WO2022181266A1 - 電池用電極合剤および非水電解質二次電池 - Google Patents

電池用電極合剤および非水電解質二次電池 Download PDF

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WO2022181266A1
WO2022181266A1 PCT/JP2022/003998 JP2022003998W WO2022181266A1 WO 2022181266 A1 WO2022181266 A1 WO 2022181266A1 JP 2022003998 W JP2022003998 W JP 2022003998W WO 2022181266 A1 WO2022181266 A1 WO 2022181266A1
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electrode mixture
positive electrode
mass
active material
layered silicate
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English (en)
French (fr)
Japanese (ja)
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拡哲 鈴木
基浩 坂田
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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 US18/277,274 priority Critical patent/US20240128448A1/en
Priority to EP22759307.6A priority patent/EP4300617A4/en
Priority to CN202280014790.1A priority patent/CN116848676A/zh
Priority to JP2023502233A priority patent/JPWO2022181266A1/ja
Publication of WO2022181266A1 publication Critical patent/WO2022181266A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/36—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
    • H01M4/621—Binders
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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 battery electrode mixture and a non-aqueous electrolyte secondary battery including an electrode configured using the electrode mixture.
  • the electrodes of non-aqueous electrolyte secondary batteries such as lithium ion batteries generally include a mixture layer containing an active material capable of intercalating and deintercalating lithium ions. Since the electrode mixture layer greatly affects battery performance such as input/output characteristics and capacity, many studies have been conducted on the electrode mixture constituting the mixture layer.
  • Patent Literature 1 discloses a negative electrode mixture containing a negative electrode active material, a binder, and a layered compound. In Patent Document 1, by adding a layered compound together with a binder, the amount of the binder added can be suppressed, and while maintaining the effect of suppressing separation and segregation during storage and drying, the negative electrode can be It is described that the deterioration of physical properties as can be suppressed.
  • Patent Document 2 discloses a negative electrode mixture containing fine particles containing at least one selected from carbon, silicon, and tin, a conductivity imparting agent, and a dispersant, and using carbon nanotubes as the conductivity imparting agent. is disclosed. Patent Literature 2 describes that by using this negative electrode mixture, it is possible to provide a highly conductive negative electrode for a lithium ion battery.
  • the conductivity of the electrode mixture layer is an important characteristic in improving battery performance such as input/output characteristics and capacity of the battery, and many studies are underway.
  • the diffusibility of lithium ions in the mixture layer is also important in improving battery performance, just like conductivity. It cannot be said that sufficient consideration has been made.
  • the techniques of Patent Literatures 1 and 2 do not take into consideration the improvement of the diffusibility of lithium ions in the mixture layer.
  • An object of the present disclosure is to provide a battery electrode mixture that can reduce the diffusion resistance of lithium ions in the electrode mixture layer.
  • a battery electrode mixture that is one aspect of the present disclosure is a battery electrode mixture containing an active material capable of intercalating and deintercalating lithium ions and a binder, wherein the electrode mixture is a layered silicate compound. and the content of the layered silicic acid compound is more than 0.1% by mass with respect to the mass of the active material.
  • a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and at least one of the mixture layers of the positive electrode and the negative electrode is composed of the electrode mixture.
  • the diffusion resistance of lithium ions in the electrode mixture layer can be reduced.
  • a non-aqueous electrolyte secondary battery using the electrode mixture according to the present disclosure has, for example, good diffusion of lithium ions in the electrode mixture layer and excellent high-rate discharge characteristics.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery that is an example of an embodiment
  • the high-rate discharge characteristics of the battery were specifically improved by using an electrode mixture to which carbon nanotubes were added together with the layered silicic acid compound. Although the mechanism is not clear, it is thought that the high-rate discharge characteristics are improved due to the synergistic effect of the reduction in diffusion resistance of lithium ions due to the addition of the layered silicate compound and the improvement in conductivity due to the addition of carbon nanotubes. Moreover, although the electrode mixture according to the present disclosure can be applied to a negative electrode, application to a positive electrode is more effective.
