WO2022044935A1 - 非水電解質二次電池用正極及び非水電解質二次電池 - Google Patents

非水電解質二次電池用正極及び非水電解質二次電池 Download PDF

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WO2022044935A1
WO2022044935A1 PCT/JP2021/030301 JP2021030301W WO2022044935A1 WO 2022044935 A1 WO2022044935 A1 WO 2022044935A1 JP 2021030301 W JP2021030301 W JP 2021030301W WO 2022044935 A1 WO2022044935 A1 WO 2022044935A1
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Prior art keywords
positive electrode
lithium metal
metal composite
composite oxide
oxide particles
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English (en)
French (fr)
Japanese (ja)
Inventor
伸宏 鉾谷
昂輝 守田
峻 野村
洋行 藤本
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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Priority to JP2022544506A priority Critical patent/JP7721542B2/ja
Priority to CN202180050509.5A priority patent/CN115943504A/zh
Priority to EP21861363.6A priority patent/EP4207355B1/en
Priority to US18/021,993 priority patent/US20230246168A1/en
Publication of WO2022044935A1 publication Critical patent/WO2022044935A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a positive electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the positive electrode.
  • Patent Document 1 discloses a non-aqueous electrolyte secondary battery using single crystal particles which are non-aggregating particles and / or secondary particles in which a plurality of primary particles are aggregated as a positive electrode active material. .. Patent Document 1 describes the effect of improving the cycle characteristics of the battery.
  • An object of the present disclosure is to provide a non-aqueous electrolyte secondary battery having a high capacity and excellent cycle characteristics.
  • the positive electrode for a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, includes a positive electrode core material and a positive electrode mixture layer formed on the surface of the positive electrode core material.
  • the positive electrode mixture layer is formed by aggregating the first lithium metal composite oxide particles, which are non-aggregated particles having a volume-based median diameter of 2 to 10 ⁇ m, and primary particles having an average particle size of 50 nm to 2 ⁇ m, and by volume.
  • a second lithium metal composite oxide particle which is a secondary particle having a median diameter of 10 to 30 ⁇ m is contained, and the positive electrode mixture layer is divided into two equal parts in the thickness direction, and the first is ordered from the surface side of the positive electrode mixture layer.
  • the content of the first lithium metal composite oxide particles in the first region is characterized by being higher than the content of the first lithium metal composite oxide particles in the second region. And.
  • the non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, is characterized by including the positive electrode, the negative electrode, and the non-aqueous electrolyte.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of an embodiment.
  • FIG. 2 is a cross-sectional view of a positive electrode which is an example of an embodiment.
  • the non-aggregated particles in the positive electrode mixture layer have the content of the non-aggregated particles in the first region on the surface side of the positive electrode mixture layer> the content of the non-aggregated particles in the second region on the core material side of the positive electrode mixture layer.
  • both high capacity and excellent cycle characteristics are specifically realized.
  • the outer body of the battery is not limited to the cylindrical outer can, for example, a square outer can. It may be a can (square battery), a coin-shaped outer can (coin-shaped battery), or an outer body (pouch-type battery) composed of a laminated sheet including a metal layer and a resin layer. Further, the electrode body may be a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately laminated via a separator.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery 10 which is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 includes a winding type electrode body 14, a non-aqueous electrolyte, and an outer can 16 for accommodating the electrode body 14 and the non-aqueous electrolyte.
  • the electrode body 14 has 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 spirally wound via the separator 13.
  • the outer can 16 is a bottomed cylindrical metal container having an opening on one side in the axial direction, and the opening of the outer can 16 is closed by a sealing body 17.
  • the sealing body 17 side of the battery is on the top, and the bottom side of the outer can 16 is on the bottom.
  • the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 are all strip-shaped long bodies, and are alternately laminated in the radial direction of the electrode body 14 by being wound in a spiral shape.
  • the negative electrode 12 is formed to have a size one size larger than that of the positive electrode 11 in order to prevent the precipitation of lithium. That is, the negative electrode 12 is formed longer than the positive electrode 11 in the longitudinal direction and the width direction (short direction).
  • the two separators 13 are formed at least one size larger than the positive electrode 11, and are arranged so as to sandwich the positive electrode 11, for example.
