WO2023063360A1 - リチウム二次電池 - Google Patents

リチウム二次電池 Download PDF

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Publication number
WO2023063360A1
WO2023063360A1 PCT/JP2022/038073 JP2022038073W WO2023063360A1 WO 2023063360 A1 WO2023063360 A1 WO 2023063360A1 JP 2022038073 W JP2022038073 W JP 2022038073W WO 2023063360 A1 WO2023063360 A1 WO 2023063360A1
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WO
WIPO (PCT)
Prior art keywords
negative electrode
positive electrode
layer
laminate
width
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Ceased
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PCT/JP2022/038073
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English (en)
French (fr)
Japanese (ja)
Inventor
憲吾 大石
茂樹 岡田
健 嶋岡
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2023554585A priority Critical patent/JP7751651B2/ja
Publication of WO2023063360A1 publication Critical patent/WO2023063360A1/ja
Priority to US18/632,396 priority patent/US20240291041A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • 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

  • Patent Literature 1 discloses a lithium secondary battery in which a positive electrode layer, a ceramic separator and a negative electrode layer are composed of an integrally bonded sintered plate and impregnated with an electrolytic solution.
  • the separator of the lithium secondary battery disclosed in Patent Document 1 is a ceramic separator composed of MgO and glass.
  • Patent Document 2 discloses an all-solid battery having a laminate in which a plurality of positive electrode layers and negative electrode layers are alternately laminated via solid electrolyte layers.
  • side margin layers are provided on the outer peripheral sides of the positive electrode layer and the negative electrode layer, respectively.
  • the side margin layers are made of the same material as the solid electrolyte layer.
  • one of the objects of the invention according to the present disclosure is to provide a lithium secondary battery that has a large discharge capacity and high rate characteristics even when discharging at a large current and at a high speed.
  • a lithium secondary battery includes a plurality of positive electrode layers, a plurality of negative electrode layers, and a plurality of separators, and the positive electrode layers and the negative electrode layers are alternately laminated with the separators interposed therebetween. and a laminate.
  • the laminate includes a first insulating layer and a second insulating layer.
  • the first insulating layer is provided in contact with the positive electrode layer at a first end portion in the width direction of each of the positive electrode layers.
  • the second insulating layer is provided in contact with the negative electrode layer at a second widthwise end portion of each of the negative electrode layers located opposite to the first end portion in the widthwise direction.
  • lithium secondary battery it is possible to provide a lithium secondary battery that has a large discharge capacity and high rate characteristics even when discharging at high current and high speed.
  • FIG. 1 is a schematic cross-sectional perspective view showing a stack of lithium secondary batteries according to the present disclosure.
  • FIG. 2 is a schematic diagram showing how sheets are stacked to form a laminate of a lithium secondary battery according to the present disclosure.
  • FIG. 3 is a schematic diagram showing cutting positions of the green sheet laminate shown in FIG.
  • FIG. 4 is a schematic diagram showing a state in which a current collector is added to the laminate shown in FIG.
  • FIG. 5 is a schematic cross-sectional schematic diagram showing a lithium secondary battery according to the present disclosure.
  • FIG. 6 is a schematic diagram showing a lamination state of various green sheets for producing a laminate included in the lithium secondary battery of Example 1.
  • FIG. FIG. 7 is a schematic perspective view showing a stack of lithium secondary batteries according to the present disclosure.
  • the lithium secondary battery of the present disclosure includes a plurality of positive electrode layers, a plurality of negative electrode layers, and a plurality of separators, and the positive electrode layers and the negative electrode layers are alternately laminated with the separators interposed.
  • the laminate includes a first insulating layer and a second insulating layer.
  • the first insulating layer is provided in contact with the positive electrode layer at a first end portion in the width direction of each of the positive electrode layers.
  • the second insulating layer is provided in contact with the negative electrode layer at a second widthwise end portion of each of the negative electrode layers located opposite to the first end portion in the widthwise direction.
  • lithium secondary batteries that include a plurality of positive electrode layers and a plurality of negative electrode layers, and in which a plurality of cells are configured within one electrode (for example, Patent Document 2).
  • Patent Document 2 In the laminated body of Patent Document 2, side margin layers are provided on the outer peripheral sides of the positive electrode layer and the negative electrode layer, respectively. The side margin layer is provided to eliminate a step between the solid electrolyte layer and the positive electrode layer or the negative electrode layer.
  • Patent Literature 2 describes that the side margin layer increases the density of the solid electrolyte layer and the electrode layer, and prevents delamination and warping due to firing of the all-solid-state battery.
  • lithium secondary batteries that are small, have a large capacity, and maintain their discharge capacity even when discharged at a large current.
  • An electrode with a laminated structure that includes a plurality of cells may provide a battery with a small size and a large capacity.
  • the inventors have found that it is difficult to maintain the rate characteristics even during discharge at a large current while maintaining the capacity when an electrode having a laminated structure is employed.