  • a cylindrical battery in which the wound electrode body 14 is housed in a bottomed cylindrical outer can 16 will be exemplified. It may be a prismatic battery), a coin-shaped outer can (coin-shaped battery), or an outer body (laminate battery) composed of a laminate sheet including a metal layer and a resin layer. Further, the electrode assembly is not limited to the wound type, and may be a laminated electrode assembly in which a plurality of positive electrodes and a plurality of negative electrodes are alternately laminated with separators interposed therebetween.
  • the battery electrode mixture according to the present disclosure can be applied to aqueous electrolyte secondary batteries using an aqueous electrolyte, but is particularly effective in non-aqueous electrolyte secondary batteries using a non-aqueous electrolyte.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery 10 that is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 includes a wound electrode body 14, a non-aqueous electrolyte, and an outer can 16 that accommodates the electrode body 14 and the non-aqueous electrolyte.
  • Electrode body 14 has positive electrode 11 , negative electrode 12 , and separator 13 , and has a wound structure in which positive electrode 11 and negative electrode 12 are spirally wound with separator 13 interposed therebetween.
  • the outer can 16 is a bottomed cylindrical metal container that is open on one side in the axial direction. In the following description, for convenience of explanation, the side of the sealing member 17 of the battery will be referred to as the upper side, and the bottom side of the outer can 16 will be referred to as the lower side.
  • the non-aqueous electrolyte contains 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.
  • non-aqueous solvents include ethylene carbonate (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), mixed solvents thereof, and the like.
  • a lithium salt such as LiPF 6 is used as the electrolyte salt.
  • the non-aqueous electrolyte is not limited to a liquid electrolyte, and may be a solid electrolyte.
  • the positive electrode 11, the negative electrode 12, and the separator 13, which constitute the electrode assembly 14, are all strip-shaped elongated bodies, and are alternately laminated in the radial direction of the electrode assembly 14 by being spirally wound.
  • the negative electrode 12 is formed with a size one size larger than that of the positive electrode 11 in order to prevent deposition of lithium. That is, the negative electrode 12 is formed longer than the positive electrode 11 in the longitudinal direction and the width direction (transverse direction).
  • the separator 13 is at least one size larger than the positive electrode 11, and two separators 13 are arranged so as to sandwich the positive electrode 11, for example.
  • 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.
  • Insulating plates 18 and 19 are arranged above and below the electrode body 14, respectively.
  • the positive electrode lead 20 extends through the through hole of the insulating plate 18 toward the sealing member 17
  • the negative electrode lead 21 extends through the outside of the insulating plate 19 toward the bottom of the outer can 16 .
  • the positive electrode lead 20 is connected to the lower surface 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 electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner surface of the bottom of the outer can 16 by welding or the like, and the outer can 16 serves as a negative electrode terminal.
  • a gasket 28 is provided between the outer can 16 and the sealing body 17 to ensure hermeticity inside the battery.
  • the outer can 16 is formed with a grooved portion 22 that supports the sealing member 17 and has a portion of the side surface projecting inward.
  • the grooved portion 22 is preferably annularly formed along the circumferential direction of the outer can 16 and supports the sealing member 17 on its upper surface.
  • the sealing member 17 is fixed to the upper portion of the outer can 16 by the grooved portion 22 and the open end of the outer can 16 that is crimped to the sealing member 17 .
  • the sealing body 17 has a structure in which an internal terminal plate 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 at their central portions, and an insulating member 25 is interposed between their peripheral edge portions.
  • the positive electrode 11, the negative electrode 12, and the separator 13 that make up the electrode assembly 14 will be described in detail below, particularly the electrode mixture that makes up the mixture layer of the positive electrode 11 and the negative electrode 12.
  • An electrode mixture which is an example of an embodiment, includes an active material capable of intercalating and deintercalating lithium ions, a binder, and a layered silicate compound.
  • the content of the layered silicate compound in the electrode mixture is more than 0.1% by mass, preferably 0.2% by mass or more, relative to the mass of the active material.
  • the electrode mixture which is an example of the embodiment, can be applied to the negative electrode 12, but is particularly effective for the positive electrode 11.
