WO2023013617A1 - 円筒形リチウム一次電池 - Google Patents

円筒形リチウム一次電池 Download PDF

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Publication number
WO2023013617A1
WO2023013617A1 PCT/JP2022/029577 JP2022029577W WO2023013617A1 WO 2023013617 A1 WO2023013617 A1 WO 2023013617A1 JP 2022029577 W JP2022029577 W JP 2022029577W WO 2023013617 A1 WO2023013617 A1 WO 2023013617A1
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Prior art keywords
lithium
positive electrode
negative electrode
current collector
electrode current
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PCT/JP2022/029577
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English (en)
French (fr)
Japanese (ja)
Inventor
辻協志
川邊啓祐
金子玄洋
須和田裕貴
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Maxell Ltd
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Maxell Ltd
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Priority to JP2023540350A priority Critical patent/JP7630627B2/ja
Priority to EP22853036.6A priority patent/EP4369442A4/en
Priority to US18/293,941 priority patent/US20240339648A1/en
Priority to CN202280051115.6A priority patent/CN117678093A/zh
Publication of WO2023013617A1 publication Critical patent/WO2023013617A1/ja
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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • 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
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound 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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cylindrical lithium primary battery having an electrode body with a wound structure using lithium as the negative electrode.
  • LPWA Low Power Wide Area
  • a lithium primary battery (non-aqueous electrolyte primary battery), for example, can be cited as a battery suitable for such a purpose, and various studies are being conducted to increase its capacity and improve its characteristics.
  • Patent Literature 1 discloses a cylindrical non-aqueous electrolyte primary battery that has excellent heavy-load pulse discharge characteristics so that it can be used for applications such as gas meter shut-off valves and wireless communications.
  • the negative electrode has a metallic lithium-containing layer composed of only one continuous layer on one side of the current collector, and the metallic lithium-containing layer in the current collector is 85% or more of the area of the formation surface is covered with the metallic lithium-containing layer, and a lithium-aluminum alloy is formed on at least part of the surface of the metallic lithium-containing layer opposite to the current collector.
  • the active material layers of the positive electrode and the negative electrode are thickened to increase the amount of active material per unit area, thereby increasing the capacity of the battery.
  • the thickness of the negative electrode sandwiched between the winding cores increases when the negative electrode, positive electrode, and separator are wound.
  • the winding center diameter which is the sum of the thickness of the winding core and the thickness of the negative electrode, increases, and the winding diameter of the electrode body wound around the winding core increases, albeit slightly, and the inner diameter of the outer can. , there is a problem that insertion failure tends to occur when inserting the electrode body into the outer can.
  • the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a high-capacity cylindrical lithium primary battery that suppresses the insertion failure of the wound electrode assembly.
  • a cylindrical lithium primary battery of the present application includes an electrode body in which a positive electrode and a negative electrode are spirally wound with a separator interposed therebetween, and the positive electrode includes a positive electrode current collector and the positive electrode current collector. and a positive electrode mixture layer containing manganese dioxide as a positive electrode active material disposed on both sides of the positive electrode current collector, wherein the content of manganese dioxide per unit area of the positive electrode mixture layer is 0 per side of the positive electrode current collector. .205 to 0.227 g/cm 2 , and the negative electrode comprises a negative electrode current collector and two lithium layers laminated on one side of the negative electrode current collector and separated in the longitudinal direction by an interval of 6 mm or more and 12 mm or less.
  • each of the two lithium layers has a lithium content per unit area of 0.014 to 0.017 g/cm 2
  • the negative electrode is between the two lithium layers and one is folded back at a position close to the lithium layer
  • the negative electrode current collectors overlap each other
  • the inner peripheral side ends of the two lithium layers are each positioned outside the winding center part. It is characterized by being
  • FIG. 1 is a longitudinal sectional view schematically showing an example of a cylindrical lithium primary battery according to an embodiment.
  • 2 is a cross-sectional view of the cylindrical lithium primary battery of FIG. 1.
  • FIG. 3 is a partial cross-sectional view schematically showing an example of an electrode body having a wound structure that constitutes the cylindrical lithium primary battery of the embodiment.
  • FIG. 4 shows a laminated body in which a negative electrode current collector, two sheets of metallic lithium foil, and a separator are integrated, which is used when producing an electrode body having a wound structure that constitutes a cylindrical lithium primary battery of the embodiment.
