WO2016039264A1 - Électrode positive pour cellule secondaire au lithium-ion et, cellule secondaire au lithium-ion - Google Patents

Électrode positive pour cellule secondaire au lithium-ion et, cellule secondaire au lithium-ion Download PDF

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Publication number
WO2016039264A1
WO2016039264A1 PCT/JP2015/075193 JP2015075193W WO2016039264A1 WO 2016039264 A1 WO2016039264 A1 WO 2016039264A1 JP 2015075193 W JP2015075193 W JP 2015075193W WO 2016039264 A1 WO2016039264 A1 WO 2016039264A1
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Prior art keywords
active material
positive electrode
material layer
ion secondary
lithium ion
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PCT/JP2015/075193
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English (en)
Japanese (ja)
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秋草　順
翔 清水
繁成 柳
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三菱マテリアル株式会社
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Priority claimed from JP2015107685A external-priority patent/JP5983821B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to US15/510,417 priority Critical patent/US20170263933A1/en
Priority to EP15840381.6A priority patent/EP3193392A4/fr
Priority to KR1020177006676A priority patent/KR20170052592A/ko
Priority to CN201580048387.0A priority patent/CN106688126A/zh
Publication of WO2016039264A1 publication Critical patent/WO2016039264A1/fr

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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • 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 positive electrode for a lithium ion secondary battery and a lithium ion secondary battery.
  • Lithium ion secondary batteries have attracted attention as high-capacity secondary batteries, and various developments have been made to improve the performance of lithium ion secondary batteries (see Patent Documents 1 to 6, etc.).
  • Patent Document 1 a current collecting layer having conductivity and formed in a thin film shape, an active material layer having irregularities formed on the side opposite to the current collecting layer, and the current collecting layer and the active material layer are bonded.
  • An electrode comprising an adhesive layer is disclosed. In the electrode disclosed in Patent Document 1, the distance from the surface of the active material layer to the current collecting layer is reduced in the concave portion of the active material layer, and the internal resistance is reduced.
  • Patent Document 2 discloses a positive electrode sheet in which a positive electrode mixture made of an active material, a conductive material, and a binder is provided on a current collector surface of a metal foil.
  • the positive electrode mixture is applied at a coating amount of 15 mg / cm 2 per side, and the positive electrode mixture density is 2.5 g / cm 3 .
  • the positive electrode sheet is provided with small holes and / or slits that penetrate the current collector and the positive electrode mixture.
  • the positive electrode sheet is superimposed on the negative electrode sheet via a separator to form an electrode body.
  • Patent Document 2 discloses that the gas accumulated in the positive electrode mixture and the like is released to the outside of the electrode body by the small holes formed in the positive electrode sheet, and the safety of the lithium ion secondary battery is improved. ing.
  • Patent Document 3 includes an active material layer having a thickness of 100 ⁇ m and a porosity of approximately 30% and a positive electrode current collector formed on the surface of the active material layer, and a hole penetrating them is formed. A positive electrode is disclosed. Patent Document 3 discloses that by making a hole in the positive electrode, it is possible to ensure the electrolyte impregnation ability and the drying ability during adhesion drying.
  • Patent Document 4 a first composite material layer region having a low porosity and a second composite material layer region having a high porosity are alternately formed on the surface of the current collector, and the direction along the surface of the current collector An active material layer having a thickness of about 50 ⁇ m with different porosity depending on the position is disclosed.
  • Patent Document 4 since lithium ions move in the second mixture layer region having a high porosity, the movement resistance of lithium ions is reduced, and the active material layer is used as an electrode of a lithium ion secondary battery. It is disclosed that the internal resistance is lowered.
  • Patent Document 5 discloses a lithium ion secondary battery in which the active material coating thickness is 80 ⁇ m or less, the porosity of the active material layer on the current collector side is 30 to 50%, and the porosity on the separator side is 50 to 60%.
  • An electrode is disclosed.
  • Patent Document 5 by using the lithium ion secondary battery electrode, the amount of electrolyte in the electrode increases, the lithium ion transport capacity in the electrode electrolyte in the film thickness direction increases, and the output density is further improved. It is disclosed that it can be made.
  • Patent Document 6 includes LiCoO 2 , a carbon material, and polyvinylidene fluoride in a weight ratio of 95: 2.5: 2.5 formed on the surface of a current collector, and having a weight of 50 mg / cm 2 , A positive electrode for a lithium ion secondary battery having an active material layer having a thickness of about 140 ⁇ m and a large number of independent holes formed so as not to penetrate the current collector is disclosed.
  • JP 2013-187468 A (paragraph 0007, paragraph 0008) JP 2001-6749 A (see paragraphs 0010, 0023, 0026, and 0057) Japanese Patent Laid-Open No. 10-326628 (see paragraphs 0018, 0024, and 0070) JP 2013-8523 A (see paragraph 0010) JP 2002-151055 A (Claims 1 to 5) JP 2007-250510 A (Claim 1, paragraph 0023, paragraph 0024)
  • the electrode disclosed in Patent Document 1 has a rate of decrease in internal resistance of about 3 to 16% as compared with the case where no unevenness is formed, and there is a possibility that the decrease in internal resistance is insufficient.
  • the internal resistance of the electrode increases when the active material layer is thickened, it is impossible to increase the amount of active material supported by increasing the thickness of the active material layer if the internal resistance is reduced. Therefore, it is difficult for the electrode to increase the capacity of the battery.
  • the positive electrode mixture contains 10 parts by mass of the conductive material and the binder, respectively, with respect to 80 parts by mass of the active material.
  • the positive electrode sheet the true density of about 4.2 g / cm 3 lithium manganate as an active material contained in the positive-electrode mixture, the active material density in the positive electrode material and 2.5 g / cm 3 Low and carries less active material.
  • the active material density in the positive electrode mixture is about 59% with respect to the true density of the active material. Therefore, the lithium ion secondary battery using the positive electrode sheet has a small capacity per volume.
  • the positive electrode disclosed in Patent Document 3 has a porosity of around 30%, and the active material layer contains 87 wt% lithium cobaltate, 8 wt% graphite powder, and 5 wt% polyvinylidene fluoride. The material density is small. Further, the positive electrode has a thickness of the active material layer of 100 ⁇ m and has a small amount of active material supported. Therefore, the lithium ion secondary battery using the positive electrode has a small capacity.
  • a second composite layer region having a high porosity in which lithium ions move preferentially is formed in a slit shape.
  • the active material density of the second composite material layer region is low, there is a problem that the overall average active material density is lowered. Therefore, the lithium ion secondary battery using the active material layer cannot increase the energy density per unit volume (charge / discharge capacity).
  • the electrode for a lithium ion secondary battery disclosed in Patent Document 5 has an active material layer thickness of 20 to 80 ⁇ m and a porosity on the separator side of 50% or more and 60% or less. Is low. Therefore, the lithium ion secondary battery using the electrode has a problem that the energy density per unit volume (charge / discharge capacity) is low.
  • the positive electrode for a lithium ion secondary battery described in Patent Document 6 has an active material layer thickness of about 140 ⁇ m, which is thicker than a conventional active material layer having a thickness of about 100 ⁇ m, but the density of the active material layer is unknown Therefore, the capacity of the lithium ion secondary battery using the positive electrode may not be sufficiently large.
  • an object of the present invention is to provide a positive electrode for a lithium ion secondary battery and a lithium ion secondary battery that can be charged and discharged quickly with a high capacity.
  • a first aspect of the present invention includes a current collector and an active material layer formed on a surface of the current collector, and the active material layer has a plurality of holes formed on the surface, and the active material
  • the density is 68 to 83% of the true density of the active material contained in the active material layer, and the thickness is 150 to 1000 ⁇ m.
  • a second aspect of the present invention is the invention based on the first aspect, wherein the active material layer includes LiCoO 2 as the active material, and the active material density is 3.45 to 4.19 g / cm 3. It is characterized by being.
  • a fourth aspect of the present invention is the invention based on the first aspect, wherein the active material layer includes LiMn 2 O 4 as the active material, and the active material density is 2.86 to 3.48 g / It is characterized by being cm 3 .
  • a fifth aspect of the present invention is the invention based on the first aspect, wherein the active material layer includes LiNiO 2 as the active material, and the active material density is 3.26 to 3.98 g / cm 3. It is characterized by being.
  • a sixth aspect of the present invention is the invention based on the first aspect, wherein the active material layer includes LiNi 0.8 Co 0.15 Al 0.05 O 2 as the active material, and the active material The density is 3.33 to 4.06 g / cm 3 .
  • a seventh aspect of the present invention is the invention based on the first aspect, wherein the active material layer includes LiFePO 4 as the active material, and the active material density is 2.45 to 2.98 g / cm 3. It is characterized by being.
  • a ninth aspect of the present invention is the invention based on any one of the first to eighth aspects, wherein the active material layer comprises 0.5 to 10 wt% of a conductive additive and 0.5% of a binder. It is characterized by containing ⁇ 10 wt%.
  • a tenth aspect of the present invention is the invention based on any one of the first to ninth aspects, wherein the maximum diameter of the plurality of holes is 5 to 2000 ⁇ m.
  • An eleventh aspect of the present invention is the invention based on any one of the first to tenth aspects, characterized in that a center interval between the plurality of holes is 500 to 8000 ⁇ m.
  • a twelfth aspect of the present invention is the invention based on any one of the first to eleventh aspects, wherein the opening of the plurality of holes has a round shape, a triangular shape, a quadrangular shape or a polygonal shape having a pentagon or more. It is one or more selected from.
  • a thirteenth aspect of the present invention is the invention based on any one of the first to twelfth aspects, wherein the depth of the plurality of holes is 5% or more of the thickness of the active material layer. It is characterized by.
  • a fourteenth aspect of the present invention is the invention based on any one of the first to thirteenth aspects, wherein the plurality of holes have a bottom portion formed of the current collector.
  • a fifteenth aspect of the present invention is the invention based on any one of the first to thirteenth aspects, wherein the active material layer is formed on both surfaces of the current collector, and the plurality of holes are formed. An opening is formed on the surface of one of the active material layers, the active material layer and the current collector are penetrated, and a bottom is formed by the other active material layer.
  • a sixteenth aspect of the present invention is the invention based on the fifteenth aspect, wherein the plurality of holes are formed with openings in the surface of the other active material layer, and the active material layer, the current collector, Including a hole having a bottom formed by the one active material layer, and an opening formed in the surface of the one active material layer and an opening formed in the surface of the other active material layer.
  • the holes are alternately formed.
  • a seventeenth aspect of the present invention is characterized by comprising a positive electrode for a lithium ion secondary battery based on any one of the first to sixteenth aspects.