  • the inventors focused on the width of the insulating layer provided at the end of the positive electrode layer and the negative electrode layer in the electrode having a laminated structure, and by controlling this, it is possible to achieve both capacity and rate characteristics. It has been found that a superior lithium secondary battery can be obtained.
  • the lithium secondary battery according to the present disclosure includes a plurality of positive electrode layers, a plurality of negative electrode layers, and a plurality of separators, and the positive electrode layers and the negative electrode layers are alternately arranged with the separators interposed therebetween.
  • An electrode is provided that includes a stack of laminates. Insulating layers are provided next to the positive electrode layer and the negative electrode layer so as to be arranged side by side.
  • the average width wave of the insulating layers with respect to the outer dimension width W of the laminate is It ranges from 0.8 to 40%. Although it is not bound by any particular theory, it is believed that this range reduces the volume resistivity, and thus achieves both capacity and rate characteristics.
  • an average absolute value of a difference between the width of each of the first insulating layer and the second insulating layer and the wave is taken as an average ws of variations in insulating layer width. Then, (w s /w ave ) ⁇ 100 ⁇ 20(%). Within this range, a lithium secondary battery with particularly high rate characteristics can be obtained.
  • the positive electrode layer, the negative electrode layer, the separator, the first insulating layer and the second insulating layer may be an integrally sintered body.
  • the lithium secondary battery further comprises: an exterior body including a positive electrode can and a negative electrode can; a first current collector interposed between the positive electrode can and the positive electrode layer; and the negative electrode can and the negative electrode. and a second current collector interposed between the layers.
  • the first current collector extends from a first side surface of the laminated body where the positive electrode layer is exposed to a surface of the upper or lower surface of the laminated body that is closer to the positive electrode can. shall and can.
  • the second current collector extends from a second side surface of the laminate where the negative electrode layer is exposed to a surface of a top surface or a bottom surface of the laminate that is closer to the negative electrode can. shall and can.
  • the so-called coin-type battery can ensure electrical connection between the electrode, which is a thin laminate including a plurality of positive electrodes and a plurality of negative electrodes, and the outside of the battery.
  • the negative electrode layer includes a current collector layer provided inside the negative electrode layer in the thickness direction
  • the positive electrode layer includes a current collector layer provided inside the negative electrode layer in the thickness direction. It may be nothing. With such a configuration, the internal resistance of the battery can be reduced, current collection at the negative electrode can be ensured, and the positive electrode having a low volume resistivity does not include a current collector layer, thereby reducing the number of constituent members in the laminate.
  • FIG. 5 is a schematic cross-sectional view showing the structure of a lithium secondary battery 10 that is one embodiment according to the present disclosure.
  • members of the same kind are indicated by hatching of the same kind, and the display of reference numerals is partly omitted. The same applies to other figures.
  • lithium secondary battery 10 includes a plurality of positive electrode layers 12 , a plurality of negative electrode layers 16 , and a plurality of separators 20 laminated inside outer package 24 .
  • an electrolytic solution 22 is sealed inside the exterior body 24 .
  • the positive electrode layer 12 is composed of, for example, a sintered body containing lithium cobaltate.
  • the negative electrode layer 16 is composed of, for example, a titanium-containing sintered body.
  • the separator 20 is made of ceramic and interposed between the positive electrode layer 12 and the negative electrode layer 16 .
  • a first insulating layer 11 a is provided in contact with the positive electrode layer 12 at one end in the width direction of the positive electrode layer 12 .
  • a second insulating layer 11b is provided in contact with the negative electrode layer 16 at one end in the width direction of the negative electrode layer 16 and opposite to the end where the first insulating layer 11a is provided. It is
  • 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 housed in this closed space. Electrolyte solution 22 is impregnated into positive electrode layer 12 , negative electrode layer 16 and separator 20 .
  • the positive electrode layer 12, the separator 20, the negative electrode layer 16, and the insulating layers 11a and 11b are one integrated sintered body. That is, the positive electrode layer 12, the separator 20, the negative electrode layer 16 and the insulating layers 11a and 11b are bonded to each other.
  • the term “integrated sintered body” means that each member constituting the sintered body is connected and bonded to each other without relying on a bonding method other than sintering (for example, an adhesive).
  • the positive electrode layer 12 and the separator 20 may form an integrally sintered body, and the negative electrode layer 16 may be a sintered body formed separately from the integrally fired body.
  • the exterior body 24 may be appropriately selected according to the type of the lithium secondary battery 10.
  • the outer package 24 typically includes a positive electrode can 24a, a negative electrode can 24b and a gasket 24c.
  • the positive electrode can 24a and the negative electrode can 24b are crimped via a gasket 24c to form a closed 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 can be an annular member made of insulating resin such as polypropylene, polytetrafluoroethylene, PFA resin, etc., and is not particularly limited.
