WO2022230661A1 - 二次電池用負極、二次電池、及び二次電池用負極の製造方法 - Google Patents

二次電池用負極、二次電池、及び二次電池用負極の製造方法 Download PDF

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WO2022230661A1
WO2022230661A1 PCT/JP2022/017625 JP2022017625W WO2022230661A1 WO 2022230661 A1 WO2022230661 A1 WO 2022230661A1 JP 2022017625 W JP2022017625 W JP 2022017625W WO 2022230661 A1 WO2022230661 A1 WO 2022230661A1
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negative electrode
secondary battery
based material
mixture layer
average particle
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English (en)
French (fr)
Japanese (ja)
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明宏 谷口
基浩 坂田
薫 井上
健祐 名倉
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2023517426A priority Critical patent/JP7756326B2/ja
Priority to CN202280028935.3A priority patent/CN117178384A/zh
Priority to EP22795575.4A priority patent/EP4333106A4/en
Priority to US18/556,013 priority patent/US20240204166A1/en
Publication of WO2022230661A1 publication Critical patent/WO2022230661A1/ja
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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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a negative electrode for secondary batteries, a secondary battery, and a method for manufacturing a negative electrode for secondary batteries.
  • Si-based materials are currently attracting attention as materials that can increase the capacity of batteries.
  • a Si-based material is a material that can electrochemically store and release lithium ions, and is capable of charging and discharging with a much larger capacity than carbon materials such as graphite.
  • Patent Document 1 discloses a negative electrode active material for a lithium ion secondary battery containing a Si-based material represented by SiOx (0 ⁇ x ⁇ 2) and a carbon material.
  • a negative electrode active material for a lithium ion secondary battery is disclosed, wherein the active material has voids therein.
  • Si-based materials can increase the capacity of secondary batteries, they cause problems such as swelling of the negative electrode and deterioration of charge-discharge cycle characteristics.
  • Patent Document 1 can also suppress deterioration in charge-discharge cycle characteristics, further improvement is desired.
  • the present disclosure provides a negative electrode for a secondary battery, a secondary battery, and a secondary battery that can increase the capacity, suppress the swelling of the negative electrode, and further suppress the deterioration of the charge-discharge cycle characteristics.
  • An object of the present invention is to provide a method for manufacturing a negative electrode.
  • a negative electrode for a secondary battery which is one aspect of the present disclosure, includes a negative electrode current collector and a negative electrode mixture layer disposed on the negative electrode current collector, the negative electrode mixture layer including a carbon material and Si
  • the pore size distribution of the negative electrode mixture layer measured by a mercury porosimetry method has two peak values R1 and R2, and the peak value R1 is 0.5 ⁇ m.
  • the peak value R2 is 2 ⁇ m or more and 10 ⁇ m or less, the average particle size of the Si-based material is 4 ⁇ m or more, and the content of the Si-based material is It is characterized by being 30% by mass or more with respect to the total amount.
  • a secondary battery according to one aspect of the present disclosure includes the negative electrode for a secondary battery.
  • a method for manufacturing a negative electrode for a secondary battery which is one aspect of the present disclosure, includes applying a negative electrode paste containing a negative electrode active material containing a carbon material and a Si-based material, and a pore-forming material to a negative electrode current collector. After the first step of rolling the coating film, after the first step, the coating film is heat-treated to decompose and vaporize the pore-forming material to form a negative electrode mixture layer. and a second step of forming, and the pore size distribution of the negative electrode mixture layer measured by a mercury intrusion method has two peak values R1 and R2, and the peak value R1 is 0.5 ⁇ m or more.
  • the peak value R2 is 2 ⁇ m or more and 10 ⁇ m or less
  • the average particle size of the Si-based material is 4 ⁇ m or more
  • the content of the Si-based material is the total amount of the negative electrode active material. It is characterized by being 30% by mass or more.