  • FIG. 3 is a schematic partial cross-sectional view.
  • FIG. 1 is a longitudinal sectional view schematically showing an example of a cylindrical lithium primary battery according to an embodiment.
  • 2 is a cross-sectional view of the cylindrical lithium primary battery of FIG. 1.
  • FIG. 3 is a partial cross-sectional view schematically showing an example of an electrode body having a wound structure that constitutes the cylindrical lithium primary battery of the embodiment
  • FIG. 5 is a diagram for explaining a method of manufacturing an electrode assembly having a wound structure that constitutes the cylindrical lithium primary battery of the embodiment.
  • FIG. 6 is a diagram for explaining a method of manufacturing an electrode body having a wound structure that constitutes the cylindrical lithium primary battery of the embodiment.
  • FIG. 1 is a longitudinal sectional view schematically showing an example of the cylindrical lithium primary battery of this embodiment
  • FIG. 2 is a transverse sectional view of the cylindrical lithium primary battery shown in FIG. 1
  • FIG. 2 is a partial cross-sectional view schematically showing an example of an electrode body having a wound structure that constitutes the cylindrical lithium primary battery of the present embodiment.
  • a cylindrical lithium primary battery 1 is made of iron, stainless steel, or the like. , a non-aqueous electrolytic solution, and a sealing member for sealing the upper opening of the outer can 2 .
  • the cylindrical lithium primary battery 1 of FIG. It has a power generation element such as an electrode body 3 having a spiral structure wound in a spiral shape and a non-aqueous electrolyte.
  • FIG. 2 shows a cross-sectional view of the cylindrical lithium primary battery of FIG.
  • the electrode body 3 is formed by winding a long positive electrode 4 and a long negative electrode 5 with a separator 6 interposed therebetween, and is formed in a substantially cylindrical shape as a whole.
  • the positive electrode 4 has a structure in which two positive electrode mixture sheets 41 and 42 are laminated with a positive electrode current collector 43 interposed therebetween. That is, the positive electrode 4 has a structure in which positive electrode mixture layers 41 and 42 are formed on both sides of the positive electrode current collector 43 by the two positive electrode mixture sheets.
  • the positive electrode mixture layers 41 and 42 each contain manganese dioxide as a positive electrode active material.
  • the positive electrode active material layer usually contains a conductive aid and a binder.
  • conductive aids include graphite, carbon black (ketjen black, acetylene black, furnace black, etc.) and the like, and these may be used alone or in combination of two or more. good.
  • binder fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF); rubber-based binders; and the like can be used.
  • the dispersion type may be used, or the powder may be used, but the dispersion type is particularly suitable.
  • the content of the positive electrode active material is preferably 92 to 97% by mass
  • the content of the conductive aid is preferably 2 to 4% by mass
  • the content of the binder is preferably It is preferably 1 to 4% by mass.
  • the manganese dioxide content per unit area of the positive electrode mixture layers 41 and 42 is 0.205 to 0.227 g/cm 2 . That is, the positive electrode 4 has, on both sides of the positive electrode current collector 43, positive electrode mixture layers each having a manganese dioxide content per unit area adjusted to 0.205 to 0.227 g/cm 2 .
  • the electrode can be capacity can be increased. Therefore, the length (volume) of the separator can be reduced to increase the ratio of the active materials of the positive electrode and the negative electrode, thereby facilitating the design of a high-capacity battery.
  • the porosity of the positive electrode mixture layer must be made lower than necessary, or It is necessary to make the mixture layer thicker than necessary.
  • the permeability of the electrolytic solution into the positive electrode mixture layer is reduced, and the reactivity of the positive electrode is reduced, thereby deteriorating the load characteristics of the battery.
  • the flexibility of the positive electrode material mixture layer is reduced, and defects occur more frequently during winding. Therefore, the content per unit area of manganese dioxide contained in the positive electrode mixture layer is set to 0.227 g/cm 2 or less per one side of the positive electrode current collector.
