WO2018025594A1 - Batterie au lithium tout solide - Google Patents

Batterie au lithium tout solide Download PDF

Info

Publication number
WO2018025594A1
WO2018025594A1 PCT/JP2017/025258 JP2017025258W WO2018025594A1 WO 2018025594 A1 WO2018025594 A1 WO 2018025594A1 JP 2017025258 W JP2017025258 W JP 2017025258W WO 2018025594 A1 WO2018025594 A1 WO 2018025594A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
solid
oriented
lithium
electrode plate
Prior art date
Application number
PCT/JP2017/025258
Other languages
English (en)
Japanese (ja)
Inventor
美香子 新村
千織 鈴木
幸信 由良
Original Assignee
日本碍子株式会社
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 日本碍子株式会社 filed Critical 日本碍子株式会社
Priority to JP2018531804A priority Critical patent/JP6906522B2/ja
Publication of WO2018025594A1 publication Critical patent/WO2018025594A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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 all solid lithium battery.
  • Patent Document 1 International Publication No. 2017/006591 discloses an alignment positive electrode plate made of a lithium composite oxide such as lithium cobaltate (LiCoO 2 ) and a lithium phosphate oxynitride glass electrolyte (LiPON).
  • An all-solid-state lithium battery including a solid electrolyte layer made of a lithium ion conductive material such as) and a negative electrode layer made of lithium metal is disclosed.
  • an intermediate layer containing a metal that can be alloyed with lithium between the solid electrolyte layer and the negative electrode layer it is possible to prevent internal short circuit and peeling of the negative electrode layer due to the reflow soldering process. are listed.
  • the positive electrode active material composed of a lithium composite oxide having a layered rock salt structure has an arbitrary diffusion plane in the plane of the (003) plane (that is, in a plane parallel to the (003) plane). It is known that lithium ions enter and exit in crystal planes other than the (003) plane (for example, (101) plane or (104) plane). Therefore, in this type of positive electrode active material, a surface that comes into contact with the electrolyte more in a crystal plane (a plane other than the (003) plane, for example, the (101) plane or the (104) plane) on which lithium ions can enter and exit satisfactorily. Attempts have been made to improve the battery characteristics of lithium secondary batteries by exposing them to the above.
  • the lithium transition metal oxide particles are oriented so that the (003) plane intersects the plate surface of the oriented positive electrode plate, so that a plane other than the (003) plane (for example, (101) ) Plane and (104) plane) are disclosed.
  • the conventional oriented positive electrode plate as disclosed in Patent Document 1 generally has the primary particles oriented such that the (003) plane is inclined by 45 to 75 ° with respect to the plate surface. Is.
  • the conventional oriented positive electrode plate is designed according to the concept that it is better to expose as many surfaces as possible to the entry and exit of lithium ions (for example, the (101) plane and the (104) plane).
  • an all-solid lithium battery as disclosed in Patent Document 1 employing such a conventional oriented positive electrode plate is short-circuited locally when a long-term cycle test is performed or when it is operated at a high temperature. May occur and the cycle performance may deteriorate.
  • orientation positive electrode plate in which the primary particles are oriented at the angles as described above tends to cause expansion and contraction during charge and discharge in the direction parallel to the plate surface of the orientation positive electrode plate, and therefore stress is applied to the interface with the fixed electrolyte layer. It is because it is easy to generate. This interfacial stress can cause defects in the solid electrolyte layer and sometimes cause a local short circuit, resulting in degradation of cycle performance and battery failure.
  • the present inventors have recently adopted an oriented positive electrode plate in which a plurality of primary particles are oriented at an average orientation angle of more than 0 ° and not more than 30 ° with respect to the plate surface of the oriented positive electrode plate, and the oriented positive electrode of the solid electrolyte layer It was found that by providing a predetermined intermediate layer on the surface opposite to the plate (that is, the surface on the negative electrode side), it is possible to provide an all-solid-state lithium battery with greatly improved cycle performance when repeated charge and discharge are performed. .
  • an object of the present invention is to provide an all-solid-state lithium battery with greatly improved cycle performance when charging and discharging are repeated.
  • an oriented positive electrode plate having a thickness of 30 ⁇ m or more constituted by an oriented sintered body, wherein the oriented sintered body comprises a plurality of lithium composite oxides having a layered rock salt structure.
  • An oriented positive electrode plate comprising primary particles, wherein the plurality of primary particles are oriented at an average orientation angle of more than 0 ° and not more than 30 ° with respect to the plate surface of the oriented positive electrode plate;
  • a solid electrolyte layer provided on the oriented positive electrode plate and made of a lithium ion conductive material;
  • An intermediate layer provided on the solid electrolyte layer and containing a metal that can be alloyed with lithium and having a thickness of 0.001 to 1 ⁇ m;
  • An all-solid lithium battery is provided.
  • FIG. 1 It is a schematic cross section which shows an example of the all-solid-state lithium battery of this invention. It is a model top view of the all-solid-state lithium battery shown by FIG. It is a schematic cross section which shows another example of the all-solid-state lithium battery of this invention. It is a schematic cross section which shows another example of the all-solid-state lithium battery of this invention. It is a schematic cross section for conceptually explaining the lithium ion conduction direction and the expansion / contraction method of the lithium composite oxide primary particles contained in the oriented positive electrode plate of the present invention. It is a schematic cross section for conceptually explaining a lithium ion conduction direction and an expansion / contraction method in an example of a conventional oriented positive electrode plate.
  • FIG. 8 is a schematic cross-sectional view for conceptually explaining the lithium ion conduction direction and the expansion / contraction method in the oriented positive electrode plate used in the present invention as shown in FIG. 7. It is a SEM image which shows an example of a cross section perpendicular
  • FIGS. 1 and 2 schematically show an example of an all solid lithium battery according to the present invention.
  • the all solid lithium battery 10 shown in FIGS. 1 and 2 includes an oriented positive electrode plate 12, a solid electrolyte layer 14, an intermediate layer 15, and optionally a negative electrode layer 16.
  • the all-solid lithium battery 10 shown in FIG. 1 includes two unit batteries each composed of an oriented positive electrode plate 12, an intermediate layer 13, a solid electrolyte layer 14, an intermediate layer 15, a negative electrode layer 16, and a positive electrode current collector 20. It has a configuration in which the negative electrode current collector 24 is laminated in parallel vertically symmetrically.
  • the present invention is not limited to this, and may be configured by one unit cell 10 ′ as schematically shown in FIG.
  • the oriented positive plate 12 is a plate having a thickness of 30 ⁇ m or more constituted by an oriented sintered body, and the oriented sintered body includes a plurality of primary particles constituted by a lithium composite oxide having a layered rock salt structure.
  • the plurality of primary particles are oriented at an average orientation angle of more than 0 ° and not more than 30 ° with respect to the plate surface of the oriented positive electrode plate.
  • the average orientation angle is an average value of inclination angles formed by the (003) planes of the primary particles with respect to the plate surface direction.
  • the solid electrolyte layer 14 is made of a lithium ion conductive material and is provided on the oriented positive electrode plate 12.
  • the intermediate layer 15 is a layer having a thickness of 0.001 to 1 ⁇ m containing a metal that can be alloyed with lithium, and is provided on the solid electrolyte layer 14.
  • the oriented positive electrode plate 12 in which a plurality of primary particles are oriented at an average orientation angle of more than 0 ° and not more than 30 ° with respect to the plate surface of the oriented positive electrode plate 12, and (ii) a solid electrolyte is employed.
  • a plurality of primary particles are more than 0 ° and 30 ° with respect to the plate surface of the alignment positive electrode plate 12.
  • the primary particles 11 of the lithium composite oxide have a lithium ion movement direction LiD parallel to the (003) plane and an expansion / contraction direction ECD perpendicular to the (003) plane. is doing. Therefore, as shown in FIG. 6, in the conventional oriented positive electrode plate 12 ′ in which the primary particles are oriented so that the (003) plane is inclined by 45 to 75 ° with respect to the plate surface, a plurality of primary particles 11 are formed.
  • the expansion / contraction causes expansion / contraction in the direction parallel to the plate surface of the oriented positive electrode plate 12 ′ as a whole, that is, the expansion / contraction direction ECD is parallel to the plate surface.
  • the oriented positive electrode plate 12 employed in the present invention has an average orientation angle of primary particles, that is, an average orientation angle of the (003) plane of more than 0 ° and 30 °, as conceptually depicted in FIG.
  • an average orientation angle of the (003) plane of more than 0 ° and 30 °, as conceptually depicted in FIG.
  • miniaturization becomes small.
  • the tensile stress to the solid electrolyte layer 14 due to the expansion and contraction of the oriented positive electrode plate 12 at the time of charging / discharging is reduced, and an electrical short circuit or an increase in resistance due to the breakage or peeling of the solid electrolyte layer 14 or the occurrence of cracks is prevented.
  • the orientation positive electrode plate having an average orientation angle of more than 0 ° and not more than 30 ° is not only a lithium ion entrance / exit surface (for example, (101) surface or (104) surface) but also lithium ion as understood from FIG.
  • the (003) surface where ions do not enter and exit is significantly exposed on the negative electrode side surface of the solid electrolyte layer 14. That is, lithium is likely to precipitate on the exposed surface of the entry / exit surface of lithium ions (for example, (101) surface or (104) surface), while lithium is difficult to precipitate on the exposed portion of the (003) surface where lithium ions do not enter or exit.
