WO2022208982A1 - コイン形リチウムイオン二次電池 - Google Patents

コイン形リチウムイオン二次電池 Download PDF

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Publication number
WO2022208982A1
WO2022208982A1 PCT/JP2021/042442 JP2021042442W WO2022208982A1 WO 2022208982 A1 WO2022208982 A1 WO 2022208982A1 JP 2021042442 W JP2021042442 W JP 2021042442W WO 2022208982 A1 WO2022208982 A1 WO 2022208982A1
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Prior art keywords
coin
electrode layer
secondary battery
ion secondary
positive electrode
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Ceased
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PCT/JP2021/042442
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English (en)
French (fr)
Japanese (ja)
Inventor
幸信 由良
春男 大塚
俊介 水上
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to KR1020237033454A priority Critical patent/KR20230151544A/ko
Priority to JP2023510213A priority patent/JP7637228B2/ja
Priority to CN202180095658.3A priority patent/CN117296181A/zh
Priority to EP21935136.8A priority patent/EP4318638A4/en
Publication of WO2022208982A1 publication Critical patent/WO2022208982A1/ja
Priority to US18/476,746 priority patent/US20240021881A1/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H01M10/0427—Button cells
    • 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
    • H01M10/0566—Liquid 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
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    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/167—Lids or covers characterised by the methods of assembling casings with lids by crimping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/181—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for button or coin cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/184—Sealing members characterised by their shape or structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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 coin-type lithium ion secondary batteries.
  • Coin-type lithium-ion secondary batteries are widely used in various devices that require charging, and various coin-type lithium-ion secondary batteries have been proposed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2012-209178
  • a positive electrode is arranged on the inner surface of a positive electrode case that also serves as an external terminal
  • a negative electrode is arranged on the inner surface of a negative electrode sealing plate that also serves as an external terminal.
  • a coin-type battery is disclosed in which the negative electrodes are opposed to each other with a separator interposed therebetween.
  • the positive electrode case and the peripheral edge portion of the sealing plate are sealed via a gasket so as to retain the electrolytic solution inside.
  • the secondary battery as described above employs a powder-dispersed positive electrode (so-called coated electrode) that is produced by coating and drying a positive electrode mixture containing a positive electrode active material, a conductive aid, a binder, and the like. .
  • a powder dispersion type positive electrode contains a relatively large amount (for example, about 10% by weight) of components (binders and conductive aids) that do not contribute to capacity. Low packing density. Therefore, the powder-dispersed positive electrode has much room for improvement in terms of capacity and charge/discharge efficiency. Accordingly, attempts have been made to improve the capacity and charge/discharge efficiency by forming the positive electrode or positive electrode active material layer from a sintered plate of lithium composite oxide. In this case, since the positive electrode or the positive electrode active material layer does not contain a binder or a conductive aid, it is expected that high capacity and good charge-discharge efficiency can be obtained by increasing the packing density of the lithium composite oxide. be.
  • Patent Document 2 WO2019/221139
  • a positive electrode plate that is a lithium composite oxide sintered plate, a negative electrode plate that is a titanium-containing sintered plate, a separator, and an electrolytic solution are provided in an exterior body.
  • a coin-type lithium ion secondary battery is also disclosed, and it is said that by using a sintered plate as an electrode, excellent heat resistance that enables reflow soldering can be obtained.
  • the major portions of the outer can (case and cap) that are in contact with the positive electrode (or positive electrode current collector) and the negative electrode (or negative electrode current collector) are generally linear when viewed in cross section. It has a flat shape that looks like
  • the flat outer can part hits the electrodes and some of the electrodes are damaged, easily degrading battery performance. There is a problem.
  • the inventors of the present invention have recently obtained the knowledge that the battery performance is less likely to deteriorate even when subjected to reflow soldering by giving the outer can shape of the coin-type lithium ion secondary battery a bulging ratio of a predetermined ratio. rice field.
  • an object of the present invention is to provide a coin-type lithium ion secondary battery whose battery performance is less likely to deteriorate even when subjected to reflow soldering.
  • a positive electrode layer a negative electrode layer; a separator interposed between the positive electrode layer and the negative electrode layer; an electrolytic solution impregnated in the positive electrode layer, the negative electrode layer, and the separator; an exterior body having a coin shape with a bulge on at least one surface and having a closed space for accommodating the positive electrode layer, the negative electrode layer, the separator, and the electrolytic solution;
  • a coin-type lithium ion secondary battery comprising The coin-shaped lithium ion secondary battery has a main region where the positive electrode layer, the negative electrode layer and the separator all overlap, and a peripheral region lacking at least one of the positive electrode layer, the negative electrode layer and the separator.
  • a battery swelling ratio which is a ratio of the maximum thickness of the coin-shaped lithium ion secondary battery in the main area to the minimum thickness of the coin-shaped lithium ion secondary battery in the main area, is 1.01. ⁇ 1.25, a coin-type lithium-ion secondary battery for reflow soldering is provided.
  • FIG. 1 is a schematic cross-sectional view of an example of a coin-shaped lithium ion secondary battery of the present invention
  • FIG. It is a SEM image which shows an example of the cross section perpendicular
  • 3 is an EBSD image of a cross section of the oriented positive plate shown in FIG. 2;
  • 4 is a histogram showing the distribution of orientation angles of primary particles in the EBSD image of FIG. 3 on an area basis;
  • FIG. 1 schematically shows an example of the coin-shaped lithium ion secondary battery of the present invention.
  • a lithium-ion secondary battery 10 shown in FIG. A separator 20 is interposed between the positive electrode layer 12 and the negative electrode layer 16 .
  • the electrolyte solution 22 impregnates the positive electrode layer 12 , the negative electrode layer 16 and the separator 20 .
  • the exterior body 24 has a sealed space, and the positive electrode layer 12, the negative electrode layer 16, the separator 20, and the electrolytic solution 22 are accommodated in this sealed space.
