WO2022209121A1 - 非水電解液二次電池用負極、非水電解液二次電池用セパレータ、および非水電解液二次電池 - Google Patents

非水電解液二次電池用負極、非水電解液二次電池用セパレータ、および非水電解液二次電池 Download PDF

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WO2022209121A1
WO2022209121A1 PCT/JP2022/000626 JP2022000626W WO2022209121A1 WO 2022209121 A1 WO2022209121 A1 WO 2022209121A1 JP 2022000626 W JP2022000626 W JP 2022000626W WO 2022209121 A1 WO2022209121 A1 WO 2022209121A1
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negative electrode
electrolyte secondary
aqueous electrolyte
secondary battery
cyano complex
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English (en)
French (fr)
Japanese (ja)
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誠 安久津
貴夫 佐藤
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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 US18/284,644 priority Critical patent/US20240162448A1/en
Priority to EP22779354.4A priority patent/EP4318631A4/en
Priority to JP2023510282A priority patent/JP7780768B2/ja
Priority to CN202280026177.1A priority patent/CN117099224A/zh
Publication of WO2022209121A1 publication Critical patent/WO2022209121A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down 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
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode for nonaqueous electrolyte secondary batteries, a separator for nonaqueous electrolyte secondary batteries, and a nonaqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries are used as power sources for small devices such as smartphones, as well as power sources for vehicles.
  • a non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • Non-aqueous electrolyte secondary batteries include lithium ion secondary batteries, lithium (metal) secondary batteries, and the like.
  • a negative electrode of a lithium ion secondary battery absorbs lithium ions during charging and releases lithium ions during discharging. In a lithium (metal) secondary battery, lithium metal deposits on the negative electrode during charging, and the lithium metal dissolves during discharging.
  • Patent Document 1 proposes an electrolytic solution for a lithium secondary battery containing a chelating agent that forms a complex with transition metal ions in the battery, a non-aqueous solvent, and an electrolyte salt.
  • a chelating agent EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid) and the like are used.
  • lithium ion release at the positive electrode and lithium ion absorption at the negative electrode may occur.
  • some of the metals (excluding lithium, mainly including transition metals such as copper and iron) present in the positive electrode are oxidized, and metal ions are eluted into the non-aqueous electrolyte.
  • Metal ions may be reduced at the negative electrode, resulting in metal deposition. Due to deposition of metal, the charge/discharge efficiency of the secondary battery may decrease.
  • the chelating agent added to the electrolytic solution described in Patent Document 1 forms a complex with the eluted metal ions, thereby suppressing the deposition of the metal on the negative electrode to some extent. It is difficult to contain a large amount, and the effect is limited. When the amount of eluted metal ions is large, it is difficult to suppress deposition of metal on the negative electrode.
  • One aspect of the present invention relates to a negative electrode for a non-aqueous electrolyte secondary battery containing an iron cyano complex.
  • Another aspect of the present invention relates to a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the negative electrode is the negative electrode for the non-aqueous electrolyte secondary battery described above.
  • Yet another aspect of the present invention relates to a separator for non-aqueous electrolyte secondary batteries containing an iron cyano complex.
  • Still another aspect of the present invention comprises a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte, wherein the separator is the non-aqueous electrolyte secondary
  • the present invention relates to a non-aqueous electrolyte secondary battery, which is a battery separator.
  • FIG. 1 is a partially cutaway perspective view of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention
  • FIG. 2 is a diagram schematically showing the configuration of an electrode group in FIG. 1;
  • FIG. 1 is a partially cutaway perspective view of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention
  • a negative electrode for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention contains an iron cyano complex.
  • the separator for non-aqueous electrolyte secondary batteries according to one embodiment of the present invention contains an iron cyano complex.
  • at least one of the negative electrode and the separator (hereinafter also referred to as negative electrode and the like) may contain an iron cyano complex.
  • metal A mainly contains transition metals such as iron and copper, and is derived from impurities mixed in the positive electrode material (mainly the positive electrode active material) and/or the manufacturing process of the battery (preparation of the positive electrode, etc.).
  • the eluted metal A ions can form an iron cyano complex and a complex salt that is difficult to dissolve in a non-aqueous electrolyte.
