WO2023171564A1 - 非水電解液二次電池 - Google Patents

非水電解液二次電池 Download PDF

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Publication number
WO2023171564A1
WO2023171564A1 PCT/JP2023/008045 JP2023008045W WO2023171564A1 WO 2023171564 A1 WO2023171564 A1 WO 2023171564A1 JP 2023008045 W JP2023008045 W JP 2023008045W WO 2023171564 A1 WO2023171564 A1 WO 2023171564A1
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negative electrode
mass
secondary battery
graphite particles
electrode mixture
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French (fr)
Japanese (ja)
Inventor
貴之 中堤
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Panasonic Energy Co Ltd
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Panasonic Energy Co Ltd
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Priority to CN202380024659.8A priority Critical patent/CN118805282A/zh
Priority to JP2024506282A priority patent/JPWO2023171564A1/ja
Priority to US18/842,115 priority patent/US20250183300A1/en
Publication of WO2023171564A1 publication Critical patent/WO2023171564A1/ja
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • 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
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • 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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • 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

Definitions

  • the present disclosure relates to a non-aqueous electrolyte secondary battery.
  • Nonaqueous electrolyte secondary batteries that use carbon materials such as graphite as negative electrode active materials are widely used as high energy density secondary batteries.
  • Patent Document 1 For example, in Patent Document 1, two graphite particles with different internal porosity are used, and a non-aqueous electrolytic solution containing a diisocyanate compound is made to contain many graphite particles with small internal porosity on the outer surface side of the negative electrode mixture layer.
  • a non-aqueous electrolyte secondary battery using a non-aqueous electrolyte is disclosed.
  • An object of the present disclosure is to provide a non-aqueous electrolyte secondary battery that suppresses a decrease in output due to charge/discharge cycles.
  • a nonaqueous electrolyte secondary battery that is an embodiment of the present disclosure includes a positive electrode, a negative electrode, and a nonaqueous electrolyte
  • the negative electrode includes a negative electrode current collector and a negative electrode mixture layer provided on the negative electrode current collector.
  • the negative electrode mixture layer includes graphite particles A, graphite particles B, and a Si compound
  • the graphite particles A have an internal porosity of 5% or less
  • the graphite particles B have an internal porosity of 8% to 20%
  • the Si compound includes an ion conductive layer and Si particles dispersed in the ion conductive layer
  • the graphite particles A are the negative electrode current collector when the negative electrode mixture layer is divided into two equal parts in the thickness direction.
  • the non-aqueous electrolyte contains at least fluoroethylene carbonate and sultone having an unsaturated bond, and the concentration of sultone in the non-aqueous electrolyte is mass%, and when the concentration of fluoroethylene carbonate is Y mass%, satisfy 0.01 ⁇ X ⁇ 1.5, 0.5 ⁇ Y ⁇ 15, and 0.01 ⁇ X/Y ⁇ 0.5. It is characterized by
  • nonaqueous electrolyte secondary battery According to the nonaqueous electrolyte secondary battery according to the present disclosure, a decrease in output due to charge/discharge cycles can be suppressed.
  • FIG. 1 is a cross-sectional view of a nonaqueous electrolyte secondary battery that is an example of an embodiment.
  • FIG. 2 is a cross-sectional view of a negative electrode that is an example of an embodiment.
  • FIG. 3 is a cross-sectional view of graphite particles in the negative electrode mixture layer.
  • a nonaqueous electrolyte secondary battery that is an embodiment of the present disclosure includes a positive electrode, a negative electrode, and a nonaqueous electrolyte
  • the negative electrode includes a negative electrode current collector and a negative electrode mixture layer provided on the negative electrode current collector.
  • the negative electrode mixture layer includes graphite particles A, graphite particles B, and a Si compound
  • the graphite particles A have an internal porosity of 5% or less
  • the graphite particles B have an internal porosity of 8% to 20%
  • the Si compound includes an ion conductive layer and Si particles dispersed in the ion conductive layer
  • the graphite particles A are the negative electrode current collector when the negative electrode mixture layer is divided into two equal parts in the thickness direction.