  • the lithium secondary battery 10 shown in FIG. 5 is in the form of a coin-shaped battery
  • the form of the lithium secondary battery according to the present disclosure is not limited to this.
  • other forms such as a thin secondary battery including a chip-type secondary battery and a pouch-type secondary battery may be used.
  • the lithium secondary battery is a chip battery that can be built into a card
  • the exterior body is made of a base material made of resin
  • the battery elements that is, the positive electrode layer 12, the negative electrode layer 16, the separator 20, and the electrolyte 22
  • the battery element may be sandwiched between a pair of resin films.
  • the pair of resin films may be bonded together with an adhesive. Also, the pair of resin films may be heat-sealed to each other by hot pressing. Furthermore, a separator made of a solid electrolyte may be used as the separator, and the configuration may be such that the separator does not contain an electrolytic solution.
  • lithium secondary battery 10 includes positive electrode current collector 14 extending from the side surface to the bottom surface of the laminated structure.
  • the lithium secondary battery 10 also includes a negative electrode current collector 18 extending from the side surface to the upper surface of the laminated structure.
  • the positive electrode current collector 14 and the negative electrode current collector 18 may be, for example, metal foils such as copper foil and aluminum foil.
  • the positive electrode current collector 14 is preferably arranged between the positive electrode layer 12 and the outer package 24 (for example, the positive electrode can 24a).
  • the negative electrode current collector 18 is preferably arranged between the negative electrode layer 16 and the outer package 24 (for example, the negative electrode can 24b).
  • a positive electrode-side carbon layer (not shown) is preferably provided between the positive electrode layer 12 and the positive electrode current collector 14 .
  • a negative electrode-side carbon layer (not shown) is preferably provided between the negative electrode layer 16 and the negative electrode current collector 18 from the viewpoint of reducing contact resistance.
  • Both the positive electrode-side carbon layer and the negative electrode-side carbon layer are preferably made of conductive carbon.
  • a carbon layer can be formed, for example, by applying a conductive carbon paste to the surface of a metal foil used as a current collector.
  • FIG. 1 is a schematic cross-sectional perspective view showing a laminate 1 included in a lithium secondary battery according to the present disclosure.
  • laminate 1 is a laminate in which a large number of layers are laminated.
  • the laminated body 1 has a rectangular parallelepiped shape whose outer shape is defined by an outer dimension width (W), an outer dimension depth (D), and an outer dimension thickness (T).
  • W outer dimension width
  • D outer dimension depth
  • T outer dimension thickness
  • a rectangular parallelepiped does not mean only a rectangular parallelepiped in a mathematically precise sense, but also includes a three-dimensional structure having a shape similar to a rectangular parallelepiped for design and manufacturing reasons.
  • Each layer constituting the laminate 1 has a rectangular plate shape.
  • the direction parallel to the X-axis shown in FIG. 1 is called the width direction
  • the direction parallel to the Y-axis is called the depth direction
  • the direction parallel to the Z-axis is called the height direction.
  • the surfaces of the laminated body 1 where all the laminated layers are exposed are referred to as the front surface and the rear surface.
  • the front and back surfaces are planes parallel to the XZ plane.
  • the surface where the laminate structure is exposed, the surface extending between the front surface and the rear surface, and extending along the depth direction is referred to as a side surface.
  • a plurality of positive electrode layers 12 and a plurality of negative electrode layers 16 are alternately laminated.
  • a separator 20 is interposed between the positive electrode layer 12 and the negative electrode layer 16 .
  • the separator 20 extends over the entire outer dimension width W of the laminate 1 .
  • the widths of the positive electrode layer 12 and the negative electrode layer 16 are smaller than the outer dimension width W of the laminate 1 .
  • the positive electrode layer 12 and the negative electrode layer 16 are exposed only on one side of the laminate 1 .
  • the positive electrode layer 12 is exposed on the first side surface s1 of the stacked body 1 in the width direction of the stacked body 1, and extends from the side surface s1 to the end portion 12e as the first end portion of the positive electrode layer 12.
  • An insulating layer 11a as a first insulating layer is provided along with the positive electrode layer 12 in contact with the end portion 12e of the positive electrode layer 12 .
  • the negative electrode layer 16 is exposed on the second side surface s2 of the layered product 1 in the width direction of the layered product 1 and extends from the side surface s2 to an end portion 16e as a second end portion of the negative electrode layer 16 .
  • An insulating layer 11 b as a second insulating layer is provided along with the negative electrode layer 16 in contact with the end portion 16 e of the negative electrode layer 16 .