  • a negative electrode for a secondary battery, a secondary battery, and a secondary battery capable of increasing the capacity, suppressing the swelling of the negative electrode, and further suppressing the deterioration of the charge-discharge cycle characteristics It becomes possible to provide a method for manufacturing a negative electrode.
  • FIG. 1 is a cross-sectional view of a secondary battery that is an example of an embodiment
  • a negative electrode for a secondary battery which is one aspect of the present disclosure, includes a negative electrode current collector and a negative electrode mixture layer disposed on the negative electrode current collector, the negative electrode mixture layer including a carbon material and Si
  • the pore size distribution of the negative electrode mixture layer measured by a mercury porosimetry method has two peak values R1 and R2, and the peak value R1 is 0.5 ⁇ m.
  • the peak value R2 is 2 ⁇ m or more and 10 ⁇ m or less, the average particle size of the Si-based material is 4 ⁇ m or more, and the content of the Si-based material is It is 30 mass % or more with respect to the total amount.
  • the negative electrode mixture layer in which the two peak values (R1, R2) in the pore size distribution satisfy the above range improves the permeability of the electrolyte solution, and the expansion and contraction of the Si-based material due to charging and discharging. It is presumed that since the optimum voids are formed to absorb the However, even if R1 and R2 are set in appropriate ranges, if the average particle diameter of the Si-based material is too small, the side reaction between the Si-based material and the electrolytic solution will result in the effect of suppressing deterioration in charge-discharge cycle characteristics. can't get enough.
  • FIG. 1 is a cross-sectional view of a secondary battery that is an example of an embodiment.
  • the secondary battery 10 shown in FIG. It includes plates 18 and 19 and a battery case 15 that accommodates the above members.
  • the battery case 15 is composed of a bottomed cylindrical case body 16 and a sealing member 17 that closes the opening of the case body 16 .
  • the wound electrode body 14 another form of electrode body such as a stacked electrode body in which positive and negative electrodes are alternately stacked via a separator may be applied.
  • Examples of the battery case 15 include cylindrical, rectangular, coin-shaped, button-shaped, and other metal cases, and resin cases formed by laminating resin sheets (so-called laminate type).
  • the electrolytic solution may be an aqueous electrolytic solution, but is preferably a non-aqueous electrolytic solution containing a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents include esters, ethers, nitriles, amides, and mixed solvents of two or more thereof.
  • the non-aqueous solvent may contain a halogen-substituted product obtained by substituting at least part of the hydrogen atoms of these solvents with halogen atoms such as fluorine.
  • a lithium salt such as LiPF 6 is used as the electrolyte salt.
  • the case body 16 is, for example, a bottomed cylindrical metal container.
  • a gasket 28 is provided between the case body 16 and the sealing member 17 to ensure hermeticity inside the battery.
  • the case main body 16 has an overhanging portion 22 that supports the sealing member 17, for example, a portion of the side surface overhanging inward.
  • the projecting portion 22 is preferably annularly formed along the circumferential direction of the case body 16 and supports the sealing member 17 on the upper surface thereof.
  • 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 layered in order from the electrode body 14 side.
  • Each member constituting the sealing member 17 has, for example, a disk shape or a ring shape, and each member other than 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 peripheral edge portions.
  • the lower valve body 24 deforms and breaks so as to push the upper valve body 26 upward toward the cap 27 side, breaking the lower valve body 24 and the upper valve body 26 .
  • the current path between is interrupted.
  • the upper valve body 26 is broken and the gas is discharged from the opening of the cap 27 .
  • the positive electrode lead 20 attached to the positive electrode 11 extends through the through hole of the insulating plate 18 toward the sealing member 17
  • the negative electrode lead 21 attached to the negative electrode 12 extends through the insulating plate 19 . It extends to the bottom side of the case body 16 through the outside.
  • the positive electrode lead 20 is connected to the lower surface of the filter 23, which is the bottom plate of the sealing member 17, by welding or the like, and the cap 27, which is the top plate of the sealing member 17 electrically connected to the filter 23, serves as a positive electrode terminal.