  • the non-aqueous electrolyte is contained more in the outer surface half region than the side half region, and the non-aqueous electrolyte contains at least fluoroethylene carbonate and sultone having an unsaturated bond (hereinafter sometimes referred to as sultone),
  • sultone fluoroethylene carbonate and sultone having an unsaturated bond
  • concentration of sultone is X% by mass and the concentration of fluoroethylene carbonate is Y% by mass, 0.01 ⁇ X ⁇ 1.5, 0.5 ⁇ Y ⁇ 15, and 0.01. It is characterized by satisfying ⁇ X/Y ⁇ 0.5.
  • a non-aqueous electrolyte containing fluoroethylene carbonate and sultone at a predetermined concentration the fluoroethylene carbonate and sultone are decomposed to form a composite film on the surface of the graphite particles and Si compound in the negative electrode, which facilitates charging and discharging. It is thought that the decomposition reaction of the non-aqueous electrolyte on the surface of the negative electrode during this time is suppressed.
  • Si compounds have a large volume change due to charging and discharging, and the film on the surface of the Si compound is destroyed due to the volume change, and a continuous decomposition reaction of the non-aqueous electrolyte tends to occur.
  • nonaqueous electrolyte secondary battery of the present disclosure is not limited to the embodiments described below. Further, the drawings referred to in the description of the embodiments are schematically illustrated.
  • FIG. 1 is a cross-sectional view of a nonaqueous electrolyte secondary battery that is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 shown in FIG. The battery case 15 includes insulating plates 18 and 19 disposed respectively in the battery case 18 and the battery case 15 that accommodates the above-mentioned members.
  • the battery case 15 includes a case body 16 having a cylindrical shape with a bottom and a sealing body 17 that closes an opening of the case body 16.
  • the wound type electrode body 14 other forms of electrode bodies may be applied, such as a laminated type electrode body in which positive electrodes and negative electrodes are alternately laminated with separators interposed therebetween.
  • examples of the battery case 15 include metal exterior cans such as cylindrical, square, coin-shaped, button-shaped, etc., and pouch exterior bodies formed by laminating resin sheets and metal sheets.
  • the case body 16 is, for example, a metal exterior can with a bottomed cylindrical shape.
  • a gasket 28 is provided between the case body 16 and the sealing body 17 to ensure airtightness inside the battery.
  • the case main body 16 has an overhanging portion 22 that supports the sealing body 17 and has, for example, a part of a side surface overhanging inward.
  • the projecting portion 22 is preferably formed in an annular shape along the circumferential direction of the case body 16, and supports the sealing body 17 on its upper surface.
  • the sealing body 17 has a structure in which a filter 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are stacked in order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected to each other at their central portions, and an insulating member 25 is interposed between their respective peripheral portions.
  • the lower valve body 24 deforms and ruptures so as to push the upper valve body 26 toward the cap 27, and the lower valve body 24 and the upper valve body The current path between the valve bodies 26 is cut off.
  • the upper valve body 26 breaks and gas is discharged from the opening of the cap 27.
  • the positive electrode lead 20 is connected by welding or the like to the lower surface of the filter 23, which is the bottom plate of the sealing body 17, and the cap 27, which is the top plate of the sealing body 17 and electrically connected to the filter 23, serves as a positive terminal.
  • the negative electrode lead 21 is connected to the bottom inner surface of the case body 16 by welding or the like, and the case body 16 serves as a negative electrode terminal.
  • FIG. 2 is a cross-sectional view of a negative electrode that is an example of an embodiment.
  • the negative electrode 12 includes a negative electrode current collector 40 and a negative electrode mixture layer 42 provided on the negative electrode current collector 40.
  • the negative electrode current collector 40 for example, a foil made of a metal such as copper that is stable in the potential range of the negative electrode, a film with the metal disposed on the surface layer, or the like is used.