  • the density of the positive electrode mixture layer is preferably 2.7 g/cm 3 or more, more preferably 2.8 g/cm 3 or more, and 2.85 g/cm 3 or more in order to increase the capacity of the battery. Most preferably, On the other hand, the density of the positive electrode mixture layer is preferably 3.1 g/cm 3 or less, more preferably 3.0 g/cm 3 or less, in order to improve the permeability of the non-aqueous electrolyte and prevent deterioration of the discharge characteristics. is more preferable, and 2.95 g/cm 3 or less is most preferable.
  • the thickness of the positive electrode is, for example, 1.5 mm or more, preferably 2 mm or less to maintain flexibility, and more preferably 1.8 mm or less.
  • a positive electrode mixture for example, a positive electrode mixture (slurry) is prepared by mixing a positive electrode active material with a conductive agent or a binder, and adding water or the like as necessary. After drying and pulverizing this, it is again formed into a sheet shape by roll rolling or the like to form a positive electrode mixture sheet, which is placed on both sides of the current collector, and the positive electrode mixture sheet and the current collector are integrated by pressing or the like. It can be manufactured by a method of forming layers (positive electrode mixture layers) made of positive electrode mixture sheets on both sides of a current collector.
  • the outer circumference of the current collector is placed several mm inside the outer circumference of the two positive electrode mixture sheets, and the three sheets are superimposed on each other, and the longitudinal direction arranged on the winding core side when winding is performed.
  • a positive electrode having positive electrode active material layers on both sides of the current collector can be manufactured by pressing a portion 3 to 10 mm from the end of the direction.
  • the positive electrode is not limited to those manufactured by the above manufacturing method, and may be manufactured by other manufacturing methods.
  • the positive electrode may be manufactured by a manufacturing method in which a positive electrode mixture slurry is applied to both surfaces of a current collector, dried, and if necessary, subjected to a press treatment or the like to form a positive electrode mixture layer on the current collector.
  • Examples of the current collector used for the positive electrode include those made of stainless steel such as SUS316, SUS430, and SUS444, and those made of aluminum. (plate) and the like can be exemplified.
  • the thickness of the positive electrode current collector is preferably 0.1 to 0.4 mm.
  • a paste-like conductive material can be applied to the surface of the positive electrode current collector.
  • a net-like material having a three-dimensional structure is used as the positive electrode current collector, as in the case of using a material essentially consisting of a flat plate such as metal foil or punching metal, the current collection effect is remarkable by applying a conductive material. Improvement is observed. This is because not only the route through which the metal portion of the mesh current collector contacts the positive electrode mixture layer directly, but also the route through the conductive material filled in the mesh is effectively used. It is speculated that
  • silver paste or carbon paste can be used as the conductive material.
  • a binder for the conductive material a heat-resistant material such as water glass or an imide-based binder is used because it is possible to perform a drying treatment at a high temperature exceeding 200° C. in order to remove moisture in the positive electrode mixture layer. It is preferable to use
  • the content of manganese dioxide per unit area of the positive electrode mixture layer (per one side of the positive electrode current collector) per unit area of the lithium layer is preferably 0.067 to 0.077 by weight.
  • the positive electrode having a high capacity as described above has a certain thickness or more, for example, a thickness of 1.5 mm or more.
  • the thickness of the negative electrode sandwiched between the winding cores is increased by the thickness of the metallic lithium foil (for example, about 0.3 mm).
  • the winding center diameter becomes slightly larger, and when a thick positive electrode is used, it becomes difficult to adjust the winding diameter of the wound electrode body to a certain value or less.
  • the inner diameter of the outer can is slightly increased, insertion failure tends to occur when inserting the electrode assembly into the outer can, which is a factor that hinders the increase in capacity.
  • the negative electrode 5 has a structure in which two lithium layers 51, 51 made of metallic lithium foil are laminated on one side of one negative electrode current collector 52.
  • a foil of copper, nickel, iron, stainless steel, or the like can be used for the negative electrode current collector.
  • the thickness of the negative electrode current collector is preferably as thin as possible, and specifically, for example, 25 ⁇ m or less is recommended. On the other hand, if the negative electrode current collector is too thin, it is likely to break, so the thickness of the negative electrode current collector is preferably 5 ⁇ m or more.
  • the width of the negative electrode current collector is preferably the same as or wider than the width of the metallic lithium foil forming the lithium layer.
  • the area of the negative electrode current collector is preferably 100% or more of the area of the lithium layer.