  • the positive electrode layer 12 On the first side surface s1 of the laminate 1, the positive electrode layer 12, the separator 20 and the second insulating layer 11b are exposed, and the negative electrode layer 16 is not exposed. Similarly, on the second side surface s2 of the laminate 1, the negative electrode layer 16, the separator 20 and the first insulating layer 11a are exposed, and the positive electrode layer 12 is not exposed. According to this configuration, by arranging the positive electrode current collector 14 (FIG. 5) on the first side surface s1 and the negative electrode current collector 18 (FIG. 5) on the second side surface s2, a compact lithium secondary battery can be obtained. It is possible to construct an electrode that efficiently extracts electricity from a secondary battery.
  • the laminate 1 of FIG. 1 includes three first insulating layers 11a and three second insulating layers 11b. That is, the laminate 1 includes six insulating layers 11a and 11b.
  • the insulating layers 11a, 11b have a width w. Since FIG. 1 is a schematic diagram, all the six insulating layers 11a and 11b have the same width w, but the width w of each insulating layer varies depending on design and manufacturing factors. Sometimes. Also, the width of the insulating layer may vary depending on the position of the insulating layer.
  • the average value of the widths w of all the insulating layers included in the laminate is assumed to be the insulating layer width average wave .
  • the average value of the widths w of the six insulating layers is the insulating layer width average wave .
  • the width w of the insulating layer is equal to the average insulating layer width wave .
  • Both the uppermost layer and the lowermost layer in the laminate 1 are composed of separators 20 .
  • the positive electrode layer 12 and the negative electrode layer 16 facing each other with the separator 20 interposed therebetween form one cell.
  • Five cells are formed in the laminate 1 of FIG.
  • the number of cells in the laminate is not limited as long as the effect of the invention is achieved, but the laminate can have, for example, 3 to 200 cells.
  • the positive electrode layer 12, the negative electrode layer 16, the separator 20, the first insulating layer 11a, and the second insulating layer 11b may be integrally sintered.
  • the configuration of each layer will be described below.
  • the positive electrode layer 12 is composed of a plate-like sintered body containing lithium cobaltate.
  • the positive electrode layer 12 can be one that does not contain a binder or a conductive aid.
  • Specific examples of lithium cobaltate include LiCoO 2 (hereinafter sometimes abbreviated as LCO).
  • LCO LiCoO 2
  • As the plate-shaped LCO sintered body for example, those disclosed in Japanese Patent No. 5587052 and International Publication No. 2017/146088 can be used.
  • the positive electrode layer 12 is an oriented positive electrode layer that includes a plurality of primary particles composed of lithium cobalt oxide, and the plurality of primary particles are oriented at an average orientation angle of more than 0° and 30° or less with respect to the layer surface of the positive electrode layer. is preferably Examples of the structure, composition, and method for identifying such an oriented positive electrode layer include those disclosed in Patent Document 1 (International Publication No. 2019/221144).
  • Lithium cobalt oxide constituting the primary particles in the positive electrode layer 12 includes, in addition to LCO, Li x NiCoO 2 (nickel-lithium cobalt oxide), Li x CoNiMnO 2 (cobalt-nickel-lithium manganate), and Li x CoMnO. 2 (cobalt-lithium manganate) and the like. Moreover, other lithium composite oxides may be included together with the lithium cobaltate. Lithium composite oxides include, for example, Li x MO 2 (where 0.05 ⁇ x ⁇ 1.10, M is at least one transition metal, M is typically Co, Ni and Mn including one or more of).
  • the average particle size of the plurality of primary particles that constitute the positive electrode layer 12 is preferably 5 ⁇ m or more.
  • the average particle diameter of the primary particles used for calculating 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 positive electrode layer 12 may contain pores. Since the sintered body contains pores, particularly open pores, when it is incorporated in a battery as a positive electrode layer, the electrolyte can permeate the inside of the sintered body, and as a result, the lithium ion conductivity is improved. be able to.
  • the porosity of the positive electrode layer 12 is preferably 20-60%, more preferably 25-55%, even more preferably 30-50%, and particularly preferably 30-45%.
  • the porosity of the sintered body can be measured according to a known method.
  • the average pore diameter of the positive electrode layer 12 is preferably 0.1 to 10.0 ⁇ m, more preferably 0.2 to 5.0 ⁇ m, still more preferably 0.25 to 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. In addition, it is possible to more effectively improve the lithium ion conductivity due to internal permeation of the electrolytic solution through the pores.
  • the thickness of the positive electrode layer 12 in the laminate 1 is not particularly limited, it is preferably, for example, 2 to 80 ⁇ m, more preferably 4 to 60 ⁇ m, still more preferably 10 to 40 ⁇ m. Within such a range, the electronic resistance is suppressed, and the movement resistance of Li ions contained in the electrolytic solution is also suppressed, so that the battery resistance can be reduced.
  • the separator 20 is composed of a ceramic microporous membrane. Separator 20 contains magnesia (MgO). Specifically, for example, it can be made of magnesia (MgO) and glass. In the separator 20, MgO and glass are present in particle form bonded together by sintering. Ceramics contained in the separator 20 may include Al 2 O 3 , ZrO 2 , SiC, Si 3 N 4 , AlN, etc. in addition to MgO and glass.