  • the above problem becomes more conspicuous because the absolute amount of lithium is large.
  • the above problem is solved by providing an intermediate layer 15 having a thickness of 0.001 to 1 ⁇ m containing a metal that can be alloyed with lithium on the solid electrolyte layer 14.
  • the cycle performance when charging / discharging is repeated can be greatly improved. This is considered due to the fact that the intermediate layer 15 homogenizes the resistance of the solid electrolyte layer 14 that affects lithium deposition in the in-plane direction.
  • the oriented positive electrode plate 12 is a plate having a thickness of 30 ⁇ m or more formed of an oriented sintered body.
  • the oriented sintered body includes a plurality of primary particles composed of a lithium composite oxide having a layered rock salt structure, and the plurality of primary particles has an average orientation angle of more than 0 ° and not more than 30 ° with respect to the plate surface of the oriented positive electrode plate. Is oriented.
  • FIG. 8 shows an example of a cross-sectional SEM image perpendicular to the plate surface of the alignment positive electrode plate 12, while FIG. 9 shows an electron backscatter diffraction (EBSD) image in a cross section perpendicular to the plate surface of the alignment positive electrode plate 12. Indicates.
  • FIG. 8 shows an example of a cross-sectional SEM image perpendicular to the plate surface of the alignment positive electrode plate 12
  • FIG. 9 shows an electron backscatter diffraction (EBSD) image in a cross section perpendicular to the plate surface of the
  • FIG. 10 is a histogram showing the orientation angle distribution of the primary particles 11 in the EBSD image of FIG.
  • discontinuity of crystal orientation can be observed.
  • the orientation angle of each primary particle 11 is shown in shades of color, and the darker the color, the smaller the orientation angle.
  • the orientation angle is an inclination angle formed by the (003) plane of each primary particle 11 with respect to the plate surface direction.
  • the portions displayed in black inside the aligned positive electrode plate 12 are pores.
  • the oriented positive electrode plate 12 is an oriented sintered body composed of a plurality of primary particles 11 bonded to each other.
  • Each primary particle 11 is mainly plate-shaped, but may include particles formed in a rectangular parallelepiped shape, a cubic shape, a spherical shape, or the like.
  • the cross-sectional shape of each primary particle 11 is not particularly limited, and may be a rectangle, a polygon other than a rectangle, a circle, an ellipse, or a complex shape other than these.
  • Each primary particle 11 is 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 or more of Co, Ni, and Mn. It is an oxide represented by.
  • 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 layer and the lithium single layer are alternately arranged via oxide ions.
  • lithium composite oxide examples include Li x CoO 2 (lithium cobaltate), Li x NiO 2 (lithium nickelate), Li x MnO 2 (lithium manganate), Li x NiMnO 2 (nickel / lithium manganate) , Li x NiCoO 2 (nickel / lithium cobaltate), Li x CoNiMnO 2 (cobalt / nickel / lithium manganate), Li x CoMnO 2 (cobalt / lithium manganate), and the like, particularly preferably Li x CoO 2.
  • 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
  • One or more elements selected from Bi, Bi, and W may be included.
  • the average value of the orientation angles of the primary particles 11, that is, the average orientation angle is more than 0 ° and not more than 30 °.
  • the orientation positive electrode in the plate plane direction is reduced by reducing the inclination angle of the (003) plane with respect to the plate plane direction.
  • the expansion / contraction amount of the plate 12 is reduced, and it is possible to suppress the occurrence of stress between the oriented positive electrode plate 12 and the solid electrolyte layer 14.
  • rate characteristics can be further improved.
  • the expansion / contraction in the thickness direction is more dominant than the plate surface direction, so that the expansion / contraction of the alignment positive electrode plate 12 becomes smooth. This is because lithium ions can go in and out smoothly.
  • the average orientation angle of the primary particles 11 can be obtained by the following method. First, in an EBSD image obtained by observing a 95 ⁇ m ⁇ 125 ⁇ m rectangular region as shown in FIG. 9 at a magnification of 1000 times, three horizontal lines that equally divide the alignment positive electrode plate 12 in the thickness direction, and the alignment positive electrode plate 12 Draw three vertical lines that equally divide the Next, the average orientation angle of the primary particles 11 is obtained by arithmetically averaging the orientation angles of all the primary particles 11 intersecting at least one of the three horizontal lines and the three vertical lines.
  • the average orientation angle of the primary particles 11 is preferably 30 ° or less, more preferably 25 ° or less, from the viewpoint of further improving the rate characteristics.
  • the average orientation angle of the primary particles 11 is preferably 2 ° or more, more preferably 5 ° or more, from the viewpoint of further improving the rate characteristics.
  • the orientation angle of each primary particle 11 may be widely distributed from 0 ° to 90 °, but most of it is distributed in a region of more than 0 ° and not more than 30 °. Is preferred. That is, the oriented sintered body constituting the oriented positive electrode plate 12 has an orientation angle with respect to the plate surface of the oriented positive electrode plate 12 of the primary particles 11 included in the analyzed cross section when the cross section is analyzed by EBSD.
  • the total area of primary particles 11 (hereinafter referred to as low-angle primary particles) having an angle of 30 ° or less is included in the cross section of primary particles 11 (specifically, 30 primary particles 11 used for calculating the average orientation angle).
  • the total area is preferably 70% or more, more preferably 80% or more.
  • the total area of the low-angle primary particles having an orientation angle of 20 ° or less is more preferably 50% or more with respect to the total area of the 30 primary particles 11 used for calculating the average orientation angle. . Furthermore, the total area of the low-angle primary particles having an orientation angle of 10 ° or less is more preferably 15% or more with respect to the total area of the 30 primary particles 11 used for calculating the average orientation angle. .
  • each primary particle 11 is mainly plate-shaped, the cross-section of each primary particle 11 extends in a predetermined direction as shown in FIGS. 8 and 9, and typically has a substantially rectangular shape. That is, when the cross section of the oriented sintered body is analyzed by EBSD, the total area of the primary particles 11 having an aspect ratio of 4 or more among the primary particles 11 included in the analyzed cross section is included in the cross section.
  • the total area of the particles 11 (specifically, 30 primary particles 11 used for calculating the average orientation angle) is preferably 70% or more, more preferably 80% or more. Specifically, in the EBSD image as shown in FIG. 9, the mutual adhesion between the primary particles 11 can be further improved, and as a result, the rate characteristics can be further improved.
  • the aspect ratio of the primary particles 11 is a value obtained by dividing the maximum ferret diameter of the primary particles 11 by the minimum ferret diameter.
  • the maximum ferret diameter is the maximum distance between the straight lines when the primary particle 11 is sandwiched between two parallel straight lines on the EBSD image when the cross section is observed.
  • the minimum ferret diameter is the minimum distance between the straight lines when the primary particle 11 is sandwiched between two parallel lines on the EBSD image.
  • the average particle size of the plurality of primary particles constituting the oriented sintered body is preferably 5 ⁇ m or more.
  • the average particle diameter of the 30 primary particles 11 used for calculating the average orientation angle is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 12 ⁇ m or more.
  • the average particle diameter of the primary particles 11 is a value obtained by arithmetically averaging the equivalent circle diameters of the primary particles 11.
  • the equivalent circle diameter is the diameter of a circle having the same area as each primary particle 11 on the EBSD image.
  • the density of the oriented sintered body constituting the oriented positive electrode plate 12 is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. Thereby, since the mutual adhesiveness of primary particles 11 can be improved more, a rate characteristic can be improved more.
  • the denseness of the oriented sintered body is calculated by binarizing the obtained SEM image by observing the cross section of the positive electrode plate by CP (cross section polisher) polishing and then SEM observation at 1000 magnifications.
  • the average equivalent circle diameter of each pore formed inside the oriented sintered body is not particularly limited, but is preferably 8 ⁇ m or less.
  • the average equivalent circle diameter of each pore is smaller, the mutual adhesion between the primary particles 11 can be further improved, and as a result, the rate characteristics can be further improved.
  • the average equivalent circle diameter of the pores is a value obtained by arithmetically averaging the equivalent circle diameters of the ten pores on the EBSD image.
  • the equivalent circle diameter is the diameter of a circle having the same area as each pore on the EBSD image.
  • Each pore formed inside the oriented sintered body may be an open pore connected to the outside of the oriented positive plate 12, but preferably does not penetrate the oriented positive plate 12.
  • Each pore may be a closed pore.
  • the thickness of the alignment positive electrode plate 12 is 30 ⁇ m or more, preferably 40 ⁇ m or more, particularly preferably 50 ⁇ m or more, from the viewpoint of improving the energy density of the all-solid lithium battery 10 by increasing the active material capacity per unit area. Preferably it is 55 micrometers or more.
  • the thickness of the alignment positive electrode plate 12 is preferably less than 200 ⁇ m, more preferably from the viewpoint of suppressing deterioration of battery characteristics (particularly increase in resistance value) due to repeated charge and discharge. It is 150 ⁇ m or less, more preferably 120 ⁇ m or less, particularly preferably 100 ⁇ m or less, most preferably 90 ⁇ m or less, 80 ⁇ m or less, or 70 ⁇ m or less.
