WO2024116814A1 - 非水電解質二次電池用負極活物質および非水電解質二次電池 - Google Patents

非水電解質二次電池用負極活物質および非水電解質二次電池 Download PDF

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WO2024116814A1
WO2024116814A1 PCT/JP2023/040865 JP2023040865W WO2024116814A1 WO 2024116814 A1 WO2024116814 A1 WO 2024116814A1 JP 2023040865 W JP2023040865 W JP 2023040865W WO 2024116814 A1 WO2024116814 A1 WO 2024116814A1
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negative electrode
phase
electrolyte secondary
sodium aluminate
active material
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French (fr)
Japanese (ja)
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拓弥 神
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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 CN202380079121.7A priority Critical patent/CN120188284A/zh
Priority to EP23897465.3A priority patent/EP4629330A4/en
Priority to JP2024561320A priority patent/JPWO2024116814A1/ja
Publication of WO2024116814A1 publication Critical patent/WO2024116814A1/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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/38—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

  • This disclosure relates to a negative electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the negative electrode active material.
  • non-aqueous electrolyte secondary batteries such as lithium-ion batteries have been widely used in applications requiring high capacity, such as in-vehicle applications and power storage applications.
  • the negative electrode active material which is the main component of the negative electrode, is one of the important factors in increasing the capacity of the battery, and various studies on negative electrode active materials are being conducted. Among these, the use of materials containing silicon (Si-containing materials) has attracted attention as negative electrode active materials with high theoretical capacity density.
  • Si-containing material examples include a material in which nanosilicon is dispersed in a SiO2 phase (hereinafter referred to as "SiOx”), and a material in which nanosilicon is dispersed in a lithium silicate phase represented by Li2zSiO2 +z (0 ⁇ z ⁇ 2) (hereinafter referred to as "LSX”) (for details of LSX, see, for example, Patent Document 1).
  • SiOx a material in which nanosilicon is dispersed in a SiO2 phase
  • LSX lithium silicate phase represented by Li2zSiO2 +z (0 ⁇ z ⁇ 2)
  • LSX Compared to SiOx, LSX has a smaller irreversible capacity and excellent initial charge/discharge efficiency. However, the lithium silicate phase in LSX has low alkali resistance and can still undergo side reactions with Li ions during initial charging, so there is a need for further improvement in the initial charge/discharge efficiency.
  • the inventors have succeeded in reducing side reactions during the initial charging stage and improving charge/discharge efficiency by using a material in which nanosilicon is dispersed in a highly alkaline-resistant lithium aluminate phase as the negative electrode active material.
  • this has created a new problem in that voids are more likely to occur inside the particles than with LSX, resulting in lower durability (cycle characteristics). It is believed that if there are many voids inside the particles of the negative electrode active material, the particle structure will collapse from the voids due to the expansion and contraction of the particles during charging and discharging, reducing durability.
  • the negative electrode active material for non-aqueous electrolyte secondary batteries is characterized in that it is a composite particle that includes a sodium aluminate phase that includes Na and Al, and a silicon phase that is dispersed within the sodium aluminate phase.
  • the nonaqueous electrolyte secondary battery according to the present disclosure comprises a positive electrode, a negative electrode, and a nonaqueous electrolyte, and the negative electrode contains the above-mentioned negative electrode active material.
  • the negative electrode active material according to the present disclosure can realize a non-aqueous electrolyte secondary battery with high capacity and high durability.
  • a non-aqueous electrolyte secondary battery using the negative electrode active material according to the present disclosure has a higher initial charge/discharge efficiency than, for example, a battery using LSX.
  • FIG. 1 is a cross-sectional view of a nonaqueous electrolyte secondary battery according to an embodiment
  • FIG. 2 is a diagram showing a cross section of a particle of a negative electrode active material according to an embodiment of the present invention.
  • composite materials with nanosilicon dispersed in a lithium aluminate phase have higher alkali resistance and better initial charge/discharge efficiency than LSX, but are more susceptible to voids forming inside the particles than LSX. It is believed that when the porosity of active material particles becomes high, the particle structure collapses from the voids due to the expansion and contraction of the particles during charging and discharging, resulting in reduced durability.
  • a nonaqueous electrolyte secondary battery 10 is exemplified, which is a cylindrical battery in which a wound electrode body 14 is housed in a cylindrical exterior can 16 with a bottom, but the exterior body of the battery is not limited to a cylindrical exterior can.
  • Other embodiments of the nonaqueous electrolyte secondary battery according to the present disclosure include a prismatic battery with a prismatic exterior can, a coin battery with a coin-shaped exterior can, and a pouch-type battery with an exterior body composed of a laminate sheet including a metal layer and a resin layer.
  • the electrode body is not limited to a wound type, and may be a laminated type electrode body in which multiple positive electrodes and multiple negative electrodes are alternately stacked with separators between them.
  • the nonaqueous electrolyte secondary battery 10 includes a wound electrode assembly 14, a nonaqueous electrolyte, and an exterior can 16 that contains the electrode assembly 14 and the nonaqueous electrolyte.
  • the electrode assembly 14 includes a positive electrode 11, a negative electrode 12, and a separator 13, and has a wound structure in which the positive electrode 11 and the negative electrode 12 are wound in a spiral shape with the separator 13 interposed therebetween.
  • the exterior can 16 is a cylindrical metal container with a bottom that is open at one axial end, and the opening of the exterior can 16 is closed by a sealing body 17.