  • the negative lead 21 is connected to the inner surface of the bottom of the case body 16 by welding or the like, and the case body 16 serves as a negative terminal.
  • the positive electrode 11, the negative electrode 12, and the separator 13 are described in detail below.
  • the positive electrode 11 has a positive electrode current collector and a positive electrode mixture layer disposed on the positive electrode current collector.
  • a foil of a metal such as aluminum that is stable in the potential range of the positive electrode 11, a film having the metal 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 material, and the like.
  • a positive electrode paste containing a positive electrode active material, a binder, a conductive material, and the like is applied to the surface of a positive electrode current collector, the coating is dried, and then rolled to form a positive electrode mixture layer into a positive electrode collector. It can be produced by forming on both sides of the electric body.
  • Examples of conductive materials contained in the positive electrode mixture layer include carbon materials such as carbon black, acetylene black, ketjen black, graphite, and carbon nanotubes.
  • Binders contained in the positive electrode mixture layer include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide, acrylic resins, polyolefins, styrene-butadiene rubber ( SBR), cellulose derivatives such as carboxymethyl cellulose (CMC) or salts thereof, and polyethylene oxide (PEO).
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • PEO polyethylene oxide
  • a lithium transition metal composite oxide or the like is used as the positive electrode active material.
  • Metal elements contained in the lithium-transition metal composite oxide include Ni, Co, Mn, Al, B, Mg, Ti, V, Cr, Fe, Cu, Zn, Ga, Sr, Zr, Nb, In, Sn , Ta, W, and the like. Among them, it is preferable to contain at least one of Ni, Co, and Mn.
  • An example of a suitable lithium-transition metal composite oxide is represented by the general formula LiMO 2 (M is Ni and X, X is a metal element other than Ni, and the proportion of Ni is the total number of moles of the metal elements excluding Li is 50 mol % or more and 95 mol % or less with respect to ).
  • X in the above formula includes, for example, Co, Mn, Al, B, Mg, Ti, V, Cr, Fe, Cu, Zn, Ga, Sr, Zr, Nb, In, Sn, Ta, W, etc. .
  • the negative electrode 12 has a negative electrode current collector and a negative electrode mixture layer disposed on the negative electrode current collector.
  • a foil of a metal such as copper that is stable in the potential range of the negative electrode 12, a film having the metal on the surface layer, or the like can be used.
  • the negative electrode mixture layer contains a negative electrode active material and may also contain a binder, a conductive material, and the like.
  • the negative electrode active material contains a carbon material and a Si-based material.
  • the negative electrode active material may contain a material capable of reversibly intercalating and deintercalating lithium ions in addition to the carbon material and the Si-based material. Examples of the binder and the conductive material are the same as in the case of the positive electrode 11 .
  • the pore size distribution of the negative electrode mixture layer measured by mercury porosimetry has two peak values R1 and R2.
  • the peak value R1 is 0.5 ⁇ m or more and 1.5 ⁇ m or less
  • the peak value R2 is 2 ⁇ m or more and 10 ⁇ m or less.
  • mercury intrusion method mercury is forced into the pores of a solid sample by pressurizing it, and the diameter and volume of the pores are calculated from the pressure applied to the mercury and the amount of mercury injected into the pores. .
  • the diameter D of the pore can be obtained from the pressure P, the contact angle ⁇ of mercury, and the surface tension ⁇ of mercury according to the following equation. be done.
  • the pore volume is calculated from the amount of mercury injected into the pores.
  • the pore size distribution measured by the mercury intrusion method is a graph plotting the log differential pore volume (cm 3 /g) against the average pore size ( ⁇ m) of the section of each measurement point, where the horizontal axis is fine.
  • the pore diameter ( ⁇ m) and the log differential pore volume (cm 3 /g) are plotted on the vertical axis.