  • the size of the oriented positive electrode plate is preferably 5 mm ⁇ 5 mm square or more, more preferably 10 mm ⁇ 10 mm to 200 mm ⁇ 200 mm square, and further preferably 10 mm ⁇ 10 mm to 100 mm ⁇ 100 mm square. if, preferably 25 mm 2 or more, more preferably 100 ⁇ 40000 mm 2, more preferably from 100 ⁇ 10000 mm 2.
  • the oriented positive electrode plate 12 may include a conductive film 12a having a thickness of 0.01 ⁇ m or more and less than 5 ⁇ m on the surface opposite to the solid electrolyte layer 14 (that is, the surface on the positive electrode current collector 20 side).
  • the conductive film 12a is preferably made of metal and / or carbon. When the conductive film 12a is made of a metal, the conductive film 12a has a low electron conduction resistance with the positive electrode current collector 20 and the alignment positive electrode plate 12 and is a layer made of a metal that does not adversely affect the characteristics of the alignment positive electrode plate 12, in particular.
  • preferred examples include an Au sputtered layer and a Si sputtered layer.
  • a carbon layer may be used instead of a metal conductive film such as an Au sputter layer.
  • the thickness of the conductive film 12a is 0.01 ⁇ m or more and less than 5 ⁇ m, preferably 0.02 ⁇ m or more and 2 ⁇ m or less, more preferably 0.02 ⁇ m or more and 1 ⁇ m or less, and further preferably 0.04 ⁇ m or more and 1 ⁇ m or less.
  • the lithium ion conductive material constituting the solid electrolyte layer 14 is a garnet-based ceramic material, a nitride-based ceramic material, a perovskite-based ceramic material, a phosphate-based ceramic material, a sulfide-based ceramic material, or a lithium-chloride-based material. Or at least one selected from the group consisting of garnet-based ceramic materials, nitride-based ceramic materials, perovskite-based ceramic materials, and phosphate-based ceramic materials. is there.
  • garnet based ceramic materials include Li—La—Zr—O based materials (specifically, Li 7 La 3 Zr 2 O 12 etc.), Li—La—Ta—O based materials (specifically, Li 7 La 3 Ta 2 O 12 etc.).
  • An example of a nitride ceramic material is Li 3 N.
  • perovskite ceramic materials include Li—La—Zr—O based materials (specifically, LiLa 1-x Ti x O 3 (0.04 ⁇ x ⁇ 0.14), etc.).
  • phosphate ceramic materials include lithium phosphate, nitrogen-substituted lithium phosphate (LiPON), Li—Al—Ti—PO, Li—Al—Ge—PO, and Li—Al—Ti—.
  • Si—P—O 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), etc.
  • the lithium ion conductive material constituting the solid electrolyte layer 14 is composed of a Li—La—Zr—O based ceramic material and / or a lithium phosphate oxynitride (LiPON) based ceramic material.
  • the Li—La—Zr—O-based material is an oxide sintered body having a garnet-type or garnet-type similar crystal structure including Li, La, Zr, and O. Specifically, Li 7 It is a garnet-based ceramic material such as La 3 Zr 2 O 12 , and details thereof are disclosed in Patent Document 1, for example.
  • a lithium phosphate oxynitride (LiPON) ceramic material is also preferable.
  • LiPON is a group of compounds represented by the composition of Li 2.9 PO 3.3 N 0.46 . For example, Li a PO b N c (wherein a is 2 to 4 and b is 3 to 5 , C is 0.1 to 0.9).
  • the dimensions of the solid electrolyte layer 14 are not particularly limited, but the thickness is preferably 0.0005 mm to 0.1 mm, more preferably 0.001 mm to 0.05 mm, and still more preferably, from the viewpoint of charge / discharge rate characteristics and mechanical strength. Is 0.002 to 0.02 mm, particularly preferably 0.003 to 0.01 mm.
  • various particle jet coating methods, solid phase methods, solution methods, and gas phase methods can be used.
  • the particle jet coating method include an aerosol deposition (AD) method, a gas deposition (GD) method, a powder jet deposition (PJD) method, a cold spray (CS) method, and a thermal spraying method.
  • the aerosol deposition (AD) method is particularly preferable because it can form a film at room temperature, and does not cause a composition shift in the process or formation of a high resistance layer by reaction with an oriented positive electrode plate.
  • the solid phase method include a tape lamination method and a printing method.
  • the tape lamination method is preferable because the solid electrolyte layer 14 can be formed thin and the thickness can be easily controlled.
  • the solution method include a solvothermal method, a hydrothermal synthesis method, a sol-gel method, a precipitation method, a microemulsion method, and a solvent evaporation method.
  • the hydrothermal synthesis method is particularly preferable in that it is easy to obtain crystal grains having high crystallinity at a low temperature.
  • microcrystals synthesized using these methods may be deposited on the positive electrode or may be directly deposited on the positive electrode.
  • gas phase method examples include laser deposition (PLD) method, sputtering method, evaporation condensation (PVD) method, gas phase reaction method (CVD) method, vacuum deposition method, molecular beam epitaxy (MBE) method and the like.
  • PLD laser deposition
  • PVD evaporation condensation
  • CVD gas phase reaction method
  • MBE molecular beam epitaxy
  • the sputtering method is particularly preferable because there is little composition deviation and a film with relatively high adhesion can be easily obtained.
  • the interface between the oriented positive electrode plate 12 and the solid electrolyte layer 14 may be subjected to a treatment for reducing the interface resistance.
  • a treatment for reducing the interface resistance includes niobium oxide, titanium oxide, tungsten oxide, tantalum oxide, lithium-nickel composite oxide, lithium-titanium composite oxide, lithium-niobium compound, lithium-tantalum compound, lithium-
  • This can be done by coating the surface of the oriented positive electrode plate 12 and / or the surface of the solid electrolyte layer 14 with a tungsten compound, a lithium / titanium compound, and any combination or composite oxide thereof.
  • a coating film can exist at the interface between the oriented positive electrode plate 12 and the solid electrolyte layer 14, but the thickness of the coating film is extremely thin, for example, 20 nm or less.
  • the intermediate layer 15 is a layer having a thickness of 0.001 to 1 ⁇ m containing a metal that can be alloyed with lithium, and is provided on the surface of the solid electrolyte layer 14 opposite to the oriented positive electrode plate 12 (that is, the surface on the negative electrode side). It is done.
  • Metals that can be alloyed with lithium are Al (aluminum), Si (silicon), Zn (zinc), Ga (gallium), Ge (germanium), Ag (silver), Au (gold), Pt (platinum), Cd.
  • the intermediate layer may be formed by a known method such as an aerosol deposition (AD) method, a pulse laser deposition (PLD) method, a sputtering method, or an evaporation method.
  • the dimension of the intermediate layer is not particularly limited, but the thickness is 0.001 to 1 ⁇ m, preferably 0.001 to 0.5 ⁇ m, more preferably 0.001 to 0.1 ⁇ m, from the viewpoint of homogenizing resistance. Particularly preferred is 0.003 to 0.03 ⁇ m.
  • the negative electrode layer all solid lithium battery 10 typically further includes a negative electrode layer 16 on the intermediate layer 15.
  • the all solid lithium battery 10 of the present invention can operate without the negative electrode layer 16. This is because the lithium metal deposited on the intermediate layer 15 during charging can also be used as the negative electrode active material.
  • the negative electrode layer 16 is a layer containing lithium and is typically made of lithium metal.
  • the negative electrode layer 16 may be produced by placing a lithium metal in the form of a foil on the intermediate layer 15 or the negative electrode current collector 24, or a thin film of lithium metal on the intermediate layer 15 or the negative electrode current collector 24. May be formed by forming a lithium metal layer by vacuum deposition, sputtering, CVD, or the like.
  • the dimensions of the negative electrode layer 16 are not particularly limited, but the thickness is preferably 10 ⁇ m or more, more preferably 50 to 10 ⁇ m, from the viewpoint of securing a large amount of lithium in the all-solid lithium battery 10 with the adoption of the thick oriented positive electrode plate 12. More preferably, it is 40 to 10 ⁇ m, particularly preferably 20 to 10 ⁇ m.
  • the end insulating portion 18 may be provided so as to insulate the end portion of the solid electrolyte layer 14.
  • the end insulating portion 18 preferably includes an organic polymer material that can be adhered or adhered to the solid electrolyte layer 14.
  • the organic polymer material is preferably at least one selected from the group consisting of a binder, a hot melt resin, and an adhesive.
  • the binder include a cellulose resin, an acrylic resin, and a combination thereof.
  • the heat fusion resin include a fluorine resin, a polyolefin resin, and any combination thereof.
  • the hot-melt resin is preferably provided in the form of a heat-sealing film as will be described later.
  • a preferable example of the adhesive is a thermosetting adhesive using a thermosetting resin such as an epoxy resin. Therefore, as disclosed in Patent Document 1, the organic polymer material is preferably at least one selected from the group consisting of a cellulose resin, an acrylic resin, a fluorine resin, a polyolefin resin, and an epoxy resin. I can say that.
  • the end insulating portion 18 is preferably formed by applying a liquid or slurry containing an organic polymer material (preferably a binder) and optionally a filler or the like.
  • a liquid or slurry application method include a dispensing method, a screen printing method, a spray method, a stamping method, and the like.
  • the positive electrode current collector all solid lithium battery 10 preferably further includes a positive electrode current collector 20 on the surface of the oriented positive electrode plate 12 opposite to the solid electrolyte layer 14.
  • the positive electrode current collector 20 is a metal foil.
  • the thickness of the metal foil is 5 to 30 ⁇ m, preferably 5 to 25 ⁇ m, more preferably 10 to 25 ⁇ m, and still more preferably 10 to 20 ⁇ m. By increasing the thickness as described above, a sufficient current collecting function can be ensured. Moreover, since it is rich in flexibility when it is a very thin metal foil as described above, it becomes easy to adhere to the entire surface of the oriented positive electrode plate 12 uniformly.
  • the metal constituting the positive electrode current collector 20 is not particularly limited as long as it does not react with the aligned positive electrode plate 12, and may be an alloy.
  • Preferred examples of such metals include stainless steel, aluminum, copper, platinum, and nickel, and more preferably stainless steel and nickel.