  • the negative electrode mixture layer 42 contains graphite particles and a Si compound as a negative electrode active material. Further, it is preferable that the negative electrode mixture layer 42 contains a binder or the like.
  • the negative electrode 12 is produced by, for example, preparing a negative electrode mixture slurry containing a negative electrode active material, a binder, etc., applying this negative electrode mixture slurry onto the negative electrode current collector 40, and drying it to form the negative electrode mixture layer 42. , can be produced by rolling this negative electrode mixture layer 42. Note that details of the method for manufacturing the negative electrode mixture layer 42 will be described later.
  • FIG. 3 is a cross-sectional view of graphite particles in the negative electrode mixture layer.
  • the graphite particle 30 has closed voids 34 (hereinafter referred to as internal voids 34) that are not connected from the inside of the particle to the particle surface, and closed voids 34 that are not connected from the inside of the particle to the particle surface. It has a void 36 (hereinafter referred to as external void 36).
  • the graphite particles 30 include graphite particles A with an internal porosity of 5% or less and graphite particles B with an internal porosity of 8% to 20%.
  • the internal porosity of the graphite particles A may be 5% or less in order to suppress the decomposition reaction of the non-aqueous electrolyte, but is preferably 1% to 5%, more preferably 3% to 5%. %.
  • the internal porosity of the graphite particles B may be 8% to 20% in terms of suppressing the decomposition reaction of the non-aqueous electrolyte, preferably 10% to 18%, and more preferably 12%. ⁇ 16%.
  • the internal porosity of the graphite particle is a two-dimensional value determined from the ratio of the area of the internal voids 34 of the graphite particle to the cross-sectional area of the graphite particle. Then, the internal porosity of the graphite particles is determined by the following procedure.
  • ⁇ Method for measuring internal porosity> Expose the cross section of the negative electrode mixture layer. Examples of the method for exposing the cross section include cutting off a part of the negative electrode and processing it with an ion milling device (for example, IM4000PLUS, manufactured by Hitachi High-Tech Corporation) to expose the cross section of the negative electrode mixture layer. (2) Using a scanning electron microscope, take a backscattered electron image of the cross section of the exposed negative electrode mixture layer. The magnification when photographing a backscattered electron image is 3,000 to 5,000 times.
  • an ion milling device for example, IM4000PLUS, manufactured by Hitachi High-Tech Corporation
  • the area of the graphite particle cross section refers to the area of the region surrounded by the outer periphery of the graphite particle, that is, the area of the entire cross section of the graphite particle.
  • voids that exist in the cross section of graphite particles, it may be difficult to distinguish between internal voids and external voids on image analysis, so voids with a width of 3 ⁇ m or less are internal voids.
  • the internal porosity of the graphite particle (area of the internal voids in the graphite particle cross section x 100/area of the graphite particle cross section) is calculated from the calculated area of the graphite particle cross section and the area of the internal voids in the graphite particle cross section.
  • the internal porosity of graphite particles A and B is the average value of 10 graphite particles A and B, respectively.
  • Graphite particles A and B are produced, for example, as follows.
  • Graphite particles A with internal porosity of 5% or less For example, coke (precursor), which is the main raw material, is crushed into a predetermined size, aggregated with a binder, fired at a temperature of 2600°C or higher, graphitized, and then sieved. Graphite particles A of a desired size are obtained.
  • the internal porosity can be adjusted to 5% or less depending on the particle size of the precursor after pulverization, the particle size of the agglomerated precursor, and the like.
  • the average particle size (volume-based median diameter D50) of the precursor after pulverization is preferably in the range of 12 ⁇ m to 20 ⁇ m. Further, when reducing the internal porosity within the range of 5% or less, it is preferable to increase the particle size of the precursor after pulverization.
  • Graphite particles B with internal porosity of 8% to 20%> For example, coke (precursor), which is the main raw material, is crushed into a predetermined size, agglomerated with a binder, and then pressure-formed into a block shape, which is then fired at a temperature of 2,600°C or higher to graphitize it. let Graphite particles B of a desired size are obtained by crushing and sieving the block-shaped compact after graphitization.