  • the sealing body 17 side of the battery is referred to as the top
  • the bottom side of the exterior can 16 is referred to as the bottom.
  • the non-aqueous electrolyte has ionic conductivity (e.g., lithium ion conductivity).
  • the non-aqueous electrolyte may be a liquid electrolyte (electrolytic solution) or a solid electrolyte.
  • the liquid electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • a non-aqueous solvent for example, esters, ethers, nitriles, amides, and mixed solvents of two or more of these are used as the non-aqueous solvent.
  • the non-aqueous solvent include ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and mixed solvents of these.
  • the non-aqueous solvent may contain a halogen-substituted product (e.g., fluoroethylene carbonate, etc.) in which at least a part of the hydrogen of these solvents is replaced with a halogen atom such as fluorine.
  • a halogen-substituted product e.g., fluoroethylene carbonate, etc.
  • a lithium salt such as LiPF6 is used as the electrolyte salt.
  • the solid electrolyte for example, a solid or gel-like polymer electrolyte, an inorganic solid electrolyte, etc. are used.
  • the polymer electrolyte includes, for example, a lithium salt and a matrix polymer, or a non-aqueous solvent, a lithium salt, and a matrix polymer.
  • the matrix polymer for example, a polymer material that absorbs the non-aqueous solvent and gels is used.
  • the polymer material for example, a fluororesin, an acrylic resin, a polyether resin, etc. are used.
  • the inorganic solid electrolyte for example, a material known in all-solid-state lithium ion secondary batteries, etc. (for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a halide-based solid electrolyte, etc.) is used.
  • the positive electrode 11, negative electrode 12, and separator 13 that make up the electrode body 14 are all long, strip-like bodies that are wound in a spiral shape and stacked alternately in the radial direction of the electrode body 14.
  • the negative electrode 12 is formed to be slightly larger than the positive electrode 11 in order to prevent lithium precipitation. That is, the negative electrode 12 is formed to be longer in the longitudinal direction and width direction (short direction) than the positive electrode 11.
  • the separator 13 is formed to be at least slightly larger than the positive electrode 11, and for example, two separators 13 are arranged to sandwich the positive electrode 11.
  • the electrode body 14 has a positive electrode lead 20 connected to the positive electrode 11 by welding or the like, and a negative electrode lead 21 connected to the negative electrode 12 by welding or the like.
  • the positive electrode 11 has a positive electrode core and a positive electrode mixture layer disposed on the positive electrode core.
  • a foil of a metal that is stable in the potential range of the positive electrode 11, such as aluminum or an aluminum alloy, or a film with the metal disposed on the surface layer can be used.
  • the positive electrode mixture layer contains a positive electrode active material, a conductive agent, and a binder, and is preferably formed on both sides of the positive electrode core except for the exposed portion to which the positive electrode lead 20 is welded.
  • the positive electrode 11 can be produced, for example, by applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, and a binder onto the positive electrode core, drying the coating, and then compressing it to form a positive electrode mixture layer on both sides of the positive electrode core.
  • the positive electrode mixture layer contains particulate lithium metal composite oxide as a positive electrode active material.
  • the lithium metal composite oxide is a composite oxide containing metal elements such as Co, Mn, Ni, and Al in addition to Li.
  • the metal element constituting the lithium metal composite oxide is, for example, at least one selected from Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Sn, Sb, W, Pb, and Bi. Of these, it is preferable to contain at least one selected from Co, Ni, and Mn.
  • Examples of the conductive agent contained in the positive electrode mixture layer include carbon black such as acetylene black and ketjen black, graphite, carbon nanotubes (CNT), carbon nanofibers, graphene, and other carbon materials.
  • Examples of the binder contained in the positive electrode mixture layer include fluorine-containing resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide, acrylic resin, polyolefin, and the like. These resins may also be used in combination with carboxymethylcellulose (CMC) or a salt thereof, polyethylene oxide (PEO), and the like.
  • the negative electrode 12 has a negative electrode core and a negative electrode mixture layer disposed on the negative electrode core.
  • a foil of a metal that is stable in the potential range of the negative electrode 12, such as copper or a copper alloy, or a film with the metal disposed on the surface layer can be used.
  • the negative electrode mixture layer contains a negative electrode active material, a binder, and if necessary, a conductive agent, and is preferably formed on both sides of the negative electrode core except for the exposed portion to which the negative electrode lead 21 is welded.
  • the negative electrode 12 can be produced by applying a negative electrode mixture slurry containing a negative electrode active material and a binder, etc., to the surface of the negative electrode core, drying the coating, and then compressing it to form a negative electrode mixture layer on both sides of the negative electrode core.
  • the binder contained in the negative electrode mixture layer can be fluororesin, PAN, polyimide, acrylic resin, polyolefin, etc., but styrene-butadiene rubber (SBR) is preferably used.
  • the negative electrode mixture layer also preferably contains CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA), etc. Among these, it is preferable to use SBR in combination with CMC or a salt thereof, or PAA or a salt thereof.
  • the negative electrode mixture layer may contain a conductive agent such as CNT.
  • a porous sheet having ion permeability and insulating properties is used.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • Suitable materials for the separator 13 include polyolefins such as polyethylene and polypropylene, and cellulose.
  • the separator 13 may have a single-layer structure or a multi-layer structure.
  • a highly heat-resistant resin layer such as an aramid resin may be formed on the surface of the separator 13.
  • a filler layer containing an inorganic filler may be formed at the interface between the separator 13 and at least one of the positive electrode 11 and the negative electrode 12.