  • the electrode body 14 includes 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 to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 extends to the bottom side of the outer can 16 through the outside of the insulating plate 19.
  • 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 the airtightness inside the battery.
  • the outer can 16 is formed with a grooved portion 22 that supports the sealing body 17, with a part of the side surface portion protruding inward.
  • the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the outer can 16, and the sealing body 17 is supported on the upper surface thereof.
  • the sealing body 17 is fixed to the upper part of the outer can 16 by the grooved portion 22 and the opening end portion of the outer can 16 crimped against the sealing body 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 laminated in this order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at the central portion of each, and an insulating member 25 is interposed between the peripheral portions of each.
  • the positive electrode 11, the negative electrode 12, the separator 13, and the non-aqueous electrolyte will be described in detail, particularly the positive electrode 11.
  • the positive electrode 11 includes a positive electrode core material 30 and a positive electrode mixture layer 31 formed on the surface of the positive electrode core material 30.
  • a metal foil stable in the potential range of the positive electrode 11 such as aluminum or an aluminum alloy, a film on which the metal is arranged on the surface layer, or the like can be used.
  • An example of the positive electrode core material 30 is an aluminum or aluminum alloy foil having a thickness of 10 to 20 ⁇ m.
  • the positive electrode mixture layer 31 contains a positive electrode active material, a conductive agent, and a binder, and is preferably formed on both surfaces of the positive electrode core material 30.
  • the thickness of the positive electrode mixture layer 31 is, for example, 30 to 100 ⁇ m on one side of the positive electrode core material 30.
  • a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, a binder, and the like is applied onto the positive electrode core material 30, the coating film is dried, and then compressed to compress the positive electrode mixture layer 31.
  • a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, a binder, and the like is applied onto the positive electrode core material 30, the coating film is dried, and then compressed to compress the positive electrode mixture layer 31.
  • Examples of the conductive agent contained in the positive electrode mixture layer 31 include carbon materials such as carbon black, acetylene black, ketjen black, graphite, carbon nanotubes, carbon nanofibers, and graphene.
  • the content of the conductive agent is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • binder contained in the positive electrode mixture layer 31 examples include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimides, acrylic resins, and polyolefins. .. Further, these resins may be used in combination with carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO) and the like.
  • the content of the binder is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the positive electrode mixture layer 31 contains particulate lithium metal composite oxide as the positive electrode active material.
  • the lithium metal composite oxide is a composite oxide containing a metal element such as Co, Mn, Ni, and Al in addition to Li.
  • the metal elements constituting the lithium metal composite oxide are, for example, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Sn, Sb. , W, Pb, and Bi. Above all, it is preferable to contain at least one selected from Co, Ni, and Mn.
  • suitable composite oxides include lithium metal composite oxides containing Ni, Co and Mn, and lithium metal composite oxides containing Ni, Co and Al.
  • the positive electrode mixture layer 31 contains two types of lithium metal composite oxide particles. Further, when the positive electrode mixture layer 31 is divided into two equal parts in the thickness direction and defined as the first region 31a and the second region 31b in order from the surface side of the positive electrode mixture layer 31, the first region 31a and the second region 31b are defined. The materials contained in are different from each other. In the present embodiment, when the types of lithium metal composite oxide particles contained in the first region 31a and the second region 31b are different, and each region contains two types of lithium metal composite oxide particles, The mass ratio is different. On the other hand, the types and contents of the conductive agent and the binder may be the same or different between the first region 31a and the second region 31b.
  • the positive electrode mixture layer 31 is a second lithium metal composite oxide which is a secondary particle formed by agglomerating a first lithium metal composite oxide particle which is a non-aggregating particle and a primary particle having an average particle size of 50 nm to 2 ⁇ m. Including object particles.
  • the positive electrode mixture layer 31 may contain only the first and second lithium metal composite oxide particles as the positive electrode active material, and the third lithium metal composite oxide may be oxidized as long as the object of the present disclosure is not impaired. It may contain physical particles.
  • the third lithium metal composite oxide particles there are composite oxide particles that do not satisfy the condition of particle size described later.
  • the volume-based median diameter of the first lithium metal composite oxide particles (hereinafter, may be referred to as “D50”) is 2 to 10 ⁇ m, preferably 3 to 8 ⁇ m.