  • the exterior body 24 has a coin shape with a bulge on at least one surface.
  • This coin-shaped lithium ion secondary battery 10 has a main region M where all of the positive electrode layer 12, the negative electrode layer 16 and the separator 20 overlap, and a peripheral region B lacking at least one of the positive electrode layer 12, the negative electrode layer 16 and the separator 20.
  • the battery swelling ratio which is the ratio of the maximum thickness of the coin-shaped lithium ion secondary battery 10 in the main region M to the minimum thickness of the coin-shaped lithium ion secondary battery 10 in the main region M, is 1. 0.01 to 1.25. In this manner, the coin-shaped lithium-ion secondary battery 10 has a bulge of a predetermined ratio in the outer can shape, so that the battery performance is less likely to deteriorate even when subjected to reflow soldering.
  • the present invention advantageously solves this problem. This is because the shape of the outer can of the battery (particularly the main region M) has a bulge of a predetermined ratio, which relieves the stress that can occur at high temperatures during reflow soldering (for example, the maximum temperature can reach 260°C). It is thought that this is because the damage to the electrodes is reduced as a result.
  • the lithium ion secondary battery 10 is preferably used for reflow soldering.
  • the lithium-ion secondary battery 10 includes a positive electrode terminal (not shown) bonded to the outer surface of the exterior body 24 closer to the positive electrode layer 12 and a negative electrode terminal bonded to the outer surface of the exterior body 24 closer to the negative electrode layer 16 . terminals (not shown).
  • the positive terminal and/or the negative terminal are preferably used for reflow soldering for mounting the coin-shaped lithium ion secondary battery 10 on the substrate.
  • the positive electrode terminal is preferably joined to the positive electrode can 24a of the exterior body 24 by diffusion welding, laser welding, or the like.
  • the negative electrode terminal is preferably joined to the negative electrode can 24b of the outer package 24 by a technique such as diffusion welding or laser welding.
  • the exterior body 24 has a coin shape with a bulge on at least one surface. More preferably, the coin-shaped exterior body 24 has bulges on both sides.
  • the battery swelling ratio which is the ratio of the maximum thickness of the coin-shaped lithium ion secondary battery in the main region M to the minimum thickness of the coin-shaped lithium ion secondary battery 10 in the main region M, is from 1.01 to 1.25, preferably 1.02 to 1.23, more preferably 1.02 to 1.20, still more preferably 1.03 to 1.18, particularly preferably 1.05 to 1.15 .
  • the main region M refers to the region where the positive electrode layer 12, the negative electrode layer 16 and the separator 20 all overlap.
  • primary region M is distinguished from peripheral region P, which lacks at least one (and possibly all) of positive electrode layer 12 , negative electrode layer 16 and separator 20 .
  • the maximum and minimum values of the thickness of the secondary battery 10 in the main region M can be measured using a commercially available laser displacement gauge, and the measured maximum and minimum values can be used to calculate the battery swelling ratio. good.
  • the thickness of the battery in the main region M is measured for each of the two straight lines perpendicular to the center of the lithium ion secondary battery 10, the battery swelling ratio is calculated, and the battery swelling obtained for the two straight lines It is desirable to take the average value of the ratios.
  • the outer diameter of the lithium ion secondary battery 10 is not particularly limited, it is typically 8 to 25 mm, more typically 9.5 to 22 mm, still more typically 12.5 to 20 mm.
  • the positive electrode layer 12 is a layer containing a positive electrode active material.
  • the positive electrode layer 12 is a powder-dispersed positive electrode (a so-called coated electrode) prepared by applying and drying a positive electrode mixture containing a positive electrode active material (for example, lithium cobaltate), a conductive aid, a binder, and the like.
  • a ceramic positive electrode plate is preferable, and a lithium composite oxide sintered body plate is more preferable. That the positive electrode layer 12 is a ceramic positive electrode plate or a sintered plate means that the positive electrode layer 12 does not contain a binder or a conductive aid. This is because even if the green sheet contains a binder, the binder disappears or is burned off during firing.
  • the lithium composite oxide forming the sintered plate is particularly preferably lithium cobaltate (typically LiCoO 2 (hereinafter sometimes abbreviated as LCO)).
  • LCO lithium cobaltate
  • Various lithium composite oxide sintered plates or LCO sintered plates are known, and for example, those disclosed in Patent Document 2 (WO2019/221139) can be used.
  • the lithium composite oxide sintered plate that constitutes the positive electrode layer 12 includes a plurality of primary particles that are composed of a lithium composite oxide, and the plurality of primary particles are formed on the plate surface of the positive electrode plate. It is an oriented positive electrode plate oriented at an average orientation angle of more than 0° and 30° or less with respect to FIG. 2 shows an example of a cross-sectional SEM image perpendicular to the plate surface of the oriented positive plate, while FIG. 3 shows an electron backscatter diffraction (EBSD) image in a cross section perpendicular to the plate surface of the oriented positive plate. .
  • FIG. 1 electron backscatter diffraction
  • FIG. 4 shows a histogram showing the distribution of orientation angles of the primary particles 11 in the EBSD image of FIG. 3 on an area basis.
  • a discontinuity in crystal orientation can be observed in the EBSD image shown in FIG.
  • the orientation angle of each primary particle 11 is indicated by the shade of color, and the darker the color, the smaller the orientation angle.
  • the orientation angle is the inclination angle formed by the (003) plane of each primary particle 11 with respect to the plate surface direction.
  • the portions shown in black inside the oriented positive plate are pores.
  • the positive electrode layer 12 which is an oriented positive electrode plate, is an oriented sintered body composed of a plurality of mutually bonded primary particles 11.
  • Each primary particle 11 is mainly plate-shaped, but may include rectangular parallelepiped, cubic, and spherical primary particles.