  • the addition of the iron cyano complex to the negative electrode can be performed by adhering the iron cyano complex to the surface of the negative electrode mixture layer and/or the negative electrode current collector sheet (hereinafter also referred to as the negative electrode surface). It may also be carried out by the addition of an iron cyano complex into the medium. Further, the addition of the iron cyano complex to the separator can be performed by attaching the iron cyano complex to the surface of the base sheet (hereinafter also referred to as the separator surface). You may carry out by addition.
  • the amount of metal A is large (for example, when the transition metal derived from the positive electrode active material is large), the amount of the iron cyano complex added is adjusted according to the amount of metal A within a range that does not impair the performance of the negative electrode and the like. be able to.
  • the iron cyano complex contains complex ions composed of iron ions (central metal ions) and cyanide ions (CN ⁇ ) (ligands) bonded to the iron ions.
  • the iron cyano complex is contained in the negative electrode or the like as a salt of an alkali metal element (excluding lithium), a group 2 element, ammonium, or the like.
  • the iron cyano complex added to the negative electrode and the like is difficult to dissolve in the non-aqueous electrolyte, and tends to remain in the negative electrode and the like even after the battery is constructed.
  • the iron cyano complex added to the negative electrode or the like is formed of a cation and an anion (complex ion).
  • cations for example, cations of alkali metal elements, cations of Group 2 elements, and ammonium cations (NH 4 + ) are preferable.
  • cations of alkali metal elements include potassium (K) cations and sodium (Na) cations.
  • Calcium (Ca) cation etc. are mentioned as a cation of a 2nd group element. Among them, potassium cation is more preferable.
  • complex ions include ferrocyanide ions: [Fe(CN) 6 ] 4 ⁇ and ferricyanide ions: [Fe(CN) 6 ] 3 ⁇ .
  • the iron cyano complex is included in the negative electrode or the like as a salt of an alkali metal element, a salt of a Group 2 element, or an ammonium salt
  • the iron cyano complex is combined with metal A (mainly a transition metal) from the viewpoint of chemical stability. Easy to form stable complex salts.
  • the iron cyano complex is preferably at least one selected from the group consisting of ferrocyanide and ferricyanide.
  • the ferrocyanide is preferably at least one selected from the group consisting of potassium ferrocyanide, sodium ferrocyanide, calcium ferrocyanide, and ammonium ferrocyanide.
  • Ferricyanide is preferably at least one selected from the group consisting of potassium ferricyanide, sodium ferricyanide, calcium ferricyanide, and ammonium ferricyanide.
  • potassium ferrocyanide and potassium ferricyanide are more preferable from the viewpoint of easily forming a salt insoluble in the ion of metal A and the non-aqueous electrolyte.
  • the shape of the iron cyano complex is not particularly limited, it is preferably particulate.
  • the iron cyano complex is difficult to dissolve in the non-aqueous electrolyte, tends to remain in a solid state even after the battery is constructed, and tends to remain in the negative electrode and the like.
  • the average particle diameter of the particles of the iron cyano complex may be 0.1 ⁇ m or more and 50 ⁇ m or less, or may be 1 ⁇ m or more and 50 ⁇ m or less. When the average particle size of the iron cyano complex particles is 0.1 ⁇ m or more (or 1 ⁇ m or less), deposition of metal A on the negative electrode is easily suppressed, and charging and discharging efficiency is easily improved.
  • particle is a concept including primary particles, secondary particles, and agglomerates of these, and in addition to general particles or particles, aggregation, agglomeration ( Also includes concepts such as agglomeration.
  • the particle diameter (or aggregate diameter) can be regarded as the diameter of an equivalent circle having the same area as the area surrounded by the outline of the particle (or aggregate) in observation of a cross-sectional sample as described later.
  • the average particle size of the iron cyano complex particles can be determined by the following method.
  • a battery battery before initial charge or battery in an initial fully discharged state
  • the negative electrode is taken out, and an image of the surface of the negative electrode (or the cross section of the negative electrode) is obtained with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the above-mentioned fully discharged state means a state in which the secondary battery is discharged to a depth of discharge (DOD) of 90% or more. This is a state in which the secondary battery has been discharged to the lower limit voltage.
  • DOD depth of discharge
  • an SEM image of the negative electrode surface (or negative electrode cross section) immediately after production may be obtained.