  • the mixture layer of the positive electrode 11 is made of an electrode mixture that is an example of the embodiment.
  • the positive electrode 11 has a positive electrode core 30 and a positive electrode mixture layer 31 provided on the surface of the positive electrode core 30 .
  • a foil of a metal such as aluminum or an aluminum alloy 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 layers 31 are preferably provided on both surfaces of the positive electrode core 30 .
  • the positive electrode 11 can be produced, for example, by applying slurry of a positive electrode mixture onto the positive electrode core 30 , drying the coating film, and then compressing it to form the positive electrode mixture layers 31 on both sides of the positive electrode core 30 . .
  • the positive electrode mixture layer 31 contains a positive electrode active material, a binder, and a layered silicate compound.
  • the positive electrode mixture layer 31 preferably further contains a conductive agent.
  • the positive electrode mixture layer 31 is formed, for example, by applying a positive electrode mixture slurry containing a positive electrode active material, a binder, a conductive agent, and a layered silicate compound onto the positive electrode substrate 30 .
  • the dispersion medium for the positive electrode mixture slurry is not particularly limited as long as it can disperse the positive electrode mixture, but one example is N-methyl-2-pyrrolidone (NMP).
  • the layered silicate compound may be mixed with a powder of the positive electrode active material or the like and then slurried, or may be added to a slurry in which the positive electrode active material or the like is dispersed and mixed with the positive electrode active material or the like.
  • Binders contained in the positive electrode mixture layer 31 include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide, acrylic resin, and polyolefin. etc. can be exemplified. These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or salts thereof, polyethylene oxide (PEO), and the like.
  • the content of the binder is, for example, 0.5 to 2.0 mass % with respect to the mass of the positive electrode mixture layer 31 .
  • the positive electrode active material is preferably a lithium-containing transition metal composite oxide.
  • Elements contained in the lithium-containing transition metal composite oxide include Ni, Co, Mn, Na, K, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd. , Tb, Dy, Ho, Er, Tm, Yb, Lu, Ge, Sn, Pb, Sc, Ti, Si, V, Cr, Fe, Cu, Zn, Ru, Rh, Re, Pd, Ir, Ag, Bi , Sb, B, Al, Ga, In, P, Zr, Hf, Nb, Mo, W and the like.
  • a preferred example of the lithium-containing transition metal composite oxide has a layered rock salt crystal structure and has the general formula: LiNi x M 1-x O 2 (wherein M is selected from the group consisting of Al, Mn and Co and at least one compound oxide represented by 0.3 ⁇ x ⁇ 1.0).
  • Composite oxides with a high Ni content are effective in increasing the capacity of batteries.
  • the composite oxide represented by the above general formula has good compatibility with the layered silicate compound, and by using the composite oxide, it is possible to increase the capacity of the battery while diffusing lithium ions in the positive electrode mixture layer 31. It is possible to improve the performance more effectively.
  • the main component of the positive electrode active material is the lithium-containing transition metal composite oxide represented by the above general formula.
  • the main component means the component having the highest mass ratio among the constituent components of the composite oxide.
  • a composite oxide other than the composite oxide represented by the general formula may be used as the positive electrode active material, but the content of the composite oxide is 50% by mass or more. is preferred, and may be substantially 100% by mass.
  • the composition of the composite oxide can be measured using an ICP emission spectrometer (iCAP6300 manufactured by Thermo Fisher Scientific).
  • the lithium-containing transition metal composite oxide is, for example, secondary particles formed by agglomeration of a plurality of primary particles.
  • An example of the volume-based median diameter (D50) of the lithium-containing transition metal composite oxide is 1 to 20 ⁇ m, or 2 to 15 ⁇ m. D50 is the particle size at which the volume integrated value is 50% in the particle size distribution measured by the laser diffraction scattering method.
  • the BET specific surface area of the composite oxide is, for example, 1.0-4.0 mm 2 /g. If the BET specific surface area is within this range, it becomes easier to achieve both high durability and high capacity. The BET specific surface area is measured according to the BET method (nitrogen adsorption method) described in JIS R1626.