  • inorganic fillers include oxides and phosphate compounds containing metal elements such as Ti, Al, Si, and Mg.
  • the filler layer can be formed by applying a slurry containing the filler to the surface of the positive electrode 11, the negative electrode 12, or the separator 13.
  • Insulating plates 18, 19 are arranged above and below the electrode body 14.
  • the positive electrode lead 20 passes through a through hole in the insulating plate 18 and extends toward the sealing body 17, and the negative electrode lead 21 passes outside the insulating plate 19 and extends toward the bottom side of the outer can 16.
  • the positive electrode lead 20 is connected to the underside of the internal terminal plate 23 of the sealing body 17 by welding or the like, and the cap 27, which is the top plate of the sealing body 17 and is electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner bottom inner surface of the outer can 16 by welding or the like, and the outer can 16 serves as the negative electrode terminal.
  • a gasket 28 is provided between the exterior can 16 and the sealing body 17 to ensure airtightness inside the battery.
  • the exterior can 16 has a grooved portion 22 formed with a portion of the side surface that protrudes inward to support the sealing body 17.
  • the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the exterior can 16, and supports the sealing body 17 on its upper surface.
  • the sealing body 17 is fixed to the top of the exterior can 16 by the grooved portion 22 and the open end of the exterior can 16 that is crimped against the sealing body 17.
  • the sealing body 17 has a structure in which, in order from the electrode body 14 side, an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are stacked.
  • Each member constituting the sealing body 17 has, for example, a disk or ring shape, and each member except for the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at their respective centers, and the insulating member 25 is interposed between their respective peripheral edges.
  • the negative electrode active material is explained in detail below with reference to Figure 2.
  • FIG. 2 is a schematic diagram showing a cross section of a composite particle 30, which is an example of an embodiment.
  • the negative electrode 12 contains at least composite particles 30 as the negative electrode active material.
  • the negative electrode active material may be substantially composed of only composite particles 30, but preferably contains composite particles 30 and a carbon material.
  • the use of composite particles 30 in combination with a carbon material as the negative electrode active material makes it easier to achieve both high capacity and excellent cycle characteristics.
  • the content of the composite particles 30 is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and particularly preferably 3% by mass or more and 20% by mass or less, based on the total mass of the negative electrode active material.
  • Examples of carbon materials include graphite, easily graphitized carbon (soft carbon), and difficult-to-graphitize carbon (hard carbon). Of these, graphite is preferred because of its excellent charge/discharge stability and low irreversible capacity.
  • the graphite may be any of artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB), and natural graphite such as flake graphite, massive graphite, and earthy graphite.
  • MAG massive artificial graphite
  • MCMB graphitized mesophase carbon microbeads
  • the composite particle 30 includes a sodium aluminate phase 31 and a silicon phase 32 dispersed within the sodium aluminate phase 31.
  • the composite particle 30 also preferably includes a conductive layer 34 formed on the surface of a mother particle 33 consisting of the sodium aluminate phase 31 and the silicon phase 32.
  • the mother particle 33 has a sea-island structure in which fine silicon phases 32 are dispersed within a matrix of the sodium aluminate phase 31.
  • the sodium aluminate phase 31 includes Na and Al.
  • the composite particle 30 may be substantially free of lithium silicate and SiO 2.
  • the composite particle 30 may contain lithium silicate and SiO 2 , but it is desirable that the amount is small.
  • the total content of lithium silicate and SiO 2 in the composite particle 30 is, for example, 10 mass% or less.
  • the Al content (MAl) relative to the total mass of elements other than oxygen constituting the sodium aluminate phase 31 and the silicon phase 32 (mother particle 33) is preferably 4.0 mass% or more and 20.0 mass% or less, and more preferably 8.0 mass% or more and 15.0 mass% or less.
  • the Na content (MNa) relative to the total mass of elements other than oxygen constituting the mother particle 33 is preferably 0.5 mass% or more and 20.0 mass% or less, more preferably 1.0 mass% or more and 15.0 mass% or less, and particularly preferably 2.0 mass% or more and 10.0 mass% or less.
  • MNa may be 3.0 mass% or more and 8.0 mass% or less, 3.0 mass% or more and 7.0 mass% or less, or 3.5 mass% or more and 6.5 mass% or less.
  • Al content (MAl) and Na content (MNa) are within the above ranges, a sodium aluminate phase with excellent stability and ionic conductivity is easily obtained.
  • the above stability includes both chemical stability (alkali resistance) and thermal stability.
  • the porosity inside the particles is more effectively reduced, which enhances the effect of improving cycle characteristics.
  • the ratio of the Na content to the Al content (MAl) is preferably 0.1 to 2.0, more preferably 0.15 to 1.5, and particularly preferably 0.2 to 1.0, from the viewpoints of the stability of the sodium aluminate phase 31, ionic conductivity, and reduced porosity.
  • the ratio (MO/MAl) of the O content (MO) to the Al content (MAl) is, for example, 0.5 to 4.0.
  • the Si content (MSi) relative to the total mass of elements other than oxygen constituting the mother particle 33 is preferably 50 mass% or more and 95 mass% or less, and more preferably 70 mass% or more and 90 mass% or less. In this case, it is easy to achieve both high capacity and high durability.
  • the Si content (MSi) is the amount of Si that mainly constitutes the silicon phase 32.
  • a fine Al2O3 phase having high crystallinity may be dispersed in the sodium aluminate phase 31.