  • the width and length of the negative electrode current collector become equal to or greater than the width and length of the lithium layer, so even if the metallic lithium foil cracks during discharge, Even if it occurs, it is possible to prevent disconnection of the electrical connection.
  • the area of the negative electrode current collector should be 120% or less of the area of the lithium layer. is preferred. That is, the area of the lithium layer laminated on the negative electrode current collector is preferably 83% or more of the area of the negative electrode current collector.
  • the separator-side surfaces of the two lithium layers 51, 51 may each be alloyed with aluminum, which can improve the load characteristics of the battery. may be formed.
  • the lithium-aluminum alloy is formed on the separator-side surface of the lithium layer, it is preferable that the lithium-aluminum alloy is formed in a portion of 90% or more of the total area of the lithium layer.
  • the ratio of the total amount of aluminum to the total amount of lithium in the entire lithium layer (including lithium in the lithium-aluminum alloy) should be 0.095 or more by weight. is preferred.
  • the weight ratio is preferably 0.105 or less.
  • a lithium-aluminum alloy can be formed on the surface of the lithium layer in the battery by fabricating a negative electrode by laminating an aluminum foil on a metallic lithium foil and assembling a battery using the negative electrode.
  • the thickness of the metallic lithium foil used for producing the negative electrode is, for example, 0.25 to 0.35 mm, and the thickness of the aluminum foil is, for example, 5 to 20 ⁇ m.
  • the two lithium layers 51 , 51 are composed of two metallic lithium foils 51 , 51 separated in the longitudinal direction by an interval of 6 mm or more and 12 mm or less on the negative electrode current collector 52 . That is, between the two lithium layers 51, 51, there is a portion with a width of 6 mm or more and 12 mm or less in the longitudinal direction (winding direction) where the lithium layer is not formed and the negative electrode current collector 52 is exposed.
  • one long negative electrode 5 is positioned between the two lithium layers 51, 51 and one lithium layer (the positive electrode mixture layer 42 on the inner surface side of the positive electrode 4).
  • Lithium layer opposite to for example, at a position about 1 mm from the inner peripheral side end (winding start side end) of the lithium layer, so that it is substantially along the winding core extracted after winding
  • the negative electrode current collectors overlap each other, and the inner peripheral side ends of the two lithium layers 51 , 51 are respectively positioned outside the winding center portion 18 .
  • the winding center portion 18 refers to a portion of the negative electrode that is sandwiched between winding cores (for example, width: about 3 mm) and wound during winding. approximately the same width.
  • the thickness of the negative electrode sandwiched between the winding cores becomes thinner than when the lithium layer is formed as one continuous body, so that the winding diameter of the wound electrode body can be reduced.
  • the two lithium layers 51 and 51 are arranged with a distance of 6 mm or more in the longitudinal direction, in the negative electrode current collector on the inner surface side among the stacked negative electrode current collectors, the distance from the winding center to the positive electrode 4 It is possible to form a portion where the lithium layer is not laminated with a certain width or more toward the positive electrode mixture layer 41 on the outer surface side.
  • the width of the portion where the lithium layer is not laminated may be appropriately adjusted depending on the length from the winding center to the positive electrode mixture layer 41 on the outer surface side, but it is preferably 2 mm or more from the winding center. It is more preferably 4 mm or more.
  • the portion between the winding center portion 18 and the winding start side end portion of the positive electrode mixture layer 41 of the positive electrode 4 does not face the positive electrode.
  • the amount of lithium not involved in discharge can be reduced and the discharge efficiency can be improved.
  • the winding diameter of the wound electrode body can be made smaller by reducing the thickness of the winding start portion of the negative electrode. From these points of view, the distance between the two lithium layers 51, 51 is preferably 8 mm or more.
  • the negative electrode 5 in the electrode body 3 By configuring the negative electrode 5 in the electrode body 3 as described above, it is possible to prevent insertion failure when inserting the wound electrode body 3 into the outer can 2 .
  • the distance between the two lithium layers 51, 51 is too large, the winding start portion of the positive electrode mixture layer will no longer face the lithium layer, which may reduce the discharge capacity.
  • the distance between the two lithium layers 51, 51 is 12 mm or less, preferably 10 mm or less.
  • the distance between the two lithium layers 51, 51 is preferably 8 mm or more and 10 mm or less.