  • a positive electrode for a lithium ion secondary battery includes a current collector and an active material layer formed on a surface of the current collector, and the active material layer has a plurality of holes formed on the surface.
  • the active material density is 68 to 83% of the true density of the active material contained in the active material layer, and the thickness is 150 to 1000 ⁇ m.
  • the active material at a deep position in the thickness direction can be used effectively, and the active material can be used more effectively because the movement distance of the lithium ion in the positive electrode is not too long, and the high-capacity lithium ion secondary battery Can provide.
  • the positive electrode for a lithium ion secondary battery is used in a lithium ion secondary battery, the lithium ion released from the active material is located in the hole at a position deep in the thickness direction from the surface of the active material layer. Since the battery can be moved, the internal resistance of the battery is low, the battery can be charged and discharged quickly, and a high-power lithium ion secondary battery can be provided.
  • the active material layer contains LiCoO 2 as the active material, and the active material density is 3.45 to 4.19 g / cm 3. Can be provided at high density, and a high-capacity lithium ion secondary battery can be provided.
  • a positive electrode and a high-capacity lithium ion secondary battery can be provided.
  • the active material layer contains LiMn 2 O 4 as the active material, and the active material density is 2.86 to 3.48 g / cm 3 .
  • the active material layer contains LiNiO 2 as the active material, and the active material density is 3.26 to 3.98 g / cm 3. Can be provided at high density, and a high-capacity lithium ion secondary battery can be provided.
  • the active material layer contains LiNi 0.8 Co 0.15 Al 0.05 O 2 as the active material, and the active material density is 3.33 to Since it is 4.06 g / cm 3 , it is a positive electrode having a high density of active materials, and a high-capacity lithium ion secondary battery can be provided.
  • the active material layer contains LiFePO 4 as the active material, and the active material density is 2.45 to 2.98 g / cm 3. Can be provided at high density, and a high-capacity lithium ion secondary battery can be provided.
  • the active material layer contains 0.5 to 10 wt% of the conductive additive and 0.5 to 10 wt% of the binder. It is possible to bind the active material sufficiently and to have sufficient conductivity without reducing the thickness.
  • the positive electrode for a lithium ion secondary battery according to the tenth aspect of the present invention has a maximum diameter of a plurality of holes of 5 to 2000 ⁇ m. Therefore, in a lithium ion secondary battery using the positive electrode, the hole diameter is lithium ion.
  • a lithium ion secondary battery that is suitable for movement and can be quickly charged and discharged with higher capacity can be provided.
  • the center interval between the plurality of holes is 500 to 8000 ⁇ m, the number of holes and the interval between the holes are more suitable, and the capacity is increased quickly.
  • a lithium ion secondary battery that can be charged and discharged can be provided.
  • the shape of the hole opening is one or more selected from a round shape, a triangular shape, a quadrangular shape, or a polygonal shape that is a pentagon or more.
  • a lithium ion secondary battery that is suitable for battery reaction and can be charged and discharged quickly with a higher capacity can be provided.
  • the hole depth is suitable for the battery reaction. Therefore, an active material deep in the thickness direction from the surface of the active material layer can be effectively used, and a lithium ion secondary battery that can be charged and discharged quickly with a higher capacity can be provided.
  • the positive electrode for a lithium ion secondary battery according to the fourteenth aspect of the present invention since the plurality of holes have a bottom portion formed of a current collector, no holes are formed in the current collector. In the manufacturing process of the positive electrode for an ion secondary battery and the battery, the current collector is not easily broken, and the positive electrode for the lithium ion secondary battery and the battery can be efficiently manufactured.
  • an active material layer is formed on both surfaces of a current collector, and a plurality of holes are formed on the surface of one active material layer. Since the bottom is formed by another active material layer through the active material layer and the current collector, the active material is as much as the surface of the bottom compared to the case where the bottom is formed by the current collector. Since the surface area of the layer increases, the number of active materials that easily contribute to the battery reaction increases, and charge and discharge can be performed more efficiently.
  • the positive electrode for a lithium ion secondary battery has a plurality of holes at the bottom, the depth of the holes is deeper, and the liquid retention is higher, so the battery may be inclined and the electrolyte may be biased to one side.
  • the lithium ion secondary battery in which the electrolytic solution is held in the hole and the performance is not easily lowered can be provided.
  • a plurality of holes are formed in the surface of another active material layer, penetrates the active material layer and the current collector, A hole having a bottom formed by an active material layer is formed, and a hole having an opening formed on the surface of one active material layer and a hole having an opening formed on the surface of another active material layer are alternately formed. Therefore, when it is used for a lithium ion secondary battery in which a plurality of positive electrodes and negative electrodes are laminated, the opening of the hole always faces the separator, and charge and discharge can be performed more efficiently.
  • the lithium ion secondary battery according to the seventeenth aspect of the present invention includes the positive electrode for a lithium ion secondary battery based on any one of the first to sixteenth aspects, it has a high capacity and can be charged and discharged quickly.
  • FIG. 1 is a schematic end view showing a longitudinal section of an electrode structure of a lithium ion secondary battery according to an embodiment of the present invention. It is a top view which shows arrangement
  • FIG. 3A is a schematic end view showing a longitudinal section of a positive electrode for a lithium ion secondary battery according to a modification of the present invention, FIG. 3A is a positive electrode having a hole whose bottom is formed by a current collector, and FIG. 3B is an active material layer; A positive electrode having a through hole penetrating the current collector, FIG.
  • FIG. 3C shows an opening formed on the surface of one active material layer, penetrating the active material layer and the current collector, and a bottom portion formed by another active material layer.
  • FIG. 3D shows a hole in which an opening is formed on the surface of one active material layer, penetrates the active material layer and the current collector, and a bottom is formed by another active material layer; It is a positive electrode in which openings are formed on the surface of another active material layer, and holes that penetrate through the other active material layer and the current collector and have the bottom formed by one active material layer are alternately arranged .
  • FIG. 4A is a schematic end view showing a vertical cross-sectional shape of an active material layer according to a modification of the present invention
  • FIG. 4A is an active material layer having a triangular cross-sectional shape
  • FIG. 4B is a U-shaped vertical cross-sectional shape
  • FIG. 4C shows an active material layer in which a pentagonal hole is formed. It is a top view which shows roughly arrangement
  • FIG. 6A is a plan view schematically showing the arrangement of holes on the surface of an active material layer according to a modified example of the present invention.
  • FIG. 6A shows a triangular opening
  • FIG. 6B shows a rectangular opening
  • FIG. 6C shows an opening. It is an active material layer having a hexagonal hole.
  • FIG. 7A is a plan view showing the shape of an opening of a hole formed in an active material layer according to a modification of the present invention.
  • FIG. 7A shows three vertices
  • FIG. 7B shows four vertices
  • FIG. 7 is the number of vertices
  • FIG. 7E is the number of vertices
  • FIG. 7F is the number of vertices
  • FIG. 7G is a star-shaped opening with the number of vertices is 10 It is.
  • FIG. 8A is a schematic end view showing a longitudinal section of an electrode structure of a lithium ion secondary battery according to a modification of the present invention.
  • FIG. 8A shows a positive electrode and a negative electrode having holes formed on both surfaces
  • FIG. 2 shows an electrode structure of a lithium ion secondary battery in which a plurality of positive electrodes and negative electrodes in which holes and holes on the bottom surface are alternately arranged are stacked.
  • a lithium ion secondary battery 1 includes a positive electrode 2 for lithium ion secondary battery (hereinafter referred to as positive electrode 2) and a negative electrode according to the present invention. 3 and a separator 4 are provided. The positive electrode 2 and the negative electrode 3 are disposed to face each other with the separator 4 interposed therebetween.
  • the positive electrode 2, the negative electrode 3, and the separator 4 are made of, for example, LiPF 6 , LiBF 4 , LiClO in a nonaqueous solvent containing EC (ethylene carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), MEC (methyl ethyl carbonate), and the like. It is immersed in an electrolytic solution in which a lithium salt such as 4 is mixed.
  • the positive electrode 2 has a hole 7 having an opening 9 on the surface of the positive electrode 2.
  • the positive electrode 2 is disposed so that the opening 9 of the hole 7 faces the separator 4.
  • active material layers 11 are formed on both surfaces of a current collector 10, and, similarly to the positive electrode 2, holes 12 having openings 13 are formed on the surface.
  • the hole 12 formed in the negative electrode 3 is disposed so as to face the opening 9 of the hole 7 of the positive electrode 2 with the separator 4 interposed therebetween.
  • the opening 9 of the hole 7 formed in the positive electrode 2 and the opening 13 of the hole 12 formed in the negative electrode 3 do not necessarily face each other, but the opening 9 of at least one hole 7 and the opening of the hole 12 are not necessarily required to face each other. It is desirable that 13 is facing.
  • a lithium ion and a counter ion between the holes 12 of the hole 7 and the negative electrode 3 of the positive electrode 2 (for example, PF 6 - ions) can be moved smoothly, more battery reaction Get faster.
  • the negative electrode 3 is not particularly limited, and a known negative electrode for a lithium ion secondary battery can be used.
  • the negative electrode 3 may be, for example, a conventional composite electrode having active material layers formed of a composite material containing an active material on both surfaces of the current collector.
  • the positive electrode 2 includes a current collector 5 and two active material layers 6, and is active on both sides of the current collector 5.
  • a material layer 6 is formed.
  • the current collector 5 is a plate-like member, preferably a thin-film member having a thickness of 5 to 20 ⁇ m. The size, shape, and the like of the current collector 5 can be changed as appropriate according to the lithium ion secondary battery to be manufactured.
  • the current collector 5 is not particularly limited as long as it is stable with respect to a chemical reaction that occurs during charging / discharging of the battery and is formed of a conductive member.
  • the current collector 5 can be a foil formed of aluminum, copper, silver, gold, platinum, nickel, titanium, iron, stainless steel, or the like.
  • a nonwoven fabric formed of metal fibers or carbon fibers can be used as the current collector 5.
  • the active material layer 6 is formed of a mixture containing an active material, a conductive additive, and a binder, and is generally called a composite material.
  • the active material layer 6 is composed of 80.0 to 99.0 wt% of the active material and 0.5 to 10.0 wt% of the conductive auxiliary when the total mass of the active material, the conductive auxiliary and the binder is 100 wt%. And 0.5 to 10.0 wt% of the binder. It is desirable to contain the active material or the like at this ratio, but it may deviate from this ratio as long as the active material is contained at the active material density described below.
  • LMO LiMn 2 O 4
  • LNO LiNiO 2
  • NCA Al 0.05 O 2
  • LFP LiFePO 4
  • acetylene black hereinafter referred to as AB
  • KB ketjen black
  • CNT carbon nanotube
  • binder polyvinylidene fluoride (hereinafter referred to as PVDF) or the like can be used.