  • the D50 of the second lithium metal composite oxide particles is 10 to 30 ⁇ m, preferably 12 to 20 ⁇ m.
  • D50 means a particle size in which the cumulative frequency is 50% from the smallest particle size in the volume-based particle size distribution.
  • the particle size distribution of the lithium metal composite oxide particles can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrac Bell Co., Ltd.) and water as a dispersion medium.
  • the first lithium metal composite oxide particle is a particle having no grain boundary inside, and is, for example, a single crystal primary particle.
  • the crystallinity of the lithium metal composite oxide particles can be confirmed using a scanning ion microscope.
  • the first lithium metal composite oxide particles synthesized by the production method described later may contain, for example, particles containing five or less primary particles.
  • the second lithium metal composite oxide particles are secondary particles in which primary particles having an average particle size of 50 nm to 2 ⁇ m, preferably 500 nm to 2 ⁇ m are aggregated.
  • the second lithium metal composite oxide particles have grain boundaries of primary particles.
  • the primary particles can be confirmed by observing the second lithium metal composite oxide particles with a scanning electron microscope (SEM). It should be noted that the plurality of primary particles adhere to each other with a strength that does not disintegrate even when a strong force is applied, such as when crushing the second lithium metal composite oxide particles after synthesis or when preparing a positive electrode mixture slurry. There is.
  • the average particle size of the primary particles constituting the second lithium metal composite oxide particles can be obtained by analyzing the SEM image of the particle cross section.
  • the positive electrode 11 is embedded in a resin, a cross section is prepared by cross-section polisher (CP) processing, and the cross section is photographed by SEM. From the SEM image, 30 primary particles are randomly selected and the grain boundaries are observed, the diameter of the circumscribed circle of each of the 30 primary particles is obtained, and the average value is used as the average particle size.
  • Each lithium metal composite oxide particle can be synthesized by the method described in Examples described later.
  • the first lithium metal composite oxide particle synthesizes a precursor (metal composite hydroxide) containing Ni, Co, Mn, Al, etc., as compared with the case of synthesizing the second lithium metal composite oxide particle. It can be synthesized by raising the pH of the alkaline aqueous solution used in the above and / or raising the firing temperature of the precursor.
  • An example of a suitable pH of an alkaline aqueous solution is 10 to 11, and a suitable example of a firing temperature is 950 to 1100 ° C.
  • an alkaline aqueous solution having a pH of 9 to 10 is used, and the firing temperature is set to 950 ° C. or lower.
  • the main component means the component having the largest mass among the components constituting the lithium metal composite oxide particles.
  • the composition of each lithium metal composite oxide particle may be the same as or different from each other.
  • the positive electrode mixture layer 31 contains the first and second lithium metal composite oxide particles, but the materials contained in the first region 31a and the second region 31b are different from each other. It has become.
  • the content of the first lithium metal composite oxide particles in the positive electrode mixture layer 31 is not uniform and is higher in the first region 31a than in the second region 31b.
  • the first lithium metal composite oxide particles are less likely to cause particle cracking in the manufacturing process of the positive electrode 11 than the second lithium metal composite oxide particles, this is the surface side of the positive electrode mixture layer 31.
  • the flow path of the electrolytic solution is secured in the 1st region 31a. In this case, it is considered that the permeability of the electrolytic solution into the second region 31b becomes good and the cycle characteristics are improved.
  • the ratio of the mass of the first lithium metal composite oxide particles to the mass of the positive electrode active material in the first region 31a is the mass of the first lithium metal composite oxide particles to the mass of the positive electrode active material in the second region 31b. It is preferably higher than the ratio of.
  • the content of the positive electrode active material may be different between the first region 31a and the second region 31b, but is preferably substantially the same.
  • the content of the positive electrode active material is, for example, 90 to 99.9% by mass, preferably 95 to 99% by mass, based on the mass of the positive electrode mixture layer 31.
  • the first region 31a may substantially contain only the first lithium metal composite oxide particles as the positive electrode active material. Further, the first lithium metal composite oxide particles may be contained only in the first region 31a and may not be present in the second region 31b, for example. When the second lithium metal composite oxide particles are present in the first region 31a, each composite oxide particle in the first region 31a has the content of the first lithium metal composite oxide particles> the second lithium metal composite. It is preferable to satisfy the relationship of the content of oxide particles.