  • FIGS. 1 and 2 show the separator 6 as having a single-layer structure
  • the separator 6 inserted between the positive electrode 4 and the negative electrode 5 is preferably multi-layered.
  • the two separators can also be a combination of a resin microporous film and a non-woven fabric.
  • the sealing member of the cylindrical lithium primary battery 1 is, as shown in FIG. , a terminal body 9 mounted through an insulating packing 8 made of polypropylene or the like, and an insulating plate 10 arranged below the cover plate 7 .
  • the insulating plate 10 is formed in the shape of an upwardly-opening round plate with an annular side wall 12 erected on the periphery of a disk-shaped base portion 11.
  • a gas vent 13 is formed in the center of the base portion 11. there is
  • the lid plate 7 is fixed to the inner peripheral edge of the upper opening of the outer can 2 by laser welding or by crimp sealing via packing while being received by the upper end of the side wall 12 .
  • a thin portion (vent) can be provided in the cover plate 7 or the bottom portion 2a of the outer can 2 as a countermeasure against a sudden increase in the internal pressure of the battery.
  • the positive electrode 4 and the lower surface of the terminal body 9 are connected by a positive electrode lead body 15 .
  • a negative electrode lead body 16 attached to the negative electrode 5 is welded to the upper inner surface of the outer can 2 .
  • An insulating plate 14 made of resin is arranged on the bottom portion 2a of the outer can 2. As shown in FIG.
  • the terminal body 9 is not hatched to indicate a cross section for easy viewing of the drawing. Note that the positive electrode lead body 15 and the negative electrode lead body 16 are arranged at positions deviated from the cross section of FIG. 1, so the cross section is not originally shown.
  • the electrode body 3 to be inserted inside the outer can 2 can be manufactured, for example, by the procedures shown in FIGS. 4, 5, and 6. 4, 5, and 6, the separator 6 has a single layer structure, and the two separators 61 and 62 are not distinguished.
  • the adhesive tape 31 and the separator 6 are placed on the upper surface of the negative electrode current collector 52 at the central portion in the longitudinal direction, thereby fixing the separator 6 to the negative electrode current collector 52 .
  • a double-sided tape can be used for the adhesive tape 31 .
  • two metallic lithium foils 51, 51 are crimped and fixed on both sides in the longitudinal direction of the negative electrode current collector 52 with the fixed portion of the separator 6 interposed therebetween.
  • a portion where the negative electrode current collector 52 is exposed without forming the lithium layer, which is the negative electrode active material is provided, and the separator 6 is fixed to this exposed portion 30 with the adhesive tape 31. do.
  • the width of the exposed portion 30 (the interval in the longitudinal direction of the two metallic lithium foils 51, 51) is set to 6 mm or more and 12 mm or less as described above. In this way, the laminate 32 in which the negative electrode current collector 52, the two lithium metal foils 51, 51, and the separator 6 are integrated can be obtained.
  • the lithium layer 51 shown as a single layer structure in FIGS. 4, 5, and 6 is a laminate of a metallic lithium foil 51a and an aluminum foil 51b, as shown in the enlarged view of FIG. can be done.
  • the laminated body 32 is inserted between the lateral split grooves 35 of the winding core 33 .
  • the width of the horizontal split groove 35 of the winding core 33 is 2.8 mm.
  • the distance between the left end of the lateral split groove 35 of the winding core 33 and the end of the metallic lithium foil 51 in FIG. Positioning is performed so that the fixed portion is positioned between the horizontal split grooves 35 of the winding core 33 .
  • the winding core 33 is rotated in one direction (clockwise direction in FIG. 5) by about half a turn, and the laminate 32 is wound around the outer peripheral surface of the winding core 33 as shown in FIG.
  • the positive electrode 4 composed of the positive electrode mixture sheets 41 and 42 and the positive electrode current collector 43 is placed on the separator 6 and wound around the winding core 33 together with the laminate 32 .
  • the winding core 33 is pulled out from the winding body, and finally, the winding end portion of the metallic lithium foil 51 is fixed with a fixing tape.
  • the negative electrode 5 is folded back between the two metallic lithium foils 51, 51 at a position about 1 mm from one of the metallic lithium foils 51, and the negative electrode current collectors 52 overlap each other and are wound so that the inner peripheral ends of the metal lithium foils 51, 51 are located outside the winding center portion 18, respectively.