  • the active material layer 6 contains an active material with an active material density representing the amount of the active material contained in a unit volume of the active material layer 6 being 68 to 83% of the true density of the active material. Furthermore, the active material layer 6 preferably contains an active material with an active material density of 70 to 83% of the true density, and more preferably contains an active material with an active material density of 73 to 83% of the true density. preferable. When the ratio of the active material density to the true density is large, the positive electrode 2 carries more active material, and by forming the holes 7, the electrolyte solution reaches a deep position in the depth direction of the active material layer 6.
  • lithium ions can reach more active materials than when no holes 7 are formed, and more active materials carried by the active material layer 6 can be used more effectively.
  • a lithium ion secondary battery having a capacity can be provided. And since the positive electrode 2 can move the lithium ion in the electrolyte solution in the hole 7, it can provide the lithium ion secondary battery which can charge / discharge quickly with high capacity more reliably.
  • the ratio of the active material density to the true density of the active material layer 6 is smaller than 68%, the active material layer 6 can easily reach the inside even if the hole 7 is not formed in the active material layer 6. Even if the hole 7 is formed in the material layer 6, there are few active materials that can be effectively used for the first time by forming the hole 7, and it is difficult to increase the discharge capacity.
  • the ratio of the active material density to the true density of the active material layer 6 is greater than 83%, the active material density is extremely high, so that the voids in the active material layer 6 are small, and lithium ions are present in the active material layer 6. It is difficult to move. Therefore, even if the hole 7 is formed in the active material layer 6, only the active material in the portion exposed in the internal space of the hole 7 can be used, and the active material inside the active material layer cannot be effectively used. Even if the carrying amount increases, the discharge capacity is unlikely to increase.
  • the active material density of the active material layer 6 is 3.45 to 4.19 g / cm 3 .
  • the true density of the ternary positive electrode is 4.6 g / cm 3
  • the active material density of the active material layer 6 is 3.12 to 3.81 g / cm 3. 3 .
  • the true density of a ternary positive electrode having a composition of Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 is used, but the true density is the same value even if the composition changes. It is.
  • the true density of LMO is 4.2 g / cm 3 , so that the active material density of the active material layer 6 is 2.86 to 3.48 g / cm 3 .
  • the active material density of the active material layer 6 is 3.26 to 3.98 g / cm 3 .
  • the active material density of the active material layer 6 is 3.33 to 4.06 g / cm 3 .
  • the active material density of the active material layer 6 is 2.45 to 2.98 g / cm 3 .
  • the true density of the active material mixture is at least greater than the true density of 3.6 g / cm 3 when 100% of LFP having the lowest true density is contained, and the true density is the highest. True density less than 5.05 g / cm 3 with 100% high LCO.
  • the active material density of the active material layer 6 in this case is in the range of less than 2.45 g / cm 3 Ultra 4.19 g / cm 3.
  • the active material layer 6 is formed in a thin film shape on the surface of the current collector 5.
  • a plurality of holes 7 are formed in the active material layer 6.
  • the hole 7 has an opening 9 on the surface of the active material layer 6 and is formed from the surface toward the current collector 5.
  • the hole 7 has a bottom portion 8 formed on the surface of the active material layer 6 that contacts the current collector 5. That is, the hole 7 does not penetrate the current collector 5, and the bottom 8 is formed by the active material layer 6.
  • the hole 7 is formed in a columnar shape, and the vertical cross-sectional shape is a quadrangle.
  • the thickness of the active material layer 6 is 150 to 1000 ⁇ m.
  • the positive electrode 2 can carry a sufficient active material and can provide a lithium ion secondary battery having a large battery capacity. Then, positive electrode 2, when used in lithium ion secondary batteries, lithium ion and its counter ion (e.g., PF 6 - ions) moving distance is not too long, and improve the charge-discharge characteristics of the lithium ion secondary battery it can.
  • the thickness of the active material layer 6 is more preferably 500 to 1000 ⁇ m.
  • the positive electrode 2 can provide a lithium ion secondary battery that can be charged and discharged quickly with higher capacity and more reliably.
  • the hole 7 has a round opening 9.
  • the holes 7 are arranged on the surface of the active material layer 6 so that the openings 9 are arranged at equal intervals in the vertical and horizontal directions at a predetermined interval.
  • the maximum diameter of the hole 7 is not particularly limited, but is preferably 5 to 2000 ⁇ m.
  • the maximum diameter of the hole 7 is 5 to 2000 ⁇ m, when the positive electrode 2 is used in a lithium ion secondary battery, the lithium ions can move smoothly in the electrolyte existing in the hole 7, thereby further improving the battery reaction speed. it can.
  • the positive electrode 2 has few voids in the active material layer 6 that are reduced by compression when forming the holes 7, and the active material that can be effectively used increases by forming the holes 7.
  • the maximum diameter of the hole 7 is 500 to 2000 ⁇ m.
  • the positive electrode 2 has a larger diameter of the hole 7, so that when used in a lithium ion secondary battery, the lithium ions are smoother in the electrolyte present in the hole 7. The speed of the battery reaction is further improved.
  • the length between the centers of adjacent holes 7 is not particularly limited, but is preferably 500 to 8000 ⁇ m.
  • the positive electrode 2 does not overlap the range in which the lithium ions in the electrolytic solution reach from one hole 7, and the lithium ions in the electrolytic solution are difficult to reach in the active material layer 6. Since the area decreases, the active material that can be effectively used increases by forming the holes 7.
  • the center interval of the holes 7 is 500 to 4000 ⁇ m.
  • the positive electrode 2 is more likely to cause lithium ions in the electrolytic solution to spread throughout the positive electrode 2, and the active material that can be effectively used increases.
  • the depth of the hole 7 is not particularly limited, but is preferably 5% or more of the thickness of the active material layer 6.
  • the depth of the hole 7 is 5% or more, lithium ions in the electrolytic solution easily reach a deep position in the depth direction of the active material layer 6, and the active material that can be effectively used increases.
  • the depth of the hole 7 is 67% or more of the thickness of the active material layer 6.
  • the depth of the hole is 67% or more, lithium ions in the electrolytic solution are more likely to reach a deep position in the depth direction of the active material layer 6, and the number of active materials that can be effectively used increases.
  • a method for producing the positive electrode 2 for lithium ion secondary battery will be described.
  • the active material, the binder, and the conductive assistant are weighed so as to have a predetermined mass ratio. After weighing, the binder is added to the solvent and stirred for a predetermined time. Furthermore, an active material and a conductive additive are added and stirred, and the viscosity is adjusted to prepare a positive electrode slurry.
  • the positive electrode slurry is a liquid used for forming the active material layer 6 on the surface of the current collector 5. Incidentally, the positive electrode slurry is generally called a composite slurry.
  • the positive electrode slurry produced on both surfaces of the current collector 5 formed into a predetermined size is applied and dried at a predetermined temperature for a predetermined time to form the active material layer 6.
  • the coating method is not particularly limited, and for example, a doctor blade method or a die coating method can be used.
  • such an active material layer 6 is generally called a composite material.
  • the amount of the active material contained in the active material layer 6 can be adjusted by changing the viscosity of the positive electrode slurry and the coating thickness of the positive electrode slurry.
  • the current collector 5 on which the active material layer 6 is formed is passed through a roll press, and the active material layer 6 is formed to a predetermined thickness.
  • the active material density of the active material layer 6 can be adjusted by changing the thickness of the active material layer 6 by adjusting the gap distance between the rolls of the roll press machine.
  • a sword-like jig with a large number of needles is pierced into the surface of the active material layer 6 to form a hole 7 to obtain the positive electrode 2 for a lithium ion secondary battery.
  • the small hole 7 having a diameter of 500 ⁇ m or less can be formed by laser processing.
  • the size of the hole 7 to be formed can be adjusted by changing the diameter of the laser beam to be irradiated, and for example, the frustum-shaped hole 7 can be formed by changing the incident angle.
  • the lithium ion secondary battery 1 using the positive electrode 2 according to the embodiment of the present invention will be described.
  • the positive electrode 2 and the negative electrode 3 are immersed in the electrolytic solution, and the electrolytic solution is also present in the hole 7 formed in the active material layer 6 of the positive electrode 2. Since the hole 7 is formed in the active material layer 6, the electrolytic solution also exists at a deep position in the thickness direction from the surface of the active material layer 6.
  • Electrons emitted from the active material move to the negative electrode 3 through an external circuit (not shown).
  • lithium ions move to the negative electrode 3 through the electrolytic solution, are inserted into the active material, and receive electrons.
  • the lithium ion secondary battery 1 is charged as described above.
  • the positive electrode 2 and the negative electrode 3 are connected to an external load (not shown). Then, lithium in the active material is released into the electrolytic solution as lithium ions at the negative electrode 3.
  • Electrons released from the active material move from the negative electrode 3 to the positive electrode 2 through an external load.
  • the lithium ions are desorbed from the active material and move to the positive electrode 2 through the electrolytic solution.
  • Lithium ions are inserted into the active material at the positive electrode 2. Also in this case, since the hole 7 is formed in the active material layer 6, the lithium ions move in the electrolytic solution existing in the hole 7, and the movement of the lithium ions becomes smooth, and the surface of the active material layer 6 is In addition, lithium ions are inserted into the active material even at positions deep in the thickness direction of the active material layer 6. In this way, the lithium ion secondary battery 1 is discharged.
  • the positive electrode 2 for a lithium ion secondary battery is configured to include the current collector 5 and the active material layer 6 formed on the surface of the current collector 5. did.
  • the active material layer 6 has a plurality of holes 7 formed on the surface, the active material density is 68 to 83% of the true density of the active material contained in the active material layer 6, and the thickness is 150 to 1000 ⁇ m. It was configured as follows.
  • the positive electrode 2 has a plurality of holes 7 formed on the surface of the active material layer 6, when used in the lithium ion secondary battery 1, in addition to the surface of the active material layer 6, the surface of the active material layer 6 is used. Even at deep positions in the thickness direction, the movement of lithium ions is smooth, so that electrons can be exchanged, lithium ions can be inserted and desorbed.
  • the positive electrode 2 can move in the electrolytic solution in which the lithium ions released from the active material exist in the holes 7 at a position deep in the thickness direction from the surface of the active material layer 6.
  • the positive electrode 2 for a lithium ion secondary battery according to the embodiment of the present invention supports a larger amount of active material, can effectively use most of the supported active material, and has a high capacity.
  • a lithium ion secondary battery that can quickly charge and discharge quickly and has a low internal resistance and a high output can be provided.