  • the positive electrode mixture layer 31 contains the layered silicate compound as described above.
  • the content of the layered silicate compound is 0.1% by mass, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, relative to the mass of the positive electrode active material.
  • the content of the layered silicate compound is, for example, 1% by mass or less, preferably less than 0.9% by mass, relative to the mass of the positive electrode active material.
  • the content of the layered silicate compound is more preferably 0.8% by mass or less, particularly preferably 0.7% by mass or less.
  • An example of a suitable range for the content of the layered silicate compound is 0.2 to 0.8% by mass (0.2% by mass or more and 0.8% by mass or less) relative to the mass of the positive electrode active material, Or 0.3 to 0.7% by mass, or 0.4 to 0.6% by mass.
  • the content of the layered silicate compound in the positive electrode mixture layer 31 is, for example, 0.2 to 0.8% by mass, and is preferably the same as the above content in the positive electrode active material.
  • the mass ratio of the layered silicate compound to the binder is not particularly limited, but is preferably 1:2 to 2:1 or 1:1.5 to 1.5:1.
  • the mass ratio of the layered silicate compound and the conductive agent is not particularly limited, but is preferably 1:1.5 to 1.5:1 or 1:1.3 to 1.3:1.
  • the content of the layered silicate compound is, for example, less than or equal to the content of the binder and greater than or equal to the content of the conductive agent.
  • the layered silicate compound is preferably at least one type of smectite.
  • Suitable smectites include montmorillonite, hectorite, beidellite, nontronite, saponite, sauconite, and the like.
  • smectite has a high affinity with lithium ions, and effectively improves the diffusibility of lithium ions in the positive electrode mixture layer 31 .
  • the positive electrode mixture layer 31 contains, for example, at least one smectite selected from the group consisting of montmorillonite, hectorite, beidellite, nontronite, saponite, and sauconite. Among them, montmorillonite is preferred.
  • An ion-exchanged smectite may be used as the layered silicate compound.
  • Smectite has a weak layer charge and a structure in which exchangeable cations (sodium ion, calcium ion, etc.) are held between the layers. This cation is also called an exchangeable cation.
  • a suitable ion-exchanged smectite is one in which the exchangeable cations are exchanged for lithium ions.
  • exchangeable cations such as sodium ions are, for example, 95% by mass or more exchanged with lithium ions.
  • smectite in which exchangeable cations are exchanged for tium ions may be used as the layered silicate compound.
  • smectite in which exchangeable cations are exchanged with lithium ions and smectite without ion exchange treatment may be used in combination.
  • the mass ratio of the former to the latter is, for example, 5:1 to 1:5, and a preferred example is 4:1 to 1:1 or 4:1 to 2:1.
  • the layered silicate compound is preferably dispersed throughout the positive electrode mixture layer 31 without being unevenly distributed in a part of the positive electrode mixture layer 31 .
  • the layered silicate compound is distributed in an arbitrary region of the positive electrode mixture layer 31 with a substantially uniform concentration.
  • the layered silicate compound exists between the particles of the positive electrode active material and is in contact with the surface of the particles of the positive electrode active material.
  • a layered silicate compound is a scaly particle in which many layers are laminated. A part of the layered silicate compound may be dispersed in the positive electrode mixture layer 31 by separating the layers that constitute the particles, and be finely divided.
  • the conductive agent contained in the positive electrode mixture layer 31 forms a good conductive path in the mixture layer.
  • Conductive agents include particulate conductive agents such as carbon black, acetylene black, ketjen black, and graphite, vapor grown carbon fiber (VGCF), electrospun carbon fiber, polyacrylonitrile (PAN)-based carbon fiber, and pitch-based carbon fiber.
  • the positive electrode mixture layer 31 preferably contains at least carbon nanotubes (CNT), although it may be a fibrous conductive agent such as a conductive agent such as graphene.
  • CNT carbon nanotubes
  • the content of CNTs is, for example, 0.05 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, and particularly preferably 0.2 to 2.0% by mass, based on the mass of the positive electrode mixture layer 31. It is 1.0% by mass. If the CNT content is within this range, high rate discharge characteristics can be improved more effectively.