  • the folded position of the negative electrode is preferably within 1.5 mm, more preferably within 1.0 mm, from one of the metallic lithium foils 51 .
  • the positive electrode 4 and the negative electrode 5 were wound with the separator 6 interposed therebetween, with the exposed portion 30 sandwiched between the winding cores serving as the winding central portion 18.
  • An electrode body 3 can be obtained.
  • a microporous resin film, non-woven fabric, or the like is used.
  • Polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyphenylene sulfide (PPS); 1 type or 2 types or more can be used.
  • the thickness of the separator is preferably 7 ⁇ m or more, more preferably 10 ⁇ m or more, preferably 20 ⁇ m or less, and more preferably 18 ⁇ m or less.
  • the thickness is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 80 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the non-aqueous electrolyte of the cylindrical lithium primary battery of the present embodiment includes electrolytes such as LiClO 4 , LiCF 3 SO 3 , LiC 2 F 5 SO 3 , LiN(FSO 2 ) 2 and LiN(CF 3 SO 2 ) 2 . is dissolved in an organic solvent.
  • organic solvents include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; 1,2-dimethoxyethane (ethylene glycol dimethyl ether), diglyme ( diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), methoxyethoxyethane, 1,2-diethoxyethane, ethers such as tetrahydrofuran; cyclic esters such as ⁇ -butyrolactone; nitrile; One of these may be used alone, or two or more thereof may be used in combination. In particular, it is preferable to use the cyclic carbonate and ether together.
  • Ethylene carbonate and propylene carbonate are preferably used as the cyclic carbonate.
  • ether 1,2-dimethoxyethane is preferably used.
  • concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.3 mol/L or more, more preferably 0.4 mol/L or more, from the viewpoint of ensuring good lithium ion conductivity. It is preferably 1.2 mol/L or less, more preferably 1.0 mol/L or less.
  • FIGS. In describing the cylindrical lithium primary battery of the present embodiment, reference was made to FIGS. It is not limited to what is illustrated in the drawings.
  • cylindrical lithium primary battery disclosed in the present application will be described in detail below based on examples, but the following examples do not limit the cylindrical lithium primary battery disclosed in the present application.
  • a positive electrode mixture was prepared by the following procedure. 2 parts by mass of Ketjenblack “EC300J” (trade name) having a BET specific surface area of 800 m 2 /g as a conductive agent and 94.5 parts by mass of manganese dioxide having an average particle diameter of 35 ⁇ m as a positive electrode active material were added to the planet. After dry mixing for 5 minutes using a Lee mixer, water was added in an amount corresponding to 20% (mass ratio) of the total solid content, and the mixture was further mixed for 5 minutes.
  • Ketjenblack “EC300J” trade name
  • PTFE dispersion (“D-1" manufactured by Daikin Industries, Ltd.) is added at a ratio of 3.5 parts by mass of PTFE, and finally, water is added until the total solid content ratio reaches 74% by mass. Then, the mixture was further mixed for 5 minutes to obtain a positive electrode mixture.
  • the positive electrode mixture was rolled into a sheet by rolls having a diameter of 250 mm and a temperature of 125 ⁇ 5° C., and the residual water content was reduced to 2% by mass or less in a temperature environment of 105 ⁇ 5° C.
  • a preliminary sheet was formed by drying until the Furthermore, the preliminary sheet is pulverized with a pulverizer until it becomes powder having a particle size of about 0.5 mm or less, and then rolled again using the rolls to obtain a sheet having a thickness of 0.79 mm and a density of 2.
  • a positive electrode mixture sheet of 0.89 g/cm 3 was used. The content of manganese dioxide per unit area in this positive electrode material mixture sheet was 0.216 g/cm 2 .
  • the obtained positive electrode mixture sheet was cut into a positive electrode mixture sheet (positive electrode mixture sheet 42 in FIG.