  • the positive electrode current collector 20 is preferably brought into full contact with the surface of the oriented positive electrode plate 12 opposite to the solid electrolyte layer 14 in a non-adhesive state containing no adhesive. By doing so, no interfacial stress is generated between the aligned positive electrode plate 12 and the positive electrode current collector 20, and therefore, deterioration factors such as interfacial delamination can be eliminated, and long-term reliability is improved. Can do. That is, interfacial peeling caused by expansion and contraction of the alignment positive electrode plate 12 due to charge and discharge and an increase in contact resistance caused thereby can be significantly suppressed, and long-term reliability can be improved.
  • the positive electrode current collector 20 also serves as a positive electrode exterior material that covers the outer side of the aligned positive electrode plate 12.
  • the positive electrode current collector 20 also serves as a positive electrode exterior material that covers the outer side of the aligned positive electrode plate 12.
  • two unit cells are stacked in parallel symmetrically via a single negative electrode current collector 24 to expose the positive electrode current collector 20 to the outside of the all-solid-state lithium battery 10. It is good also as a structure.
  • the negative electrode current collector 24 can function as a current collector common to two adjacent unit batteries.
  • the positive electrode current collector 20 is preferably pressed against the aligned positive electrode plate 12. Since the metal foil which is the positive electrode current collector 20 is a flexible thin conductive material, a large number of contact points between the positive electrode current collector 20 and the alignment positive electrode plate 12 can be secured by pressing, and the alignment positive electrode plate 12 can be secured. Can be more uniformly adhered to the entire surface. Thereby, even in the case of an adhesive-free non-adhesive state, a desirable current collecting effect can be obtained.
  • the method of pressing is not particularly limited. For example, the pressing is performed from the outside of the positive electrode current collector 20 toward the alignment positive electrode plate 12 using a flexible pressing member (for example, foam metal) that does not damage the positive electrode current collector 20.
  • a method, a method using a pressure difference between the inside and outside of the positive electrode current collector 20, or the like can be employed.
  • the positive current collector 20 is pressed against the oriented positive electrode plate 12 due to a difference in internal and external pressures of the positive current collector 20. That is, it is only necessary that the orientation positive electrode plate 12 side of the positive electrode current collector 20 is depressurized or the side opposite to the orientation positive electrode plate 12 of the positive electrode current collector 20 is pressurized.
  • the metal foil as the positive electrode current collector 20 is a flexible thin conductive material according to the pressing using the internal and external pressure difference of the positive electrode current collector 20, the surface of the oriented positive electrode plate 12 Thus, the contact can be made at more contact points, and the current collecting effect can be further enhanced.
  • the positive electrode current collector 20 and the aligned positive electrode plate 12 are in a non-adhered state. This means that the positive electrode current collector 20 and the aligned positive electrode plate 12 are partially (for example, part of the outer peripheral portion of the aligned positive electrode plate 12) and are adhesive resins. It is not excluded that it is fixed by, for example. Such a resin is used for the purpose of temporary adhesion to prevent misalignment of the oriented positive electrode plate when assembling the battery.
  • the laminate including the oriented positive electrode plate 12, the solid electrolyte layer 14, the intermediate layer 15, and the negative electrode layer 16 (if present) is packaged or sealed with an exterior material.
  • the positive electrode current collector 20 constitutes a part of the exterior material, and the accommodation space of the laminate that is packaged or sealed with the exterior material is decompressed.
  • the storage space can be depressurized, for example, by packaging or sealing with an exterior material under reduced pressure, or by degassing the storage space after packaging or sealing the exterior material.
  • the metal foil that is the positive electrode current collector 20 is a flexible thin conductive material, the contact point of the positive electrode current collector 20 with the surface of the aligned positive electrode plate 12 is increased by reducing the storage space. Can be brought into close contact with. Moreover, if the packaging material is packaged or sealed in an airtight manner, it is possible to maintain a reduced pressure in the accommodation space of the laminate over a long period of time. Can be exerted over.
  • the degree of vacuum may be set as appropriate based on the flexibility of the metal and the strength of the laminate.
  • a negative electrode current collector 24 is preferably provided outside the negative electrode current collector negative electrode layer 16 (outside of the intermediate layer 15 when there is no negative electrode layer 16).
  • the negative electrode current collector 24 may also serve as a negative electrode exterior material that covers the outside of the negative electrode.
  • FIG. 4 contrary to the configuration shown in FIG. 1, two unit cells are stacked vertically and symmetrically via one positive current collector 20 to form a negative current collector 24. May be exposed to the outside of the all-solid-state lithium battery.
  • the positive electrode current collector 20 can function as a current collector common to two adjacent unit batteries.
  • the negative electrode current collector 24 may be made of the same or different material as the positive electrode current collector 20, but is preferably made of the same kind of material.
  • the metal constituting the negative electrode current collector 24 is not particularly limited as long as it does not react with the negative electrode layer 16 and may be an alloy. Preferred examples of such a metal include stainless steel, aluminum, copper, platinum and nickel, and more preferred are stainless steel and nickel.
  • the negative electrode current collector 24 is preferably a metal plate or a metal foil, and more preferably a metal foil. Therefore, it can be said that the most preferred current collector is a stainless steel foil or a nickel foil.
  • the preferred thickness of the metal foil is 1 to 30 ⁇ m, more preferably 5 to 25 ⁇ m, and still more preferably 10 to 20 ⁇ m.
  • the all-solid-state lithium battery 10 in the end sealing portion includes an oriented positive electrode plate 12, a solid electrolyte layer 14, an intermediate layer 15, a negative electrode layer 16, and (not present) that are not covered with the positive electrode current collector 20 and the negative electrode current collector 24.
  • an end sealing portion 26 made of a sealing material for sealing the exposed portion of the end insulating portion 18 is further provided.
  • the end sealing part 26 is provided, and the orientation positive electrode plate 12, the solid electrolyte layer 14, the intermediate layer 15, the negative electrode layer 16, and the end insulating part 18 are not covered with the positive electrode current collector 20 and the negative electrode current collector 24.
  • the end sealing portion 26 is made of a sealing material.
  • the sealing material can seal the exposed portion not covered with the positive electrode current collector 20, the negative electrode current collector 24, and the end insulating portion 18 to ensure excellent moisture resistance (preferably moisture resistance at high temperature). If it is a thing, it will not specifically limit. However, it goes without saying that it is desirable that the sealing material ensure electrical insulation between the positive electrode current collector 20 and the negative electrode current collector 24. In that sense, the sealing material preferably has a 1 ⁇ 10 6 ⁇ cm or more resistivity, more preferably 1 ⁇ 10 7 ⁇ cm or more, still more preferably 1 ⁇ 10 8 ⁇ cm or more.
  • the sealing material is preferably a resin-based sealing material containing a resin
  • the resin-based sealing material may be made of a mixture of a resin (preferably an insulating resin) and an inorganic material.
  • the sealing material may be a glass-based sealing material containing glass.
  • these sealing agents known ones as disclosed in Patent Document 1 can be used.
  • the all-solid lithium battery preferably has a thickness of 60 to 5000 ⁇ m, more preferably 70 to 4000 ⁇ m, still more preferably 80 to 3000 ⁇ m, and particularly preferably. Is from 90 to 2000 ⁇ m, most preferably from 100 to 1000 ⁇ m.
  • the oriented positive electrode plate can be made relatively thick, while the current collector also serves as an exterior material, so that the thickness of the entire battery can be made relatively thin.
  • the oriented positive electrode plate or oriented sintered plate used in the all solid lithium battery of the present invention may be produced by any method, but preferably, as exemplified below (1) Production of LiCoO 2 template particles, (2) Production of matrix particles, (3) Production of green sheets, and (4) Production of oriented sintered plates.
  • LiCoO 2 template particles Co 3 O 4 raw material powder and Li 2 CO 3 raw material powder are mixed.
  • the obtained mixed powder is fired at 500 to 900 ° C. for 1 to 20 hours to synthesize LiCoO 2 powder.
  • the obtained LiCoO 2 powder is pulverized to a volume-based D50 particle size of 0.1 to 10 ⁇ m by a pot mill to obtain plate-like LiCoO 2 particles capable of conducting lithium ions parallel to the plate surface.
  • the obtained LiCoO 2 particles are easily cleaved along the cleavage plane. It is to cleave by crushing the LiCoO 2 particles to prepare a LiCoO 2 template particles.
  • Such LiCoO 2 particles can be obtained by a method of crushing after growing a green sheet using LiCoO 2 powder slurry, a plate method such as a flux method, hydrothermal synthesis, single crystal growth using a melt, or a sol-gel method. It can also be obtained by a method of synthesizing crystals.
  • the profile of the primary particles 11 constituting the oriented positive electrode plate 12 can be controlled as follows. -By adjusting at least one of the aspect ratio and the particle size of the LiCoO 2 template particles, the total area ratio of the low-angle primary particles having an orientation angle of more than 0 ° and not more than 30 ° can be controlled. Specifically, the larger the aspect ratio of LiCoO 2 template particles, also, the larger the particle size of the LiCoO 2 template particles, it is possible to increase the total area ratio of the low-angle primary particles.