  • the Al2O3 phase is distributed in an island shape in the matrix of the sodium aluminate phase 31, for example.
  • the expansion and cracking of the sodium aluminate phase 31 due to the expansion and contraction of the silicon phase 32 is easily suppressed, and the effect of improving the cycle characteristics is enhanced.
  • the content of the Al2O3 phase in the composite particle 30 is, for example, 10 mass% or less.
  • the mother particle 33 of the composite particle 30 has a sea-island structure in which fine silicon phases 32, which are islands, are dispersed within sodium aluminate phase 31, which is the sea portion.
  • the sodium aluminate phase 31 has good ionic conductivity, and the silicon phase 32 smoothly absorbs and releases Li ions via the sodium aluminate phase 31.
  • the sodium aluminate phase 31 also mitigates the effects of expansion and contraction of the silicon phase 32.
  • the sodium aluminate phase 31 may be amorphous, in which case the effects of expansion and contraction of the silicon phase 32 can be more effectively mitigated.
  • the composite particle 30 for example, a plurality of primary particles including a sodium aluminate phase 31 and a silicon phase 32 are aggregated to form a secondary particle.
  • the volume-based median diameter (D50) of the composite particle 30 (secondary particle) is, for example, 1 ⁇ m or more and 25 ⁇ m or less, and may be 4 ⁇ m or more and 15 ⁇ m or less. In this case, it is easy to alleviate the stress caused by the volume change of the composite particle 30 accompanying charging and discharging, and it is easy to obtain good cycle characteristics.
  • the surface area of the composite particle 30 is also of a moderate size, and the capacity decrease due to a side reaction with the non-aqueous electrolyte is also suppressed.
  • the volume-based median diameter (D50) of composite particle 30 means the particle diameter at which the cumulative frequency in the volume-based particle size distribution is 50% from the smallest particle diameter.
  • the particle size distribution of composite particle 30 can be measured using a laser diffraction particle size distribution measuring device (e.g., MT3000II manufactured by Microtrack Bell Co., Ltd.) with water as the dispersion medium.
  • a laser diffraction particle size distribution measuring device e.g., MT3000II manufactured by Microtrack Bell Co., Ltd.
  • the thickness of the conductive layer 34 is thin enough not to substantially affect the particle diameter of the composite particle 30, so the particle diameter of the composite particle 30 including the conductive layer 34 may be regarded as the D50 of the composite particle 30.
  • the composite particles 30 can be removed from the battery by the following method. First, a fully discharged battery is disassembled to remove the negative electrode, which is washed with anhydrous ethyl methyl carbonate or dimethyl carbonate to remove the non-aqueous electrolyte components. The negative electrode mixture layer is peeled off from the copper foil that is the negative electrode core, and the mixture layer is crushed in a mortar to obtain a sample powder. Next, the sample powder is dried for 1 hour in a dry atmosphere and immersed in weakly boiled 6M hydrochloric acid for 10 minutes to remove elements derived from other than the composite particles. Next, the sample powder is washed with ion-exchanged water, filtered, and dried at 200°C for 1 hour.
  • the conductive layer 34 is removed by heating to 900°C in an oxygen atmosphere, and only the mother particles 33 can be isolated.
  • the fully discharged state is a state in which the depth of discharge (DOD) is 90% or more (the state of charge (SOC) is 10% or less).
  • the sodium aluminate phase 31 is a composite oxide phase containing Na and Al.
  • the alkali aluminate phase 31 contains Na in an amount of 80 mass % or more, more preferably 85 mass % or more, and particularly preferably 90 mass % or more of the total mass of the alkali metal elements contained in the phase.
  • the alkali metal elements are elements belonging to Group 1 in the periodic table, and the sodium aluminate phase 31 may contain a small amount of at least one element selected from the group consisting of Li, K, Rb, Cs, and Fr.
  • the alkali aluminate phase 31 contains substantially only Na as the alkali metal element.
  • the ratio (MNa/MAl) of the Na content (MNa) to the Al content (MLi) relative to the total mass of elements other than oxygen constituting the mother particle 33 is preferably 0.25 or more and 3.0 or less.
  • MNa/MAl is more preferably 0.3 or more and 2.0 or less, more preferably 0.35 or more and 1.5 or less, and particularly preferably 0.4 or more and 1.0 or less. If MNa/MAl is within this range, the porosity inside the particles is more effectively reduced, and cycle characteristics are greatly improved.
  • the sodium aluminate phase 31 may further contain another element M in addition to Na (alkali metal), Al, and O.
  • An example of the element M is at least one selected from the group consisting of Ca, Mg, Zr, Fe, Si, B, P, and La. Among them, at least one of Si and B is preferable, and B is more preferable.
  • the sodium aluminate phase 31 may contain at least one of Si and B in addition to Na, Al, and O, or may contain substantially only B.
  • the addition of the element M improves the stability and ionic conductivity of the sodium aluminate phase 31, and can further reduce the porosity of the composite particle 30.
  • the element M may form a compound.
  • the compound may be, for example, an oxide of element M or an aluminate of element M depending on the type of element M.
  • the content of element M relative to the total amount of elements other than oxygen constituting the mother particle 33 is, for example, 1.0 mass% to 10.0 mass% or less.
  • the sodium aluminate phase 31 may further contain trace amounts of elements such as chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), and molybdenum (Mo).