  • Expanded metal made of stainless steel (SUS316) was used for the positive electrode current collector. This expanded metal was cut into a width of 39 mm and a length of 60 mm, and a stainless steel ribbon having a thickness of 0.1 mm and a width of 3 mm was attached to the center in the length direction by resistance welding as a positive electrode lead. . Further, carbon paste (manufactured by Nippon Graphite Co., Ltd.) was applied to the expanded metal so as not to clog the mesh, and then dried at a temperature of 105 ⁇ 5° C. to obtain a positive electrode current collector. The amount of the carbon paste applied was set to 5 mg/cm 2 after drying.
  • the positive electrode current collector interposed between the positive electrode mixture sheet on the inner surface side and the positive electrode mixture sheet on the outer surface side, only one end in the length direction was fixed to separate the positive electrodes.
  • the mixture sheet and the positive electrode current collector were integrated. Specifically, the positive electrode mixture sheet on the inner surface side and the positive electrode mixture sheet on the outer surface side are aligned at one end in the length direction, and the ends of the positive electrode current collector are separated into two positive electrode mixture sheets. In this state, the two positive electrode mixture sheets are crimped at a distance of 5 mm from the end of each positive electrode mixture sheet and the positive electrode current collector. and integrated. Then, it was dried with hot air at 300 ⁇ 10° C. for 15 minutes to obtain a sheet-like positive electrode with a thickness of 1.6 mm and a width of 42.5 mm.
  • metal lithium foil aluminum foils having a width of 40 mm, a length of 96 mm, and a thickness of 6 ⁇ m, and a width of 40 mm, a length of 57 mm, and a thickness of 6 ⁇ m are stacked to form a sheet.
  • a negative electrode was constructed. The ratio of the area of the aluminum foil to the area of the metallic lithium foil is 95%, and the metallic lithium foil and the aluminum foil are arranged at both ends in the longitudinal direction and the ends in the width direction that become the bottom side of the battery when inserted into the outer can. Aligned in the department.
  • the content of lithium in the lithium layer is 0.0155 g/cm 2 per unit area
  • the area of the entire lithium layer is 95% of the area of the negative electrode current collector
  • the formed lithium - The weight ratio of the total amount of aluminum to the total amount of lithium contained in the entire lithium layer, including the aluminum alloy, was 0.0995.
  • Electrode body Width: 49 mm, length: 180 mm, thickness: 16 ⁇ m PE microporous film (porosity: 46%, air permeability: 200 seconds/100 mL, puncture strength: 380 g) was superimposed and used as a separator. .
  • the distance between the folded back portion of the negative electrode formed by the winding core during winding and the inner peripheral edge of the metallic lithium foil facing the inner surface of the positive electrode is about 1 mm, and the outer surface of the positive electrode is opposed.
  • the distance between the inner peripheral end of the metal lithium foil and the winding center is about 5 mm, and the distance from the winding center to the positive electrode mixture layer on the outer surface side of the positive electrode is about 5 mm on the negative electrode current collector.
  • a widthwise portion where the lithium layer was not laminated was formed.
  • one end in the width direction of the separator protrudes 1.5 mm from the end of the negative electrode (the end arranged on the upper side of the battery).
  • the other end of the separator protruding from the positive electrode was bent toward the positive electrode side so that the end face of the positive electrode was covered with the separator.
  • FIG. 1 A process for assembling a cylindrical lithium primary battery will be described with reference to FIG.
  • An insulating plate 14 made of PP with a thickness of 0.2 mm is inserted into the bottom 2a of a bottomed cylindrical outer can 2 made of a nickel-plated stainless steel can. I inserted it in a posture facing the
  • the negative lead body 16 of the electrode body 3 was resistance welded to the inner surface of the outer can 2, and the positive lead body 15 was resistance welded to the lower surface of the terminal body 9 after the insulating plate 10 was inserted.
  • the electrolytic solution was a non-aqueous solution in which LiCF 3 SO 3 was dissolved at a concentration of 0.7 mol/L in a mixed solvent of ethylene carbonate, propylene carbonate, and dimethoxyethane (1:1:3 by volume). 3.5 mL of this was prepared and injected into the outer can 2 . The injection was divided into three times, and the entire amount was injected while reducing the pressure in the final step. After the electrolyte is injected, the cover plate 7 is fitted into the upper opening of the outer can 2, and the inner peripheral portion of the open end of the outer can 2 and the outer peripheral portion of the cover plate 7 are welded by laser welding to complete the outer can. 2 was sealed.