  • the aspect ratio and particle size of the LiCoO 2 template particles are the particle size of the Co 3 O 4 raw material powder and the Li 2 CO 3 raw material powder, the pulverization conditions (pulverization time, pulverization energy, pulverization method, etc.), and pulverization, respectively. It can be controlled by adjusting at least one of the subsequent classifications. -By adjusting the aspect ratio of the LiCoO 2 template particles, the total area ratio of the primary particles 11 having an aspect ratio of 4 or more can be controlled. Specifically, the total area ratio of the primary particles 11 having an aspect ratio of 4 or more can be increased as the aspect ratio of the LiCoO 2 template particles is increased.
  • the method for adjusting the aspect ratio of the LiCoO 2 template particles is as described above.
  • the average particle size of the primary particles 11 can be controlled by adjusting the particle size of the LiCoO 2 template particles.
  • the density of the aligned positive electrode plate 12 can be controlled by adjusting the particle size of the LiCoO 2 template particles. Specifically, the density of the aligned positive electrode plate 12 can be increased as the particle size of the LiCoO 2 template particles is reduced.
  • Co 3 O 4 raw material powder is used as matrix particles.
  • the volume-based D50 particle size of the Co 3 O 4 raw material powder is not particularly limited and can be, for example, 0.1 to 1.0 ⁇ m, but is preferably smaller than the volume-based D50 particle size of LiCoO 2 template particles.
  • the matrix particles can also be obtained by subjecting a Co (OH) 2 raw material to heat treatment at 500 to 800 ° C. for 1 to 10 hours. Further, the matrix particles, other Co 3 O 4, may be used Co (OH) 2 particles, may be used LiCoO 2 particles.
  • the profile of the primary particles 11 constituting the oriented positive electrode plate 12 can be controlled as follows. -Low angle primary whose orientation angle is greater than 0 ° and less than 30 ° by adjusting the ratio of the particle size of matrix particles to the particle size of LiCoO 2 template particles (hereinafter referred to as “matrix / template particle size ratio”)
  • matrix / template particle size ratio the ratio of the particle size of matrix particles to the particle size of LiCoO 2 template particles.
  • the total area ratio of the particles can be controlled. Specifically, the smaller the matrix / template particle size ratio, that is, the smaller the particle size of the matrix particles, the easier it is for the matrix particles to be incorporated into the LiCoO 2 template particles in the firing step described later.
  • the total area ratio can be increased.
  • the total area ratio of the primary particles 11 having an aspect ratio of 4 or more can be controlled by adjusting the matrix / template particle size ratio. Specifically, the smaller the matrix / template particle size ratio, that is, the smaller the particle size of the matrix particles, the higher the total area ratio of the primary particles 11 having an aspect ratio of 4 or more.
  • the density of the aligned positive electrode plate 12 can be controlled by adjusting the matrix / template particle size ratio. Specifically, the smaller the matrix / template particle size ratio, that is, the smaller the particle size of the matrix particles, the higher the density of the aligned positive electrode plate 12 can be.
  • the profile of the primary particles 11 constituting the oriented positive electrode plate 12 can be controlled as follows. -By adjusting the molding speed, the total area ratio of the low-angle primary particles whose orientation angle is more than 0 ° and not more than 30 ° can be controlled. Specifically, the higher the molding speed, the higher the total area ratio of the low-angle primary particles. -The average particle diameter of the primary particles 11 can be controlled by adjusting the density of the compact. Specifically, the average particle diameter of the primary particles 11 can be increased as the density of the molded body is increased. -The density of the aligned positive electrode plate 12 can also be controlled by adjusting the mixing ratio between the LiCoO 2 template particles and the matrix particles. Specifically, the density of the aligned positive electrode plate 12 can be lowered as the number of LiCoO 2 template particles is increased.
  • a slurry compact is placed on a zirconia setter and heat-treated (primary firing) at 500 to 900 ° C. for 1 to 10 hours to obtain a sintered plate as an intermediate .
  • This sintered plate is placed on a zirconia setter while being sandwiched between lithium sheets (for example, Li 2 CO 3 -containing sheets) and subjected to secondary firing to obtain a LiCoO 2 sintered plate.
  • a setter on which a sintered plate sandwiched between lithium sheets is placed is placed in an alumina sheath and baked at 700 to 850 ° C. for 1 to 20 hours in the atmosphere. It is sandwiched between sheets and fired at 750 to 900 ° C.
  • This firing step may be performed in two steps or may be performed once. When firing twice, it is preferable that the first firing temperature is lower than the second firing temperature.
  • the total amount of lithium sheet used in the secondary firing may be such that the Li / Co ratio, which is the molar ratio of the amount of Li in the green sheet and the lithium sheet, to 1.0 with respect to the amount of Co in the green sheet. .
  • the profile of the primary particles 11 constituting the oriented positive electrode plate 12 can be controlled as follows. -The total area ratio of the low-angle primary particles whose orientation angle is more than 0 ° and not more than 30 ° can be controlled by adjusting the heating rate during firing. Specifically, the higher the rate of temperature rise, the more the sintering of the matrix particles is suppressed, and the total area ratio of the low-angle primary particles can be increased. -The total area ratio of low-angle primary particles whose orientation angle is more than 0 ° and not more than 30 ° can also be controlled by adjusting the heat treatment temperature of the intermediate.
  • the lower the heat treatment temperature of the intermediate the more the sintering of the matrix particles is suppressed, and the total area ratio of the low-angle primary particles can be increased.
  • the average particle diameter of the primary particles 11 can be controlled by adjusting at least one of the heating rate during firing and the heat treatment temperature of the intermediate. Specifically, the average particle diameter of the primary particles 11 can be increased as the rate of temperature increase is increased and the heat treatment temperature of the intermediate is decreased. -Controlling the average particle diameter of the primary particles 11 also by adjusting at least one of the amount of Li (for example, Li 2 CO 3 ) and the amount of sintering aid (for example, boric acid or bismuth oxide) during firing. Can do.
  • Li for example, Li 2 CO 3
  • the amount of sintering aid for example, boric acid or bismuth oxide
  • the average particle diameter of the primary particles 11 can be increased as the amount of Li is increased and as the amount of the sintering aid is increased.
  • the density of the alignment positive electrode plate 12 can be controlled by adjusting the profile during firing. Specifically, the density of the aligned positive electrode plate 12 can be increased as the firing temperature is lowered and the firing time is lengthened.
  • Examples A1 to A8 (1) Preparation of oriented positive electrode plate (1a) Preparation of LCO template particles Co 3 O 4 raw material powder (volume basis D50 particle size 0.8 ⁇ m, manufactured by Shodo Chemical Co., Ltd.) and Li 2 CO 3 raw material powder (volume basis) D50 particle size 2.5 ⁇ m, manufactured by Honjo Chemical Co., Ltd.) was mixed and fired at 800 ° C. to 900 ° C. for 5 hours to synthesize LiCoO 2 raw material powder. The obtained LiCoO 2 powder was pulverized to obtain plate-like LiCoO 2 particles (hereinafter referred to as LCO template particles). The volume-based D50 particle size of the LCO template particles was adjusted to 0.5 ⁇ m.
  • Co 3 O 4 raw material powder (manufactured by Shodo Chemical Industry Co., Ltd.) was prepared as matrix particles.
  • the volume-based D50 particle size of the matrix particles was 0.3 ⁇ m.
  • the mixture was degassed by stirring under reduced pressure, and a slurry was prepared by adjusting the viscosity to 4000 cP.
  • the viscosity was measured with an LVT viscometer manufactured by Brookfield.
  • the prepared slurry was formed into a sheet shape on a PET film by a doctor blade method so that the thickness after drying was 48 ⁇ m at a forming speed of 100 m / h, and an LCO / Co 3 O 4 green sheet was formed. Obtained.
  • the resulting mixture was stirred and degassed under reduced pressure, and the viscosity was adjusted to 4000 cP to prepare a Li 2 CO 3 slurry.
  • the viscosity was measured with an LVT viscometer manufactured by Brookfield.
  • the prepared Li 2 CO 3 slurry was formed into a sheet on a PET film by a doctor blade method to form a Li 2 CO 3 green sheet (hereinafter referred to as a lithium sheet).
  • the sheet was sandwiched between upper and lower sheets and fired at 900 ° C. for 20 hours.
  • a LiCoO 2 sintered plate having a thickness of 40 ⁇ m was obtained as an oriented positive plate.
  • a lithium phosphate sintered body target having a length of 5 inches (about 12.7 cm) ⁇ width of 15 inches (about 38.1 cm) was prepared, and a sputtering apparatus (ILC- manufactured by Canon Anelva Co., Ltd.) was prepared. 702), an RF magnetron method was used to perform sputtering so that the gas type N 2 was 0.4 Pa, the output was 1.2 kW, and the film thickness was 3 ⁇ m.
  • a LiPON-based solid electrolyte layer having a thickness of 3 ⁇ m was formed on the oriented positive electrode plate.
  • the Au intermediate layer (Example A1), an Au film having a thickness of 20 nm was formed on the solid electrolyte layer by sputtering using an ion sputtering apparatus (manufactured by JEOL Ltd., JFC-1500). At this time, the size of the intermediate layer was set to 10 mm square using a mask so that the intermediate layer could be accommodated in the positive electrode region of 10.5 mm square.
  • a Sn target having a diameter of 4 inches (about 10 cm) A Si target, Bi target, or Al target is prepared, and is shown in Table 1 with a sputtering apparatus (SPF-210HS, manufactured by Canon Anelva Co., Ltd.) using an RF magnetron method with an Ar gas of 1 Pa and an output of 0.1 kW. Sputtering was performed to obtain a film thickness.
  • SPF-210HS sputtering apparatus
  • an RF magnetron method with an Ar gas of 1 Pa and an output of 0.1 kW.
  • Sputtering was performed to obtain a film thickness.
  • an intermediate layer having the composition and thickness shown in Table 1 was formed on the solid electrolyte layer.
  • the size of the intermediate layer was set to 10 mm square using a mask so that the intermediate layer could be accommodated in the positive electrode region of 10.5 mm square.