  • the cross-sectional shape of each primary particle 11 is not particularly limited, and may be rectangular, polygonal other than rectangular, circular, elliptical, or any other complex shape.
  • Each primary particle 11 is composed of a lithium composite oxide.
  • Lithium composite oxide means 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 including).
  • a lithium composite oxide has a layered rock salt structure.
  • the layered rock salt structure is a crystal structure in which a lithium layer and a transition metal layer other than lithium are alternately laminated with an oxygen layer sandwiched therebetween, that is, a transition metal ion layer and a lithium single layer are alternately formed via oxide ions.
  • lithium composite oxides include Li x CoO 2 (lithium cobalt oxide), Li x NiO 2 (lithium nickel oxide), Li x MnO 2 (lithium manganate), and Li x NiMnO 2 (lithium nickel-manganese oxide). . _ _ _ _ _ _ _ _ _ _ (lithium cobaltate, typically LiCoO 2 ).
  • Lithium composite oxides include Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te, Ba , 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 30° or less.
  • This provides various advantages: First, since each primary particle 11 lies in a state inclined with respect to the thickness direction, the adhesion between the primary particles can be improved. As a result, it is possible to improve the lithium ion conductivity between a certain primary particle 11 and other primary particles 11 adjacent to both sides in the longitudinal direction of the primary particle 11, thereby improving the rate characteristics. Second, rate characteristics can be further improved. This is because, as described above, when lithium ions enter and leave the oriented positive plate, the expansion and contraction in the thickness direction is more dominant than in the plate surface direction, so the expansion and contraction of the oriented positive plate becomes smooth.
  • the average orientation angle of the primary particles 11 is obtained by the following method. First, in an EBSD image of a rectangular region of 95 ⁇ m ⁇ 125 ⁇ m observed at a magnification of 1000 times as shown in FIG. Draw three vertical lines that divide the plane into four equal parts. 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 rate characteristics. 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.
  • the orientation angle of each primary particle 11 may be widely distributed from 0° to 90°, but most of them are distributed in the region of more than 0° and 30° or less. is preferred. That is, when the cross section of the oriented sintered body constituting the oriented positive electrode plate is analyzed by EBSD, the orientation angle of the primary particles 11 included in the analyzed cross section with respect to the surface of the oriented positive electrode plate is more than 0° and 30°. ° or less of the primary particles 11 (hereinafter referred to as low-angle primary particles) is the total area of the primary particles 11 (specifically, 30 primary particles 11 used to calculate the average orientation angle) included in the cross section. The area is preferably 70% or more, more preferably 80% or more.
  • the ratio of the primary particles 11 having high mutual adhesion can be increased, so that the rate characteristics can be further improved.
  • the total area of the low-angle primary particles having an orientation angle of 20° or less is more preferably 50% or more of the total area of the 30 primary particles 11 used to calculate the average orientation angle.
  • the total area of the low-angle primary particles having an orientation angle of 10° or less is more preferably 15% or more of the total area of the 30 primary particles 11 used to calculate the average orientation angle. .
  • each primary particle 11 is mainly plate-shaped, as shown in FIGS. 2 and 3, the cross section of each primary particle 11 extends in a predetermined direction and is typically substantially rectangular. 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 the total area of the primary particles 11 included in the cross section. It is preferably 70% or more, more preferably 80% or more, of the total area of the particles 11 (specifically, 30 primary particles 11 used for calculating the average orientation angle). Specifically, in the EBSD image shown in FIG. 3, 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 Feret diameter of the primary particles 11 by the minimum Feret diameter.
  • the maximum Feret diameter is the maximum distance between two parallel straight lines sandwiching the primary particles 11 on the EBSD image when the cross section is observed.
  • the minimum Feret diameter is the minimum distance between two parallel straight lines sandwiching the primary particle 11 on the EBSD image.
  • the average particle diameter of the plurality of primary particles constituting the oriented sintered body is 5 ⁇ m or more.
  • the average particle size of the 30 primary particles 11 used to calculate the average orientation angle is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and even more 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 lithium composite oxide sintered plate forming the positive electrode layer 12 preferably contains pores. Since the sintered body contains pores, particularly open pores, when it is incorporated into a battery as a positive electrode plate, the electrolyte can permeate the inside of the sintered body, and as a result, the lithium ion conductivity is improved. be able to. This is because there are two types of lithium ion conduction in the sintered body: conduction through the constituent particles of the sintered body and conduction through the electrolyte in the pores. This is because it is overwhelmingly fast.
  • the lithium composite oxide sintered plate constituting the positive electrode layer 12 preferably has a porosity of 20 to 60%, more preferably 25 to 55%, still more preferably 30 to 50%, and particularly preferably 30 to 45%. %.
  • a stress releasing effect and a high capacity can be expected by the pores, and the mutual adhesion between the primary particles 11 can be further improved, so that the rate characteristics can be further improved.
  • the porosity of the sintered body is calculated by binarizing the obtained SEM image after polishing the cross section of the positive electrode plate by CP (cross section polisher), observing it with an SEM at a magnification of 1000.
  • the average circle equivalent 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 pores is a value obtained by arithmetically averaging the equivalent circle diameters of 10 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 is preferably an open pore leading to the outside of the lithium composite oxide sintered body plate.
  • the average pore diameter of the lithium composite oxide sintered plate that constitutes the positive electrode layer 12 is preferably 0.1 to 10.0 ⁇ m, more preferably 0.2 to 5.0 ⁇ m, still more preferably 0.3 to 0.3 ⁇ m. 3.0 ⁇ m. Within the above range, stress concentration in large pores is suppressed, and the stress in the sintered body is easily released uniformly.