  • the positive electrode mixture layer 31 may contain only CNT as a conductive agent.
  • the CNTs may be either single-walled CNTs (SWCNTs) or multi-walled CNTs (MWCNTs), but are more preferably MWCNTs.
  • MWCNT include tubular structure CNTs in which graphene sheets made of six-membered carbon rings are wound parallel to the fiber axis, and poollets in which graphene sheets made of six-membered carbon rings are arranged perpendicular to the fiber axis.
  • a CNT with a structure, a CNT with a herringbone structure in which a graphene sheet composed of a six-membered carbon ring is wound at an oblique angle with respect to the fiber axis, or the like can be used. Two or more types of CNTs may be added to the positive electrode mixture layer 31 .
  • the average diameter of CNTs is, for example, 50 nm or less, preferably 40 nm or less, more preferably 25 nm or less, and particularly preferably 20 nm or less.
  • the lower limit of the average diameter of CNTs is not particularly limited, it is 1 nm or 5 nm as an example.
  • An example of a suitable range for the average diameter of CNTs is 1-20 nm, or 5-20 nm. If the average diameter of the CNTs is within this range, the effect of improving high-rate discharge characteristics is enhanced compared to the case of using CNTs having an average diameter outside this range.
  • the average fiber length of CNT is, for example, 0.5 ⁇ m or longer, preferably 0.7 ⁇ m or longer, more preferably 0.8 ⁇ m or longer, and particularly preferably 1 ⁇ m or longer.
  • the upper limit of the average fiber length of CNT is not particularly limited, it is 10 ⁇ m or 5 ⁇ m as an example.
  • An example of a suitable range for the average fiber length of CNTs is 1-10 ⁇ m, or 1-5 ⁇ m. If the average fiber length of the CNTs is within this range, the effect of improving the high-rate discharge characteristics is enhanced compared to the case of using CNTs having an average fiber length outside this range.
  • 100 CNTs were selected from the surface TEM image of the positive electrode mixture layer 31 for the average diameter of the CNTs, and from the cross-sectional SEM image of the positive electrode mixture layer 31 for the average fiber length, and the diameter and fiber length were measured. It is obtained by averaging these measured values.
  • the negative electrode 12 has a negative electrode core 40 and a negative electrode mixture layer 41 provided on the surface of the negative electrode core 40 .
  • 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 layers 41 are preferably provided on both surfaces of the negative electrode core 40 .
  • the negative electrode 12 can be produced, for example, by applying slurry of a negative electrode mixture onto the negative electrode core 40 , drying the coating film, and then compressing to form negative electrode mixture layers 41 on both sides of the negative electrode core 40 .
  • the negative electrode mixture layer 41 (negative electrode mixture) includes a negative electrode active material and a binder.
  • the negative electrode mixture layer 41 may further contain the layered silicate compound described above.
  • the negative electrode mixture layer 41 contains, as a negative electrode active material, a carbon-based active material that reversibly absorbs and releases lithium ions, for example.
  • Suitable carbon-based active materials are graphite such as natural graphite such as flake graphite, massive graphite and earthy graphite, artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB).
  • a Si-based active material composed of at least one of Si and a Si-containing compound may be used as the negative electrode active material, or a carbon-based active material and a Si-based active material may be used in combination.
  • the binder contained in the negative electrode mixture layer 41 fluororesin, PAN, polyimide, acrylic resin, polyolefin, etc. can be used as in the case of the positive electrode 11, but styrene-butadiene rubber (SBR) is used. is preferred.
  • the negative electrode mixture layer 41 preferably further contains CMC or its salt, polyacrylic acid (PAA) or its salt, polyvinyl alcohol (PVA), or the like. Among them, it is preferable to use SBR together with CMC or its salt or PAA or its salt.
  • the negative electrode mixture layer 41 may contain a conductive agent.
  • a porous sheet having ion permeability and insulation is used for the separator 13 .
  • porous sheets include microporous thin films, woven fabrics, and non-woven fabrics.