  • the ratio (MAl/MB) of the Al content (MAl) to the B content (MB) relative to the total mass of elements other than oxygen constituting the mother particle 33 is preferably 1.0 to 30, more preferably 1.0 to 20, and particularly preferably 1.0 to 10.0. If MAl/MB is within this range, the effect of reducing the porosity becomes more pronounced.
  • the composite particle 30 preferably has a porosity of 25% or less, more preferably 20% or less, inside the particle before the first charge/discharge.
  • the porosity means the proportion of voids 35 in the cross section of the composite particle 30, and is determined from a scanning electron microscope (SEM) image of the cross section of the particle.
  • SEM scanning electron microscope
  • the lower limit of the porosity is not particularly limited, but an example is 1%.
  • the voids 35 are present, for example, approximately uniformly throughout the mother particle 33. Each void 35 is small, and similar to the silicon phase 32, a large number of voids 35 may be present so as to be dispersed throughout the sodium aluminate phase 31.
  • the porosity of composite particle 30 is calculated by using image analysis software (e.g., ImageJ) to binarize an SEM image of the particle cross section to extract the area of voids 35, and then dividing the total area of voids 35 by the total area of the particle cross section.
  • image analysis software e.g., ImageJ
  • the porosity of composite particle 30 can be controlled by the firing temperature of composite particle 30, the compressive force applied to the particle during firing, the addition of element M (especially B), etc.
  • the composite particle 30 has a Vickers hardness of, for example, 300 HV or more. Since the conductive layer 34 has almost no effect on the Vickers hardness, the Vickers hardness of the composite particle 30 and the Vickers hardness of the mother particle 33 are substantially the same. When the composite particle 30 has a high Vickers hardness, it is easier to suppress the volume change of the silicon phase 32 during charging and discharging, and deterioration of the particle structure can be reduced. As a result, the effect of improving the cycle characteristics becomes more significant.
  • the Vickers hardness of the composite particle 30 may be 350 HV or more, 400 HV or more, or 500 HV or more.
  • the Vickers hardness of the composite particle 30 can be measured using a Vickers hardness tester. Specifically, the composite particle 30 is embedded in a thermosetting resin and polished with #400 abrasive paper to expose the cross section of the composite particle 30. The cross section is then mirror-finished with #2000 abrasive paper and buff polishing. The Vickers hardness is measured under conditions of a load of 1 kg and a holding time of 15 seconds. There is no particular limit to the upper limit of the Vickers hardness of the composite particle 30, but one example is 1500 HV.
  • the contents of Na, Al, and element M in the sodium aluminate phase 31 can be measured, for example, by analyzing a cross section of the negative electrode mixture layer.
  • a fully discharged battery is disassembled, the negative electrode is removed, and the negative electrode is washed with anhydrous ethyl methyl carbonate or dimethyl carbonate to remove the non-aqueous electrolyte components and dried, after which a cross section of the negative electrode mixture layer is obtained using a cross section polisher (CP).
  • CP cross section polisher
  • the cross section of the negative electrode mixture layer is observed using an SEM.
  • the content of each element in the sodium aluminate phase 31 is measured by one of the following methods.
  • the composition of the sodium aluminate phase 31 can be determined from the content of each element.
  • Desirable measurement conditions for cross-sectional SEM-EDX analysis are shown below.
  • Processing equipment JEOL, SM-09010 (Cross Section Polisher) Processing conditions: Acceleration voltage 6 kV Current value: 140 ⁇ A Degree of vacuum: 1 ⁇ 10 ⁇ 3 to 2 ⁇ 10 ⁇ 3 Pa
  • Measuring device Hitachi SU-70 electron microscope Acceleration voltage during analysis: 10 kV Field: Free mode Probe current mode: Medium Probe current range: High Anode Ap.: 3 OBJ Apr.: 2 Analysis area: 1 ⁇ m square Analysis software: EDAX Genesis CPS: 20500 Lsec: 50 Time constant: 3.2
  • AES Alger Electron Spectroscopy
  • the EDX and AES analyses are performed within a range of 1 ⁇ m or more inside the peripheral edge of the cross section of the composite particle 30.
  • ICP Inductively Coupled Plasma Atomic Emission Spectroscopy
  • the quantitative analysis of each element can be performed using an electron probe microanalyzer (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray photoelectron spectroscopy (XPS), etc.
  • EPMA electron probe microanalyzer
  • LA-ICP-MS laser ablation inductively coupled plasma mass spectrometry
  • XPS X-ray photoelectron spectroscopy
  • the content of the alkali metal elements, Al, and B contained in the composite particles 30 can be quantitatively analyzed in accordance with JIS R3105 (1995) (method of analysis of borosilicate glass).
  • the content of Ca can be quantitatively analyzed in accordance with JIS R3101 (1995) (method of analysis of soda-lime glass).
  • the carbon content of the composite particles 30 can be measured using a carbon/sulfur analyzer (for example, EMIA-520 model manufactured by Horiba, Ltd.).
  • a carbon/sulfur analyzer for example, EMIA-520 model manufactured by Horiba, Ltd.
  • a sample is weighed out onto a magnetic board, a combustion improver is added, and the board is inserted into a combustion furnace (carrier gas: oxygen) heated to 1350°C, and the amount of carbon dioxide gas generated during combustion is detected by infrared absorption.
  • a calibration curve is created using, for example, carbon steel (carbon content 0.49%) manufactured by Bureau of Analysed Samples. Ltd, and the carbon content of the sample is calculated (high-frequency induction heating furnace combustion - infrared absorption method).