  • the glass contained in the separator 20 preferably contains 25% by weight or more of SiO 2 , more preferably 30 to 95% by weight, even more preferably 40 to 90% by weight, particularly preferably 50 to 80% by weight.
  • the glass content in the separator 20 is preferably 3 to 70% by weight, more preferably 5 to 50% by weight, still more preferably 10 to 40% by weight, particularly preferably 15% by weight, based on the total weight of the separator 20. ⁇ 30% by weight. Within this range, it is possible to effectively achieve both a high yield and excellent charge-discharge cycle characteristics.
  • the addition of the glass component to the separator 20 is preferably carried out by adding glass frit to the raw material powder of the separator.
  • the glass frit preferably contains at least one of Al 2 O 3 , B 2 O 3 and BaO as components other than SiO 2 .
  • the thickness of the separator 20 in the laminate 1 is not particularly limited, it is preferably about 5 to 50 ⁇ m, more preferably about 10 to 30 ⁇ m.
  • the porosity of the separator 20 is also not particularly limited, but can be, for example, about 30 to 70%, preferably about 40 to 60%.
  • the negative electrode layer 16 is composed of, for example, a plate-like sintered body containing a titanium-containing composition.
  • the negative electrode layer 16 can be one that does not contain a binder or a conductive aid.
  • the titanium-containing sintered body 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 discharging.
  • LTO is not limited to spinel structures.
  • a part of LTO may be substituted with another element.
  • examples of other elements include Nb, Ta, W, Al, Mg, and the like.
  • the LTO sintered body can be produced, for example, according to the method described in JP-A-2015-185337.
  • the negative electrode layer 16 has a structure in which a plurality (that is, a large number) of primary particles are bonded. These primary particles preferably consist of LTO or Nb 2 TiO 7 .
  • the negative electrode layer 16 may be configured as an integral sintered body together with the positive electrode layer 12 and the separator 20 . Further, the negative electrode layer 16 may be formed as a sintered body separate from the integrally sintered body of the positive electrode layer 12 and the separator 20 and then combined.
  • the thickness of the negative electrode layer 16 in the laminate 1 is not particularly limited, it is preferably, for example, 1 to 40 ⁇ m, more preferably 2 to 30 ⁇ m, still more preferably 5 to 20 ⁇ m.
  • the primary particle diameter, which is the average particle diameter of the plurality of primary particles forming the negative electrode layer 16, is preferably 1.2 ⁇ m or less, more preferably 0.02 to 1.2 ⁇ m, and still more preferably 0.05 to 0.7 ⁇ m. be.
  • the negative electrode layer 16 preferably contains pores. By including pores, particularly open pores, the electrolyte can permeate inside when incorporated into a battery as a negative electrode layer, and as a result, the lithium ion conductivity can be improved.
  • the porosity of the negative electrode layer 16 is preferably 20-60%, more preferably 30-55%, still more preferably 35-50%.
  • the average pore size of the negative electrode layer 16 is preferably 0.08-5.0 ⁇ m, more preferably 0.1-3.0 ⁇ m, and still more preferably 0.12-1.5 ⁇ m.
  • the negative electrode layer 16 may contain the current collector layer 19 .
  • the current collector layer 19 may be provided inside the negative electrode layer 16 in the thickness direction. Alternatively, it may be formed so as to be exposed on one of the main surfaces of the negative electrode layer 16 .
  • the current collector layer 19 can be made of a material with excellent conductivity.
  • the current collector layer 19 may be made of gold, silver, platinum, palladium, aluminum, copper, nickel, or the like, for example. By including the current collector layer 19, the internal resistance of the laminate, particularly in the negative electrode, can be reduced.
  • the insulating layers 11a and 11b are composed of ceramic microporous membranes.
  • the insulating layers 11a and 11b contain magnesia (MgO). Specifically, for example, it can be composed of magnesia (MgO) and TiO 2 .
  • MgO and TiO 2 are present in the form of particles bonded together by sintering.
  • the ceramic contained in the insulating layers 11a and 11b may contain Al2O3 , ZrO2 , SiC , Si3N4 , AlN, etc. in addition to MgO and TiO2 .
  • the insulating layers 11a and 11b may be layers having the same composition. Also, the insulating layers 11a and 11b and the separator 20 may be made of materials having the same composition.
  • the thickness of the insulating layers 11a and 11b in the laminate 1 is not particularly limited.
  • the thickness of the insulating layers 11a and 11b is preferably the same as that of the positive electrode layer 12 or the negative electrode layer 16 arranged side by side with the insulating layers 11a and 11b.
  • the porosity of the insulating layers 11a and 11b is also not particularly limited. For example, it can be about 20 to 70%, preferably about 30 to 60%.