  • the positive electrode 2 for a lithium ion secondary battery according to an embodiment of the present invention can effectively use an active material without excessively moving the lithium ion within the positive electrode, a high capacity lithium ion secondary battery can be used. Battery can be provided.
  • lithium ions have a very small ion radius, it is considered that lithium ions are solvated with many solvents in the electrolytic solution. And the solvated lithium ion has a large movement resistance. Further, in the case of a conventional composite electrode formed by drying an electrode paste coated on the surface of a current collector and having no holes in the active material layer, an electrolyte solution containing LiPF 6 as a lithium salt, for example, as a lithium salt PF 6 ⁇ ions, which are counter ions when added to the electrolyte, migrated through the electrolyte contained in the micropores formed between the active materials in the electrode.
  • LiPF 6 lithium salt
  • the electrolyte solution in which the micropores are impregnated with solvated lithium ions (Li + ) and PF 6 ⁇ ions is used. Therefore, lithium ions and PF 6 ⁇ ions were easily caught in the constricted portion between the active materials, and the movement resistance was further increased.
  • the hole 7 is formed in the active material layer 6 of the positive electrode 2, lithium ions and PF 6 ⁇ ions preferentially pass through the electrolytic solution existing in the hole 7, and the hole 7 is a priority path through which ions can move quickly, and can move through the positive electrode 2 without being inhibited by lithium ions.
  • the battery reaction is fast even if the active material layer 6 carries the active material at a high density, and the active material layer 6 is further formed. Even when it is formed thick, the battery reaction is fast.
  • lithium ion or PF 6 solvated - ions maximum rate-limiting movement resistance cell reaction when passing through the fine pores formed between the active material particles in the mixed material electrode It is thought that.
  • the positive electrode 2 can provide a lithium ion secondary battery that can be charged and discharged quickly.
  • lithium-ion or PF 6 is a deep position in the thickness direction of the electrode - hardly reach ion, active material can be effectively utilized Was limited to those in the range of about 100 ⁇ m from the surface.
  • the positive electrode 2 includes the active material layer 6 having an active material density as high as 68 to 83% of the true density of the active material and a thickness of 150 to 1000 ⁇ m. Even in the case of a thick electrode carrying an active material at a high density, when used in the lithium ion secondary battery 1, lithium ions can move in the electrolyte present in the hole 7, so that a deep position in the thickness direction of the positive electrode 2. In addition, lithium ions can move, and an active material located deep in the thickness direction of the positive electrode 2 can also be used effectively.
  • the lithium ion secondary battery 1 using the positive electrode 2 for a lithium ion secondary battery according to the embodiment of the present invention can be charged and discharged quickly with a high capacity.
  • the positive electrode 2 for a lithium ion secondary battery of the present invention can increase the capacity of the battery by forming the active material layer 6 thick and increasing the active material density, a high capacity battery can be realized with the single-layer positive electrode 2.
  • the number of separators 4 can be reduced.
  • the positive electrode 2 for lithium ion secondary batteries of this invention makes the liquid retention property of the hole 7 good by making the some hole 7 have the bottom part 8, and the lithium ion secondary battery 1 is attached.
  • the positive electrode 2 prevents the current collector 5 from being broken in the manufacturing process of the positive electrode 2 and the lithium ion secondary battery 1 by preventing the hole 7 from penetrating the current collector 5.
  • the lithium ion secondary battery 1 can be manufactured.
  • the present invention is not limited to the above-described embodiment, and can be appropriately changed within the scope of the gist of the present invention.
  • the materials of the active material, the binder, the conductive auxiliary agent, the electrolytic solution, the separator, and the current collector can be appropriately changed.
  • the positive electrode 2 has the hole 7 in which the opening 9 is formed on the surface of the active material layer 6 and the bottom portion 8 is formed by the active material layer 6 has been described. Is not limited to this.
  • the positive electrode 2A has a hole 7A in which an opening 9A is formed on the surface of the active material layer 6A, penetrates the active material layer 6A, and a bottom 8A is formed by the current collector 5A. You may do it.
  • the positive electrode 2B has an opening 9B formed on the surface of one active material layer 6B and the other active material layer 6B, and the current collector 5B, the one active material layer 6B and the other active material layer 6B. You may have the hole 7B which penetrates the substance layer 6B. In this case, in the manufacturing process of the lithium ion secondary battery, the positive electrode 2B can easily inject the electrolytic solution, and can easily discharge the gas generated during the initial charge.
  • the positive electrode 2C has an opening 9C formed on the surface of one active material layer 6C, penetrates the active material layer 6C and the current collector 5C, and is bottomed by the other active material layer 26C. You may have the hole 7C in which 8C is formed.
  • the surface area of the active material layer is increased by the surface of the bottom 8C as compared with the case where the bottom 8A of the hole 7A is formed by the current collector 5A.
  • a lithium ion secondary battery capable of generating electricity more efficiently can be provided.
  • the hole 7C has the bottom 8C and the depth of the hole is deeper than that of the hole 7, the liquid retaining property is further higher. Therefore, in the lithium ion secondary battery using the positive electrode 2C, even when the battery is tilted and the electrolyte is biased to one side, the electrolyte is sufficiently held in the hole 7C, and the performance is hardly deteriorated.
  • the positive electrode 2D has an opening 9D formed on the surface of one active material layer 6D, penetrates the active material layer 6D and the current collector 5D, and is bottomed by the other active material layer 26D.
  • 27D, and the holes 7D and the holes 27D may be alternately arranged.
  • the hole 7 has a quadrangular cross-sectional shape
  • the present invention is not limited to this, and the vertical cross-sectional shape of the hole 7 can be changed as appropriate.
  • the hole 7E may be formed in the active material layer 6E so that the longitudinal cross-sectional shape is a triangle and the apex of the triangle is the bottom 8E.
  • the hole 7F may be formed in the active material layer 6F so that the longitudinal cross-sectional shape of the tip portion is a semicircular shape, and the vertex of the semicircle becomes the bottom portion 8F. .
  • the vertical cross-sectional shape of the hole 7F is U-shaped.
  • the hole 7G may be formed in the active material layer 6G so that the longitudinal cross-sectional shape of the tip portion is triangular and the apex of the triangle is the bottom 8G.
  • the vertical cross-sectional shape of the hole 7G is a pentagon.
  • the vertical cross-sectional shape of the holes 7A, 7B, 7C, 7D, and 27D shown in the above modification may be a triangle, a U shape, or a pentagon as described above.
  • the current collectors 5A and 5B are exposed at the vertex at the deepest part of the hole or a hole is formed at the vertex so that the vertical cross-sectional shape is slightly Deform.
  • the vertical cross-sectional shape is a trapezoid whose lower base is shorter than the upper base.
  • the holes 7 formed in the active material layer 6 do not have to have the same vertical cross-sectional shape of all the holes 7, and holes 7 having different vertical cross-sectional shapes may be mixed, And the hole 7 having the bottom 8 may be mixed.
  • the holes 7 are arranged on the surface of the active material layer 6 so that the openings 9 are arranged at equal intervals in the vertical and horizontal directions with a predetermined interval.
  • the present invention is not limited to this. I can't.
  • the holes 7H may have openings 9H arranged on the surface of the active material layer 6H so as to be arranged at equal intervals along an axis parallel to the diagonal line at a predetermined interval.
  • the holes 7 may be arranged so that the openings 9 are arranged at a predetermined interval along a concentric circle centering on the center of the active material layer 6.
  • the shape of the opening 9 can be changed as appropriate.
  • the shape of the opening 9J may be a triangle like the hole 7J shown in FIG. 6A
  • the shape of the opening 9K may be a square like the hole 7K shown in FIG. 6B
  • the hole 7L shown in FIG. As described above, the shape of the opening 9L may be a hexagon.
  • the shape of the opening 9 may be a pentagon, or a heptagon or more polygon.
  • the opening 9 of the hole 7 may be a star shape having about 3 to 10 vertices.
  • the opening 9 of all the holes 7 does not need to have the same shape, and the opening 9 of a different shape may be mixed. .
  • the cross-sectional shape of the hole 7 described in the above modification and the surface shape of the hole 7 may be appropriately combined.
  • the hole 7 may have a rectangular opening 9 and a triangular cross-sectional shape.
  • the hole 7 is a quadrangular pyramid.
  • the lithium ion secondary battery 1 having a single-layer structure in which the positive electrode 2 and the negative electrode 3 are stacked one by one with the separator 4 interposed therebetween has been described.
  • the present invention is not limited to this, and the separator 4
  • a lithium-ion secondary battery having a multilayer structure in which the positive electrode 2 and the negative electrode 3 are further laminated can be obtained.
  • the lithium ion secondary battery 1 ⁇ / b> A may have a multilayer structure in which four layers of the positive electrode 2 and the negative electrode 3 are alternately stacked via the separator 4.
  • the opening 9 of the hole 7 of the positive electrode 2 and the opening 13 of the hole 12 of the negative electrode 3 can face each other with the separator 4 interposed therebetween.
  • lithium ions easily move between the negative electrode 3 and charge and discharge can be performed more efficiently.
  • the lithium ion secondary battery 1B has a multilayer structure in which a positive electrode 2D and a negative electrode 3D formed in the same shape as the positive electrode 2D are stacked in the same manner as the lithium ion secondary battery 1A. May be.
  • the opening 9D of the hole 7D of the positive electrode 2D the opening 29D of the hole 27D of the positive electrode 2D, the opening 13D of the hole 12D of the negative electrode 3D, and the hole 32D of the negative electrode 3D. Since any of the openings 33D faces the separator 4, charging and discharging can be performed more efficiently.
  • the active material layer 6 is formed on both surfaces of the current collector 5 has been described.
  • the present invention is not limited to this, and the active material layer 6 includes the current collector 5. It may be formed only on one side.
  • Example I Production of electrochemical cell
  • a positive electrode for a lithium ion secondary battery of the present invention using LCO as an active material was produced and applied to the positive electrode of the electrochemical cell.
  • the electrochemical cells of Examples 1 to 6 are different in the depth of the hole formed in the active material layer, but the other configurations are the same, and therefore, a method for manufacturing the electrochemical cell will be described using Example 1 as an example.
  • the LCO as the active material, the PVDF as the binder, and the AB as the conductive assistant were weighed so that the mass ratio was 95: 3: 2. Thereafter, the weighed PVDF was added to N-methyl-2-pyrrolidone (NMP) as a solvent and stirred for 20 minutes. Further, LCO and AB were added and stirred to obtain a positive electrode slurry having a viscosity adjusted to 5 Pa ⁇ s.