  • the peak value in the pore size distribution means the pore size at the apex of the peak in the pore size distribution.
  • the peak value R1 may be 0.5 ⁇ m or more and 1.5 ⁇ m or less, but is preferably 0.8 ⁇ m or more and 1.2 ⁇ m or less, for example. If the peak value R1 is less than 0.5 ⁇ m, there are many small voids between particles in the negative electrode mixture layer, which reduces the permeability of the electrolytic solution and makes it impossible to increase the capacity of the secondary battery. . Moreover, when the peak value R1 is more than 1.5 ⁇ m (less than 2 ⁇ m), the density of the negative electrode active material is lowered, making it impossible to increase the capacity of the secondary battery.
  • the peak value R2 may be 2 ⁇ m or more and 10 ⁇ m or less, and is preferably 4 ⁇ m or more and 8 ⁇ m or less, for example. If the peak value R2 is less than 2 ⁇ m, there are few voids in the negative electrode mixture layer that can absorb the expansion and contraction of the Si-based material due to charging and discharging, so swelling of the negative electrode cannot be suppressed. Further, when the peak value R2 is 10 ⁇ m or more, many large voids are present in the negative electrode mixture layer, so that the density of the negative electrode active material is lowered and the capacity of the secondary battery cannot be increased.
  • Mercury porosimetry is used to measure the pore size distribution of the negative electrode mixture layer before initial charging. For example, using a measurement sample obtained by punching a negative electrode for a secondary battery into a predetermined shape before initial charging, the pore size distribution of the negative electrode mixture layer of the measurement sample is measured by a mercury intrusion method. It can be carried out.
  • the measurement sample may have at least the negative electrode mixture layer on the surface, and may have other structures such as a negative electrode current collector.
  • the measurement of the pore size distribution by the mercury intrusion method can be performed, for example, using an apparatus such as Autopore IV9500 series manufactured by Micromeltics.
  • a sample for measurement is enclosed in a sample container in an inert atmosphere, mercury is injected into the sample container, and pressure is applied to the mercury.
  • the pressure to be applied to the mercury is appropriately adjusted according to the size of the pores that the measurement sample may have, and is not particularly limited. It is preferable to measure by changing the pressure, since the pore size can be measured over a wide range.
  • the peak value R1 should be 0.5 ⁇ m or more and 1.5 ⁇ m or less.
  • the peak value R2 being 2 ⁇ m or more and 10 ⁇ m or less, it is necessary to set the content of the Si-based material and the average particle diameter within an appropriate range.
  • the Si-based material and carbon material contained in the negative electrode active material will be described below.
  • the Si-based material contained in the negative electrode active material is not particularly limited as long as it can reversibly occlude and release ions such as lithium ions.
  • Examples include Si particles, alloy particles containing Si, and Si compound particles. are mentioned. These may be used alone or in combination of two or more.
  • Si particles can be obtained by a vapor phase method or by pulverizing silicon shavings, but they can be produced by any method.
  • Alloy particles containing Si include, for example, alloys containing Si and metals selected from alkali metals, alkaline earth metals, transition metals, rare earth metals, or combinations thereof.
  • Si compound particles are, for example, Si compound particles having a silicate phase and Si particles dispersed in the silicate phase, Si having a silicon oxide phase and Si particles dispersed in the silicon oxide phase Examples include compound particles, Si compound particles having a carbon phase and Si particles dispersed in the carbon phase, and the like. Among these, Si compound particles having a silicate phase and Si particles dispersed in the silicate phase, carbon phase and the Si compound particles having Si particles dispersed in a carbon phase are preferred.
  • the silicate phase contains, for example, at least one element selected from lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium in terms of high lithium ion conductivity. preferably included.
  • the silicate phase is preferably a silicate phase containing lithium (hereinafter sometimes referred to as a lithium silicate phase) because of its high lithium ion conductivity.