  • FIG. 7 shows a schematic perspective view of a laminate 91 according to the second embodiment.
  • 7A is a perspective view showing the appearance of the laminate 91
  • FIG. 7B is a schematic diagram showing the lamination structure inside the laminate 91.
  • the shape of the laminate is not limited to a rectangular parallelepiped shape.
  • the cross-sectional shape perpendicular to the lamination direction has a shape obtained by cutting a part of a circle. More specifically, the laminate 91 is composed of two sides whose cross-sectional shape perpendicular to the stacking direction is two parallel straight lines and two arcs connecting the ends of the two sides. be done.
  • the laminated body 91 has a part of the cylinder cut away parallel to the tangential line, and the side surfaces of the cylinder are formed with a first side surface s5 and a second side surface s6, which are two opposing planes. shape. This shape is called "round".
  • the surfaces of s7 and s8, which are arc-shaped side surfaces of the laminate 91, are entirely composed of separators 920. As shown in FIG.
  • the positive electrode layer 912, the separator 920 and the second insulating layer 911b are exposed on the first side surface s5, and the negative electrode layer 916 is not exposed. Since the separator 120 and the second insulating layer 911b have the same composition and become an integral layer after firing, they are expressed as an integral layer in FIG. 7(a). Also, the negative electrode layer 916, the separator 920 and the first insulating layer 911a are exposed on the second side surface s6, and the positive electrode layer 916 is not exposed.
  • a first insulating layer 911 a provided in contact with the positive electrode layer 912 is provided at an end portion in the width direction of the positive electrode layer 912 .
  • the width w of the first insulating layer 911a is the length from the end in the width direction (X-axis direction) of the positive electrode layer 912 to the side surface s6.
  • the width w of the second insulating layer 911b is the length from the end in the width direction (X-axis direction) of the negative electrode layer 916 to the side surface s5. That is, when the laminate 91 has a round shape, the outer dimension width W of the laminate, the first insulating layer and the second insulating A layer width w is defined.
  • a cross section AA is a cross section along the width direction (X-axis direction) of the laminate 91 .
  • FIG. 2 is a schematic diagram showing a state in which sheets are stacked to form a laminate.
  • FIG. 3 is a schematic diagram showing cutting positions of the sheet laminate shown in FIG.
  • FIG. 4 is a schematic diagram showing a state in which a positive electrode current collector and a negative electrode current collector are added to the obtained laminate.
  • a positive electrode green sheet 112 a negative electrode green sheet 116, a separator green sheet 120, a first insulating layer green sheet (positive electrode side green sheet) 111a, and a second insulating layer, which are materials constituting the laminate.
  • the green sheets (negative electrode side green sheets) 111b are separately prepared.
  • a green sheet can be prepared by first preparing a slurry containing raw materials for forming each layer, and then forming the prepared slurry into a sheet on a resin film.
  • a current collector layer 119 may be formed on one of the main surfaces of the negative electrode green sheet 116 . Each sheet cut into a predetermined width is stacked in order so as to form a predetermined layer structure.
  • the positive electrode green sheet 112 and the first insulating layer green sheet (positive electrode side green sheet) 111a are arranged adjacent to each other to form a single layer.
  • the negative electrode green sheet 116 and the second insulating layer green sheet (negative electrode side green sheet) 111b are arranged adjacent to each other to form a single layer.
  • the separator green sheet 120 is arranged to form a single layer over the entire width direction.
  • the positive electrode green sheet 112 and the first insulating layer green sheet 111a may be used singly in the thickness direction, or two or more sheets of the same kind may be continuously stacked in the thickness direction.
  • the negative electrode green sheet 116 and the second insulating layer green sheet 111b may be used singly in the thickness direction, or two or more sheets of the same kind may be continuously stacked in the thickness direction.
  • the stacked sheets are integrated in the sintering step, so that the sintered body becomes one layer.
  • two negative electrode green sheets 116 having current collector layers 119 are stacked, it is preferable to stack the current collector layers 119 so that they are in contact with each other.
  • the green sheet laminate can be crimped between the green sheets by pressing.
  • the pressing method may be, for example, cold isostatic pressing (CIP), hot water isostatic pressing (WIP), isostatic pressing, or the like, and is not particularly limited. Pressing may be performed while heating.
  • the green sheet laminate may be cut on both side surfaces so as to have a predetermined width, and cut perpendicularly to the length direction so as to obtain a laminate having a predetermined depth. .
  • the lamination form and cutting points may be set.
  • FIG. 3 simply shows the layer structure, the negative electrode green sheet 116 and the second insulating layer green sheet 111b, the separator green sheet 120, the positive electrode green sheet 112 and the first insulating layer green sheet 111a,
  • the unit U including the separator green sheets 120 in this order may be repeatedly laminated to form a multi-layer laminate.
  • the green sheet laminate cut into a predetermined shape is degreased and sintered to obtain a laminate that is a laminated integrally sintered body.