  • the thickness of the lithium composite oxide sintered plate forming the positive electrode layer 12 is preferably 60-600 ⁇ m, more preferably 70-550 ⁇ m, and still more preferably 90-500 ⁇ m. Within such a range, the energy density of the lithium ion secondary battery 10 is improved by increasing the active material capacity per unit area, and the battery characteristics deteriorate due to repeated charging and discharging (especially an increase in resistance value). can be suppressed.
  • the negative electrode layer 16 is a layer containing a negative electrode active material.
  • the negative electrode layer 16 may be a powder-dispersed negative electrode (a so-called coated electrode) prepared by applying and drying a negative electrode mixture containing a negative electrode active material, a conductive aid, a binder, etc., but is preferably It is a ceramic negative plate, more preferably a titanium-containing sintered plate.
  • the titanium-containing sintered plate preferably contains lithium titanate Li 4 Ti 5 O 12 (hereinafter referred to as LTO) or niobium titanium composite oxide Nb 2 TiO 7 , more preferably LTO.
  • LTO lithium titanate Li 4 Ti 5 O 12
  • Nb 2 TiO 7 niobium titanium composite oxide
  • LTO is typically known to have a spinel structure
  • other structures can be adopted during charging and discharging.
  • the reaction proceeds in the two-phase coexistence of Li 4 Ti 5 O 12 (spinel structure) and Li 7 Ti 5 O 12 (rock salt structure) during charging and
  • That the negative electrode layer 16 is a ceramic negative electrode plate or a sintered plate means that the negative electrode layer 16 does not contain a binder or a conductive aid. This is because even if the green sheet contains a binder, the binder disappears or is burned off during firing. Since the negative electrode plate does not contain a binder, the filling density of the negative electrode active material (for example, LTO or Nb 2 TiO 7 ) is increased, thereby achieving high capacity and good charge/discharge efficiency.
  • the LTO sintered plate can be produced according to the method described in Patent Document 2 (WO2019/221139).
  • the titanium-containing sintered plate that constitutes the negative electrode layer 16 has a structure in which a plurality (that is, a large number) of primary particles are bonded together. Therefore, it is preferred that these primary particles consist of LTO or Nb 2 TiO 7 .
  • the thickness of the titanium-containing sintered plate forming the negative electrode layer 16 is preferably 70-500 ⁇ m, preferably 85-400 ⁇ m, more preferably 95-350 ⁇ m.
  • the thickness of the titanium-containing sintered plate can be obtained, for example, by measuring the distance between the plate surfaces observed substantially parallel when the cross section of the titanium-containing sintered plate is observed with a SEM (scanning electron microscope). can get.
  • the primary particle diameter which is the average particle diameter of a plurality of primary particles constituting the titanium-containing sintered plate, is preferably 1.2 ⁇ m or less, more preferably 0.02 to 1.2 ⁇ m, still more preferably 0.05 to 0.05 ⁇ m. 7 ⁇ m. Within such a range, it is easy to achieve both lithium ion conductivity and electronic conductivity, which contributes to the improvement of rate performance.
  • the titanium-containing sintered plate that constitutes the negative electrode layer 16 preferably contains pores. Since the sintered body plate contains pores, particularly open pores, the electrolytic solution can permeate the inside of the sintered body plate when it is incorporated in a battery as a negative electrode plate, and as a result, the lithium ion conductivity is improved. can be improved. This is because there are two types of lithium ion conduction in the sintered body: conduction through the constituent particles of the sintered body and conduction through the electrolyte in the pores. This is because it is overwhelmingly fast.
  • the porosity of the titanium-containing sintered plate forming the negative electrode layer 16 is preferably 20-60%, more preferably 30-55%, and still more preferably 35-50%. Within such a range, it is easy to achieve both lithium ion conductivity and electronic conductivity, which contributes to the improvement of rate performance.
  • the average pore diameter of the titanium-containing sintered plate forming the negative electrode layer 16 is 0.08 to 5.0 ⁇ m, preferably 0.1 to 3.0 ⁇ m, more preferably 0.12 to 1.5 ⁇ m. Within such a range, it is easy to achieve both lithium ion conductivity and electronic conductivity, which contributes to the improvement of rate performance.
  • Separator 20 is preferably a cellulose, polyolefin, polyimide, polyester (eg, polyethylene terephthalate (PET)), or ceramic separator.
  • Cellulose separators are advantageous in that they are inexpensive and have excellent heat resistance.
  • Polyimide, polyester (e.g., polyethylene terephthalate (PET)) or cellulose separators not only have excellent heat resistance, unlike the widely used polyolefin separators, which have poor heat resistance. It also has excellent wettability with respect to ⁇ -butyrolactone (GBL), which is an electrolyte component with excellent heat resistance. Therefore, when an electrolytic solution containing GBL is used, the electrolytic solution can be sufficiently permeated into the separator (without being repelled).
  • GBL ⁇ -butyrolactone
  • the separator made of ceramic has the advantage that it is excellent in heat resistance and can be produced together with the positive electrode layer 12 and the negative electrode layer 16 as one integrated sintered body as a whole.
  • the ceramic constituting the separator is preferably at least one selected from MgO, Al 2 O 3 , ZrO 2 , SiC, Si 3 N 4 , AlN, and cordierite, more preferably At least one selected from MgO, Al 2 O 3 and ZrO 2 .
  • the electrolytic solution 22 is not particularly limited, and a commercially available electrolytic solution for lithium batteries, such as a solution in which a lithium salt is dissolved in a non-aqueous solvent such as an organic solvent, may be used.
  • a commercially available electrolytic solution for lithium batteries such as a solution in which a lithium salt is dissolved in a non-aqueous solvent such as an organic solvent
  • an electrolytic solution having excellent heat resistance is preferred, and such an electrolytic solution preferably contains lithium borofluoride (LiBF 4 ) in a non-aqueous solvent.