  • the iron cyano complex contained in the negative electrode can be confirmed by SEM-EDX (energy dispersive X-ray spectroscopy) analysis.
  • SEM-EDX energy dispersive X-ray spectroscopy
  • the average particle size can be obtained using an SEM image of the surface of the negative electrode.
  • an SEM image of the cross section of the negative electrode may be used to determine the average particle size.
  • the separator contains an iron cyano complex, it can also be determined in the same manner as described above.
  • the content of the iron cyano complex in the negative electrode may be 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the negative electrode active material (for example, a carbonaceous material such as graphite).
  • the content of the iron cyano complex in the negative electrode means the amount of the iron cyano complex attached to the negative electrode surface. In this case, deposition of metal A on the negative electrode can be easily suppressed while maintaining negative electrode characteristics (for example, low negative electrode resistance).
  • the content of the iron cyano complex in the negative electrode can be determined by analysis such as inductively coupled plasma mass spectrometry (ICP-MS).
  • the iron cyano complex is preferably attached to the surface of the negative electrode (the surface of the negative electrode mixture layer and/or the negative electrode current collecting sheet). At least on the surface of the negative electrode facing the positive electrode, the iron cyano complex is preferably attached. In this case, deposition of metal A on the negative electrode and deterioration of charge-discharge efficiency caused by it can be efficiently suppressed.
  • the amount of iron derived from the iron cyano complex attached per 1 cm 2 of the negative electrode surface may be, for example, 1 nmol or more and 30 ⁇ mol or less.
  • the adhesion amount of iron derived from the iron cyano complex can be obtained, for example, by performing an analysis such as X-ray photoelectron spectroscopy (XPS) on the negative electrode in the secondary battery before the initial charge (or the negative electrode immediately after preparation). can be done.
  • XPS X-ray photoelectron spectroscopy
  • the negative electrode is attached to the negative electrode mixture layer containing the negative electrode active material, the negative electrode current collecting sheet supporting the negative electrode mixture layer, and the surface of the negative electrode mixture layer opposite to the side supported by the negative electrode current collecting sheet. and an iron cyano complex.
  • an iron cyano complex may adhere to the surface of the region of the negative electrode current collector sheet.
  • the negative electrode mixture layer may be formed on one surface of the negative electrode current collecting sheet, or may be formed on both surfaces of the negative electrode current collecting sheet.
  • the negative electrode includes a negative electrode current collecting sheet and an iron cyano complex attached to the surface of the negative electrode current collecting sheet. and may be provided.
  • the separator may include a base sheet and an iron cyano complex attached to the surface of the base sheet.
  • the iron cyano complex may be attached to one surface of the substrate sheet or may be attached to both surfaces of the substrate sheet.
  • the coverage of the negative electrode (or separator) surface with the iron cyano complex is preferably 5% or more and 95% or less, more preferably 10% or more and 90% or less.
  • the coverage is 5% or more (or 10% or more)
  • deposition of metal A on the negative electrode is likely to be suppressed, and charging/discharging efficiency is likely to be improved.
  • the coverage is 95% or less (or 90% or more)
  • the influence on the negative electrode or the like due to the addition of the iron cyano complex is easily reduced (for example, low negative electrode resistance is easily maintained), and high capacity is easily obtained. .
  • the coverage rate of the iron cyano complex on the surface of the negative electrode (or separator) is the ratio of the area of the region where the iron cyano complex is attached on the surface to the entire area of the surface of the negative electrode (or separator) facing the positive electrode.
  • the coating is applied to both the first surface and the second surface. It is preferable that the ratio is within the above range.
  • the coverage of the negative electrode surface with the iron cyano complex can be obtained by the following method.
  • a battery battery before initial charge or battery in initial fully discharged state
  • the negative electrode is taken out, and a SEM image of the negative electrode surface (the surface facing the positive electrode) is obtained.
  • An SEM image of the surface of the negative electrode immediately after fabrication may be obtained.
  • the area S0 of the entire negative electrode surface for example, the area of the field of view: 0.04 mm 2 to 1.00 mm 2
  • the area S1 of the region of the negative electrode surface to which the iron cyano complex is attached were determined. Then, the ratio (percentage) of S1 to S0 is calculated as the coverage.