  • a negative electrode layer was formed on the intermediate layer as follows. First, a tungsten boat carrying lithium metal was prepared. A Li thin film was formed on the surface of the intermediate layer by vapor deposition using a vacuum vapor deposition apparatus (Sanyu Electronics Co., Ltd., carbon coater SVC-700) while vaporizing Li by resistance heating. At this time, using a mask, the size of the negative electrode layer was set to 10 mm square so that the negative electrode layer was within the 10.5 mm square positive electrode region. In this way, a unit cell was produced in which a Li-deposited film having a thickness of 10 ⁇ m was formed as a negative electrode layer on the solid electrolyte layer.
  • a vacuum vapor deposition apparatus Sanyu Electronics Co., Ltd., carbon coater SVC-700
  • Example A8 the negative electrode layer was not formed in order to use Li precipitated during charging as the negative electrode active material. Thus, a unit cell having no negative electrode layer on the solid electrolyte layer was produced.
  • Battery assembly A laminated sheet obtained by laminating a 20 ⁇ m thick Ni foil and a 15 ⁇ m thick nylon resin was cut into a 13 mm square to form a current collector plate. Adhere 0.9mm wide frame-shaped polychlorotrifluoroethylene resin (thickness 50 ⁇ m) with 12.8mm square outer edge shape and 11mm square hole punched inside it to the Ni foil side of the current collector plate Thus, an end sealing portion was formed. The composite member thus obtained was placed with the Ni foil side of the current collector plate facing up, and the unit cell obtained in (5) above was placed in the region surrounded by the end sealing portion with the negative electrode facing down. Placed.
  • the current collector On the positive electrode of the placed unit cell, the current collector was placed with the Ni foil side down, and using a pulse heat type heating device (manufactured by Nippon Avionics Co., Ltd., HT-13X13 (40) NTN), Under reduced pressure, the end sealing part was heated at 420 ° C. while applying a load of 3 kg. In this way, the end sealing portion and the two upper and lower current collecting plates were bonded and sealed so as to cover the entire outer periphery of the unit cell, thereby obtaining an all solid lithium battery in a sealed form.
  • a pulse heat type heating device manufactured by Nippon Avionics Co., Ltd., HT-13X13 (40) NTN
  • An EBSD image in a cross section perpendicular to the plate surface of the positive electrode was obtained using a scanning electron microscope (manufactured by JEOL Ltd., model JSM-7800M) with a backscattered electron diffraction image system.
  • the average orientation angle of primary particles was measured by the following procedure. First, in an EBSD image obtained by observing a rectangular area of 95 ⁇ m ⁇ 125 ⁇ m at a magnification of 1000 times, three horizontal lines that divide the positive electrode into four equal parts in the thickness direction and three vertical lines that divide the positive electrode into four equal parts in the plate surface direction And subtracted. Next, the average orientation angle of the primary particles was obtained by arithmetically averaging the orientation angles of all the primary particles intersecting at least one of the three horizontal lines and the three vertical lines.
  • Example A9 (comparison) A battery was fabricated and evaluated in the same manner as in Example A1 except that no intermediate layer was formed. The results were as shown in Table 1.
  • Example A10 (comparison) A battery was fabricated and evaluated in the same manner as in Example A1, except that a Cu intermediate layer having a thickness of 20 nm was formed instead of the Au intermediate layer.
  • the Cu intermediate layer is formed by preparing a Cu target having a diameter of 4 inches (about 10 cm), and using a sputtering apparatus (SPF-430H, manufactured by Canon Anelva Co., Ltd.) with a DC magnetron method, the gas species Ar is 0.3 Pa, The sputtering was performed at a current of 0.5 A so that the film thickness was 20 nm.
  • the results were as shown in Table 1.
  • Example A11 (comparison) A battery was produced and evaluated in the same manner as in Example A2, except that the oriented positive electrode plate was produced as follows. The results were as shown in Table 1.
  • a binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • a plasticizer DOP : 4 parts by weight of di (2-ethylhexyl) phthalate (manufactured by Kurokin Kasei Co., Ltd.) and 2 parts by weight of a dispersant (product name: Leodol SP-O30, Kao Corporation) were mixed.
  • the mixture was defoamed by stirring under reduced pressure and adjusted to a viscosity of 4000 cP.
  • the viscosity was measured with an LVT viscometer manufactured by Brookfield.
  • the slurry prepared as described above was formed into a sheet shape on a PET (polyethylene terephthalate) film so that the thickness after drying was 45 ⁇ m by a doctor blade method to produce a green sheet.
  • the green sheet peeled off from the PET film was cut out, placed on the center of a zirconia setter (dimension 90 mm square, height 1 mm) with a protrusion height of 300 ⁇ m, and fired at 1300 ° C. for 5 hours
  • the temperature was lowered at a temperature drop rate of 50 ° C./h.
  • the portion not welded to the setter was taken out as a Co 3 O 4 oriented fired plate.
  • Examples B1 to B8 (1) orientation positive electrode plate prepared in (1a) Preparation of LCO template grains Co 3 O 4 raw material powder (volume basis D50 particle size 0.8 [mu] m, Seido Chemical Industry Co., Ltd.) and Li 2 CO 3 raw material powder (by volume D50 particle size 2.5 ⁇ m, manufactured by Honjo Chemical Co., Ltd.) was mixed and baked at 800 ° C. for 5 hours to synthesize LiCoO 2 raw material powder. At this time, by adjusting the firing temperature and firing time, the volume was adjusted reference D50 particle size of the LiCoO 2 material powder to values shown in Table 2. The obtained LiCoO 2 powder was pulverized to obtain plate-like LiCoO 2 particles (LCO template particles).
  • Example B1 In Examples B1, B2 and B4 to B8, a pot mill was used, and in Example B3, a wet jet mill was used. At this time, the volume-based D50 particle size of the LCO template particles was adjusted to the value shown in Table 2 by adjusting the pulverization time. Further, the aspect ratio of the LiCoO 2 template particles was as shown in Table 2. The aspect ratio of LiCoO 2 template particles was measured by SEM observation of the obtained template particles.
  • a binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • a plasticizer DOP : 4 parts by weight of Di (2-ethylhexyl) phthalate (manufactured by Kurokin Kasei Co., Ltd.) and 2 parts by weight of a dispersant (product name: Leodol SP-O30, manufactured by Kao Corporation) were mixed.
  • the mixture was degassed by stirring under reduced pressure, and a slurry was prepared by adjusting the viscosity to 4000 cP.
  • the viscosity was measured with an LVT viscometer manufactured by Brookfield.
  • the prepared slurry was formed into a sheet on a PET film by a doctor blade method so that the thickness after drying was 40 ⁇ m at a forming speed of 100 m / h to obtain a green sheet.
  • the sheet was sandwiched between upper and lower sheets and fired at 900 ° C. for 20 hours.
  • Battery assembly A stainless foil with a thickness of 20 ⁇ m was cut into a 13 mm square to form a positive electrode current collector plate. Also, a 1 mm wide frame-shaped modified polypropylene resin film (thickness: 100 ⁇ m) having an outer edge shape of 13 mm square and an 11 mm square hole punched inside thereof was prepared. This frame-shaped resin film was laminated on the outer peripheral portion on the positive electrode current collector plate, and heat-pressed to form an end sealing portion. The unit cell was placed in a region surrounded by the end sealing portion on the positive electrode current collector plate. Similarly to the above, a stainless steel foil having a thickness of 20 ⁇ m was placed on the negative electrode side of the placed unit cell, and heated at 200 ° C. under reduced pressure while applying a load to the end sealing portion. Thus, the end sealing part and the upper and lower two stainless steel foils were bonded together over the entire outer periphery to seal the unit cell. Thus, an all solid lithium battery in a sealed form was obtained.
  • the ratio (%) of the total area of primary particles having an orientation angle of more than 0 ° and 30 ° or less to the total area of 30 primary particles used for calculating the average orientation angle was calculated.
  • the average particle diameter of 30 primary particles used for calculating the average orientation angle was calculated.
  • the arithmetic average value of the equivalent circle diameter of each of the 30 primary particles was defined as the average particle size of the primary particles.
  • the average aspect ratio of 30 primary particles used to calculate the average orientation angle was calculated.
  • the arithmetic average value of the value obtained by dividing the maximum ferret diameter of each of the 30 primary particles by the minimum ferret diameter was taken as the average aspect ratio of the primary particles.
  • the area ratio of primary particles having an aspect ratio of 4 or more was calculated among the 30 primary particles used for calculating the average orientation angle.
  • Example B9 (comparison) Batteries were prepared and evaluated in the same manner as in Examples B1 to B8, except that the LiCoO 2 powder was used as it was as the LCO template particles without being pulverized. The results were as shown in Table 3.
  • Example B10 (comparison) Batteries were prepared and evaluated in the same manner as in Examples B1 to B8, except that the volume-based D50 particle size of the Co 3 O 4 matrix particles was larger than those in Examples B1 to B8.
  • the volume-based D50 particle size of the matrix particles of this example was 3.0 ⁇ m, and the particle size ratio of the LCO template particles to the Co 3 O 4 matrix particles was 0.2. The results were as shown in Table 3.
  • Example B11 (comparison) Batteries were produced and evaluated in the same manner as in Examples B1 to B8, except that the green sheets were produced with a slurry using only Co 3 O 4 matrix particles without using LCO template particles. The results were as shown in Table 3.
  • Example B12 (comparison) Batteries were produced and evaluated in the same manner as in Examples B1 to B8 except that the firing temperature for primary firing was 1200 ° C. The results were as shown in Table 3.
  • Example B13 (comparison) A battery was produced and evaluated in the same manner as in Example B1, except that the positive electrode plate was produced as follows. The results were as shown in Table 3.
  • Example B1 (Preparation of positive electrode plate) The slurry prepared in Example B1 was dried as it was without being formed into a sheet. The dried product was fired in the same manner as in Example B1, and then polished to a thickness of 40 ⁇ m using a # 1200 SiC abrasive paper to obtain a positive electrode plate.