  • the preferred non-aqueous solvent is at least one selected from the group consisting of ⁇ -butyrolactone (GBL), ethylene carbonate (EC) and propylene carbonate (PC), more preferably a mixed solvent consisting of EC and GBL.
  • a single solvent consisting of PC a mixed solvent consisting of PC and GBL, or a single solvent consisting of GBL, and particularly preferably a mixed solvent consisting of EC and GBL or a single solvent consisting of GBL.
  • GBL ⁇ -butyrolactone
  • the EC:GBL volume ratio in the EC and/or GBL-containing non-aqueous solvent is preferably 0:1 to 1:1 (GBL ratio 50 to 100% by volume), more preferably 0:1 to 1:1.5 (GBL ratio 60 to 100% by volume), more preferably 0:1 to 1:2 (GBL ratio 66.6 to 100% by volume), particularly preferably 0:1 to 1:3 (GBL ratio 75 to 100% by volume).
  • Lithium borofluoride (LiBF 4 ) dissolved in a non-aqueous solvent is an electrolyte with a high decomposition temperature, which also provides a significant improvement in heat resistance.
  • LiBF 4 concentration in the electrolytic solution 22 is preferably 0.5 to 2 mol/L, more preferably 0.6 to 1.9 mol/L, still more preferably 0.7 to 1.7 mol/L, and particularly preferably 0.8 to 1.5 mol/L.
  • the electrolytic solution 22 may further contain vinylene carbonate (VC) and/or fluoroethylene carbonate (FEC) and/or vinylethylene carbonate (VEC)) and/or propane sultone (PS) as additives. Both VC and FEC are excellent in heat resistance. Therefore, by including such an additive in the electrolytic solution 22 , an SEI film having excellent heat resistance can be formed on the surface of the negative electrode layer 16 .
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • VEC vinylethylene carbonate
  • PS propane sultone
  • the exterior body 24 has a closed space, and the positive electrode layer 12, the negative electrode layer 16, the separator 20, and the electrolytic solution 22 are accommodated in this closed space.
  • the exterior body 24 is not particularly limited as long as it adopts a structure that is generally used for coin batteries (see Patent Documents 1 and 2, for example).
  • the exterior body 24 includes a positive electrode can 24a, a negative electrode can 24b, and a gasket 24c, and the positive electrode can 24a and the negative electrode can 24b are crimped via the gasket 24c to form a sealed space.
  • the positive electrode can 24a and the negative electrode can 24b can be made of metal such as stainless steel, and are not particularly limited.
  • the gasket 24c may be an annular member made of insulating resin such as polypropylene, polytetrafluoroethylene, etc., and is not particularly limited.
  • a gel solution may be applied to the gasket 24c to improve the sealing performance.
  • the type of solution used for the gel-like solution includes heat-curable olefin-based and synthetic rubber-based solutions, but is not limited to these as long as the solution has viscosity or adhesiveness after volatilization of the solvent.
  • the application method is not limited, and the gasket 24c may be solution dipped, or the solution may be applied to the gasket 24c using a dispenser or the like.
  • the lithium ion secondary battery 10 preferably further includes a positive electrode current collector 14 and/or a negative electrode current collector 18 .
  • the positive electrode current collector 14 and the negative electrode current collector 18 are not particularly limited, they are preferably metal foils such as copper foil and aluminum foil.
  • the cathode current collector 14 is preferably positioned between the cathode layer 12 and the cathode can 24a, and the anode current collector 18 is preferably positioned between the anode layer 16 and the anode can 24b.
  • a negative electrode-side carbon layer 17 is preferably provided between the negative electrode layer 16 and the negative electrode current collector 18 .
  • Both the positive electrode side carbon layer 13 and the negative electrode side carbon layer 17 are preferably made of conductive carbon, and may be formed, for example, by applying a conductive carbon paste by screen printing or the like.
  • the battery element may be in the form of a multi-layered cell having a plurality of unit cells as well as in the form of a unit cell of positive electrode layer 12/separator 20/negative electrode layer 16 as shown in FIG.
  • the multi-layer cell is not limited to a flat plate laminated structure in which flat plates or layers are stacked, but may be various laminated structures including the following examples. Any of the configurations exemplified below may be one integrally sintered body as the entire cell laminate.
  • -Folded structure A multilayered structure (increased area) formed by folding a layered sheet including a unit cell and a current collecting layer once or multiple times.
  • -Wound structure A multilayered structure (large area) formed by winding and integrating a layered sheet including a unit cell and a current collecting layer.
  • MLCC Multilayer ceramic capacitor
  • MLCC-like structure multi-layered (large area) by repeating the lamination unit of collector layer/positive electrode layer/ceramic separator layer/negative electrode layer/collective layer in the thickness direction, and A laminate structure in which multiple positive electrode layers are on one side (eg, the left side) and multiple negative electrode layers are current-collecting on the other side (eg, the right side).
  • a gap can be formed between the exterior body 24 and the battery element in the bulging portion of the exterior body 24 . That is, there are gaps between the package 24 and the positive electrode layer 12 or the positive electrode current collector 14 and gaps between the package 24 and the negative electrode layer 16 or the negative electrode current collector 18 . These gaps may be filled with the electrolytic solution 22, or elastic members such as springs, washers, and members bent in a corrugated shape may be inserted to absorb the expansion and contraction of the battery members due to charging and discharging. may Such an elastic member is preferably made of metal such as stainless steel in order to ensure electrical connection with the exterior body 24 (or the positive electrode terminal and negative electrode terminal joined thereto).
  • the lithium composite oxide sintered plate which is a preferred form of the positive electrode layer 12, may be manufactured by any method, but preferably (a) a lithium composite oxide-containing green sheet. (b) optional preparation of an excess lithium source-containing green sheet; and (c) lamination and firing of the green sheets.
  • a raw material powder composed of a lithium composite oxide is prepared.
  • the powder comprises as - synthesized platelets (eg, LiCoO2 platelets) of composition LiMO 2 , where M is as previously described.