  • Si compound particles in which Si particles are dispersed in a silicon oxide phase are represented by, for example, the general formula SiO x (preferably in the range of 0 ⁇ x ⁇ 2, more preferably in the range of 0.5 ⁇ x ⁇ 1.6). be done.
  • Si compound particles in which Si particles are dispersed in a carbon phase are, for example, represented by the general formula SixC1y (preferably in the range of 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1, 0.3 ⁇ x ⁇ 0.45 and 0.7 ⁇ The range of y ⁇ 0.55 is more preferable).
  • a conductive film composed of a highly conductive material is formed on the surface of the particles of the Si-based material.
  • conductive coatings include carbon coatings, metal coatings, and metal compound coatings. Carbon coatings are preferred from the viewpoint of electrochemical stability and the like.
  • the carbon film can be formed by, for example, a CVD method using acetylene, methane, etc., a method of mixing coal pitch, petroleum pitch, phenol resin, etc. with a silicon-based active material and performing a heat treatment.
  • a conductive film may be formed by adhering a conductive filler such as carbon black to the particle surface of the Si-based material using a binder.
  • the content of the Si-based material may be 30% by mass or more with respect to the total amount of the negative electrode active material in terms of increasing the capacity of the secondary battery.
  • the content of the Si-based material is 30% by mass or more and 60% by mass or less with respect to the total amount of the negative electrode active material. is preferred, and more preferably 35% by mass or more and 55% by mass or less.
  • the average particle diameter of the Si-based material should be 4 ⁇ m or more, for example, from the viewpoint of suppressing deterioration of charge-discharge cycle characteristics due to side reactions with the electrolyte.
  • the average particle size of the Si-based material is preferably, for example, 4 ⁇ m or more and 12 ⁇ m or less, and is 6 ⁇ m or more and 10 ⁇ m or less. is more preferred.
  • Examples of the carbon material contained in the negative electrode active material include conventionally known carbon materials used as negative electrode active materials for secondary batteries.
  • Graphites such as natural graphite such as flaky graphite, massive graphite and earthy graphite, artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB) are preferred.
  • the average particle size of the carbon material is preferably 10 ⁇ m or more and 25 ⁇ m or less, more preferably 12 ⁇ m or more and 20 ⁇ m or less, in terms of, for example, further suppressing swelling of the negative electrode.
  • the average particle size of each material is the volume average particle size D50 at which the volume integrated value is 50% in the particle size distribution obtained by the laser diffraction scattering method.
  • the content of the carbon material is, for example, preferably 40% by mass or more and 70% by mass or less, more preferably 45% by mass or more and 65% by mass or less, relative to the total amount of the negative electrode active material.
  • the negative electrode 12 is formed by coating a negative electrode current collector with a negative electrode paste containing a negative electrode active material containing a carbon material and a Si-based material, a pore-forming material, and a binder added as necessary. After the first step, the coating film is subjected to heat treatment to decompose and vaporize the pore-forming material to form a negative electrode mixture layer. 2 steps. Since the average particle size and content of the Si-based material and the carbon material are as described above, they are omitted.
  • the pore-forming material By heat-treating the coating film, the pore-forming material is decomposed and vaporized (e.g., sublimated), and the pore-forming material is separated from the coating film. , a relatively large void is formed.
  • the pore distribution of the negative electrode mixture layer has a peak value R1 of 0.5 ⁇ m or more and 1.5 ⁇ m or less and a peak value of 2 ⁇ m or more and 10 ⁇ m or less. has R2.
  • the pore size distribution of the negative electrode mixture layer usually has only a peak value R1 of 0.5 ⁇ m or more and 1.5 ⁇ m or less.
  • the heat treatment temperature is not particularly limited as long as it is a temperature at which the pore-forming material is decomposed and vaporized.
  • the heat treatment time should be enough to decompose and vaporize the pore-forming material in the coating film, and may be, for example, 5 hours or longer.
  • a known pore-forming material can be used.