  • the internal porosity can be adjusted to 8% to 20% by changing the amount of volatile components added to the block-shaped molded body. If part of the binder added to the coke (precursor) volatilizes during firing, the binder can be used as a volatile component. Pitch is exemplified as such a binder.
  • Graphite particles A and B may be natural graphite, artificial graphite, or the like, but are not particularly limited, but artificial graphite is preferable in terms of ease of adjusting internal porosity.
  • the interplanar spacing (d 002 ) of the (002) planes of graphite particles A and B measured by X-ray wide-angle diffraction is, for example, preferably 0.3354 nm or more, more preferably 0.3357 nm or more, and It is preferably less than 0.340 nm, more preferably 0.338 nm or less.
  • the crystallite size (Lc(002)) of graphite particles A and B determined by X-ray diffraction is, for example, preferably 5 nm or more, more preferably 10 nm or more, and 300 nm or less. It is preferably 200 nm or less, and more preferably 200 nm or less.
  • the battery capacity of the non-aqueous electrolyte secondary battery tends to be larger than when the interplanar spacing (d 002 ) and the crystallite size (Lc(002)) satisfy the above ranges.
  • the negative electrode mixture layer 42 shown in FIG. 2 When the negative electrode mixture layer 42 shown in FIG. 2 is divided into two equal parts in the thickness direction, more graphite particles A are contained in a half region 42b on the outer surface side than in a half region 42a on the negative electrode current collector side. This suppresses the decomposition reaction of the non-aqueous electrolyte at the negative electrode, thereby suppressing a decrease in output.
  • the negative electrode mixture layer 42 is divided into two equal parts in the thickness direction, when the lamination direction of the negative electrode current collector 40 and the negative electrode mixture layer 42 is the thickness direction of the negative electrode mixture layer 42. It means dividing in half at the middle M of the thickness.
  • the negative electrode mixture layer 42 located near the negative electrode current collector 40 is defined as a half region 42a on the negative electrode current collector side, and the negative electrode mixture layer 42 is divided into two equal parts in the thickness direction.
  • the negative electrode mixture layer 42 located far away when viewed from the outside is defined as the outer surface half region 42b.
  • graphite particles A are contained in a larger amount in the outer surface half region 42b than in the negative electrode current collector half region 42a;
  • the ratio of graphite particles A to graphite particles B in the outer surface half region 42b is preferably 20:80 to 100:0 in terms of mass ratio, and more preferably 50:50 to 100:0.
  • the ratio of graphite particles A to graphite particles B in the half region 42a on the negative electrode current collector side is preferably 10:90 to 0:100 in terms of mass ratio, and more preferably 0:100.
  • the content of graphite particles A in the negative electrode mixture layer 42 is, for example, 20% to 80% by mass, and 25% to 50% by mass with respect to the total mass of graphite particles A and graphite particles B. There may be.
  • the Si compound contained in the negative electrode mixture layer 42 includes an ion conductive layer and Si particles dispersed within the ion conductive layer.
  • the content of Si particles in the Si compound is preferably 40% by mass to 70% by mass from the viewpoint of increasing capacity.
  • the ion conductive phase is a silicate phase, an amorphous carbon phase, or the like.
  • SiO which is an example of a Si compound, has a particle structure in which fine Si particles are dispersed in a silicate phase.
  • Suitable SiO has a sea-island structure in which fine Si particles are substantially uniformly dispersed in an amorphous silicon oxide matrix.
  • SiC which is another example of a Si compound, has a particle structure in which fine Si particles are dispersed in an amorphous carbon phase.
  • Suitable SiC has a sea-island structure in which fine Si particles are substantially uniformly dispersed in a matrix of an amorphous carbon phase.
  • the ion conductive layer is preferably an amorphous carbon phase. That is, the Si compound is preferably SiC.