  • the content of the second lithium metal composite oxide particles is higher in the second region 31b than in the first region 31a.
  • the ratio of the mass of the second lithium metal composite oxide particles to the mass of the positive electrode active material in the second region 31b is the ratio of the mass of the second lithium metal composite oxide particles to the mass of the positive electrode active material in the first region 31a. It is preferably higher than.
  • the positive electrode mixture layer 31 can be made denser by using this, and the battery can be charged. Contributes to higher capacity. By allowing a large amount of the second lithium metal composite oxide particles to be present on the positive electrode core material 30 side, which has little effect on the permeability of the electrolytic solution into the positive electrode mixture layer 31, the capacity is increased while maintaining good cycle characteristics. Can be planned.
  • the second region 31b may substantially contain only the second lithium metal composite oxide particles as the positive electrode active material. Further, the second lithium metal composite oxide particles may be contained only in the second region 31b and may not be present in the first region 31a, for example.
  • each composite oxide particle in the second region 31b has a content of the first lithium metal composite oxide particles ⁇ second lithium metal composite. It is preferable to satisfy the relationship of the content of oxide particles.
  • the first region 31a may contain the first and second lithium metal composite oxide particles.
  • the suitable mass ratio of the first lithium metal composite oxide particles to the second lithium metal composite oxide particles in the first region 31a is preferably 60:40 to 90:10, more preferably. Is from 65:35 to 80:20. When the mass ratio of each composite oxide particle is within the range, it becomes easy to achieve both high capacity and excellent cycle characteristics.
  • the contents of the first and second lithium metal composite oxide particles can be the same, but preferably the content of the first lithium metal composite oxide particles ⁇ second.
  • the content is the lithium metal composite oxide particles, or only the second lithium metal composite oxide particles are used as the positive electrode active material.
  • the mass ratio of the first lithium metal composite oxide particles to the second lithium metal composite oxide particles in the second region 31b is It is preferably 10:90 to 40:60, and more preferably 20:80 to 35:65. When the mass ratio of each composite oxide particle is within the range, it becomes easy to achieve both high capacity and excellent cycle characteristics.
  • the negative electrode 12 includes a negative electrode core material and a negative electrode mixture layer formed on the surface of the negative electrode core material.
  • a metal foil stable in the potential range of the negative electrode 12 such as copper or a copper alloy, a film in which the metal is arranged on the surface layer, or the like can be used.
  • An example of the negative electrode core material is a copper or copper alloy foil having a thickness of 5 to 15 ⁇ m.
  • the negative electrode mixture layer contains a negative electrode active material and a binder, and is preferably formed on both sides of the negative electrode core material. The thickness of the negative electrode mixture layer is, for example, 30 to 100 ⁇ m on one side of the negative electrode core material.
  • the negative electrode 12 is formed by applying a negative electrode mixture slurry containing a negative electrode active material, a binder, etc. on the negative electrode core material, drying the coating film, and then compressing the negative electrode mixture layer on both sides of the negative electrode core material. It can be produced by doing so.
  • the negative electrode mixture layer contains, for example, a carbon-based active material that reversibly occludes and releases lithium ions as a negative electrode active material.
  • Suitable carbon-based active materials are natural graphite such as scaly graphite, massive graphite and earthy graphite, and graphite such as 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, 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 fluororesin such as PTFE and PVdF, PAN, polyimide, acrylic resin, polyolefin, styrene-butadiene rubber (SBR) and the like can be used.
  • the negative electrode mixture layer may contain CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA) and the like.
  • the content of the binder is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the negative electrode active material.
  • a conductive agent such as carbon black, acetylene black, or Ketjen black may be added to the negative electrode mixture layer.
  • the separator 13 a porous sheet having ion permeability and insulating property is used. Specific examples of the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric.
  • the material of the separator polyethylene, polyolefin such as polypropylene, cellulose and the like are suitable.
  • the separator 13 may have a single-layer structure or a laminated structure. Further, a resin layer having high heat resistance 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.
  • the filler of the inorganic substance include oxides containing metals such as Ti, Al, Si, and Mg, and phosphoric acid compounds.