  • the volume-based D50 particle size of the raw material powder is preferably 0.3 to 30 ⁇ m.
  • a method of making LiCoO 2 tabular particles can be carried out as follows. First, Co 3 O 4 raw powder and Li 2 CO 3 raw powder are mixed and fired (500 to 900° C., 1 to 20 hours) to synthesize LiCoO 2 powder.
  • LiCoO 2 particles capable of conducting lithium ions parallel to the plate surface are obtained.
  • Such LiCoO2 particles can be produced in a plate - like form by a method of grain - growing a green sheet using a LiCoO2 powder slurry and then pulverizing it, or by 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 obtained LiCoO 2 particles are in a state where they are easily cleaved along the cleavage plane.
  • LiCoO 2 plate-like particles can be made by cleaving the LiCoO 2 particles by crushing.
  • the plate-like particles may be used alone as the raw material powder, or a mixed powder of the plate-like powder and other raw material powders (for example, Co 3 O 4 particles) may be used as the raw material powder.
  • the plate-like powder function as template particles for imparting orientation, and other raw material powders (eg, Co 3 O 4 particles) to function as matrix particles capable of growing along the template 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. is preferably smaller than the volume-based D50 particle size of This matrix particle can also be obtained by heat-treating a Co(OH) 2 raw material at 500° C. to 800° C. for 1 to 10 hours.
  • Co(OH) 2 particles or LiCoO 2 particles may be used as the matrix particles.
  • the raw material powder is composed of 100% LiCoO2 template particles, or when LiCoO2 particles are used as matrix particles, a large - sized (e.g., 90 mm x 90 mm square ) and flat LiCoO2 sintered body plate is obtained by firing. can be done. Although the mechanism is not clear, it is expected that the volume change during firing or the local unevenness is unlikely to occur because LiCoO 2 is not synthesized during the firing process.
  • a raw material powder is mixed with a dispersion medium and various additives (a binder, a plasticizer, a dispersant, etc.) to form a slurry.
  • a lithium compound other than LiMO 2 for example, lithium carbonate
  • the slurry is preferably stirred under reduced pressure to remove air bubbles and adjusted to have a viscosity of 4,000 to 10,000 cP.
  • the resulting slurry is formed into a sheet to obtain a lithium composite oxide-containing green sheet.
  • the green sheet thus obtained is an independent sheet-like compact.
  • An independent sheet refers to a sheet that can be handled independently from other supports (including flakes with an aspect ratio of 5 or more). That is, the independent sheet does not include a sheet fixed to another support (substrate or the like) and integrated with the support (it cannot be separated or becomes difficult to separate).
  • Sheet forming is preferably carried out using a forming technique capable of applying a shearing force to plate-like particles (for example, template particles) in the raw material powder. By doing so, the average tilt angle of the primary particles can be set to more than 0° and not more than 30° with respect to the plate surface.
  • a doctor blade method is suitable as a molding method capable of applying a shearing force to the plate-like particles.
  • the thickness of the lithium composite oxide-containing green sheet may be appropriately set so as to achieve the desired thickness as described above after firing.
  • a green sheet containing an excess lithium source is produced separately from the green sheet containing the lithium composite oxide.
  • This excess lithium source is preferably a lithium compound other than LiMO 2 in which the components other than Li disappear upon firing.
  • a preferred example of such a lithium compound (excess lithium source) is lithium carbonate.
  • the excess lithium source is preferably in powder form, and the volume-based D50 particle size of the excess lithium source powder is preferably 0.1-20 ⁇ m, more preferably 0.3-10 ⁇ m.
  • the lithium source powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • the molar ratio (Li/Co ratio) of the Li content in the excess lithium source-containing green sheet to the Co content in the lithium composite oxide-containing green sheet is preferably 0.1 or more. , more preferably 0.1 to 1.1.
  • Lithium composite oxide-containing green sheets e.g. LiCoO2 green sheets
  • excess lithium source-containing green sheets e.g. Li2CO3 green sheets
  • the upper and lower setters are made of ceramics, preferably zirconia or magnesia. Pores tend to be smaller when the setter is made of magnesia.
  • the upper setter may have a porous structure, a honeycomb structure, or a dense structure. If the upper setter is dense, the pores in the sintered plate tend to be small and the number of pores tends to be large.
  • the excess lithium source-containing green sheet preferably has a molar ratio (Li/Co ratio) of the Li content in the excess lithium source-containing green sheet to the Co content in the lithium composite oxide-containing green sheet. It is preferably used by being cut into a size of 1 or more, more preferably 0.1 to 1.1.
  • the green sheet may optionally be degreased and then calcined at 600 to 850° C. for 1 to 10 hours.
  • an excess lithium source-containing green sheet for example, a Li2CO3 green sheet
  • an upper setter may be sequentially placed on the obtained calcined plate.
  • heat treatment at a firing temperature in a medium temperature range (for example, 700 to 1000 ° C.) is performed to obtain a lithium composite oxide.
  • a sintered plate is obtained.
  • This firing step may be performed in two steps or in one step.
  • the first baking temperature is preferably lower than the second baking temperature.
  • the sintered plate thus obtained is also an independent sheet.
  • the titanium-containing sintered body plate which is a preferred form of the negative electrode layer 16, may be manufactured by any method.
  • the LTO sintered plate is preferably produced through (a) preparation of an LTO-containing green sheet and (b) firing of the LTO-containing green sheet.
  • a raw material powder (LTO powder) composed of lithium titanate Li 4 Ti 5 O 12 is prepared.
  • a commercially available LTO powder may be used as the raw material powder, or a new one may be synthesized.
  • a powder obtained by hydrolyzing a mixture of titanium tetraisopropoxyalcohol and isopropoxylithium may be used, or a mixture containing lithium carbonate, titania, etc. may be fired.