  • the content of the Si compound in the negative electrode mixture layer is, for example, 5% by mass to 20% by mass with respect to the total mass of the negative electrode active material. Thereby, it is possible to suppress deterioration in charge/discharge cycle characteristics while improving battery capacity.
  • the content of Si compounds in the half region 42a on the negative electrode current collector side and the content of Si compounds in the half region 42b on the outer surface side may be different, but are preferably substantially the same.
  • a negative electrode active material containing graphite particles B (graphite particles A if necessary), a binder, and a solvent such as water are mixed to prepare a negative electrode mixture slurry for the negative electrode current collector side.
  • a negative electrode active material containing a larger amount of graphite particles A (graphite particles B as necessary) than the negative electrode mixture slurry for the negative electrode current collector side, a binder, and a solvent such as water is prepared.
  • the negative electrode mixture layer 42 can be formed by applying the mixture slurry to both surfaces and drying it. In the above method, the negative electrode mixture slurry for the negative electrode current collector side was applied and dried, and then the negative electrode mixture slurry for the outer surface side was applied.
  • a negative electrode mixture slurry for the outer surface side may be applied before drying, or a negative electrode mixture slurry for the negative electrode current collector side and a negative electrode mixture slurry for the outer surface side may be applied simultaneously.
  • binders include fluororesins, polyimide resins, acrylic resins, polyolefin resins, polyacrylonitrile (PAN), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), and carboxymethyl cellulose (CMC). ) or a salt thereof, polyacrylic acid (PAA) or a salt thereof (PAA-Na, PAA-K, etc., and may also be a partially neutralized salt), polyvinyl alcohol (PVA), and the like. These may be used alone or in combination of two or more.
  • the positive electrode 11 includes, for example, a positive electrode current collector such as metal foil, and a positive electrode mixture layer formed on the positive electrode current collector.
  • a positive electrode current collector such as metal foil
  • a positive electrode mixture layer formed on the positive electrode current collector.
  • a metal foil such as aluminum that is stable in the positive electrode potential range, a film having the metal disposed on the surface layer, or the like can be used.
  • the positive electrode mixture layer includes, for example, a positive electrode active material, a binder, a conductive agent, and the like.
  • the positive electrode 11 is formed by coating a positive electrode mixture slurry containing a positive electrode active material, a binder, a conductive agent, etc. on a positive electrode current collector, drying it to form a positive electrode mixture layer, and then applying this positive electrode mixture layer. It can be produced by rolling.
  • a lithium transition metal composite oxide containing a transition metal element such as Ni can be exemplified.
  • the lithium transition metal composite oxide preferably contains Ni and at least one element selected from Mn, Co, and Al.
  • the Ni content in the lithium transition metal composite oxide is, for example, 80 mol% to 95 mol% with respect to the total number of moles of metal elements excluding Li.
  • the lithium transition metal composite oxide has, for example, the general formula Li a Ni x M1 y M1 z O 2-b (wherein, 0.8 ⁇ a ⁇ 1.2, 0.8 ⁇ x ⁇ 0.95, 0.
  • M1 is at least one element selected from Mn, Co and Al
  • M2 is Fe
  • Examples of the conductive agent include carbon-based particles such as carbon black (CB), acetylene black (AB), Ketjen black, carbon nanotube (CNT), graphene, and graphite. These may be used alone or in combination of two or more.
  • binder examples include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyimide resins, acrylic resins, polyolefin resins, and polyacrylonitrile (PAN). These may be used alone or in combination of two or more.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF)
  • PVdF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous electrolyte contains at least fluoroethylene carbonate (FEC) and a sultone having an unsaturated bond as a non-aqueous solvent.
  • FEC fluoroethylene carbonate
  • sultone having an unsaturated bond as a non-aqueous solvent.
  • concentration of sultone is X% by mass and the concentration of FEC is Y% by mass, 0.01 ⁇ X ⁇ 1.5, 0.5 ⁇ Y ⁇ 15, and 0.01 ⁇ X/Y ⁇ 0.5 is satisfied.
  • the sultone is not particularly limited as long as it has an unsaturated bond.
