each example.
  • Comparative Example 3 A comparative example was produced in the same manner as in Example 21 except that the molded body of the positive electrode layer was formed by mixing the main component and subcomponent of the LCO powder and the solid electrolyte layer in a ratio of 50 wt%: 48 wt%: 2 wt%. The lithium ion battery which concerns on 3 was produced.
  • Comparative Example 4 Comparative example according to the same steps as in Example 28 except that the molded body of the negative electrode layer was formed by mixing the main component and subcomponent of the LCO powder and the solid electrolyte layer in a ratio of 50 wt%: 48 wt%: 2 wt%. The lithium ion battery which concerns on 4 was produced.
  • the porosity was measured at four locations that divide the negative electrode layer into 5 equal parts in the thickness direction, and arithmetically averaged to obtain the negative electrode layers of Examples 21, 22, 28 to 32 The average porosity was obtained.
  • the porosity was calculated by acquiring a SEM image at a magnification of 20000 at each measurement location and dividing the total area of the pores in the solid electrolyte layer by the total area.
  • the positive electrode layer could be densified by adding the main component and subcomponents of the solid electrolyte layer to the positive electrode active material, so that the porosity of the positive electrode layer could be suppressed to 9% or less.
  • Comparative Example 3 since the minor component of the solid electrolyte layer added to the positive electrode active material was small and the positive electrode layer could not be densified, the average porosity of the positive electrode layer was 10%. Therefore, in Examples 21 to 27, the battery internal resistance could be reduced as compared with Comparative Example 3.
  • the negative electrode layer was densified by adding the main component and subcomponents of the solid electrolyte layer to the negative electrode active material, so that the porosity of the negative electrode layer was suppressed to 9% or less. did it.
  • Comparative Example 4 since the minor component of the solid electrolyte layer added to the negative electrode active material was small and the negative electrode layer could not be densified, the average porosity of the negative electrode layer was 10%. Therefore, in Examples 21, 22, 28 to 32, the battery internal resistance could be reduced as compared with Comparative Example 4.
  • Example 21, 22, 28 to 32 in Examples 21, 22, 28, and 29 in which the average content of the second solid electrolyte was 4 wt% or more and 20 wt% or less, the porosity was suppressed to 6% or less. The battery internal resistance could be further reduced.

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Abstract

La présente invention cocnerne une pile au ion-lithium (100) qui comporte: une couche d'électrode positive (106), une couche d'électrode négative (108) et une couche d'électrolyte solide (107) disposée entre la couche d'électrode positive (106) et la couche d'électrode négative (108). La couche d'électrolyte solide (107) contient un premier électrolyte solide, qui est un composant principal, et un second électrolyte solide, qui est un composant auxiliaire. La porosité moyenne de la couche d'électrolyte solide (107) est inférieure ou égale à 9 %.
PCT/JP2017/043748 2016-12-27 2017-12-06 Pile au ion-lithium, et son procédé de fabrication WO2018123479A1 (fr)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019044903A1 (fr) * 2017-08-31 2019-03-07 株式会社村田製作所 Matériau d'électrolyte solide, couche d'électrolyte solide et batterie tout solide
KR20200036971A (ko) * 2018-09-28 2020-04-08 주식회사 정관 고체전해질, 이를 포함하는 리튬이온전지 및 이의 제조방법
KR20200041189A (ko) * 2018-10-11 2020-04-21 주식회사 엘지화학 고체 전해질막 및 이를 제조하는 방법 및 이를 포함하는 전고체 전지
WO2020085015A1 (fr) * 2018-10-26 2020-04-30 株式会社豊田自動織機 Électrode et batterie secondaire au lithium-ion à semi-conducteur
WO2020090736A1 (fr) * 2018-10-29 2020-05-07 株式会社村田製作所 Batterie à électrolyte solide
JP2020145009A (ja) * 2019-03-05 2020-09-10 日本特殊陶業株式会社 イオン伝導体および蓄電デバイス
WO2020217749A1 (fr) * 2019-04-25 2020-10-29 日本碍子株式会社 Batterie secondaire au lithium
CN112242558A (zh) * 2019-07-16 2021-01-19 株式会社电装 锂离子二次电池及其制造方法
JPWO2021038922A1 (fr) * 2019-08-23 2021-03-04
JP2021163579A (ja) * 2020-03-31 2021-10-11 本田技研工業株式会社 全固体電池及びその製造方法
US11322776B2 (en) 2017-08-30 2022-05-03 Murata Manufacturing Co., Ltd. Co-fired all-solid-state battery
WO2022172612A1 (fr) 2021-02-12 2022-08-18 パナソニックＩｐマネジメント株式会社 Batterie ainsi que procédé de fabrication de celle-ci, et système de batterie
JP2022153951A (ja) * 2021-03-30 2022-10-13 トヨタ自動車株式会社 全固体電池
KR102595779B1 (ko) * 2023-03-15 2023-10-31 주식회사 베이스 전고체 전지용 고체 전해질의 소결조제 및 이를 포함하는 고체 전해질
US11955596B2 (en) * 2017-08-30 2024-04-09 Murata Manufacturing Co., Ltd. Solid electrolyte and all solid state battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012209256A (ja) * 2011-03-15 2012-10-25 Ohara Inc 全固体二次電池
JP2013140762A (ja) * 2012-01-06 2013-07-18 Toyota Central R&D Labs Inc 固体電解質、それを用いた電池及びその製造方法
WO2013175993A1 (fr) * 2012-05-24 2013-11-28 株式会社 村田製作所 Pile tout électronique
WO2014020654A1 (fr) * 2012-07-30 2014-02-06 株式会社 日立製作所 Batterie secondaire à ion entièrement solide
WO2015128982A1 (fr) * 2014-02-27 2015-09-03 株式会社日立製作所 Accumulateur au lithium