  • NMP N-methyl-2-pyrrolidone
  • the aluminum foil in which the active material layer was formed on both surfaces was subjected to a roll press machine (product name: 5 ton air hydro press), and compressed so that the thickness of the active material layer was 300 ⁇ m.
  • a sword-like needle was pierced into the surface of the compressed one active material layer to form holes having parameters shown in Table 1. Thereafter, a plurality of holes were similarly formed on the surface of the other compressed active material layer.
  • a positive electrode having an active material density of 4.0 g / cm 3 (79% of the true density) and an active material layer containing 120 mg / cm 2 of LCO on both surfaces was manufactured.
  • Example 6 when forming a hole in the active material layer, the same hole as the active material layer was formed in the aluminum foil at the same time, and a positive electrode having a through hole was produced.
  • Example 1 For comparison, an electrochemical cell similar to that of Example 1 was produced as Comparative Example 1 except that no hole was formed in the active material layer.
  • the data of the positive electrodes of Examples 1 to 6 and the positive electrode of Comparative Example 1 are shown in Table 1.
  • the active material layers of the prepared positive electrode all have the same active material density as in Example 1.
  • Example 7 a positive electrode for a lithium ion secondary battery using LMO as an active material was produced and applied to a positive electrode of an electrochemical cell.
  • the electrochemical cells of Examples 7 to 12 are different in the center spacing of the holes formed in the active material layer, but the other configurations are the same. Therefore, a method for manufacturing the electrochemical cell will be described using Example 7 as an example.
  • the LMO as the active material, the PVDF as the binder, and the AB as the conductive assistant were weighed so that the mass ratio was 94: 4: 2. Thereafter, the weighed PVDF was added to NMP as a solvent and stirred for 20 minutes. Furthermore, LMO and AB were added and stirred to obtain a positive electrode slurry having a viscosity adjusted to 7 Pa ⁇ s.
  • an aluminum foil having a thickness of 15 ⁇ m cut to a size of 3 cm ⁇ 3 cm was prepared as a current collector, and an active material layer was formed on both sides of the aluminum foil by the same method as in Example 1.
  • the formed active material layer has a thickness of 1200 ⁇ m.
  • Example 2 the aluminum foil in which the active material layer was formed on both surfaces was subjected to a roll press machine and compressed so that the thickness of the active material layer became 1000 ⁇ m.
  • holes having the parameters shown in Table 2 were formed, the active material density was 3.4 g / cm 3 (81% of the true density), and the active material layer containing LMO of 340 mg / cm 2 was produced on both sides.
  • An electrochemical cell was formed in the same manner as in Example 1 using the positive electrode.
  • the electrochemical cells of Examples 8 to 12 were produced in the same manner as Example 7.
  • Example 7 For comparison, an electrochemical cell similar to that in Example 7 was produced as Comparative Example 2 except that no hole was formed in the active material layer.
  • the data of the positive electrodes of Examples 7 to 12 and the positive electrode of Comparative Example 2 are shown in Table 2. Each of the produced positive electrode active material layers had the same active material density as in Example 7.
  • Example 13 to 18 a positive electrode for a lithium ion secondary battery using a ternary positive electrode as an active material was produced and applied to a positive electrode of an electrochemical cell.
  • the maximum diameters of the holes formed in the active material layer are different.
  • the hole forming method and the hole depth are different. Since other configurations are the same, a method for manufacturing an electrochemical cell will be described using Example 13 as an example.
  • each was measured so that the mass ratio of the ternary positive electrode as the active material, PVDF as the binder, and KB as the conductive auxiliary agent was 97: 2: 1. Thereafter, the weighed PVDF was added to NMP as a solvent and stirred for 20 minutes. Further, a ternary positive electrode and KB were added and stirred to obtain a positive electrode slurry having a viscosity adjusted to 5 Pa ⁇ s.
  • an aluminum foil having a thickness of 15 ⁇ m cut to a size of 3 cm ⁇ 3 cm was prepared as a current collector, and an active material layer was formed on both sides of the aluminum foil by the same method as in Example 1.
  • the formed active material layer has a thickness of 210 ⁇ m.
  • Example 13 For comparison, an electrochemical cell similar to that of Example 13 was produced as Comparative Example 3 except that holes were not formed in the active material layer and the current collector.
  • Table 3 shows the data of the positive electrodes of Examples 13 to 18 and the positive electrode of Comparative Example 3. Each of the produced positive electrode active material layers had the same active material density as in Example 13.
  • Examples 19 to 22 a positive electrode for a lithium ion secondary battery using LNO as an active material was produced and applied to a positive electrode of an electrochemical cell.
  • the electrochemical cells of Examples 19 to 22 are different in the shape of the opening of the hole formed in the active material layer, but the other configurations are the same. Therefore, the method for manufacturing the electrochemical cell will be described using Example 19 as an example. .
  • an aluminum foil having a thickness of 15 ⁇ m cut to a size of 3 cm ⁇ 3 cm was prepared as a current collector, and an active material layer was formed on both sides of the aluminum foil by the same method as in Example 1.
  • the formed active material layer has a thickness of 480 ⁇ m.
  • the aluminum foil in which the active material layer was formed on both surfaces was subjected to a roll press machine and compressed so that the thickness of the active material layer was 400 ⁇ m. Holes having the parameters shown in Table 4 were formed in the active material layer in the same manner as in Example 1.
  • the active material density was 3.8 g / cm 3 (79% of the true density), and 152 mg / cm 2 .
  • a positive electrode having an active material layer containing LNO on both sides was produced.
  • An electrochemical cell was produced in the same manner as in Example 1 using the positive electrode.
  • the electrochemical cells of Examples 20 to 22 were produced in the same manner as in Example 19.
  • Example 19 For comparison, an electrochemical cell similar to that of Example 19 was prepared as Comparative Example 4 except that no hole was formed in the active material layer.
  • Table 4 shows the data of the positive electrodes of Examples 19 to 22 and the positive electrode of Comparative Example 4.
  • the active material layers of the produced positive electrodes all have the same active material density as in Example 19.
  • Example 23 a positive electrode for a lithium ion secondary battery using LFP as an active material was produced and applied to the positive electrode of an electrochemical cell.
  • the LFP as the active material, the PVDF as the binder, and the carbon nanotubes (manufactured by Mitsubishi Materials) as the conductive assistant were weighed so that the mass ratio was 93: 5: 2. Thereafter, the weighed PVDF was added to NMP as a solvent and stirred for 20 minutes. Further, LFP and carbon nanotubes were added and stirred to obtain a positive electrode slurry having a viscosity adjusted to 6 Pa ⁇ s.
  • an aluminum foil having a thickness of 15 ⁇ m cut to a size of 3 cm ⁇ 3 cm was prepared as a current collector, and an active material layer was formed on both sides of the aluminum foil by the same method as in Example 1.
  • the thickness of the formed active material layer is 180 ⁇ m.
  • the aluminum foil in which the active material layer was formed on both surfaces was subjected to a roll press machine and compressed so that the thickness of the active material layer became 150 ⁇ m. Holes having the parameters shown in Table 5 were formed in the active material layer in the same manner as in Example 1.
  • the active material density was 2.88 g / cm 3 (80% of the true density), and 43.2 mg / cm.
  • a positive electrode having an active material layer containing 2 LFP on both sides was produced.
  • An electrochemical cell was produced in the same manner as in Example 1 using the positive electrode.
  • Example 23 For comparison, an electrochemical cell similar to Example 23 was produced as Comparative Example 5 except that no hole was formed in the active material layer.
  • Example 24 a positive electrode for a lithium ion secondary battery using NCA as an active material was produced and applied to the positive electrode of an electrochemical cell.
  • the NCA as the active material, the PVDF as the binder, and the acetylene black as the conductive auxiliary agent were weighed so that the mass ratio was 95: 3: 2. Thereafter, the weighed PVDF was added to NMP as a solvent and stirred for 20 minutes. Further, NCA and acetylene black were added and stirred to obtain a positive electrode slurry having a viscosity adjusted to 5 Pa ⁇ s.
  • an aluminum foil having a thickness of 15 ⁇ m cut to a size of 3 cm ⁇ 3 cm was prepared as a current collector, and an active material layer was formed on both sides of the aluminum foil by the same method as in Example 1.
  • the thickness of the formed active material layer is 620 ⁇ m.
  • the aluminum foil in which the active material layer was formed on both surfaces was subjected to a roll press machine and compressed so that the thickness of the active material layer became 500 ⁇ m. Holes having the parameters shown in Table 5 were formed in the active material layer in the same manner as in Example 1, and the active material density was 3.9 g / cm 3 (80% of the true density) and 195 mg / cm 2 .
  • a positive electrode having an active material layer containing NCA on both sides was produced.
  • An electrochemical cell was produced in the same manner as in Example 1 using the positive electrode.
  • Example 24 For comparison, an electrochemical cell similar to that of Example 24 was prepared as Comparative Example 6 except that no hole was formed in the active material layer.
  • Table 5 shows the data of the positive electrodes of Examples 23 and 24 and the positive electrodes of Comparative Examples 5 and 6.
  • Examples 25 to 29 a positive electrode for a lithium ion secondary battery using LCO as an active material was produced and applied to a positive electrode of an electrochemical cell.
  • Example 25 using a positive electrode slurry having a viscosity of 4.5 Pa ⁇ s, an active material layer having a thickness of 230 ⁇ m was formed on both surfaces of an aluminum foil having a thickness of 15 ⁇ m.
  • the positive electrode shown was made.
  • Example 26 using a positive electrode slurry having a viscosity of 4.8 Pa ⁇ s, an active material layer having a thickness of 235 ⁇ m was formed on both sides of an aluminum foil having a thickness of 15 ⁇ m.
  • the positive electrode shown was made.
  • Example 27 an active material layer having a thickness of 240 ⁇ m was formed on both surfaces of an aluminum foil having a thickness of 15 ⁇ m using a positive electrode slurry having a viscosity of 5 Pa ⁇ s, and the positive electrodes shown in Table 6 were produced in the same manner as in Example 25. Was made.
  • Example 28 a positive electrode slurry having a viscosity of 5.5 Pa ⁇ s was used to form an active material layer having a thickness of 250 ⁇ m on both sides of an aluminum foil having a thickness of 15 ⁇ m.
  • the viscosity was 5.5 Pa ⁇ s.
  • s positive electrode slurry an active material layer having a thickness of 260 ⁇ m is formed on both sides of an aluminum foil having a thickness of 15 ⁇ m, each active material layer is compressed to 200 ⁇ m, and a laser having a diameter of 100 ⁇ m using a laser processing machine.
  • the positive electrode shown in Table 6 was produced by irradiating the surface of the active material layer with light.