  • the coverage is determined for each of 5 to 10 arbitrary locations on the surface of the negative electrode, and the average value thereof is calculated.
  • the iron cyano complex on the surface of the negative electrode can be confirmed by SEM-EDX analysis. Also, the coverage of the separator surface with the iron cyano complex can be obtained in the same manner as described above.
  • the iron cyano complex can be adhered to the negative electrode surface (or the separator surface) by, for example, applying a treatment liquid containing the iron cyano complex and water to the negative electrode surface (or the separator surface) and drying it.
  • the iron cyano complex is easily dissolved in water, and an aqueous solution of the iron cyano complex is used as the treatment liquid so that the iron cyano complex can be uniformly attached to the surface of the negative electrode (or the surface of the separator).
  • the amount (coverage) of the iron cyano complex deposited on the negative electrode surface (or separator surface) may be adjusted by changing the concentration of the iron cyano complex in the treatment liquid.
  • the treatment liquid may further contain a component (for example, a binder) other than the iron cyano complex. Examples of binders include fluororesins and acrylic resins, which will be described later.
  • a method of applying the treatment liquid is not particularly limited, and a coating method using various coaters, an immersion method, a spray method, or
  • a non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the negative electrode is the above-described negative electrode for a non-aqueous electrolyte secondary battery.
  • a non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte, wherein the separator is the is a separator for a non-aqueous electrolyte secondary battery.
  • the negative electrode may be the negative electrode for a nonaqueous electrolyte secondary battery described above.
  • Each component of the non-aqueous electrolyte secondary battery will be specifically described below.
  • the positive electrode contains a positive electrode active material capable of intercalating and deintercalating lithium ions.
  • the positive electrode may include a positive electrode mixture layer containing a positive electrode active material, and a positive electrode current collector sheet carrying the positive electrode mixture layer.
  • the positive electrode mixture layer can be formed by applying a positive electrode slurry in which a positive electrode mixture is dispersed in a dispersion medium on the surface of the positive electrode current collecting sheet and drying the slurry. The dried coating film may be rolled if necessary.
  • the positive electrode material mixture layer may be formed on one surface of the positive electrode current collector sheet, or may be formed on both surfaces.
  • the positive electrode mixture contains a positive electrode active material as an essential component, and may contain a binder, a thickener, a conductive agent, etc. as optional components.
  • a lithium transition metal composite oxide having a layered rock salt structure is used as the positive electrode active material.
  • lithium-transition metal composite oxides containing Ni, Co, and at least one of Al and Mn are promising because they exhibit high capacity and high voltage.
  • the Ni content of the composite oxide NC can be increased, it is advantageous in terms of cost, and a higher capacity can be secured.
  • the composition of the composite oxide NC is, for example, Li ⁇ Ni (1-x1-x2-x3-y) Co x1 Mn x2 Al x3 M y O 2+ ⁇ (0.95 ⁇ 1.05, 0.5 ⁇ 1 -x1-x2-x3-y ⁇ 0.95, 0 ⁇ x1 ⁇ 0.04, 0 ⁇ x2 ⁇ 0.1, 0 ⁇ x3 ⁇ 0.1, 0 ⁇ x2+x3 ⁇ 0.2, 0 ⁇ y ⁇ 0 .1, ⁇ 0.05 ⁇ 0.05).
  • M is at least one selected from the group consisting of Ti, Zr, Nb, Mo, W, Fe, Zn, B, Si, Mg, Ca, Sr and Y.
  • x1 which indicates the ratio (atomic ratio) of Co, is greater than 0 and 0.04 or less, preferably 0.02 or less, and more preferably 0.015 or less.
  • x2 which indicates the ratio (atomic ratio) of Mn, is 0 ⁇ x2 ⁇ 0.1, preferably 0 ⁇ x2 ⁇ 0.1.
  • a composite oxide NC containing Mn is relatively inexpensive and has a high capacity.
  • x3 which indicates the ratio (atomic ratio) of Al, is 0 ⁇ x3 ⁇ 0.1, preferably 0.03 ⁇ x3 ⁇ 0.1, and may be 0.05 ⁇ x3 ⁇ 0.1.
  • the composite oxide NC contains Al, the crystal structure is stabilized, making it easier to ensure high cycle characteristics.