  • examples of the sultone include 1-propene 1,3-sultone and 1-butene 1,4-sultone.
  • 1-propene 1,3-sultone is preferred.
  • the non-aqueous electrolyte may contain a non-aqueous solvent other than FEC and sultone.
  • a nonaqueous solvent other than FEC and sultone carbonates, lactones, ethers, ketones, esters, etc. can be used, and two or more of these solvents can be used in combination.
  • a mixed solvent containing a cyclic carbonate and a chain carbonate For example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), etc.
  • the cyclic carbonate can be used as the cyclic carbonate, and dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate ( DEC) etc. can be used.
  • DMC dimethyl carbonate
  • EMC ethylmethyl carbonate
  • DEC diethyl carbonate
  • esters it is preferable to use carboxylic acid esters such as methyl acetate (MA) and methyl propionate (MP).
  • the nonaqueous solvent may contain a halogen substituted product other than FEC, such as methyl fluoropropionate (FMP).
  • the non-aqueous electrolyte preferably contains lithium bis(fluorosulfonyl)imide (LiFSI) as an electrolyte salt.
  • LiFSI lithium bis(fluorosulfonyl)imide
  • the concentration of LiFSI in the nonaqueous electrolyte is Z% by mass, it is preferable that 0.01 ⁇ Z ⁇ 5 and 0.1 ⁇ X/Z ⁇ 1 are satisfied.
  • the electrolyte salt may contain lithium sulfonylimide other than LiFSI.
  • lithium sulfonylimides other than LiFSI include lithium bis(trifluoromethanesulfonyl)imide, lithium bis(nonafluorobutanesulfonyl)imide, lithium bis(pentafluoroethanesulfonyl)imide (LIBETI), and the like. These may be used alone or in combination of two or more.
  • the electrolyte salt may include lithium salts other than lithium sulfonylimide.
  • lithium salts other than lithium sulfonylimide include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li(P(C 2 O 4 )F 4 ), LiPF 6-x (C n F 2n+1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic carboxylic acid Examples include borates such as lithium, Li 2 B 4 O 7 , and Li(B(C 2 O 4 )F 2 ). Among them, LiPF 6 is preferably used from the viewpoint of ionic conductivity, electrochemical stability, etc. The concentration of LiPF 6 is preferably 0.8 mol to 1.8 mol per liter of
  • the nonaqueous electrolyte may contain vinylene carbonate (VC), ethylene sulfite (ES), cyclohexylbenzene (CHB), orthoterphenyl (OTP), a propane sultone compound, and the like.
  • VC vinylene carbonate
  • ES ethylene sulfite
  • CHB cyclohexylbenzene
  • OTP orthoterphenyl
  • propane sultone compound a propane sultone compound
  • the amount of VC added is not particularly limited, but is, for example, 0.1% by mass to 5% by mass based on the total mass of the non-aqueous electrolyte.
  • separator 13 for example, a porous sheet having ion permeability and insulation properties is used. Specific examples of porous sheets include microporous thin films, woven fabrics, and nonwoven fabrics. Suitable materials for the separator include olefin resins such as polyethylene and polypropylene, cellulose, and the like.
  • the separator 13 may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin.
  • a multilayer separator including a polyethylene layer and a polypropylene layer may be used, or a separator whose surface is coated with a material such as aramid resin or ceramic may be used.
  • Example 1 [Preparation of positive electrode]
  • aluminum-containing lithium nickel cobaltate LiNi 0.91 Co 0.04 Al 0.05 O 2 ) was used. 100 parts by mass of the above positive electrode active material, 1 part by mass of acetylene black, and 0.9 parts by mass of polyvinylidene fluoride were mixed in a solvent of N-methyl-2-pyrrolidone (NMP) to prepare a positive electrode mixture. A slurry was prepared. This slurry is applied to both sides of an aluminum foil with a thickness of 15 ⁇ m, and after the coating film is dried, the coating film is rolled with a rolling roller to form a positive electrode with a positive electrode mixture layer formed on both sides of the positive electrode current collector. Created.