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)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

L'invention concerne une batterie au lithium tout solide ayant des performances de cycle considérablement améliorées lorsque la charge et la décharge sont effectuées de manière répétée. La batterie au lithium tout solide selon la présente invention comporte : une plaque d'électrode positive orientée ayant une épaisseur de 30 µm ou plus et constituée d'un corps fritté orienté; une couche d'électrolyte solide disposée sur la plaque d'électrode positive orientée et constituée d'un matériau conducteur d'ions lithium; et une couche intermédiaire ayant une épaisseur de 0,001 à 1 µm disposée sur la couche d'électrolyte à l'état solide et comprenant un métal capable de former un alliage avec du lithium. Dans la plaque d'électrode positive orientée, le corps fritté orienté comprend une pluralité de particules primaires constituées d'un oxyde composite de lithium ayant une structure stratifiée de sel gemme, et la pluralité de particules primaires sont orientées selon un angle d'orientation moyen compris entre 0° et 30° ou moins par rapport à la surface de la plaque d'électrode positive orientée.
PCT/JP2017/025258 2016-08-02 2017-07-11 Batterie au lithium tout solide WO2018025594A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018531804A JP6906522B2 (ja) 2016-08-02 2017-07-11 全固体リチウム電池

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016152278 2016-08-02
JP2016-152278 2016-08-02
JP2017-100866 2017-05-22
JP2017100866 2017-05-22