  • the content of the elements that make up the composite oxide NC can be measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES), electron probe microanalyzer (EPMA), EDX, or the like.
  • ICP-AES inductively coupled plasma atomic emission spectrometer
  • EPMA electron probe microanalyzer
  • EDX EDX
  • an olivine-type lithium-transition metal composite oxide LiFePO 4 or the like
  • a spinel-type lithium-transition metal composite oxide LiMn 2 O 4 or the like
  • a resin material is used as the binder.
  • binders include fluororesins (e.g., polyvinylidene fluoride (PVDF), polyhexafluoropropylene, polytetrafluoroethylene), polyolefin resins (e.g., polyethylene, polypropylene), polyamide resins (e.g., aramid resins), Polyimide resin (e.g., polyimide, polyamideimide), acrylic resin (e.g., polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, ethylene-acrylic acid copolymer, or salts thereof), vinyl resin ( Examples include polyvinyl acetate) and rubber-like materials (eg, styrene-butadiene copolymer rubber (SBR)).
  • the binder may be used alone or in combination of two or more.
  • thickeners include cellulose derivatives such as cellulose ethers.
  • cellulose derivatives include carboxymethyl cellulose (CMC) and modified products thereof, methyl cellulose, and the like. Modified forms of CMC also include salts of CMC. Salts include alkali metal salts (eg, sodium salts), ammonium salts, and the like.
  • a thickener may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Examples of conductive agents include conductive fibers and conductive particles.
  • Examples of conductive fibers include carbon fibers, carbon nanotubes, and metal fibers.
  • Conductive particles include conductive carbon, metal powder, and the like.
  • Examples of conductive carbon include carbon black such as acetylene black (AB), graphite, and the like. Conductive agents may be used singly or in combination of two or more.
  • Examples of the dispersion medium used for the positive electrode slurry include alcohol (eg, ethanol), ether (eg, tetrahydrofuran), amide (eg, dimethylformamide), N-methyl-2-pyrrolidone (NMP), or a mixed solvent thereof. mentioned.
  • alcohol eg, ethanol
  • ether eg, tetrahydrofuran
  • amide eg, dimethylformamide
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode current collector sheet is selected according to the type of non-aqueous electrolyte secondary battery.
  • a non-porous or perforated (mesh-like) metal sheet metal foil, etc.
  • materials for the positive electrode collector sheet include stainless steel, aluminum, aluminum alloys, and titanium.
  • the negative electrode may include a negative electrode mixture layer containing a negative electrode active material and a negative electrode current collector sheet supporting the negative electrode mixture layer.
  • the negative electrode mixture layer can be formed by applying a negative electrode slurry obtained by dispersing a negative electrode mixture in a dispersion medium on the surface of the negative electrode current collecting sheet and drying the slurry. Water can be used as the dispersion medium. The dried coating film may be rolled if necessary.
  • the negative electrode mixture layer may be formed on one surface of the negative electrode current collecting sheet, or may be formed on both surfaces. In the case of lithium secondary batteries, the negative electrode may comprise a negative electrode current collecting sheet.
  • the negative electrode mixture contains a negative electrode active material as an essential component, and may contain a binder, a thickener, a conductive agent, etc. as optional components.
  • the iron cyano complex is preferably attached to the negative electrode surface (negative electrode mixture layer and/or the surface of the negative electrode current collecting sheet), but may be included in the negative electrode mixture (layer). That is, the negative electrode may include a negative electrode mixture layer containing a negative electrode active material and an iron cyano complex, and a negative electrode current collector sheet supporting the negative electrode mixture layer. In this case, the negative electrode may be produced by adding an iron cyano complex to the negative electrode slurry.
  • the negative electrode active material metal lithium, a lithium alloy, or the like may be used, but a material that can electrochemically absorb and release lithium ions is preferably used. Examples of such materials include carbonaceous materials, Si-containing materials, Sn-containing materials, and the like.
  • the negative electrode may contain one type of negative electrode active material, or may contain two or more types in combination. Carbonaceous materials and Si-containing materials are preferable as the negative electrode active material. A carbonaceous material and a Si-containing material may be used in combination.
  • carbonaceous materials examples include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon).
  • soft carbon graphitizable carbon
  • hard carbon non-graphitizable carbon
  • Graphite is preferable as a carbonaceous material because it has excellent charge-discharge stability and low irreversible capacity.