  • NMP N-methyl-2-pyrrolidone
  • graphite particles B and SiC were mixed at a mass ratio of 92:8, and this was used as the negative electrode active material B included in the negative electrode current collector half region of the negative electrode mixture layer.
  • Negative electrode active material B carboxymethyl cellulose (CMC): styrene-butadiene copolymer rubber (SBR) are mixed so that the mass ratio is 100:1:1 to form a negative electrode mixture slurry on the negative electrode current collector side. was prepared. Note that, as described above, the ratio of the Si compound to the total mass of the negative electrode active material is the same on the outer surface side and the current collector side. Further, the content of Si particles in SiC is 50% by mass.
  • the negative electrode mixture slurry on the negative electrode current collector side is applied to both sides of a copper foil with a thickness of 8 ⁇ m, and the coating film is dried. Then, the negative electrode mixture slurry on the outer surface side is applied on the coating film, dried, and rolled with a rolling roller. By rolling the coating film, a negative electrode in which negative electrode mixture layers were formed on both sides of the negative electrode current collector was produced. That is, the mass ratio of graphite particles A to graphite particles B in the half region on the outer surface side of the negative electrode mixture layer is 60:40, and the ratio of graphite particles A to graphite particles in the half region on the negative electrode current collector side of the negative electrode mixture layer is 60:40. Particle B has a mass ratio of 0:100. Furthermore, in the produced negative electrode, the internal porosity of graphite particles A and B was measured and found to be 3% and 15%, respectively.
  • LiPF 6 was added at a concentration of 1.35 mol/L to a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a volume ratio of 20:5:75. Dissolved. Furthermore, 3% by mass of vinylene carbonate (VC) was added to the total mass of the mixed solvent and LiPF 6 , and this was used as a base non-aqueous electrolyte.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • LiFSI Fluorosulfonyl)imide
  • the secondary battery was charged with a constant current of 0.3C until the cell voltage reached 4.2V, and then the current value became 0.02C with a constant voltage of 4.2V. I charged it up to. Thereafter, the battery was discharged at a constant current of 0.5C until the voltage reached 2.5V. This charging and discharging was regarded as one cycle, and 100 cycles were performed.
  • DCIR increase rate (%) (DCIR after cycle - initial DCIR) / initial DCIR x 100
  • Example 2 In the production of the negative electrode, the mixing ratio of mixed graphite and SiC in negative electrode active material A and the mixing ratio of graphite particles B and SiC in negative electrode active material B were both changed to a mass ratio of 90:10.
  • a non-aqueous electrolyte secondary battery was produced and evaluated in the same manner as in Example 1, except that the amount of FEC added was changed to 5 parts by mass in producing the aqueous electrolyte. Note that in the non-aqueous electrolyte, the concentration X of sultone is 0.5% by mass, the concentration Y of FEC is 4.7% by mass, and the concentration Z of LiFSI is 0.9% by mass.
  • Example 3 In producing the negative electrode, the mixing ratio of mixed graphite and SiC in negative electrode active material A and the mixing ratio of graphite particles B and SiC in negative electrode active material B were both changed to a mass ratio of 88:12, and A non-aqueous electrolyte secondary battery was produced and evaluated in the same manner as in Example 1, except that the amount of FEC added was changed to 10 parts by mass in producing the aqueous electrolyte. Note that in the non-aqueous electrolyte, the concentration X of sultone is 0.4% by mass, the concentration Y of FEC is 9.0% by mass, and the concentration Z of LiFSI is 0.9% by mass.
  • Example 4 In preparing the non-aqueous electrolyte, the same procedure as Example 1 was carried out, except that the amount of 1-propene 1,3-sultone added was changed to 0.2 parts by mass, and the amount of FEC added was changed to 5 parts by mass. A non-aqueous electrolyte secondary battery was fabricated and evaluated. In addition, in the nonaqueous electrolyte, the concentration X of sultone is 0.2% by mass, the concentration Y of FEC is 4.7% by mass, and the concentration Z of LiFSI is 0.9% by mass.