  • Degreasing and baking can be carried out under known conditions and methods.
  • the thickness and width of each layer in the obtained laminated integrally sintered body can be confirmed, for example, by polishing the laminated integrally sintered body with a cross section polisher and observing the obtained cross section with an SEM.
  • a current collector is attached to both sides of the laminated integrally sintered body.
  • the positive electrode current collector 14 is attached to the side surface where the positive electrode layer 12 is exposed
  • the negative electrode current collector 18 is attached to the side surface where the negative electrode layer 16 is exposed.
  • a conductive material can be used for the positive electrode current collector 14 and the negative electrode current collector 18, and for example, aluminum foil, copper foil, or the like may be used.
  • the positive electrode current collector 14 is attached so as to cover one entire side surface of the laminate 1 , and can extend to the lower surface of the laminate 1 .
  • the negative electrode current collector 18 is attached so as to cover the entire other side surface of the laminate 1 , and can extend over the upper surface of the laminate 1 .
  • a conductive adhesive can be used to bond between the positive electrode layer 12 and the positive electrode current collector 14 and between the negative electrode layer 16 and the negative electrode current collector 18 .
  • a conductive carbon paste can be used as the conductive adhesive.
  • the thickness of the conductive adhesive layer is not particularly limited as long as it exhibits an effect as an adhesive layer and does not interfere with the effects of the invention, but can be, for example, about 1 to 500 ⁇ m.
  • a lithium secondary battery can be obtained by housing the electrode obtained by the above-described manufacturing method inside an exterior body using a known method and conditions, and encapsulating an electrolytic solution.
  • the width, depth, and height of the laminated body which is a laminated integrally sintered body, can be appropriately selected according to the desired shape of the lithium secondary battery, and are not particularly limited.
  • the laminate when constructing a coin-type battery, can have a width of about 3 to 18 mm, a depth of about 3 to 18 mm, and a height of about 0.3 to 5 mm. 3 to 200 cells can be configured in this stack.
  • lithium secondary battery 10 may include electrolyte solution 22 .
  • the electrolytic solution 22 is not particularly limited, and an electrolytic solution known as an electrolytic solution for lithium secondary batteries can be used.
  • the solvent may be one or two selected from ethylene carbonate (EC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene carbonate (PC) and ⁇ -butyrolactone (GBL). Combinations of species or more can be used.
  • the electrolytic solution 22 further contains at least one selected from vinylene carbonate (VC), fluoroethylene carbonate (FEC), vinylethylene carbonate (VEC), and lithium difluoro(oxalato)borate (LiDFOB) as an additive.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • VEC vinylethylene carbonate
  • LiDFOB lithium difluoro(oxalato)borate
  • the electrolyte 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. is 0.8 to 1.5 mol/L.
  • the electrolyte a solid electrolyte or a polymer electrolyte can be used in addition to the electrolytic solution 22 .
  • the electrolyte it is preferable that at least the inside of the pores of the separator 20 is impregnated with the electrolyte, as in the case of the electrolytic solution 22 .
  • the impregnation method is not particularly limited, but examples thereof include a method of melting the electrolyte and infiltrating into the pores of the separator 20 and a method of pressing the compacted powder of the electrolyte against the separator 20 .
  • Example 1 A lithium secondary battery was produced according to the methods described in 1 to 7 below. The obtained lithium secondary battery was evaluated by the methods described in 8 and 9.
  • 8 parts by weight of a binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • a plasticizer 2 parts by weight of (DOP: Di(2-ethylhexyl) phthalate, manufactured by Kurogane Kasei Co., Ltd.) and 4.5 parts by weight of a dispersant (product name: Rhodol SP-O30, manufactured by Kao Corporation) were mixed.
  • An LCO slurry was prepared by stirring the obtained mixture under reduced pressure to remove air bubbles and adjusting the viscosity to 4000 cP.
  • An LCO green sheet was formed by sheet-forming the prepared slurry on a PET film. The thickness of the LCO layer after firing was adjusted to 12 ⁇ m.
  • LTO green sheet negative electrode green sheet
  • LTO powder volume-based D50 particle size 0.06 ⁇ m, manufactured by Sigma-Aldrich Japan LLC
  • binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • plasticizer DOP: Di (2-ethylhexyl) phthalate, manufactured by Kurogane Kasei Co., Ltd.
  • a dispersant 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.
  • An LTO green sheet was formed by forming the prepared slurry into a sheet on a PET film. The thickness of the LTO layer after firing was adjusted to 10 ⁇ m.
  • 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.
  • a separator green sheet was formed by forming the prepared slurry into a sheet on a PET film. The thickness of the separator layer after baking was set to 25 ⁇ m.
  • a binder polyvinyl butyral: product number BM-2, Sekisui Chemical Co., Ltd. Co., Ltd.
  • a plasticizer DOP: Di (2-e
  • 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.