  • 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.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and a mixed solvent of two or more of these can be used.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • halogen substituent examples include a fluorinated cyclic carbonate ester such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate ester, and a fluorinated chain carboxylic acid ester such as methyl fluoropropionate (FMP).
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylic acid ester
  • esters examples include cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and methylpropyl carbonate.
  • cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and methylpropyl carbonate.
  • GBL ⁇ -butyrolactone
  • VL ⁇ -valerolactone
  • MP methyl propionate
  • a chain carboxylic acid ester such as ethyl propionate, and the like.
  • cyclic ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4. -Dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether and the like can be mentioned.
  • chain ethers examples include 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, Pentylphenyl ether, methoxytoluene, benzylethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1 , 1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.
  • the electrolyte salt is preferably a lithium salt.
  • lithium salts include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (P (C 2 O 4 ) F 4 ), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2 ), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic carboxylate lithium, Li 2B 4 O 7 , borates such as Li (B (C 2 O 4 ) F 2 ), LiN (SO 2 CF 3 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2 ) ⁇ l , M is an integer of 0 or more ⁇ and other imide salts.
  • lithium salt these may be used alone or in combination of two or more.
  • LiPF 6 is preferably used from the viewpoint of ionic conductivity, electrochemical stability, and the like.
  • concentration of the lithium salt is, for example, 0.8 mol to 1.8 mol per 1 L of the non-aqueous solvent.
  • Example 1 [Synthesis of first lithium metal composite oxide particles] Nickel sulfate, cobalt sulfate, and manganese sulfate were mixed at a predetermined ratio and uniformly mixed in an alkaline aqueous solution having a pH of 10 to 11 to prepare a precursor. Next, the precursor and lithium carbonate were mixed, calcined at a temperature of 1000 ° C. for 15 hours, and then pulverized to obtain first lithium metal composite oxide particles which are non-aggregated particles.
  • the composition of the particles, D50 is as follows. Composition: LiNi 0.5 Co 0.2 Mn 0.3 O 2 D50: 4.5 ⁇ m
  • the first lithium metal composite oxide particles, acetylene black (AB), and polyvinylidene fluoride (PVdF) were mixed at a mass ratio of 98: 1: 1 and N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) (as a dispersion medium) was mixed.
  • An appropriate amount of NMP was added to prepare a first positive electrode mixture slurry having a solid content concentration of 70% by mass.
  • the second lithium metal composite oxide particles were used instead of the first lithium metal composite oxide particles, the second positive electrode mixture slurry was prepared in the same manner as in the case of preparing the first positive electrode mixture slurry.
  • a positive electrode mixture slurry was prepared.
  • the second positive electrode mixture slurry was applied to both sides of the positive electrode core material made of aluminum foil, and then the first positive electrode mixture slurry was applied onto the coating film of the second positive electrode mixture slurry. After the coating film was dried and compressed (linear pressure 3000 N / m), it was cut into a predetermined electrode size to prepare a positive electrode having a positive electrode mixture layer formed on both sides of the positive electrode core material.
  • the coating amounts of the first positive electrode mixture slurry and the second positive electrode mixture slurry were set to the same value.
  • the negative electrode active material a mixture of 95 parts by mass of graphite powder and 5 parts by mass of a Si-containing compound represented by SiO x was used. 100 parts by mass of the negative electrode active material, 1 part by mass of sodium carboxymethyl cellulose (CMC-Na) and water are mixed, and 1.2 parts by mass of styrene-butadiene rubber (SBR) is further mixed. To prepare a negative electrode mixture slurry. Next, the negative electrode mixture slurry is applied to both sides of the negative electrode core material made of copper foil, the coating film is dried and compressed, and then cut into a predetermined electrode size to form negative electrode mixture layers on both sides of the negative electrode core material. The formed negative electrode was manufactured.
  • CMC-Na sodium carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • Ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed at a volume ratio of 1: 3 (25 ° C.).
  • EC Ethylene carbonate
  • DMC dimethyl carbonate
  • VC vinylene carbonate
  • LiPF 6 LiPF 6 was dissolved to a concentration of 1 mol / L to prepare a non-aqueous electrolytic solution.