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015185290A (ja) * 2014-03-22 2015-10-22 株式会社村田製作所 全固体電池及びその製造方法
JP2016066570A (ja) * 2014-09-26 2016-04-28 セイコーエプソン株式会社 電池、電池用電極体、および電池の製造方法
JP2016154140A (ja) * 2015-02-16 2016-08-25 日本碍子株式会社 リチウム二次電池用リチウム複合酸化物焼結板の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012209256A (ja) * 2011-03-15 2012-10-25 Ohara Inc 全固体二次電池
JP2013140762A (ja) * 2012-01-06 2013-07-18 Toyota Central R&D Labs Inc 固体電解質、それを用いた電池及びその製造方法
WO2013175993A1 (fr) * 2012-05-24 2013-11-28 株式会社 村田製作所 Pile tout électronique
WO2014020654A1 (fr) * 2012-07-30 2014-02-06 株式会社 日立製作所 Batterie secondaire à ion entièrement solide
WO2015128982A1 (fr) * 2014-02-27 2015-09-03 株式会社日立製作所 Accumulateur au lithium

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11322776B2 (en) 2017-08-30 2022-05-03 Murata Manufacturing Co., Ltd. Co-fired all-solid-state battery
US11955596B2 (en) * 2017-08-30 2024-04-09 Murata Manufacturing Co., Ltd. Solid electrolyte and all solid state battery
WO2019044903A1 (fr) * 2017-08-31 2019-03-07 株式会社村田製作所 Matériau d'électrolyte solide, couche d'électrolyte solide et batterie tout solide
US11942596B2 (en) 2017-08-31 2024-03-26 Murata Manufacturing Co., Ltd. Solid electrolyte material, solid electrolyte layer, and all solid state battery
KR20200036971A (ko) * 2018-09-28 2020-04-08 주식회사 정관 고체전해질, 이를 포함하는 리튬이온전지 및 이의 제조방법
KR102177718B1 (ko) * 2018-09-28 2020-11-12 주식회사 정관 고체전해질, 이를 포함하는 리튬이온전지 및 이의 제조방법
KR102661427B1 (ko) * 2018-10-11 2024-04-25 주식회사 엘지에너지솔루션 고체 전해질막 및 이를 제조하는 방법 및 이를 포함하는 전고체 전지
KR20200041189A (ko) * 2018-10-11 2020-04-21 주식회사 엘지화학 고체 전해질막 및 이를 제조하는 방법 및 이를 포함하는 전고체 전지
WO2020085015A1 (fr) * 2018-10-26 2020-04-30 株式会社豊田自動織機 Électrode et batterie secondaire au lithium-ion à semi-conducteur
WO2020090736A1 (fr) * 2018-10-29 2020-05-07 株式会社村田製作所 Batterie à électrolyte solide
JP7156387B2 (ja) 2018-10-29 2022-10-19 株式会社村田製作所 固体電池
JPWO2020090736A1 (ja) * 2018-10-29 2021-09-09 株式会社村田製作所 固体電池
JP2020145009A (ja) * 2019-03-05 2020-09-10 日本特殊陶業株式会社 イオン伝導体および蓄電デバイス
JP7202218B2 (ja) 2019-03-05 2023-01-11 日本特殊陶業株式会社 イオン伝導体および蓄電デバイス
JPWO2020217749A1 (ja) * 2019-04-25 2021-11-11 日本碍子株式会社 リチウム二次電池
JP7193622B2 (ja) 2019-04-25 2022-12-20 日本碍子株式会社 リチウム二次電池
WO2020217749A1 (fr) * 2019-04-25 2020-10-29 日本碍子株式会社 Batterie secondaire au lithium
CN112242558A (zh) * 2019-07-16 2021-01-19 株式会社电装 锂离子二次电池及其制造方法
JP2021015780A (ja) * 2019-07-16 2021-02-12 株式会社デンソー リチウムイオン二次電池及びその製造方法
JP7406932B2 (ja) 2019-07-16 2023-12-28 株式会社デンソー リチウムイオン二次電池の製造方法
JP7126028B2 (ja) 2019-08-23 2022-08-25 日本碍子株式会社 リチウムイオン二次電池
WO2021038922A1 (fr) * 2019-08-23 2021-03-04 日本碍子株式会社 Batterie secondaire au lithium-ion
JPWO2021038922A1 (fr) * 2019-08-23 2021-03-04
TWI771657B (zh) * 2019-08-23 2022-07-21 日商日本碍子股份有限公司 鋰離子二次電池
US11817549B2 (en) 2020-03-31 2023-11-14 Honda Motor Co., Ltd. All-solid-state battery and method for manufacturing same
JP2021163579A (ja) * 2020-03-31 2021-10-11 本田技研工業株式会社 全固体電池及びその製造方法
WO2022172612A1 (fr) 2021-02-12 2022-08-18 パナソニックＩｐマネジメント株式会社 Batterie ainsi que procédé de fabrication de celle-ci, et système de batterie
JP2022153951A (ja) * 2021-03-30 2022-10-13 トヨタ自動車株式会社 全固体電池
JP7484790B2 (ja) 2021-03-30 2024-05-16 トヨタ自動車株式会社 全固体電池
KR102595779B1 (ko) * 2023-03-15 2023-10-31 주식회사 베이스 전고체 전지용 고체 전해질의 소결조제 및 이를 포함하는 고체 전해질

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