WO2021171843A1 - 非水電解質二次電池用正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正極活物質および非水電解質二次電池 Download PDF

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WO2021171843A1
WO2021171843A1 PCT/JP2021/001968 JP2021001968W WO2021171843A1 WO 2021171843 A1 WO2021171843 A1 WO 2021171843A1 JP 2021001968 W JP2021001968 W JP 2021001968W WO 2021171843 A1 WO2021171843 A1 WO 2021171843A1
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positive electrode
active material
aqueous electrolyte
electrolyte secondary
secondary battery
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PCT/JP2021/001968
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English (en)
French (fr)
Japanese (ja)
Inventor
晋 張
一成 池内
日比野　光宏
名倉　健祐
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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 US17/799,761 priority Critical patent/US12531239B2/en
Priority to EP21761186.2A priority patent/EP4112555A4/en
Priority to CN202180014934.9A priority patent/CN115136352B/zh
Priority to JP2022503157A priority patent/JP7689286B2/ja
Publication of WO2021171843A1 publication Critical patent/WO2021171843A1/ja
Anticipated expiration legal-status Critical
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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
    • H01M4/48—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/13—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
    • H01M4/48—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure relates to a positive electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the positive electrode active material.
  • the positive electrode active material greatly affects the battery performance such as input / output characteristics, capacity, and cycle characteristics.
  • the positive electrode active material for example, an NCM-based lithium transition metal composite oxide containing Ni, Co, and Mn is widely used.
  • Li x Mn having a rock salt structure has been widely used as a high-capacity next-generation positive electrode active material. Attention is being paid to 1-x O 2 based Li excess type materials.
  • Patent Document 1 has a crystal structure belonging to the space group Fm-3m, a transition metal composition formula Li 1 + x Nb y Me z A p O 2 (Me is containing Fe and / or Mn, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, 0.25 ⁇ z ⁇ 1, A is an element other than Nb and Me, 0 ⁇ p ⁇ 0.2, where Li 1 + p Fe 1-q Nb q O 2 , 0.15 ⁇ p ⁇ 0.3, 0 ⁇ q ⁇ 0.3), and a positive electrode active material containing a lithium transition metal composite oxide is disclosed.
  • a material based on Li x Mn 1-x O 2 having a rock salt structure is expected as a high-capacity cathode active material, but it is necessary to improve various properties in practical use. In particular, it is necessary to improve the load characteristics. The same applies to the positive electrode active material disclosed in Patent Document 1, and it is necessary to improve the load characteristics.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, has a rock salt-related structure and has a composition formula Li a Mn b M c O 2-X F x (in the formula, M is Li, Mn. Except for at least one metal element, 2.000 ⁇ a + b + c ⁇ 2.195, 1.0 ⁇ a ⁇ 1.4, 0.4 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0.2, 0. It contains a lithium transition metal composite oxide represented by 2 ⁇ x ⁇ 0.6).
  • the non-aqueous electrolyte secondary battery includes a positive electrode containing the positive electrode active material, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
  • the present disclosure it is possible to provide a positive electrode active material having a high capacity and a high load characteristic. According to the positive electrode active material according to the present disclosure, the capacity and load characteristics of the non-aqueous electrolyte secondary battery can be improved.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of the embodiment.
  • a material based on Li x Mn 1-x O 2 having a rock salt structure is expected as a high-capacity positive electrode active material, but a non-aqueous electrolyte secondary battery using the material has load characteristics. There is a problem that is low.
  • the present inventors have introduced a predetermined amount of fluoride ions and introduced Li into the tetrahedral site of the crystal structure to obtain a cation-rich structure. As a result, it was found that the load characteristics are specifically improved.
  • the mechanism for improving load characteristics is not well understood, the technology of the present disclosure can be a breakthrough leading to the practical application of next-generation positive electrode active materials having high capacity and high load characteristics.
  • the outer body is not limited to the cylindrical outer can, for example, a square outer can (for example, a square outer can (). It may be a square battery), a coin-shaped outer can (coin-shaped battery), or an outer body (laminated battery) composed of a laminated sheet containing 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 the non-aqueous electrolyte secondary battery 10 which is an example of the embodiment.
  • the non-aqueous electrolyte secondary battery 10 includes a wound electrode body 14, a non-aqueous electrolyte, and an outer can 16 for accommodating the electrode body 14 and the 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 battery sealing body 17 side is on the top and the bottom side of the outer can 16 is on the bottom.
  • 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, amides, and a mixed solvent of two or more of these are used.
  • the non-aqueous solvent may contain a halogen substituent in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • the electrolyte salt for example, a lithium salt such as LiPF 6 is used.
  • the electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte.