  • the volume-based D50 particle size of the raw material powder is preferably 0.05 to 5.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m. If the particle size of the raw material powder is large, the pores tend to be large.
  • pulverization treatment for example, pot mill pulverization, bead mill pulverization, jet mill pulverization, etc.
  • the raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • a lithium compound other than LiMO 2 for example, lithium carbonate
  • the slurry is preferably stirred under reduced pressure to remove air bubbles and adjusted to have a viscosity of 4,000 to 10,000 cP.
  • the resulting slurry is formed into a sheet to obtain an LTO-containing green sheet.
  • the green sheet thus obtained is an independent sheet-like compact.
  • An independent sheet (sometimes referred to as a "self-supporting film") refers to a sheet that can be handled independently from other supports (including flakes with an aspect ratio of 5 or more). That is, the independent sheet does not include a sheet fixed to another support (substrate or the like) and integrated with the support (it cannot be separated or becomes difficult to separate).
  • Sheet molding can be performed by various known methods, but is preferably performed by a doctor blade method.
  • the thickness of the LTO-containing green sheet may be appropriately set so as to have the desired thickness as described above after firing.
  • (b) Firing of LTO-containing green sheet An LTO-containing green sheet is placed on a setter.
  • the setter is made of ceramics, preferably zirconia or magnesia.
  • the setter is preferably embossed.
  • the green sheet thus placed on the setter is put into a sheath.
  • the sheath is also made of ceramics, preferably alumina.
  • the LTO sintered body plate is obtained by sintering after degreasing if desired. This firing is preferably carried out at 600-900° C. for 1-50 hours, more preferably at 700-800° C. for 3-20 hours.
  • the sintered plate thus obtained is also an independent sheet.
  • the heating rate during firing is preferably 100 to 1000° C./h, more preferably 100 to 600° C./h.
  • this rate of temperature increase is preferably employed in the process of increasing temperature from 300°C to 800°C, more preferably in the process of increasing temperature from 400°C to 800°C.
  • An LTO sintered plate can be preferably produced as described above. In this preferred production method, it is effective to 1) adjust the particle size distribution of the LTO powder and/or 2) change the rate of temperature increase during firing, and these are effective in realizing various characteristics of the LTO sintered plate. It is thought that it contributes to
  • the integrated sintered plate preferably used in the lithium-ion secondary battery of the present invention and having a three-layer configuration of a positive electrode layer, a ceramic separator and a negative electrode layer is entirely covered with a metal oxide layer. preferably.
  • a metal oxide layer By covering the entire sintered body plate with a metal oxide layer, delamination of the sintered body plate due to physical impact during battery assembly can be suppressed, and capacity deterioration due to storage in a charged state can also be prevented. can be suppressed.
  • the coating of the integrally sintered plate with the metal oxide layer may be performed by any method.
  • i) prepare a coating liquid containing a metal compound, and ii) apply iii) the integrated sintered body is taken out and dried, and iv) the integrated sintered body to which the metal compound is attached is subjected to heat treatment to convert the metal compound into a metal oxide. It is preferred to convert and thereby form a metal oxide layer.
  • the coating liquid prepared in i) above is not particularly limited as long as it contains a metal compound capable of forming a metal oxide layer by heat treatment in a solvent (preferably an organic solvent). , Al, Nb and Ti are preferred, more preferably metal alkoxides.
  • metal compounds include metal alkoxides such as zirconium tetra-n-butoxide, magnesium diethoxide, triisopropoxy aluminum, niobium pentaethoxide and titanium tetraisopropoxide.
  • the integrated sintered plate immersed in the coating liquid in ii) above is placed in a vacuum or reduced pressure atmosphere so that the coating liquid can sufficiently and efficiently penetrate into the interior of the integrated sintered plate. Therefore, it is preferable.
  • the drying in iii) above may be performed at room temperature, but may be performed with heating.
  • the heat treatment in iv) above is preferably carried out at 300 to 700° C. for 2 to 24 hours, more preferably at 350 to 550° C. for 4 to 6 hours. In this way, an integrally sintered plate entirely coated with a metal oxide layer is obtained.
  • Example 1 Preparation and evaluation of a coin-shaped lithium ion secondary battery for reflow soldering were prepared as follows.
  • LCO green sheet positive electrode green sheet
  • Co 3 O 4 powder manufactured by Coremax
  • Li 2 CO 3 powder Li 2 CO 3 powder
  • An LCO slurry was prepared by stirring the obtained mixture under reduced pressure to remove air bubbles and adjusting the viscosity to 4000 cP. Viscosity was measured with a Brookfield LVT viscometer. The slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an LCO green sheet. The thickness of the LCO green sheet was set to 100 ⁇ m after firing.
  • LTO green sheet negative electrode green sheet
  • LTO powder volume-based D50 particle size 0.06 ⁇ m, manufactured by Sigma-Aldrich Japan LLC
  • 20 parts by weight of a binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • 4 parts by weight of a plasticizer DOP: Di (2-ethylhexyl) phthalate, manufactured by Kurogane Kasei Co., Ltd.
  • a dispersing agent product name: Rheodol SP-O30, manufactured by Kao Corporation
  • An LTO slurry was prepared by stirring the obtained negative electrode raw material mixture under reduced pressure to remove air bubbles and adjusting the viscosity to 4000 cP. Viscosity was measured with a Brookfield LVT viscometer. The slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an LTO green sheet. The thickness of the LTO green sheet was set to 100 ⁇ m after firing.
  • MgO green sheet (separator green sheet)
  • Magnesium carbonate powder manufactured by Kamishima Chemical Co., Ltd.
  • the obtained MgO powder and glass frit (CK0199 manufactured by Nippon Frit Co., Ltd.) were mixed at a weight ratio of 4:1.