  • Suitable materials for the separator 13 include polyolefins such as polyethylene, polypropylene, copolymers of ethylene and ⁇ -olefin, and cellulose.
  • the separator 13 may have either a single layer structure or a laminated structure.
  • a heat-resistant layer containing inorganic particles, a heat-resistant layer made of a highly heat-resistant resin such as aramid resin, polyimide, polyamideimide, or the like may be formed on the surface of the separator 13 .
  • a lithium-containing transition metal composite oxide was used as the positive electrode active material.
  • a positive electrode active material, multi-walled carbon nanotubes (MWCNT), polyvinylidene fluoride, and montmorillonite A1 (manufactured by Kunimine Industries Co., Ltd., Kunipia M) in which exchangeable cations are exchanged for lithium ions were mixed at a ratio of 100:0.4:0.
  • a positive electrode mixture slurry was prepared by mixing at a solid content mass ratio of 6:0.2 and using N-methyl-2-pyrrolidone (NMP) as a dispersion medium. Next, the positive electrode mixture slurry was applied onto a positive electrode core made of aluminum foil, the coating film was dried and compressed, and then cut into a predetermined electrode size to obtain a positive electrode.
  • NMP N-methyl-2-pyrrolidone
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed in a predetermined volume ratio. LiPF 6 was added to the mixed solvent to obtain a non-aqueous electrolyte.
  • test cell An electrode assembly was constructed by arranging the positive electrode and the negative electrode made of lithium metal foil in opposition to each other with a separator interposed therebetween, and the electrode assembly and the non-aqueous electrolyte were housed in an exterior body constructed using an aluminum laminate sheet. After that, the opening of the outer package was sealed to obtain a test cell (non-aqueous electrolyte secondary battery).
  • the diffusion resistance of lithium ions in the positive electrode mixture layer, the electronic interface resistance, and the 1C discharge capacity were evaluated by the following methods (the same applies to the examples and comparative examples described later).
  • the evaluation results of the diffusion resistance and the electronic interface resistance are calculated from the DC-IR measurement results at the time of 0.3 C discharge, and shown as relative values when the result of Comparative Example 1 is set to 100.
  • Each evaluation result is shown in Table 1 together with the type and content of the layered silicate compound.
  • test cell was charged to a depth of charge (SOC) of 50% under a temperature environment of 25°C. Next, each battery was discharged at a current value of 0.3 C for 10 seconds, the battery voltage during discharge was measured, and the battery voltage was plotted against the current value to obtain the resistance during discharge.
  • SOC depth of charge
  • Examples 2 to 9 A test cell was fabricated in the same manner as in Example 1, except that the amount of montmorillonite A1 added was changed so that the content of montmorillonite A1 was the value shown in Table 1 in fabricating the positive electrode.
  • Example 10 A test cell was produced in the same manner as in Example 4, except that montmorillonite A2 (manufactured by Kunimine Industries Co., Ltd., Knipia F) not subjected to ion exchange treatment was used instead of montmorillonite A1 in the production of the positive electrode.
  • montmorillonite A2 manufactured by Kunimine Industries Co., Ltd., Knipia F
  • Example 14 A test cell was fabricated in the same manner as in Example 1, except that 1.0% by mass of acetylene black (AB) was added to the positive electrode active material instead of MWCNT in the fabrication of the positive electrode.
  • AB acetylene black
  • Example 1 A test cell was prepared in the same manner as in Example 1, except that montmorillonite A1 was not added in the preparation of the positive electrode.
  • Example 2 A test cell was prepared in the same manner as in Example 1, except that montmorillonite A1 was added in the positive electrode so that the content of montmorillonite A1 was 0.1% by mass relative to the positive electrode active material.
  • the test cells of Examples have slightly higher electronic interfacial resistance than the test cells of Comparative Example, but the diffusion resistance of lithium ions is greatly reduced.
  • the content of the layered silicate compound is set to more than 0.1% by mass and less than 0.9% by mass, the diffusibility of lithium ions is greatly improved and excellent. High rate discharge characteristics can be realized.

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