  • a first insulating layer green sheet was formed by forming the prepared slurry into a sheet on a PET film. The thickness of the first insulating layer after firing was set to 12 ⁇ m.
  • Second insulating layer (negative electrode side insulating layer) green sheet Slurry was prepared in the same manner as in (4).
  • a second insulating layer green sheet was formed by forming the prepared slurry into a sheet on a PET film.
  • the thickness of the second insulating layer after firing was set to 10 ⁇ m.
  • the unfired laminated body after cutting was heated from room temperature to 600° C., degreased for 5 hours, heated to 800° C., fired for 10 minutes, and then cooled. Thus, a laminated integrally sintered body was obtained.
  • the number of cells formed in the laminated integrated sintered body is eleven.
  • CMC conductive carbon paste Binder
  • the carbon dispersion, the dispersant solution, and the 1.2 wt% CMC solution were weighed so that the ratio was 0.22:0.29:1, and mixed by a rotation/revolution mixer to obtain a conductive A carbon paste was prepared.
  • the conductive carbon paste obtained in was screen printed. 3. so that it fits within the undried printed pattern (the area where the conductive carbon paste is applied);
  • the laminate integrally sintered body obtained in 1. was placed so that the exposed surface of the positive electrode was adhered thereto, lightly pressed with a finger, and then vacuum-dried at 50° C. for 60 minutes. In this way, the positive electrode exposed surface of the laminated integrally sintered body and the positive electrode current collector were adhered via the conductive carbon adhesive layer.
  • the thickness of the conductive carbon adhesive layer was set to 30 ⁇ m.
  • the positive electrode current collector, the laminated integrated sintered body, and the negative electrode current collector are placed from the positive electrode can toward the negative electrode can.
  • the positive electrode can and the negative electrode can were sealed by crimping through a gasket.
  • the electrolytic solution LiPF 6 was dissolved to a concentration of 1.5 mol/L in an organic solvent in which propylene carbonate (PC) and ⁇ -butyrolactone (GBL) were mixed at a volume ratio of 1:3.
  • Evaluation 1 Measurement and calculation of laminated integrally sintered body (1) Measurement of outer dimension width of laminated integrally sintered body Using a one-shot 3D shape measuring machine (manufactured by Keyence Corporation, VR3000), laminated integrally sintered body The outer dimension width (W) was measured. (2) Calculation of Each Parameter An average wave width of the widths of the 12 insulating layers included in the laminated integrally sintered body was calculated. The ratio (%) of the insulation layer width average wave to the outer dimension width W was calculated by the following formula.
  • Examples 2 to 10, Comparative Examples 1 and 2 A lithium secondary battery was produced in the same manner as in Example 1, except that the average width and the average variation of the width of the insulating layer were as shown in [Table 1], and the measurements and battery characteristics were evaluated.
  • the juxtaposed position of the positive electrode green sheet and the positive electrode side insulating layer green sheet (the negative electrode green sheet and the negative electrode) side insulating layer green sheet and the cutting position are adjusted.
  • a sample having a predetermined insulating layer width average and variation average was obtained.
  • Examples 1 to 10 in which the average insulation layer width with respect to the outer width is in the range of 0.8 to 40% the 30C discharge capacity with respect to the 0.2C discharge capacity is 60% or more. It had good rate characteristics and a 0.2C discharge capacity of 0.13 mAh or more. For this reason, it was thought that a large capacity could be obtained even in high-speed discharge with a large current.
  • Examples 1 to 7, in which the average insulation layer width is in the range of 0.8 to 40% with respect to the outer dimension width, and the average variation in insulation layer width/average insulation layer width is 20% or less are 0.8%.
  • the 30C discharge capacity with respect to the 2C discharge capacity was 80% or more, showing particularly excellent rate characteristics.
  • Comparative Example 1 in which the average width of the insulating layer with respect to the outer width was 0.5%, the 30C discharge capacity was 58% of the 0.2C discharge capacity, and the rate characteristics were considered insufficient.
  • Comparative Example 1 in which the average width of the insulating layer with respect to the outer width is 50%, had a 0.2C discharge capacity of 0.04 mAh, and was considered to have insufficient battery capacity.

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WO2020184476A1 (ja) * 2019-03-08 2020-09-17 Tdk株式会社 全固体二次電池
WO2020195684A1 (ja) * 2019-03-26 2020-10-01 株式会社村田製作所 固体電池
WO2021090774A1 (ja) * 2019-11-07 2021-05-14 Tdk株式会社 全固体電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020184476A1 (ja) * 2019-03-08 2020-09-17 Tdk株式会社 全固体二次電池
WO2020195684A1 (ja) * 2019-03-26 2020-10-01 株式会社村田製作所 固体電池
WO2021090774A1 (ja) * 2019-11-07 2021-05-14 Tdk株式会社 全固体電池

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