  • Example 5 In the production of the negative electrode, the mixing ratio of mixed graphite and SiC in negative electrode active material A and the mixing ratio of graphite particles B and SiC in negative electrode active material B were both changed to a mass ratio of 95:5.
  • the same procedure as in Example 1 was carried out, except that the amount of 1-propene 1,3-sultone added was changed to 0.1 parts by mass, and the amount of FEC added was changed to 5 parts by mass.
  • a non-aqueous electrolyte secondary battery was manufactured and evaluated. Note that in the nonaqueous electrolyte, the concentration X of sultone is 0.1% by mass, the concentration Y of FEC is 4.7% by mass, and the concentration Z of LiFSI is 0.9% by mass.
  • Example 6 A non-aqueous electrolyte secondary battery was produced and evaluated in the same manner as in Example 1, except that the amount of LiFSI added was changed to 4 parts by mass in producing the non-aqueous electrolyte. Note that in the non-aqueous electrolyte, the concentration X of sultone is 0.5% by mass, the concentration Y of FEC is 1.9% by mass, and the concentration Z of LiFSI is 3.8% by mass.
  • Example 2 A nonaqueous electrolyte secondary battery was prepared and evaluated in the same manner as in Example 1, except that 1-propene 1,3-sultone was not added in the preparation of the nonaqueous electrolyte. Note that in the nonaqueous electrolyte, the concentration Y of FEC is 1.9% by mass, and the concentration Z of LiFSI is 1.0% by mass.
  • a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that the amount of 1-propene 1,3-sultone added was changed to 2.0 parts by mass in producing the non-aqueous electrolyte, We conducted an evaluation. Note that in the non-aqueous electrolyte, the concentration X of sultone is 1.9% by mass, the concentration Y of FEC is 1.9% by mass, and the concentration Z of LiFSI is 1.0% by mass.
  • Table 1 shows the evaluation results of the secondary batteries of Examples and Comparative Examples. All evaluations were performed under the same conditions as described in Example 1. Table 1 also shows the mass ratio of graphite particles A and graphite particles B in the outer surface side half and the current collector side half of the negative electrode mixture layer, the content of SiC in the negative electrode mixture layer, and the base non-aqueous electrolysis The concentration X of 1-propene 1,3-sultone, the concentration Y of FEC, the concentration Z of LiFSI, X/Y, and X/Z for the liquid are also shown.
  • the rate of increase in DCIR relative to the initial DCIR was suppressed.
  • the rate of increase in DCIR with respect to the initial DCIR after repeated charging and discharging is not suppressed compared to the example. Therefore, while the negative electrode mixture layer contains two graphite particles with different internal porosity and a predetermined Si compound, the outer half region of the negative electrode mixture layer contains many graphite particles with a small internal porosity, It can be seen that by containing sultone and fluoroethylene carbonate at a predetermined concentration in the non-aqueous electrolyte, it is possible to suppress a decrease in output due to charge/discharge cycles.

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WO2025105319A1 (ja) * 2023-11-13 2025-05-22 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
WO2025159013A1 (ja) * 2024-01-25 2025-07-31 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
WO2025205497A1 (ja) * 2024-03-29 2025-10-02 株式会社Ａｅｓｃジャパン リチウムイオン二次電池およびリチウムイオン二次電池モジュール
WO2025205085A1 (ja) * 2024-03-29 2025-10-02 パナソニックエナジー株式会社 非水電解質二次電池

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WO2021117550A1 (ja) * 2019-12-13 2021-06-17 パナソニックＩｐマネジメント株式会社 非水電解液二次電池
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JP2018181772A (ja) * 2017-04-20 2018-11-15 株式会社Ｇｓユアサ 非水電解質蓄電素子及びその製造方法
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WO2025205085A1 (ja) * 2024-03-29 2025-10-02 パナソニックエナジー株式会社 非水電解質二次電池

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