  • Comparative Example 7 For comparison, as Comparative Example 7, a positive electrode slurry having a viscosity of 4 Pa ⁇ s was used, and a 210 ⁇ m thick active material layer was formed on both surfaces of a 15 ⁇ m thick aluminum foil. The positive electrode shown in Table 6 was produced. As Comparative Example 8, an electrochemical cell having the same configuration as Comparative Example 7 was produced except that no hole was formed.
  • a positive electrode slurry having a viscosity of 4 Pa ⁇ s was used to form an active material layer having a thickness of 210 ⁇ m on both surfaces of an aluminum foil having a thickness of 15 ⁇ m, and the active material layer was compressed to 200 ⁇ m.
  • a positive electrode shown in Table 6 was produced in the same manner as described above.
  • an electrochemical cell having the same configuration as Comparative Example 9 was produced except that no hole was formed.
  • Comparative Example 11 using a positive electrode slurry having a viscosity of 4 Pa ⁇ s, an active material layer having a thickness of 220 ⁇ m was formed on both surfaces of an aluminum foil having a thickness of 15 ⁇ m. Was made.
  • Comparative Example 12 an electrochemical cell having the same configuration as Comparative Example 11 was produced except that no hole was formed.
  • Example 25 is opened as Comparative Example 13, Example 26 as Comparative Example 14, Example 27 as Comparative Example 15, Example 28 as Comparative Example 16, and Example 29 as Comparative Example 17.
  • An electrochemical cell having the same configuration was prepared except for the above.
  • Table 6 shows positive electrode data of Examples 25 to 29 and Comparative Examples 7 to 17.
  • the maximum diameter of the holes formed in the active material layer, the center distance between the holes, and the depth of the holes were measured with a laser microscope (manufactured by Keyence Corporation, product name: VK-X100). These values were calculated by measuring each of 30 locations and obtaining the average value.
  • the active material density was calculated by the following method. First, the positive electrode was cut to a size of 1 cm 2 and the weight and thickness were measured. Thereafter, an aluminum foil as a current collector was taken out from the cut positive electrode, and the weight and thickness of the taken out aluminum foil were measured. Then, the thickness of the active material layer was calculated by subtracting the thickness of the aluminum foil from the thickness of the positive electrode (if the active material layer was formed on both sides of the aluminum foil, it was further divided by 2). The volume of the active material layer was calculated by multiplying the calculated thickness value of the active material layer by the area of the cut current collector.
  • the value obtained by subtracting the weight of the aluminum foil from the weight of the positive electrode is multiplied by the weight fraction (for example, 0.93 in the case of the LCO of Example 1) when the electrode slurry is prepared (the active material layer is made of the aluminum foil).
  • the active material weight was calculated by further dividing by 2 if it was formed on both sides. Note that the weight of the active material was determined by cutting the positive electrode of the actual battery into a size of 1 cm 2 , peeling the current collector from a part of the cut positive electrode, and forming the active material mixture layer with N-methyl-2-pyrrolidone ( It can be measured by dissolving in NMP) and centrifuging to separate and dry only the active material and then weighing the weight.
  • NMP N-methyl-2-pyrrolidone
  • the active material density was calculated by dividing the active material weight determined above by the volume of the active material layer.
  • the value which divided the value of the active material weight by the area of the cut positive electrode was made into the active material carrying amount per unit area.
  • the characteristics of the electrochemical cell were evaluated by measuring the discharge capacity per unit mass.
  • the discharge capacity was measured at a temperature of 25 ⁇ 1 ° C. using a charge / discharge test apparatus (manufactured by Asuka Electronics Co., Ltd., model: ACD-R1APS).
  • the electrochemical cells of all examples and comparative examples had a constant current of 5 mA / cm 2 (CC: constant current), a constant voltage of 4.2 V (CV: constant voltage), and a charging current value of 0.1 mA / After charging to drop to cm 2 , the cut-off voltage was 3.0 V vs.
  • the electric capacity obtained when discharging at a constant current of 10 mA / cm 2 as Li / Li + was taken as the discharge capacity.
  • Electrochemical Cell (3-1) Relationship between Depth of Hole in Active Material Layer and Characteristics of Electrochemical Cell As shown in Table 1, the electrochemical cells of Examples 1 to 6 are active materials A hole having a ratio of the depth of the hole to the layer thickness of 5% or more is formed in the positive electrode, and compared with the electrochemical cell of Comparative Example 1, the discharge capacity per unit area and the discharge capacity per unit mass Both are expensive.
  • the positive electrode for a lithium ion secondary battery of the present invention desirably has a ratio of the hole depth to the thickness of the active material layer of 67% or more.
  • the electrochemical cell of Example 5 has a hole that penetrates the active material layer and has a bottom formed of aluminum foil.
  • the electrochemical cell of Example 6 has a through hole penetrating the aluminum foil and the active material layer.
  • Example 5 and Example 6 differ in whether or not a through hole is formed in the aluminum foil.
  • the electrochemical cells of Example 5 and Example 6 have the same discharge capacity value. Thus, even if the through hole is formed in the aluminum foil, the battery performance does not deteriorate.
  • the positive electrode for a lithium ion secondary battery of the present invention preferably has a hole center distance of 500 to 4000 ⁇ m.
  • the positive electrode for a lithium ion secondary battery of the present invention preferably has a maximum hole diameter of 500 to 2000 ⁇ m.
  • Example 25 when Example 25 is compared with Comparative Example 13 which is different from Example 25 only in that no hole is formed, Example 25 has an increase in discharge capacity of 78 mAh due to the formation of the hole.
  • Comparative Example 7 when Comparative Example 7 was compared with Comparative Example 8 which was different from Comparative Example 7 only in that no hole was formed, Comparative Example 7 had the same hole as Example 25 formed in the positive electrode. Compared to Comparative Example 8, the discharge capacity is only increased by 6 mAh. Similarly, Comparative Example 9 is 46 mAh higher than Comparative Example 10 and Comparative Example 11 is 54 mAh higher than Comparative Example 12. Compared with Example 25, the increase in discharge capacity is small.
  • the active material density of the positive electrode is as low as 53% of the true density of the active material, and a lot of voids are formed accordingly. Therefore, even if the positive electrode does not form a hole, it contains a sufficient amount of electrolytic solution, and an active material located deep in the thickness direction from the surface can also be used effectively. Therefore, even if a hole is formed in the positive electrode, the number of active materials that can be newly used effectively does not increase so much, and the increase in discharge capacity is considered to be small.
  • the positive electrodes of Comparative Examples 9 to 12 have a low ratio of the active material density to the true density and contain sufficient electrolytic solution, so that they can be used effectively even if holes are formed in the positive electrode. It is considered that there is not much active material and the increase in discharge capacity is small.
  • Comparative Example 7 and Comparative Example 8 Comparative Example 9 and Comparative Example 10, Comparative Example 11 and Comparative Example 12, Example 25 and Comparative Example 13, Example 26 and Comparative Example 14, Example 27 and Comparative Example 15, Example 28 and Comparative Example 16, and Example 29 and Comparative Example 17 are compared, and by forming holes, the discharge capacity is about 1.04 times, about 1.4 times, about 1.5 times, and about 1.9 times. About 2.04 times, about 2.4 times, about 4 times, and about 6 times. As the active material density increases, the amount of increase in discharge capacity increases.
  • the discharge capacity value decreases as the active material density increases. This is because the electrochemical cell of the comparative example increased the active material density, so that the active material carried by the positive electrode increased, but by that amount, the voids in the active material layer decreased, the amount of electrolyte decreased, and from the surface This is probably because lithium ions do not reach the active material located deep in the thickness direction, and the active material that can be used effectively is reduced.
  • the discharge capacity increases as the density of the active material increases. This is because, in the electrochemical cell of the example, the active material carried by the positive electrode increases as the active material density increases, and at the same time, the holes are formed, so that the active material is deep in the thickness direction from the surface. It is thought that this is because lithium ions have arrived and the number of active materials that can be used effectively has increased.
  • the higher the active material density the higher the effect obtained by forming the holes. This has not been clarified in the past techniques (references) disclosed so far.
  • the active material density is high, there are few positive electrode voids that can be impregnated with the electrolytic solution, and the gaps between the active materials are narrow. Therefore, lithium ions present in the electrolyte solution solvated with ethylene carbonate, which is a solvent, cannot pass through the gaps between the active materials. Ions can no longer reach.
  • the higher the active material density the narrower the gap between the active materials, and the more difficult it is for lithium ions to reach. Therefore, it is considered that the discharge capacity is extremely decreased as the active material density is higher.
  • lithium ions can move in the electrolytic solution existing in the hole to the positive electrode at a portion far from the separator, and then permeate in the lateral direction of the hole. Therefore, it is considered that lithium ions can be exchanged even at a position deep in the thickness direction from the surface, and a high discharge capacity can be obtained. It is considered that the higher the active material density, the higher the positive electrode carries more active materials, and the more active materials that can be effectively used.
  • the positive electrode of the present invention can reduce the amount of the electrolytic solution impregnated in the positive electrode.
  • the positive electrode of Example 28 has an active material density of 79%, and the other 21% contains voids, PVDF, and AB.
  • the composition of this positive electrode is LCO 95 wt%, PVDF 3 wt%, and AB 2 wt%. Considering these and the density of PVDF and AB, the volume occupied by PVDF and AB is about 13% in the positive electrode. Therefore, the porosity is about 8%.
  • the positive electrode of Comparative Example 7 has an active material density of 53%. Therefore, when the same calculation is performed, the volume occupied by PVDF and AB is about 13%. Therefore, the porosity is about 34%.
  • the porosity of Example 28 is about 1/4 of that of Comparative Example 7, and the electrolyte solution impregnated is also about 1/4.
  • the amount of the electrolyte solution impregnated in the positive electrode is reduced to about 1/4 or less. Therefore, the positive electrode for a lithium ion secondary battery of the present invention can reduce the amount of electrolyte used, and has a high discharge capacity per volume and can be charged and discharged quickly.
  • Example II Further, in order to investigate the relationship between the active material density of the active material layer of the positive electrode and the discharge capacity of the electrochemical cell using the positive electrode, as Examples 30 to 59, the active material density is in the range of 68 to 83% of the true density.
  • the positive electrode of the present invention was produced by varying the above, and an electrochemical cell similar to the above was produced using the positive electrode.
  • a ternary positive electrode Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2
  • the hole formed in the active material layer of the positive electrode was The shape of the star is a star shape (5 vertices), the vertical cross-sectional shape of the hole is U-shaped, the maximum hole diameter is 500 ⁇ m, the center distance between the holes is 2000 ⁇ m, the hole depth is 120 ⁇ m (the hole with respect to the thickness of the active material layer) The depth ratio is 80%).