Publications (1)

Publication Number Publication Date
WO2018025594A1 true WO2018025594A1 (fr) 2018-02-08

Family

ID=61074091

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/025258 WO2018025594A1 (fr) 2016-08-02 2017-07-11 Batterie au lithium tout solide

Country Status (2)

Country Link
JP (1) JP6906522B2 (fr)
WO (1) WO2018025594A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102100445B1 (ko) * 2018-10-18 2020-04-13 한국생산기술연구원 집전체간 계면접착제 적용 바이폴라 적층 구조체, 그를 포함하는 전고체 리튬이차전지 및 그의 제조방법
WO2020090470A1 (fr) * 2018-11-01 2020-05-07 日本碍子株式会社 Batterie secondaire au lithium
CN112074987A (zh) * 2018-05-17 2020-12-11 日本碍子株式会社 锂二次电池
WO2021009959A1 (fr) * 2019-07-12 2021-01-21 パナソニックＩｐマネジメント株式会社 Batterie
CN113454806A (zh) * 2019-02-19 2021-09-28 康宁股份有限公司 用于电池的烧结电极及其制造方法
US11271201B2 (en) 2019-07-15 2022-03-08 Corning Incorporated Energy device with lithium
DE112020005602T5 (de) 2019-11-12 2022-08-25 TDK Corporation Festelektrolytschicht und festkörperakkumulator mit dieser festelektrolytschicht
WO2022190378A1 (fr) * 2021-03-12 2022-09-15 日産自動車株式会社 Batterie entièrement solide
WO2023224442A1 (fr) * 2022-05-20 2023-11-23 주식회사 엘지화학 Matériau actif de cathode, son procédé de fabrication et cathode le comprenant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132887A (ja) * 2001-10-29 2003-05-09 Matsushita Electric Ind Co Ltd 固体リチウム二次電池およびその製造方法
JP2005243371A (ja) * 2004-02-26 2005-09-08 Matsushita Electric Ind Co Ltd 正極とそれを用いた捲回型電気化学素子
JP2009181871A (ja) * 2008-01-31 2009-08-13 Toyota Motor Corp 全固体リチウム二次電池
JP2011009103A (ja) * 2009-06-26 2011-01-13 Toyota Motor Corp 全固体リチウム二次電池
WO2013175993A1 (fr) * 2012-05-24 2013-11-28 株式会社 村田製作所 Pile tout électronique
WO2015029289A1 (fr) * 2013-08-29 2015-03-05 パナソニックＩｐマネジメント株式会社 Batterie rechargeable au lithium entièrement solide
JP2016033880A (ja) * 2014-07-31 2016-03-10 日本碍子株式会社 全固体リチウム電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132887A (ja) * 2001-10-29 2003-05-09 Matsushita Electric Ind Co Ltd 固体リチウム二次電池およびその製造方法
JP2005243371A (ja) * 2004-02-26 2005-09-08 Matsushita Electric Ind Co Ltd 正極とそれを用いた捲回型電気化学素子
JP2009181871A (ja) * 2008-01-31 2009-08-13 Toyota Motor Corp 全固体リチウム二次電池
JP2011009103A (ja) * 2009-06-26 2011-01-13 Toyota Motor Corp 全固体リチウム二次電池
WO2013175993A1 (fr) * 2012-05-24 2013-11-28 株式会社 村田製作所 Pile tout électronique
WO2015029289A1 (fr) * 2013-08-29 2015-03-05 パナソニックＩｐマネジメント株式会社 Batterie rechargeable au lithium entièrement solide
JP2016033880A (ja) * 2014-07-31 2016-03-10 日本碍子株式会社 全固体リチウム電池

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112074987A (zh) * 2018-05-17 2020-12-11 日本碍子株式会社 锂二次电池
CN112074987B (zh) * 2018-05-17 2024-01-26 日本碍子株式会社 锂二次电池
KR102100445B1 (ko) * 2018-10-18 2020-04-13 한국생산기술연구원 집전체간 계면접착제 적용 바이폴라 적층 구조체, 그를 포함하는 전고체 리튬이차전지 및 그의 제조방법
WO2020090470A1 (fr) * 2018-11-01 2020-05-07 日本碍子株式会社 Batterie secondaire au lithium
JPWO2020090470A1 (ja) * 2018-11-01 2021-09-30 日本碍子株式会社 リチウム二次電池
JP7061688B2 (ja) 2018-11-01 2022-04-28 日本碍子株式会社 リチウム二次電池
US11791465B2 (en) 2019-02-19 2023-10-17 Corning Incorporated Sintered electrodes for batteries and method of preparing same
CN113454806A (zh) * 2019-02-19 2021-09-28 康宁股份有限公司 用于电池的烧结电极及其制造方法
WO2021009959A1 (fr) * 2019-07-12 2021-01-21 パナソニックＩｐマネジメント株式会社 Batterie
JP7437786B2 (ja) 2019-07-12 2024-02-26 パナソニックＩｐマネジメント株式会社 電池
US11271201B2 (en) 2019-07-15 2022-03-08 Corning Incorporated Energy device with lithium
DE112020005602T5 (de) 2019-11-12 2022-08-25 TDK Corporation Festelektrolytschicht und festkörperakkumulator mit dieser festelektrolytschicht
WO2022190378A1 (fr) * 2021-03-12 2022-09-15 日産自動車株式会社 Batterie entièrement solide
WO2023224442A1 (fr) * 2022-05-20 2023-11-23 주식회사 엘지화학 Matériau actif de cathode, son procédé de fabrication et cathode le comprenant

Also Published As

Publication number Publication date
JP6906522B2 (ja) 2021-07-21
JPWO2018025594A1 (ja) 2019-05-30

Similar Documents

Publication Publication Date Title
WO2018025594A1 (fr) Batterie au lithium tout solide
KR102643570B1 (ko) 판형 리튬 복합 산화물
JP6646666B2 (ja) 全固体リチウム電池
WO2017065035A1 (fr) Batterie au lithium tout solide
JP6914285B2 (ja) リチウムイオン電池
JP6906524B2 (ja) 全固体リチウム電池
WO2016152565A1 (fr) Batterie au lithium tout solide
WO2018088522A1 (fr) Batterie secondaire
WO2018025595A1 (fr) Procédé d'utilisation de batterie au lithium tout solide
JP6820960B2 (ja) リチウムイオン電池
JP2017054792A (ja) リチウム電池
JP6430065B2 (ja) 正極の製造方法
WO2017065034A1 (fr) Procédé de fabrication de batterie au lithium tout solide
JP2017054761A (ja) 全固体リチウム電池の検査方法及び全固体リチウム電池の製造方法
JP2017135100A (ja) リチウムイオン電池
WO2022044409A1 (fr) Batterie secondaire au lithium-ion

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018531804

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 17836701

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: 17836701

Country of ref document: EP

Kind code of ref document: A1