  • Example 2 On a copper foil (negative electrode current collector) having a width of 43 mm, a length of 173 mm and a thickness of 15 ⁇ m, a lithium metal foil having a width of 42 mm, a length of 99 mm and a thickness of 0.29 mm, a width of 42 mm and a length of 42 mm. Metallic lithium foils having a thickness of 57 mm and a thickness of 0.29 mm were arranged at intervals of 6 mm in the longitudinal direction. Further, on the metal lithium foil, aluminum foils of width: 40 mm, length: 99 mm, thickness: 6 ⁇ m, width: 40 mm, length: 57 mm, thickness: 6 ⁇ m are overlapped to form a sheet. A negative electrode was constructed.
  • a cylindrical lithium primary battery was assembled in the same manner as in Example 1, except that the sheet-shaped negative electrode was used.
  • the distance between the folded back portion of the negative electrode formed by the winding core during winding and the inner peripheral edge of the metallic lithium foil facing the inner surface of the positive electrode is about 1 mm, and the outer surface of the positive electrode is opposed.
  • the distance between the inner peripheral end of the metal lithium foil and the winding center is about 2 mm, and the distance from the winding center to the positive electrode mixture layer on the outer surface side of the positive electrode is about 2 mm on the negative electrode current collector. A widthwise portion where the lithium layer was not laminated was formed.
  • a metal lithium foil having a width of 43 mm, a length of 173 mm, and a thickness of 15 ⁇ m is placed on a copper foil having a width of 42 mm, a length of 162 mm, and a thickness of 0.29 mm. , width: 40 mm, length: 162 mm, and thickness: 6 ⁇ m.
  • Example 1 The sheet-like negative electrode and the same two PE microporous films as in Example 1 are superimposed, and in plan view, the same position as that sandwiched between the winding cores in Example 1 is sandwiched between the winding cores. 100 electrode bodies were produced in the same manner as above, and a cylindrical lithium primary battery was assembled.
  • the 100 wound electrode bodies of Examples 1, 2, and Comparative Example 1 each have a certain degree of variation in the winding diameter, but the electrode bodies produced in Examples 1 and 2 Therefore, even in the electrode assembly with the maximum winding diameter, the insertion failure did not occur because the winding diameter did not exceed the upper limit of the diameter that can be inserted into the outer can.
  • the lithium layer was continuously present on the winding center and also on the negative electrode current collector that continued outward from the winding center and did not face the positive electrode.
  • the winding inner diameter of the electrode assembly becomes large, and along with this, the winding diameter of some electrode assemblies exceeds the range that can be inserted into the outer can, resulting in insertion failure in a certain number of electrode assemblies. rice field.
  • Example 2 A sheet-like negative electrode was produced in the same manner as in Example 1, except that two sheets of metallic lithium foil were arranged with an interval of 20 mm in the longitudinal direction. Thereafter, a cylindrical lithium primary battery was assembled in the same manner as in Example 1.
  • Example 1 and Example 2 in which two lithium layers were arranged on the negative electrode current collector at intervals of 6 to 12 mm in the longitudinal direction, and Comparative Example in which a continuous lithium layer was arranged without separating the lithium layers.
  • the lithium layer was sufficiently opposed to the positive electrode active material, so the designed discharge capacity was obtained.
  • the winding center and the negative electrode current collector that continues outward from the winding center and does not face the positive electrode are also continuous. Since the lithium layer was formed on the substrate, the winding diameter of some electrode bodies exceeded the design upper limit, resulting in defects in the battery assembly process.
  • the content of manganese dioxide per unit area of the positive electrode mixture layer was adjusted in the range of 0.205 to 0.227 g/cm 2 per side of the positive electrode current collector. Since the lithium content of the lithium layer of the negative electrode is also adjusted to 0.014 to 0.017 g/cm 2 per unit area in accordance with the capacity of the positive electrode, the thickness of the positive electrode mixture layer is increased. It was possible to increase the capacity of the battery without increasing the density of the positive electrode mixture layer too much or increasing the density of the positive electrode mixture layer too much.

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PCT/JP2022/029577 2021-08-04 2022-08-02 円筒形リチウム一次電池 Ceased WO2023013617A1 (ja)

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US18/293,941 US20240339648A1 (en) 2021-08-04 2022-08-02 Cylindrical lithium primary battery
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