  • the active material density is 50%, 60%, and 85% of the true density, respectively, and the positive electrode with holes having the same holes as the Examples and Comparative Example 19
  • the positive electrode with the same active material density as the positive electrode of Comparative Example 18, the positive electrode with the same active material density as the positive electrode of Comparative Example 20 as Comparative Example 21, and the positive electrodes of Examples 30 to 33 as Comparative Examples 22 to 25 A positive electrode without holes having the same active material density was produced, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1.
  • the electrochemical cell of Examples 30-34 and Comparative Examples 18-26 was charged to a charging current of 1 mA / cm 2, the charging current value in the constant voltage of 4.20V drops to 0.1 mA / cm 2, The cut-off voltage is set to 3.0 Vvs.
  • the discharge capacity was measured by discharging at a discharge current of 5 mA / cm 2 as Li / Li + . At this time, 10 mAh / cm 2 was discharged in the first discharge.
  • Examples 35 to 39 LMO is used as the active material, and the hole formed in the active material layer of the positive electrode has a quadrangular hole shape, a pentagonal longitudinal sectional shape, a maximum hole diameter of 1000 ⁇ m, The holes were unified with a center distance of 4000 ⁇ m and a hole depth of 180 ⁇ m (the ratio of the hole depth to the thickness of the active material layer was 90%).
  • the active material density is 50%, 60%, and 85% of the true density, respectively, and the positive electrode with holes having the same holes as in the Examples and Comparative Example 28 are used.
  • the positive electrode with the same active material density as the positive electrode of Comparative Example 27, the positive electrode with the same active material density as the positive electrode of Comparative Example 29 as Comparative Example 30, and the positive electrodes of Examples 35 to 38 as Comparative Examples 31 to 34 A positive electrode without holes having the same active material density was produced, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1.
  • the electrochemical cell of Examples 35-39 and Comparative Examples 27 to 35 was charged to a charging current of 1 mA / cm 2, the charging current value in the constant voltage of 4.35V drops to 0.1 mA / cm 2,
  • the cut-off voltage is set to 3.0 Vvs.
  • the discharge capacity was measured by discharging at a discharge current of 5 mA / cm 2 as Li / Li + . At this time, 10 mAh / cm 2 was discharged in the first discharge.
  • LNO is used as the active material
  • the hole formed in the active material layer of the positive electrode has a round hole shape, a pentagonal vertical sectional shape, a maximum hole diameter of 1000 ⁇ m, The center spacing of the holes was 3000 ⁇ m, and the hole depth was 143 ⁇ m (the ratio of the hole depth to the thickness of the active material layer was 95%).
  • the active material density is 50%, 60%, and 85% of the true density, respectively, and the positive electrode with holes having the same holes as in the examples and Comparative Example 37
  • the positive electrode without holes having the same active material density as the positive electrode of Comparative Example 36, the positive electrode without holes having the same active material density as the positive electrode of Comparative Example 38 as Comparative Example 39, and the positive electrodes of Examples 40 to 43 as Comparative Examples 40 to 43 A positive electrode without holes having the same active material density was produced, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1.
  • NCA was used as the active material
  • the hole formed in the active material layer of the positive electrode had a hexagonal shape, a U-shaped vertical cross-sectional shape, and a maximum hole diameter of 800 ⁇ m.
  • the center distance between the holes was 2500 ⁇ m
  • the hole depth was 162 ⁇ m (the ratio of the hole depth to the thickness of the active material layer was 90%).
  • the active material density is 50%, 60%, and 85% of the true density, respectively.
  • the positive electrode without holes having the same active material density as the positive electrode of Comparative Example 45, the positive electrode without holes having the same active material density as the positive electrode of Comparative Example 47 as Comparative Example 48, and the positive electrodes of Examples 45 to 48 as Comparative Examples 49 to 52 A positive electrode without holes having the same active material density was produced, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1.
  • the electrochemical cells of Examples 45 to 49 and Comparative Examples 45 to 53 were charged with a charging current of 1 mA / cm 2 and a constant voltage of 4.40 V until the charging current value decreased to 0.1 mA / cm 2 .
  • the cut-off voltage is set to 3.0 Vvs.
  • the discharge capacity was measured by discharging at a discharge current of 5 mA / cm 2 as Li / Li + . At this time, discharge of 5 mAh / cm 2 was performed in the first discharge.
  • LFP was used as the active material
  • the hole formed in the active material layer of the positive electrode had a round hole shape, a square hole cross-sectional shape, a maximum hole diameter of 100 ⁇ m, a hole
  • the center spacing of the holes was unified to 1000 ⁇ m, and the hole depth was 150 ⁇ m (the ratio of the hole depth to the thickness of the active material layer was 100%).
  • the hole is a through hole that also penetrates the positive electrode current collector.
  • the active material density is 50%, 60%, and 85% of the true density, respectively, and a positive electrode with holes having the same holes as in the examples and Comparative Example 55
  • the positive electrode with the same active material density as the positive electrode of Comparative Example 54, the positive electrode with the same active material density as the positive electrode of Comparative Example 56 as Comparative Example 57, and the positive electrodes of Examples 50 to 53 as Comparative Examples 58 to 61 A positive electrode without holes having the same active material density was produced, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1.
  • the electrochemical cells of Examples 50 to 54 and Comparative Examples 54 to 62 were charged at a charging current of 1 mA / cm 2 at a constant voltage of 3.70 V until the charging current value decreased to 0.1 mA / cm 2 .
  • the cut-off voltage is 2.5 Vvs.
  • the discharge capacity was measured by discharging at a discharge current of 5 mA / cm 2 as Li / Li + . At this time, discharge of 5 mAh / cm 2 was performed in the first discharge.
  • an active material layer containing 80 wt% LCO and 20 wt% LFP is used as the active material, and the hole formed in the active material layer has a round opening shape and a vertical sectional shape of the hole.
  • the maximum hole diameter is 500 ⁇ m
  • the hole center distance is 4000 ⁇ m
  • the hole depth is 190 ⁇ m (the ratio of the hole depth to the thickness of the active material layer is 95%).
  • the active material density is 50%, 60%, and 85% of the true density, respectively, and the positive electrode with holes having the same holes as in the examples and Comparative Example 64 are used.
  • the positive electrode with the same active material density as the positive electrode of Comparative Example 63, the positive electrode with the same active material density as the positive electrode of Comparative Example 65 as Comparative Example 66, and the positive electrodes of Examples 55 to 58 as Comparative Examples 67 to 70 A positive electrode without holes having the same active material density was produced, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1. After the electrochemical cells of Examples 55 to 59 and Comparative Examples 63 to 71 were charged at a charging current of 1 mA / cm 2 and a constant voltage of 4.20 V until the charging current value decreased to 0.1 mA / cm 2 , The cut-off voltage is 2.5 Vvs.
  • the discharge capacity was measured by discharging at a discharge current of 5 mA / cm 2 as Li / Li + . At this time, discharge of 5 mAh / cm 2 was performed in the first discharge.
  • Table 7 shows the measurement results of the parameters and discharge capacity of the positive electrodes of the electrochemical cells of Examples 30 to 59
  • Table 8 shows the measurement results of the parameters and discharge capacity of the positive electrodes in Comparative Examples 18 to 71.
  • the active material utilization rate (%) was calculated by dividing the discharge capacity per mass by the theoretical discharge capacity per mass.
  • Examples and comparative examples having positive electrodes in which holes are formed in an active material layer carrying a ternary positive electrode as an active material, and comparative examples having positive electrodes without holes carrying the same active material at the same active material density are compared.
  • the ratio of the active material density to the true density is 50% or 60%
  • the positive electrode electrochemical cell having the active material layer in which the hole is formed has the same ratio of the active material density to the true density and no hole is formed.
  • the discharge capacity per mass is about 1.00 times and about 1.06 times, and it is almost increased even if holes are formed in the active material layer. Absent.
  • a positive electrode electrochemical cell having an active material layer in which holes are formed at a ratio of the active material density to the true density of 68% has the same ratio of the active material density to the true density and no holes are formed.
  • the discharge capacity per mass is about 1.33 times that the hole is formed. The amount of increase in the discharge capacity per mass due to the formation of the holes is greatly increased when the ratio of the active material density to the true density is 68% or more.
  • the active material carried by the active material layer can be effectively used even if no hole is formed. Therefore, it was considered that the discharge capacity per mass did not increase so much even when the holes were formed because there were few active materials that could be effectively used for the first time by forming the holes.
  • the active cell which has been effectively used for the first time after the hole has been formed. Since there were many substances, it is thought that the discharge capacity per mass greatly increased by forming holes in the active material layer.
  • the discharge capacity per mass of the positive electrode electrochemical cell having the active material layer in which the hole is formed is about 1.35 times when the ratio of the active material density to the true density is 70%.
  • the ratio of density is 73%, it is about 1.40 times, and when the ratio of active material density to true density is 80%, it is about 1.53 times, and increases as the ratio of active material density to true density increases.
  • the discharge capacity per unit is about 1.00 times, about 1.05 times, about 1.24 times, about 1.29 times, about 1.40 times, about 1.66 times. The same tendency as when the positive electrode is used is shown.
  • the discharge capacity per unit is about 1.00 times, about 1.04 times, about 1.24 times, about 1.29 times, about 1.47 times, about 1.66 times. The same tendency as when the positive electrode is used is shown.
  • the discharge capacity per unit is about 1.00 times, about 1.10 times, about 1.21 times, about 1.28 times, about 1.45 times, about 1.62 times. The same tendency as when the positive electrode is used is shown.
  • a positive electrode electrochemical cell having an active material layer in which holes are formed in an active material layer supporting LFP as an active material, and a positive electrode having a holeless active material layer supporting the same active material at the same active material density as these
  • Each of the positive electrode electrochemical cells having a ratio of the active material density to the true density of 50%, 60%, 68%, 70%, 73%, and 80%, the discharge capacity per mass is obtained by forming the holes. Is about 1.00 times, about 1.09 times, about 1.28 times, about 1.33 times, about 1.40 times, about 1.59 times, and uses a ternary positive electrode as an active material. It shows the same tendency as the case.
  • a positive electrode electrochemical cell having an active material layer in which holes are formed in an active material layer supporting a mixture of LCO and LFP as an active material, and a holeless active material layer supporting the same active material at the same active material density
  • the positive electrode electrochemical cells having a ratio of the active material density to the true density of 50%, 60%, 68%, 70%, 73%, and 80% formed holes when compared with the positive electrode electrochemical cells having As a result, the discharge capacity per mass is about 1.00 times, about 1.10 times, about 1.28 times, about 1.32 times, about 1.39 times, and about 1.46 times. It shows the same tendency as when a ternary positive electrode is used as the substance.