  • the oxygen content of the composite particle 30 can be measured using an oxygen/nitrogen/hydrogen analyzer (for example, EGMA-830 manufactured by Horiba, Ltd.).
  • EGMA-830 manufactured by Horiba, Ltd.
  • the sample is placed in a Ni capsule, and then placed in a carbon crucible heated at 5.75 kW together with Sn pellets and Ni pellets as flux, and the released carbon monoxide gas is detected.
  • a calibration curve is created using a standard sample Y 2 O 3 , and the oxygen content of the sample is calculated (inert gas fusion-non-dispersive infrared absorption method).
  • the amount of Si constituting the silicon phase 32 in the composite particle 30 can be quantified using Si-NMR. Desirable measurement conditions for Si-NMR are shown below. Measurement equipment: Solid-state nuclear magnetic resonance spectrometer (INOVA-400), manufactured by Varian Probe: Varian 7mm CPMAS-2 MAS: 4.2kHz MAS speed: 4kHz Pulse: DD (45° pulse + signal acquisition time 1H decoupled) Repeat time: 1200 sec to 3000 sec Observation width: 100kHz Observation center: Around -100 ppm Signal acquisition time: 0.05 sec Accumulation count: 560 Sample amount: 207.6 mg
  • the silicon phase 32 is a phase of simple silicon, and repeatedly absorbs and releases Li ions as the battery is charged and discharged. The capacity is generated by a Faraday reaction involving the silicon phase 32. Since the silicon phase 32 has a large capacity, it also expands and contracts to a large extent as the battery is charged and discharged, but the silicon phase 32 is dispersed within the sodium aluminate phase 31. Therefore, the stress caused by the expansion and contraction of the silicon phase 32 is mitigated by the sodium aluminate phase 31.
  • the silicon phase 32 is composed of, for example, multiple crystallites.
  • the crystallite size of the silicon phase 32 calculated by the Scherrer formula from the half-width of the diffraction peak of the Si (111) plane obtained by XRD measurement of the composite particle 30 (mother particle 33) is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less. In this case, the volume change of the composite particle 30 due to the expansion and contraction of the silicon phase 32 accompanying charging and discharging can be reduced, and the effect of improving the cycle characteristics becomes more significant.
  • the lower limit of the crystallite size of the silicon phase 32 is not particularly limited, but an example is 1 nm.
  • An example of a suitable crystallite size of the silicon phase 32 is 1 nm or more and 15 nm or less, and may be 5 nm or more and 11 nm or less.
  • the crystallite size of the silicon phase 32 is 1 nm or more, for example, the surface area of the silicon phase 32 can be kept small, making it difficult for deterioration of the silicon phase 32 that is accompanied by the generation of irreversible capacity to occur.
  • the crystallite size is 15 nm or less, the expansion and contraction of the silicon phase 32 is easily made uniform, and the stress generated in the composite particle 30 is effectively alleviated.
  • the silicon phase 32 is, for example, particulate at least before the first charge.
  • the average particle size of the particulate silicon phase 32 is preferably 500 nm or less, more preferably 200 nm or less, and particularly preferably 50 nm or less.
  • the average particle size of the silicon phase 32 after the first charge is preferably 400 nm or less, more preferably 100 nm or less.
  • the content of silicon phase 32 in composite particle 30 is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 55% by mass or more, from the viewpoint of increasing capacity.
  • the upper limit of the content of silicon phase 32 is preferably 95% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less, from the viewpoint of ensuring good cycle characteristics. In this case, the amount of silicon phase 32 exposed on the surface of composite particle 30 without being covered by sodium aluminate phase 31 is reduced, and side reactions between the non-aqueous electrolyte and silicon phase 32 are also suppressed.
  • the composite particle 30 preferably has a conductive layer 34 formed on the surface of the mother particle 33 composed of the sodium aluminate phase 31 and the silicon phase 32.
  • the conductive layer 34 covers at least a part of the surface of the mother particle 33, and preferably substantially covers the entire surface of the mother particle 33.
  • the conductive layer 34 is a thin film layer containing a conductive material, and improves the conductivity of the composite particle 30.
  • the thickness of the conductive layer 34 is preferably thin enough not to affect the particle size of the composite particle 30.
  • the thickness of the conductive layer 34 is preferably 1 nm or more and 200 nm or less, and more preferably 5 nm or more and 100 nm or less.
  • the thickness of the conductive layer 34 can be measured by observing a cross section of the composite particle using a SEM or a transmission electron microscope (TEM).
  • the conductive material constituting the conductive layer 34 is preferably a conductive carbon material.
  • amorphous carbon graphite (natural graphite, artificial graphite, graphitized mesophase carbon, etc.), soft carbon, hard carbon, etc. can be used. Among them, amorphous carbon is preferable because it is easy to form a thin conductive layer 34 that covers the surface of the base particle 33. Examples of amorphous materials include carbon black, burned pitch, coke, activated carbon, etc.
  • the composite particle 30 is produced, for example, by a production method including the following first to fifth steps.
  • First step A step of obtaining sodium aluminate as a raw material (hereinafter referred to as "raw aluminate").
  • Second step A step of compositing the raw aluminate and raw silicon to disperse the silicon phase 32 in the sodium aluminate phase 31 to obtain a composite intermediate.
  • the third step is to heat treat the composite intermediate body to obtain a sintered body containing a sodium aluminate phase 31 and a silicon phase 32 dispersed within the sodium aluminate phase 31.
  • Fourth step A step of pulverizing the sintered body to obtain composite particles 30.