  • a slurry was prepared by stirring the obtained raw material mixture under reduced pressure to remove air bubbles and adjusting the viscosity to 4000 cP. Viscosity was measured with a Brookfield LVT viscometer. The slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form a separator green sheet. The thickness of the separator green sheet was set to 25 ⁇ m after firing.
  • the integrated sintered body plate was taken out on a non-woven fabric wiper with tweezers, and after lightly wiping off the coating liquid, it was dried at room temperature for 2 hours.
  • the dried integrated sintered plate was placed on an alumina setter and heat-treated at 400° C. for 5 hours in a medium-sized superkanthal furnace (manufactured by Kyowa Konetsu Kogyo Co., Ltd.).
  • a metal oxide layer a layer composed of an oxide of Zr or a composite oxide of Zr and Li
  • a liquid obtained by dissolving LiBF 4 to a concentration of 1.5 mol/L was used as the solvent, and 1171G manufactured by ThreeBond Co., Ltd. was applied as a sealing material for the gaskets.
  • the thickness of the shim attached to the knockout pin that pushes the negative electrode can (hereinafter referred to as the knockout shim) is 0 mm, and the thickness of the shim on the positive electrode can side is 50 ⁇ m. gone.
  • ⁇ Battery outer diameter> The external dimensions of the battery were measured using an image size measuring instrument (IM7000 manufactured by KEYENCE CORPORATION) to determine the external diameter of the battery.
  • ⁇ Battery thickness and battery swelling ratio> Using a laser displacement gauge (SI series manufactured by Keyence Corporation), the thickness of the battery in the main region (that is, the region where the three layers of positive electrode layer/separator/negative electrode layer overlap) was measured for two straight lines perpendicular to the center of the battery. . At this time, the minimum value and maximum value of the battery thickness in the main region were measured for each straight line. The average value of the obtained maximum values was taken as the battery thickness. For each straight line, a value was obtained by dividing the maximum value of battery thickness by the minimum value of battery thickness, and the average value of the values obtained for the two straight lines was taken as the battery swelling ratio.
  • the battery was mounted on the substrate by reflow soldering with a maximum temperature of 260°C.
  • the battery mounted on the substrate was charged at a constant voltage (CV) of 2.7 V at 25° C. and then discharged at 0.5 mA.
  • CV constant voltage
  • ii) repeating a 1 second discharge at 20 mA followed by a 2 second discharge rest for a total of 400 times; A total of 100 cycles including the above (that is, the above i) and ii) were performed as one cycle).
  • the battery was again charged at a constant voltage (CV) of 2.7 V at 25° C. and then discharged at 0.5 mA.
  • the value obtained by dividing the post-deterioration capacity by the initial capacity and multiplying by 100 exceeded 95%, it was judged as acceptable, and when it was not, it was judged as unacceptable.
  • Example 2 A battery was fabricated and evaluated in the same manner as in Example 1, except that the thickness of the knockout shim for pressing the negative electrode can was 1 mm and the thickness of the shim on the positive electrode can side was 50 ⁇ m as crimping conditions.
  • Example 3 A battery was fabricated and evaluated in the same manner as in Example 1, except that the thickness of the knockout shim for pressing the negative electrode can was set to 2 mm and the thickness of the shim on the positive electrode can side was set to 0 ⁇ m as crimping conditions.
  • Example 4 A battery was fabricated and evaluated in the same manner as in Example 1 except that the thickness of the knockout shim for pressing the negative electrode can was 3 mm and the thickness of the shim on the positive electrode can side was 0 ⁇ m as the caulking conditions.
  • example 5 A battery was prepared and evaluated in the same manner as in Example 1 except for the following a) to c). a) Five LCO green sheets (positive electrode green sheets), four MgO green sheets (separator green sheets) and four LTO green sheets (negative electrode green sheets) were used in the lamination pressure bonding process, and the punching diameter of the laminate was 16.5 mm. made it b) The outer can of the battery had an outer diameter of 20 mm and a thickness of 1.6 mm. c) As crimping conditions, the thickness of the knockout shim for pressing the negative electrode can was set to 2 mm, and the thickness of the shim on the positive electrode can side was set to 0 ⁇ m.
  • Example 6 (Comparison) A battery was fabricated and evaluated in the same manner as in Example 1 except that the thickness of the knockout shim for pressing the negative electrode can was 0 mm and the thickness of the shim on the positive electrode can side was 100 ⁇ m as the caulking conditions.
  • Example 7 (Comparison) A battery was fabricated and evaluated in the same manner as in Example 1 except that the thickness of the knockout shim for pressing the negative electrode can was 4 mm and the thickness of the shim on the positive electrode can side was 0 ⁇ m as crimping conditions.

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PCT/JP2021/042442 2021-03-30 2021-11-18 コイン形リチウムイオン二次電池 Ceased WO2022208982A1 (ja)

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CN202180095658.3A CN117296181A (zh) 2021-03-30 2021-11-18 纽扣型锂离子二次电池
EP21935136.8A EP4318638A4 (en) 2021-03-30 2021-11-18 COIN TYPE LITHIUM-ION SECONDARY BATTERY
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JP2012209178A (ja) 2011-03-30 2012-10-25 Panasonic Corp コイン形電池
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JP2008084752A (ja) * 2006-09-28 2008-04-10 Sanyo Electric Co Ltd コイン型電池
JP2008123875A (ja) * 2006-11-14 2008-05-29 Nec Tokin Corp コイン型電気化学素子
JP2012209178A (ja) 2011-03-30 2012-10-25 Panasonic Corp コイン形電池
WO2019221139A1 (ja) 2018-05-17 2019-11-21 日本碍子株式会社 コイン形リチウム二次電池及びＩｏＴデバイス
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WO2026014124A1 (ja) * 2024-07-08 2026-01-15 株式会社村田製作所 正極、二次電池および正極の製造方法

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