  • pore-forming materials include metal oxalates, camphor, naphthalene, and the like.
  • Dicarboxylic acids such as fumaric acid, malonic acid and malic acid may also be used as the pore-forming material.
  • the average particle size of the pore-forming material is preferably, for example, 2 ⁇ m or more and 10 ⁇ m or less. By setting the average particle size of the pore-forming material within the above range, it becomes easy to control the peak value R2 in the pore size distribution of the negative electrode mixture layer within the range of 2 ⁇ m or more and 10 ⁇ m or less.
  • the peak values R2 and R1 in the pore size distribution of the negative electrode mixture layer may be controlled by adjusting the line pressure during coating rolling.
  • Raw materials such as the negative electrode active material, pore-forming material, and binding material when obtaining the negative electrode paste can be mixed using, for example, a cutter mill, a pin mill, a bead mill, a fine particle compounding device (a rotor with a special shape that rotates at high speed inside the tank, and devices that generate shear force between collision plates), granulators, kneaders such as twin-screw extruder kneaders and planetary mixers.
  • a slit die coater, reverse roll coater, lip coater, blade coater, knife coater, gravure coater, and dip coater are used to apply the negative electrode paste.
  • the temperature for drying by heating is desirably a temperature at which the pore-forming material does not decompose/vaporize, but a part of the pore-forming material may be decomposed/vaporized by the drying by heating.
  • Rolling of the coating film may be performed several times with a predetermined linear pressure, for example, using a roll press until the coating film reaches a predetermined thickness.
  • separator 13 for example, a porous sheet having ion permeability and insulation is used. Specific examples of porous sheets include microporous thin films, woven fabrics, and non-woven fabrics.
  • material of the separator 13 polyolefins such as polyethylene and polypropylene, cellulose, and the like are suitable.
  • the separator 13 may have either a single layer structure or a laminated structure. A heat-resistant layer or the like may be formed on the surface of the separator.
  • Example 1 [Preparation of negative electrode] Graphite particles with an average particle size of 17 ⁇ m and a Si-based material with an average particle size of 8 ⁇ m in which Si particles are dispersed in the carbon phase were mixed at a mass ratio of 50:50. This mixture was used as a negative electrode active material.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene copolymer rubber
  • This negative electrode paste was applied to both sides of a negative electrode current collector made of copper foil, and after drying the coating film, the coating film was rolled with a rolling roller. After that, the coating film was heat-treated at 200° C. for 5 hours to prepare a negative electrode having negative electrode mixture layers formed on both sides of the negative electrode current collector.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. .
  • a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol/L in a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a mass ratio of 1:3.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a positive electrode and a negative electrode were laminated so as to face each other with a polyolefin separator interposed therebetween, and wound to produce an electrode body.
  • the electrode assembly was housed in a bottomed cylindrical battery case main body, and after the non-aqueous electrolyte was injected, the opening of the battery case main body was sealed with a gasket and a sealing member to prepare a test cell.
  • Example 2 A negative electrode was prepared in the same manner as in Example 1 except that fumaric acid having an average particle size of 2 ⁇ m was used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 3 A negative electrode was prepared in the same manner as in Example 1 except that fumaric acid having an average particle size of 10 ⁇ m was used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 4 Graphite particles with an average particle size of 17 ⁇ m and a Si-based material with an average particle size of 8 ⁇ m in which Si particles are dispersed in the carbon phase were mixed at a mass ratio of 70:30.
  • a negative electrode was prepared in the same manner, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 5 Graphite particles with an average particle size of 17 ⁇ m and a Si-based material with an average particle size of 8 ⁇ m in which Si particles are dispersed in the carbon phase were mixed at a mass ratio of 40:60.