  • 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 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 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 to 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 their respective central portions, and an insulating member 25 is interposed between the respective peripheral portions.
  • the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 will be described in detail, and in particular, the positive electrode active material constituting the positive electrode 11 will be described in detail.
  • the positive electrode 11 has a positive electrode core body and a positive electrode mixture layer provided on the surface of the positive electrode core body.
  • a foil of a metal stable in the potential range of the positive electrode 11 such as aluminum or an aluminum alloy, a film in which the metal is arranged on the surface layer, or the like can be used.
  • the positive electrode mixture layer contains a positive electrode active material, a conductive material, and a binder, and is preferably provided on both sides of the positive electrode core body.
  • a positive electrode mixture slurry containing a positive electrode active material, a conductive material, a binder, and the like is applied onto the positive electrode core, the coating film is dried, and then compressed to form the positive electrode mixture layer into the positive electrode core. It can be produced by forming it on both sides of the body.
  • Examples of the conductive material contained in the positive electrode mixture layer include carbon materials such as carbon black, acetylene black, ketjen black, and graphite.
  • Examples of the binder contained in the positive electrode mixture layer include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. .. 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 positive electrode active material has a rock salt-related structure and has a composition formula of Li a Mn b M c O 2-X F x (in the formula, M is at least one metal element excluding Li and Mn, and 2.000 ⁇ Lithium transition represented by a + b + c ⁇ 2.195, 1.0 ⁇ a ⁇ 1.4, 0.4 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0.2, 0.2 ⁇ x 0.6) Contains metal composite oxides.
  • the composite oxide is a Li-rich material having a molar ratio of Li exceeding 1, and is a cation-rich composite oxide having a molar ratio of at least Li and Mn-containing metal elements exceeding 2. .. Further, a predetermined amount of fluoride ion is introduced, and a part of O is replaced with F.
  • the positive electrode active material contains the composite oxide represented by the above composition formula as a main component.
  • the principal 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 above composition formula (for example, a composite oxide that is not an excess Li system or a composite compound that does not contain fluoride ions) is used in combination with the positive electrode 11 as a positive electrode active material.
  • the content of the composite oxide is preferably 50% by mass or more, and may be substantially 100% by mass.
  • the composition of the composite oxide can be measured using an ICP emission spectrophotometer (iCAP6300 manufactured by Thermo Fisher Scientific).
  • the composite oxide represented by the above composition formula has a rock salt-related structure similar to the rock salt structure in which Li ions are introduced into the tetrahedral sites existing around the octahedral site in addition to the octahedral site of the rock salt structure.
  • the crystal structure of the composite oxide represented by the above composition formula is similar to the rock salt type crystal structure, but is not attributed to the space group Fm-3m.
  • the fact that the composite oxide has a rock salt-related structure in which Li ions are introduced into the tetrahedral site is a powder X-ray diffractometer (Desktop X-ray diffractometer manufactured by Rigaku Co., Ltd. MiniFlex, X-ray source: CuK ⁇ ). It is identified from the X-ray diffraction pattern measured using.
  • the lithium transition metal composite oxide which is one aspect of the embodiment, contains substantially only Li and Mn as metal elements. Further, the lithium transition metal composite oxide which is another aspect of the embodiment contains another metal element M in addition to Li and Mn.
  • Other metal elements M include Ni, Co, Fe, Al, Sn, Cu, Nb, Mo, Bi, Ti, V, Cr, Y, Zr, Zn, Na, K, Ca, Mg, Pt, Au, At least one selected from Ag, Ru, Ta, W, La, Ce, Pr, Sm, Eu, Dy and Er can be mentioned. Among them, at least one selected from Ni, Sn, Mo, Ti, W, Zn, and Al is preferable.
  • the molar ratio (a + b + c) of Li, Mn, which are cationic components, and the metal element M optionally added is 2.000 ⁇ a + b + c ⁇ 2.195.
  • the molar ratio (a + b) of Li and Mn is preferably 1.900 ⁇ x ⁇ 2.195, more preferably 1.950 ⁇ x ⁇ 2.150.
  • the molar ratio (a) of Li is 1.0 ⁇ a ⁇ 1.4, preferably 1.10 ⁇ a ⁇ 1.35, more preferably 1.15 ⁇ a ⁇ 1.35. ..
  • the molar ratio (b) of Mn is 0.4 ⁇ b ⁇ 0.9, preferably 0.65 ⁇ b ⁇ 0.89, and more preferably 0.70 ⁇ b ⁇ 0.88.
  • the molar ratio (x) of F is 0.2 ⁇ x ⁇ 0.6, preferably 0.2 ⁇ x ⁇ 0.5, and more preferably 0. .20 ⁇ x ⁇ 0.35. In this case, the effect of improving the load characteristics appears more remarkably.