  • Electrode terminals were attached to the positive electrode and the negative electrode, respectively, and the positive electrode and the negative electrode were spirally wound via a separator to prepare a wound electrode body.
  • the electrode body was housed in a bottomed cylindrical outer can, welded to the inner surface of the bottom of the outer can of the negative electrode lead, and the positive electrode lead was welded to the internal terminal plate of the sealing body. Then, the non-aqueous electrolyte was injected into the outer can, and the opening edge of the outer can was crimped and fixed to the sealing body to prepare a cylindrical secondary battery having a battery capacity of 2500 mAh.
  • Example 2 A mixture of the first lithium metal composite oxide particles and the second lithium metal composite oxide particles at a mass ratio of 7: 3, and AB and PVdF at a mass ratio of 98: 1: 1. The mixture was mixed and an appropriate amount of NMP was added as a dispersion medium to prepare a first positive electrode mixture slurry having a solid content concentration of 70% by mass. Further, a mixture of the first lithium metal composite oxide particles and the second lithium metal composite oxide particles at a mass ratio of 3: 7, and AB and PVdF in a mass ratio of 98: 1: 1. The mixture was mixed at a ratio and an appropriate amount of NMP was added as a dispersion medium to prepare a second positive electrode mixture slurry having a solid content concentration of 70% by mass. A positive electrode and a non-aqueous electrolyte secondary battery were produced in the same manner as in Example 1 except that these two types of positive electrode mixture slurries were used in the production of the positive electrode.
  • Example 2 A positive electrode and a non-aqueous electrolyte secondary battery were produced in the same manner as in Example 1 except that only the first positive electrode mixture slurry was used in the production of the positive electrode.
  • Example 3 A positive electrode and a non-aqueous electrolyte secondary battery were produced in the same manner as in Example 1 except that only the second positive electrode mixture slurry was used in the production of the positive electrode.
  • ⁇ Comparative Example 4> A mixture of the first lithium metal composite oxide particles and the second lithium metal composite oxide particles at a mass ratio of 1: 1 and AB and PVdF at a mass ratio of 98: 1: 1. The mixture was mixed and an appropriate amount of NMP was added as a dispersion medium to prepare a positive electrode mixture slurry having a solid content concentration of 70% by mass. A positive electrode and a non-aqueous electrolyte secondary battery were produced in the same manner as in Example 1 except that the positive electrode mixture slurry was used in the production of the positive electrode.
  • the batteries of the examples have a high capacity retention rate and excellent cycle characteristics. Further, the filling density of the positive electrode active material is high, and the capacity of the battery can be increased.
  • the positive electrode of Comparative Example 1 has the same filling density as the positive electrode of Example 1, the capacity retention rate of the battery of Comparative Example 1 is significantly lower than that of the battery of Example. This is because the secondary particles are cracked when the positive electrode is compressed, and the gap between the particles that becomes the flow path of the electrolytic solution is closed in the first region on the surface side of the positive electrode mixture layer, and the core material of the positive electrode mixture layer is closed. It is presumed that the main factor was that the supply of the electrolytic solution to the second region on the side was obstructed.
  • Comparative Example 2 Although the cycle characteristics are good, the packing density of the positive electrode active material is greatly reduced, and it becomes difficult to increase the capacity. Further, in the case of Comparative Example 3, although the packing density of the positive electrode active material is high, the cycle characteristics are greatly deteriorated due to the blockage of the flow path of the electrolytic solution. In Comparative Example 3, it is possible to reduce the linear pressure at the time of compression of the positive electrode to adjust the filling density to 3.5 g / cc, but even in that case, the capacity retention rate is not improved.
  • the capacity retention rate of the battery of Comparative Example 4 is the same as the capacity retention rate of the batteries of Comparative Examples 1 and 3, and the cycle characteristics are inferior to those of the battery of the example. That is, the cycle characteristics of the battery cannot be improved by simply mixing the non-aggregated particles and the secondary particles.
  • the non-aggregating particles satisfy the relationship of the content of the non-aggregating particles in the first region of the positive electrode mixture layer> the content of the non-aggregating particles in the second region, the flow path of the electrolytic solution is set. While ensuring, the packing density of the positive electrode active material can be increased, and a non-aqueous electrolyte secondary battery having a high capacity and excellent cycle characteristics can be realized.

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