  • the electrochemical cell has a large discharge capacity per mass by forming holes in the active material layer of the positive electrode. If it is 70% or more, the discharge capacity per mass increases by about 30% or more, and if it is 73% or more, the discharge capacity per mass increases by about 40% or more, the ratio of the active material density to the true density increases. It can be seen that the larger the value, the larger the increase in discharge capacity per mass.
  • Example 33 having an active material layer carrying a ternary positive electrode as an active material and having holes formed therein, the ratio of the active material density to the true density being 80%, and the active material density to the true density being true density Comparison is made between Example 34 in which the ratio is 83% and Comparative Example 26 in which the ratio of the active material density to the true density is 85% of the true density.
  • the ratio of the active material density to the true density is increased from 80% to 83%, the discharge capacity per mass is reduced by about 3%.
  • the ratio of the active material density to the density is increased from 83% to 85%, the discharge capacity per mass is reduced by about 26%, which is greatly reduced. This tendency is also observed in electrochemical cells using other active materials.
  • the positive electrode of Comparative Example 26 Since the active material density of the positive electrode of Comparative Example 26 is extremely high, there are few voids present in the active material layer, and the size thereof is also small. For this reason, it is considered that the positive electrode of Comparative Example 26 has a very large lithium ion migration resistance because the amount of the electrolyte present in the positive electrode is small and the voids existing between the active materials are small. Therefore, even if a hole is formed in the active material layer, only the portion of the active material exposed in the internal space of the hole can be used, and the active material inside the active material layer cannot be used effectively, so the discharge capacity value per mass Is thought to have greatly decreased.
  • the ratio of the active material density to the true density is greater than 83%, there is an active material that cannot be effectively used even if the active material loading is increased by increasing the active material density or forming a hole. As a result, the discharge capacity per unit mass rapidly decreases, resulting in a significant decrease in battery capacity.
  • the positive electrode for a lithium ion secondary battery according to the present invention has a ratio of the active material density to the true density of the active material of 68 to 83% when holes are not formed by forming holes. Active materials that could not be used effectively can be used effectively.
  • the ratio of the active material density to the true density of the active material is preferably 70 to 83%, and more preferably 73 to 83%.
  • Example III In order to investigate the relationship between the thickness of the active material layer and the discharge capacity of the electrochemical cell, as Examples 60 to 63, the thickness of the active material layer was changed in the range of 150 to 1000 ⁇ m to produce the positive electrode of the present invention. An electrochemical cell was produced using the positive electrode.
  • an active material layer containing LCO at an active material density of 68% of the true density is used as the active material, and the hole formed in the active material layer has a round opening shape, The vertical cross-sectional shape is a triangle, the maximum hole diameter is 1000 ⁇ m, the center distance between the holes is 3000 ⁇ m, and the ratio of the depth of the hole to the thickness of the active material layer is 90%.
  • Comparative Examples 72, 74, and 80 the same positive electrodes as those in Examples were prepared except that the thicknesses of the active material layers were 50, 100, and 1200 ⁇ m, respectively, and Comparative Examples 73, 75 to 79, A positive electrode was produced in the same manner as in Examples 60 to 63 and Comparative Examples 72, 74, and 80 except that no hole was formed as 81, and an electrochemical cell was produced.
  • the electrochemical cell was produced by the same method as in Example 1.
  • the discharge capacity of these electrochemical cells is 1 mA / cm 2 charging current, 4.2 Vvs.
  • the electrochemical cells of Examples 60 to 63 were compared with the electrochemical cells of Comparative Examples 76 to 79 each having a positive electrode without a hole having the same active material layer thickness as that of each Example. It can be seen that the discharge capacity per unit is high and the discharge capacity is increased by forming the holes.
  • Each electrochemical cell having an active material layer in which holes are formed and each electrochemical cell having an active material layer in which holes are not formed are compared between electrochemical cells having the same active material layer thickness.
  • a positive electrode electrochemical cell having a hole and having an active material layer with a thickness of 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 500 ⁇ m, 1000 ⁇ m, and 1200 ⁇ m has a discharge capacity per mass of about It is 1.07 times, about 1.39 times, about 1.45 times, about 1.47 times, about 1.62 times, about 3.44 times, and about 3.10 times.
  • a positive electrode electrochemical cell having a relatively thin active material layer such as an active material layer having a thickness of 50 ⁇ m has a small increase in discharge capacity due to the formation of holes in the active material layer.
  • the thickness of the active material layer is thin, lithium ions in the electrolyte solution can easily reach the active material inside the active material layer, and many active materials can be used effectively even if holes are not formed. It is done. Therefore, it is considered that the positive electrode having a thin active material layer has few active materials that can be newly utilized by forming holes in the active material layer, and the increase in discharge capacity is small.
  • the thickness of the active material layer is 150 ⁇ m or more
  • the discharge capacity per mass is greatly increased to about 50% or more, and the thickness of the active material layer is increased. Is 500 ⁇ m or more, the discharge capacity per mass is further increased to about 60% or more.
  • the amount of increase in discharge capacity per mass is large.
  • the positive electrode electrochemical cell in which the active material layer is thick and no hole is formed has a high resistance to movement of lithium ions because lithium ions move through the voids of the active material layer for a long distance. Furthermore, since the electrochemical cell is thick, it is considered that the active material at a position deep in the thickness direction from the surface of the active material layer cannot be effectively used, and the discharge capacity per mass is particularly small.
  • lithium ions preferentially pass through the electrolyte present in the hole, so that the movement of lithium ions is smooth and the movement resistance is lowered.
  • the active material that is not available when the hole is not formed is located deep in the thickness direction from the surface of the active material layer, the discharge capacity per mass is considered to increase. It is done.
  • the positive electrode electrochemical cell having an active material layer of 1200 ⁇ m has a larger active material layer thickness than the positive electrode electrochemical cell having an active material layer of 1000 ⁇ m in thickness, thereby increasing the amount of active material supported.
  • the discharge capacity per mass has decreased significantly, and the discharge capacity per area has also decreased slightly.
  • the positive electrode electrochemical cell having an active material layer having a thickness of 1200 ⁇ m has an increase in discharge capacity per mass due to the formation of holes, and the positive electrode electrochemical cell having an active material layer having a thickness of 1000 ⁇ m. It is lower than the cell.
  • a positive electrode electrochemical cell having an active material layer with a thickness of 1200 ⁇ m has a thick active material layer.
  • the active material layer becomes thicker, the movement distance of lithium ions becomes longer even if lithium ions are moving in the electrolytic solution accommodated in the holes of the active material layer. Therefore, a positive electrode electrochemical cell having an active material layer having a thickness of 1200 ⁇ m cannot perform a battery reaction more efficiently than a positive electrode electrochemical cell having an active material layer having a thickness of 1000 ⁇ m. It is considered that the discharge capacity per mass is greatly reduced, the discharge capacity per area is lowered, and the increase in discharge capacity per mass due to the formation of holes is also reduced.
  • the positive electrode for a lithium ion secondary battery of the present invention cannot be effectively used when a hole is not formed by forming a hole if the thickness of the active material layer is 150 to 1000 ⁇ m.
  • the active material can be used effectively and the discharge capacity is increased.
  • the thickness of the active material layer is more preferably 500 to 1000 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

　L'électrode positive (2) pour cellule secondaire au lithium-ion selon la présente invention comporte un collecteur (5) et une couche de matière active (6) disposée sur la surface du collecteur (5). La couche de matière active (6) a une pluralité de trous (7) disposée sur sa surface, a une densité de matière active qui est de 68-83 % de la densité vraie de la matière active contenue dans la couche de matière active (6), et a une épaisseur de 150-1 000 μm, et a ainsi plus de la matière active. Lorsqu'elle est utilisée dans une batterie secondaire au lithium-ion, l'électrode positive (2) fournit une cellule secondaire au lithium-ion dans laquelle des électrons sont transférés et des ions de lithium sont insérés et désorbés non seulement sur la surface de la couche de matière active (6) mais aussi au niveau de positions profondes par rapport à la surface de la couche de matière active (6) dans la direction d'épaisseur ; la matière active située en profondeur par rapport à la surface de la couche de matière active (6) dans la direction d'épaisseur peut être utilisée de manière efficace ; et la charge/décharge peut être effectuée plus rapidement à une capacité plus élevée.
PCT/JP2015/075193 2014-09-10 2015-09-04 Électrode positive pour cellule secondaire au lithium-ion et, cellule secondaire au lithium-ion WO2016039264A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/510,417 US20170263933A1 (en) 2014-09-10 2015-09-04 Positive electrode for lithium-ion secondary cell, and lithium-ion secondary cell
EP15840381.6A EP3193392A4 (fr) 2014-09-10 2015-09-04 Électrode positive pour cellule secondaire au lithium-ion et, cellule secondaire au lithium-ion
KR1020177006676A KR20170052592A (ko) 2014-09-10 2015-09-04 리튬 이온 이차 전지용 정극 및 리튬 이온 이차 전지
CN201580048387.0A CN106688126A (zh) 2014-09-10 2015-09-04 锂离子二次电池用正极及锂离子二次电池

Applications Claiming Priority (4)

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JP2014184153 2014-09-10
JP2014-184153 2014-09-10
JP2015107685A JP5983821B2 (ja) 2014-09-10 2015-05-27 リチウムイオン二次電池用正極及びリチウムイオン二次電池
JP2015-107685 2015-05-27

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WO2018038479A1 (fr) * 2016-08-25 2018-03-01 주식회사 엘지화학 Électrode pour batterie secondaire comprenant des trous fins
CN107925061A (zh) * 2016-03-28 2018-04-17 株式会社Lg化学 用于制造电极的方法
CN108292737A (zh) * 2016-08-25 2018-07-17 株式会社Lg化学 具有细孔的二次电池用电极
US20200358099A1 (en) * 2017-10-10 2020-11-12 Nissan Motor Co., Ltd. Electrode for non-aqueous electrolyte secondary battery

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CN107925061A (zh) * 2016-03-28 2018-04-17 株式会社Lg化学 用于制造电极的方法
CN107925061B (zh) * 2016-03-28 2020-12-11 株式会社Lg化学 用于制造电极的方法
WO2018038479A1 (fr) * 2016-08-25 2018-03-01 주식회사 엘지화학 Électrode pour batterie secondaire comprenant des trous fins
CN108292737A (zh) * 2016-08-25 2018-07-17 株式会社Lg化学 具有细孔的二次电池用电极
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US20200358099A1 (en) * 2017-10-10 2020-11-12 Nissan Motor Co., Ltd. Electrode for non-aqueous electrolyte secondary battery

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