  • Fifth step a step of forming a conductive layer 34 on the surface of the base particle 33 consisting of the sodium aluminate phase 31 and the silicon phase 32.
  • the first step includes, for example, a step of mixing an aluminum compound, a sodium compound, and, if necessary, a compound containing element M to obtain a mixture, and a step of calcining the mixture to obtain a raw aluminate.
  • the calcination is performed, for example, in an oxidizing atmosphere.
  • the calcination temperature is preferably 400° C. or higher and 1200° C. or lower, more preferably 700° C. or higher and 1100° C. or lower.
  • Examples of aluminum compounds include aluminum oxide, aluminum hydroxide, aluminum carbonate, etc.
  • One aluminum compound may be used alone, or two or more may be used in combination.
  • Examples of sodium compounds include sodium carbonate, sodium oxide, sodium hydroxide, sodium hydride, etc.
  • boron compound As a compound containing element M, for example, it is preferable to use a boron compound.
  • boron compounds include boron oxide, boric acid, borax, sodium tetraborate, etc.
  • One type of boron compound may be used alone, or two or more types may be used in combination.
  • the first step aluminum compounds that have not reacted with the compound containing an alkali metal element during the preparation of the raw aluminate may remain in the raw aluminate.
  • the amount of aluminum compound used is large relative to the compound containing an alkali metal element, the aluminum compounds may remain.
  • the aluminum compound remaining in the raw aluminate is Al 2 O 3
  • an Al 2 O 3 phase dispersed in the sodium aluminate phase 31 may be formed in the composite particles 30 finally obtained.
  • the mixture of the raw aluminate and the raw silicon is pulverized while applying a shear force to obtain a finely divided composite intermediate.
  • coarse silicon particles with an average particle size of several ⁇ m to several tens of ⁇ m may be used.
  • the silicon particles are preferably prepared so that the crystallite size of the silicon phase 32 calculated from the half-width of the diffraction peak assigned to the Si (111) plane in the XRD pattern using Scherrer's formula is 15 nm or less. It is also possible to synthesize silicon nanoparticles and raw aluminate nanoparticles and mix them together without using a grinding device.
  • the composite intermediate is sintered while applying pressure to the finely divided composite intermediate by hot pressing or the like to obtain a sintered body.
  • the pressure applied to the composite intermediate is, for example, 100 MPa or more, and may be 100 MPa or more and 300 MPa or less.
  • the higher the pressure in the third step the smaller the porosity of the composite particles 30 tends to be.
  • the composite intermediate is preferably sintered in an inert atmosphere (for example, an atmosphere of argon, nitrogen, etc.).
  • the sintering conditions in the third step also affect the crystallites of the silicon phase 32, and generally, the higher the sintering temperature, the larger the crystallite size.
  • the firing temperature is 450°C or higher and 1000°C or lower. If the firing temperature is within this range, it is easy to form a structure in which minute silicon phases 32 are dispersed within the sodium aluminate phase 31 with low crystallinity.
  • the raw material aluminate is stable at this temperature and hardly reacts with silicon.
  • the firing temperature is preferably 550°C or higher and 950°C or lower, and more preferably 650°C or higher and 900°C or lower.
  • the firing time is, for example, 1 hour or higher and 10 hours or lower. To reduce the porosity to 25% or less, firing at a temperature of 650°C or higher is preferable.
  • the fourth step is a step of pulverizing the base particles 33 so that the base particles 33 have a desired particle size distribution.
  • the base particles 33 are pulverized so that D50 is, for example, 1 ⁇ m or more and 25 ⁇ m or less.
  • the manufacturing process of the composite particle 30 of this embodiment includes a fifth step of forming a conductive layer 34 on the surface of the base particle 33.
  • the conductive material constituting the conductive layer 34 is preferably a conductive carbon material.
  • Examples of a method for coating the surface of the base particle 33 with a carbon material include a CVD method using a hydrocarbon gas such as acetylene or methane as a raw material, and a method of mixing coal pitch, petroleum pitch, phenolic resin, etc. with the base particle 33 and heating to carbonize it. Carbon black may also be attached to the surface of the base particle 33.
  • a mixture of the base particles 33 and the carbon material is heated at 700°C or higher and 950°C or lower in an inert atmosphere (e.g., an atmosphere of argon, nitrogen, etc.) to obtain a composite particle 30 in which a conductive layer 34 is formed on the surface of the base particle 33.
  • an inert atmosphere e.g., an atmosphere of argon, nitrogen, etc.
  • Example 1 [Preparation of Composite Particles] (First step) A raw aluminate was obtained by mixing Al 2 O 3 , Na 2 CO 3 , and B 2 O 3 and firing the mixture in air at 800° C. for 10 hours. In the first step, the mixing ratio of Al 2 O 3 , Na 2 CO 3 , and B 2 O 3 was adjusted so that the constituent elements of the sodium aluminate phase had the element ratio shown in Table 1. The raw aluminate was also pulverized to have a D50 of 10 ⁇ m.
  • the powdered mixture obtained in the second step was taken out into an inert atmosphere, and sintered at 700° C. for 4 hours in the inert atmosphere while applying a pressure of 200 MPa using a hot press machine, thereby obtaining a sintered body of the mixture.
  • the sintered body obtained in the third step was pulverized and passed through a 40 ⁇ m mesh to obtain base particles in which a silicon phase was dispersed in a sodium aluminate phase.