  • the molar ratio (c) of the metal element M other than Li and Mn is 0.2 or less, preferably 0.15 or less, and more preferably 0.12 or less.
  • the lithium transition metal composite oxide uses, for example, lithium fluoride (LiF), lithium manganate (LiMnO 2 ), and lithium oxide (Li 2 O) as raw materials, and is a planet in an inert gas atmosphere such as Ar. It can be synthesized by mixing with a ball mill. Further, instead of the planetary ball mill, a mixer capable of applying the same stirring shear force to the powder may be used, or the powder may be heated during the mixing process.
  • the composition of the composite oxide can be adjusted to a desired range by changing, for example, the mixing ratio of the raw materials and the mixing conditions (rotation speed, treatment time, treatment temperature, etc.).
  • the negative electrode 12 has a negative electrode core body and a negative electrode mixture layer provided on the surface of the negative electrode core body.
  • a metal foil stable in the potential range of the negative electrode 12 such as copper, a film in which the metal is arranged on the surface layer, or the like can be used.
  • the negative electrode mixture layer contains a negative electrode active material and a binder, and is preferably provided on both sides of the negative electrode core body.
  • a negative electrode mixture slurry containing a negative electrode active material, a conductive material, a binder, and the like is applied to the surface of the negative electrode core, the coating film is dried, and then compressed to compress the negative electrode mixture layer into a negative electrode. It can be manufactured by forming it on both sides of the core body.
  • 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, 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 conductive material contained in the negative electrode mixture layer carbon materials such as carbon black, acetylene black, ketjen black, and graphite can be used as in the case of the positive electrode 11.
  • the binder contained in the negative electrode mixture layer fluororesin, PAN, polyimide, acrylic resin, polyolefin or the like can be used as in the case of the positive electrode 11, but styrene-butadiene rubber (SBR) is used. Is preferable.
  • the negative electrode mixture layer preferably further contains CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA) and the like. Above all, it is preferable to use SBR in combination with CMC or a salt thereof, PAA or a salt thereof.
  • a porous sheet having ion permeability and insulating property is used as the separator 13.
  • the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric.
  • the material of the separator 13 polyethylene, polypropylene, polyolefin such as a copolymer of ethylene and ⁇ -olefin, cellulose and the like are suitable.
  • 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 an aramid resin, polyimide, or polyamide-imide may be formed on the surface of the separator 13.
  • the obtained positive electrode active material, acetylene black, and polyvinylidene fluoride are mixed at a solid content mass ratio of 7: 2: 1, and N-methyl-2-pyrrolidone (NMP) is used as a dispersion medium for the positive electrode.
  • NMP N-methyl-2-pyrrolidone
  • a mixture slurry was prepared.
  • a 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 to a predetermined electrode size to obtain a positive electrode.
  • 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 solution.
  • the positive electrode and the negative electrode made of lithium metal foil were arranged to face each other via a separator to form an electrode body, and the electrode body was housed in a coin-shaped outer can. After injecting the non-aqueous electrolyte solution into the outer can, the outer can was sealed to obtain a coin-shaped test cell (non-aqueous electrolyte secondary battery).
  • the load characteristics of the test cell were evaluated by the following method, and the evaluation results are shown in Table 1 together with the composition of the positive electrode active material.
  • Charging / discharging conditions for the second cycle The test cell was CC-charged to a battery voltage of 5.2 V with a constant current of 0.2 C in a room temperature environment, then paused for 20 minutes, and the battery voltage was 2. CC discharge was performed up to 5V.
  • Load characteristics (%) (Discharge capacity in the second cycle / Discharge capacity in the first cycle) x 100 ⁇ Examples 2 to 10, Comparative Examples 1 to 4> Added in the synthesis of lithium transition metal composite oxide, as the composition shown in Table 1 is obtained, LiF, for LiMnO 2, and Li 2 O mixing ratio (Example 5,6,17, further nickel oxide ) Was changed, a test cell was prepared in the same manner as in Example 1, and the load characteristics were evaluated.
  • the load characteristics of the battery are specifically improved. ..
  • Non-aqueous electrolyte secondary battery 11 Positive electrode 12 Negative electrode 13 Separator 14 Electrode body 16 Exterior can 17 Sealing body 18, 19 Insulating plate 20 Positive electrode lead 21 Negative electrode lead 22 Grooving part 23 Internal terminal plate 24 Lower valve body 25 Insulating member 26 Upper valve Body 27 Cap 28 Gasket

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PCT/JP2021/001968 2020-02-26 2021-01-21 非水電解質二次電池用正極活物質および非水電解質二次電池 Ceased WO2021171843A1 (ja)

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