  • a negative electrode was prepared in the same manner, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 6 A negative electrode was prepared in the same manner as in Example 1 except that a Si-based material having an average particle size of 4 ⁇ m in which Si particles were dispersed in the carbon phase was used, and the negative electrode was used. A test cell was prepared in the same manner as. In the negative electrode of Example 6, the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 7 A negative electrode was prepared in the same manner as in Example 1 except that a Si-based material having an average particle size of 12 ⁇ m in which Si particles were dispersed in the carbon phase was used, and the negative electrode was used. A test cell was prepared in the same manner as. In the negative electrode of Example 7, the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 8 A negative electrode was prepared in the same manner as in Example 1 except that graphite particles with an average particle size of 10 ⁇ m were used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 9 A negative electrode was prepared in the same manner as in Example 1 except that graphite particles with an average particle size of 25 ⁇ m were used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 10 Graphite particles with an average particle size of 17 ⁇ m and a Si-based material with an average particle size of 8 ⁇ m in which Si particles are dispersed in the carbon phase were mixed at a mass ratio of 30:70, except that they were mixed with Example 1.
  • a negative electrode was prepared in the same manner, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 11 A negative electrode was prepared in the same manner as in Example 1 except that a Si-based material having an average particle size of 14 ⁇ m in which Si particles were dispersed in the carbon phase was used, and the negative electrode was used. A test cell was prepared in the same manner as. In the negative electrode of Example 11, the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 12 A negative electrode was prepared in the same manner as in Example 1 except that graphite particles with an average particle size of 8 ⁇ m were used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 13 A negative electrode was prepared in the same manner as in Example 1 except that graphite particles with an average particle diameter of 40 ⁇ m were used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 1 A negative electrode was prepared in the same manner as in Example 1 except that fumaric acid having an average particle size of 12 ⁇ m was used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 2 A negative electrode was prepared in the same manner as in Example 1 except that fumaric acid having an average particle size of 1 ⁇ m was used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury porosimetry method. As a result, one peak value R1 was shown, and the peak value R1 was 1 ⁇ m.
  • Example 3 A negative electrode was prepared in the same manner as in Example 1 except that fumaric acid was not used, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury porosimetry method. As a result, one peak value R1 was shown, and the peak value R1 was 1 ⁇ m.
  • Graphite particles with an average particle size of 17 ⁇ m and a Si-based material with an average particle size of 8 ⁇ m in which Si particles are dispersed in the carbon phase were mixed at a mass ratio of 80:20.
  • a negative electrode was prepared in the same manner, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used.
  • the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 5 A negative electrode was prepared in the same manner as in Example 1 except that a Si-based material having an average particle size of 3 ⁇ m in which Si particles were dispersed in the carbon phase was used, and the negative electrode was used. A test cell was prepared in the same manner as. In the negative electrode of Comparative Example 5, the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. rice field.
  • Example 6 A negative electrode was prepared in the same manner as in Example 1 except that the compressive force for rolling the coating film was increased, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used. In the negative electrode of Comparative Example 6, the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. Met.
  • Example 7 A negative electrode was prepared in the same manner as in Example 1 except that the compressive force for rolling the coating film was weakened, and a test cell was prepared in the same manner as in Example 1 except that the negative electrode was used. In the negative electrode of Comparative Example 7, the pore size distribution of the negative electrode mixture layer was measured by a mercury intrusion method. Met.
  • the pore size distribution measured by the mercury porosimetry has two peak values R1 and R2, and the peak value R1 is , 0.5 ⁇ m or more and 1.5 ⁇ m or less, the peak value R2 is 2 ⁇ m or more and 10 ⁇ m or less, the average particle size of the Si-based material is 4 ⁇ m or more, and the content of the Si-based material is the negative electrode active material

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WO2024242077A1 (ja) * 2023-05-24 2024-11-28 パナソニックＩｐマネジメント株式会社 二次電池用負極、二次電池、及び二次電池用負極の製造方法
WO2025141848A1 (ja) * 2023-12-28 2025-07-03 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 リチウム２次電池
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WO2026034443A1 (ja) * 2024-08-06 2026-02-12 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

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