  • Coal pitch (MCP250, manufactured by JFE Chemical Corporation) was mixed with the base particles obtained in the fourth step. The mixture was fired at 800°C for 5 hours in an inert atmosphere to form a conductive layer containing a conductive carbon material on the surface of the base particles. The coating amount of the conductive layer was 5 mass% based on the total mass of the base particles and the conductive layer. Then, composite particles having a conductive layer and a D50 of 5 ⁇ m were obtained using a sieve.
  • the composite particles and graphite were mixed in a mass ratio of 5:95 to be used as the negative electrode active material.
  • Water was added to the negative electrode mixture containing the negative electrode active material, the Na salt of CMC, and SBR in a mass ratio of 97.5:1:1.5, and the mixture was stirred to prepare a negative electrode mixture slurry.
  • the negative electrode mixture slurry was applied to the surface of the negative electrode core body made of copper foil, and the coating was dried and then rolled to prepare a negative electrode having a negative electrode mixture layer with a density of 1.5 g/cm 3 formed on both sides of the copper foil.
  • NMP N-methyl-2-pyrrolidone
  • a non-aqueous electrolyte was prepared by dissolving LiPF6 at a concentration of 1.0 mol/L in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 3:7 (25° C.).
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • non-aqueous electrolyte secondary battery The positive and negative electrodes with the leads attached were wound with a separator interposed therebetween to prepare a wound electrode body, which was then inserted into an exterior body made of an aluminum laminate film and vacuum dried at 105° C. for 2 hours. After that, a nonaqueous electrolyte was injected, and the opening of the exterior body was sealed to obtain a nonaqueous electrolyte secondary battery.
  • Examples 2 to 5> In the above first step, composite particles were synthesized in the same manner as in Example 1, except that the mixing ratios of Al 2 O 3 , Na 2 CO 3 , and B 2 O 3 were changed so that the contents of each element constituting the composite material were the values shown in Table 1, and a nonaqueous electrolyte secondary battery was fabricated.
  • Composite particles were synthesized and a non-aqueous electrolyte secondary battery was fabricated in the same manner as in Example 1, except that in the first step, SiO 2 was added instead of Al 2 O 3 and B 2 O 3 was not added.
  • a composite material having a sodium aluminate phase as the dispersed phase of nanosilicon contributes to improved durability more than a composite material having a lithium aluminate phase (Comparative Example 1), a lithium silicate phase (Comparative Example 2), or a sodium silicate phase as the dispersed phase.
  • the ratio of the Na content to the Al content (MNa/MAl) is 0.60 or more and 1.0 or less, or even 0.65 or more and 0.90 or less, the effect of reducing the porosity inside the particles is remarkable, and durability is greatly improved.
  • Configuration 1 A negative electrode active material for a non-aqueous electrolyte secondary battery, which is a composite particle including a sodium aluminate phase containing Na and Al, and a silicon phase dispersed within the sodium aluminate phase.
  • Configuration 2 The negative electrode active material for a nonaqueous electrolyte secondary battery according to Configuration 1, wherein the sodium aluminate phase contains Na in an amount of 80 mass % or more of the total mass of alkali metal elements contained in the phase.
  • Configuration 3 The negative electrode active material for a nonaqueous electrolyte secondary battery according to configuration 1, wherein the sodium aluminate phase contains substantially only Na as an alkali metal element.
  • Configuration 4 The negative electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 3, wherein the ratio (MNa/MAl) of the Na content (MNa) to the Al content (MAl) relative to the total mass of elements other than oxygen constituting the sodium aluminate phase and the silicon phase is 0.25 or more and 3.0 or less.
  • Configuration 5 The negative electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 4, wherein the sodium aluminate phase further contains at least one of Si and B.
  • Aspect 6 The negative electrode active material for a nonaqueous electrolyte secondary battery according to Aspect 5, wherein the sodium aluminate phase contains at least B, and a ratio (MAl/MB) of an Al content (MAl) to a B content (MB) relative to a total mass of elements other than oxygen constituting the sodium aluminate phase and the silicon phase is 1.0 or more and 30 or less.
  • Configuration 7 The negative electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 6, wherein the composite particles have an internal porosity of 25% or less before an initial charge/discharge.
  • Configuration 8 The negative electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 7, wherein the composite particle includes a conductive layer formed on a surface of a base particle composed of the sodium aluminate phase and the silicon phase.
  • Configuration 9 A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, the negative electrode including the negative electrode active material according to any one of configurations 1 to 8.

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PCT/JP2023/040865 2022-11-30 2023-11-14 非水電解質二次電池用負極活物質および非水電解質二次電池 Ceased WO2024116814A1 (ja)

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EP23897465.3A EP4629330A4 (en) 2022-11-30 2023-11-14 NEGATIVE ELECTRODE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERIES, AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERIES
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WO2017199606A1 (ja) * 2016-05-17 2017-11-23 Ｊｆｅケミカル株式会社 Ｌｉイオン二次電池用負極材料、Ｌｉイオン二次電池用負極およびＬｉイオン二次電池
WO2022113500A1 (ja) * 2020-11-30 2022-06-02 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用負極材料および非水電解質二次電池
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WO2020045257A1 (ja) * 2018-08-30 2020-03-05 パナソニックＩｐマネジメント株式会社 二次電池用負極活物質および二次電池
CN113471442B (zh) * 2019-01-02 2022-08-02 宁德新能源科技有限公司 负极活性材料和使用其的负极极片、电化学装置和电子装置
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