  • Examples of graphite include natural graphite, artificial graphite, and graphitized mesophase carbon particles.
  • the graphite particles may include, in part, amorphous carbon, graphitizable carbon, and non-graphitizable carbon.
  • Si-containing materials include simple Si, silicon alloys, and silicon compounds (silicon oxides, silicates, etc.). Silicon oxides include SiOx particles. x is, for example, 0.5 ⁇ x ⁇ 2, and may be 0.8 ⁇ x ⁇ 1.6. One Si-containing material may be used alone, or two or more may be used in combination.
  • the resin materials exemplified for the positive electrode can be used.
  • the conductive agent can be selected from, for example, those exemplified for the positive electrode.
  • the negative electrode current collector sheet a non-porous or perforated (mesh-like) metal sheet (metal foil, etc.) can be used. Examples of materials for the negative electrode current collector sheet include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the separator has high ion permeability and moderate mechanical strength and insulation.
  • the base sheet constituting the separator for example, a microporous thin film, a woven fabric, a nonwoven fabric, or a laminate of at least two selected from these can be used.
  • Polyolefin eg, polypropylene, polyethylene
  • the iron cyano complex is preferably attached to the separator surface (the surface of the base sheet), but may be included in the base sheet.
  • the iron cyano complex may be contained in the pores of a microporous thin film, and a fiber material to which the iron cyano complex is attached may be used to obtain a woven fabric or non-woven fabric.
  • Non-aqueous electrolyte contains, for example, a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • concentration of the lithium salt in the non-aqueous electrolyte is, for example, 0.5 mol/L or more and 2 mol/L or less.
  • non-aqueous solvents examples include cyclic carbonates, chain carbonates, cyclic carboxylates, and chain carboxylates.
  • Cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), and the like.
  • Chain carbonates include diethyl carbonate (DEC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • Cyclic carboxylic acid esters include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • Chain carboxylic acid esters include methyl formate, ethyl formate, propyl formate, methyl acetate (MA), ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.
  • the non-aqueous electrolyte may contain one type of non-aqueous solvent, or may contain two or more types in combination.
  • Lithium salts include, for example, LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , lithium lower aliphatic carboxylate, LiCl , LiBr, LiI, borates, and imide salts.
  • borates include bis(1,2-benzenediolate(2-)-O,O')lithium borate and bis(2,3-naphthalenediolate(2-)-O,O')boric acid.
  • the non-aqueous electrolyte may contain one type of lithium salt, or may contain two or more types in combination.
  • Non-aqueous electrolyte secondary battery is a structure in which an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween, and a non-aqueous electrolyte are accommodated in an exterior body.
  • another type of electrode group may be applied, such as a laminated electrode group in which a positive electrode and a negative electrode are laminated with a separator interposed therebetween.
  • the non-aqueous electrolyte secondary battery may be of any shape such as cylindrical, square, coin, button, and laminate.
  • FIG. 1 is a partially cutaway schematic perspective view of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a diagram schematically showing the configuration of the electrode group in FIG.
  • the battery includes a prismatic battery case 4 with a bottom, and an electrode group 1 and a non-aqueous electrolyte (not shown) housed in the battery case 4 .
  • the electrode group 1 is composed of a long strip-shaped positive electrode 9, a long strip-shaped negative electrode 10, and a separator 11 interposed therebetween.
  • the electrode group 1 is formed by winding the positive electrode 9, the negative electrode 10, and the separator 11 around a flat plate-shaped core and extracting the core.
  • the negative electrode 10 has a negative electrode main body 12 and a coating layer 15 of an iron cyano complex that covers both surfaces of the negative electrode main body 12 .
  • the negative electrode main body 12 includes a negative electrode collector sheet 13 and negative electrode mixture layers 14 supported on both sides of the negative electrode collector sheet 13 .
  • a coating layer 15 of an iron cyano complex is formed on the surface of the negative electrode mixture layer 14 (the surface opposite to the side supported by the negative electrode current collecting sheet 13).
  • the iron cyano complex can be formed in layers like the coating layer 15 in FIG.
  • FIG. 2 shows the iron cyano complex formed in layers (coating layer 15).
  • an iron cyano complex may be dispersed in the form of particles on the surface of the negative electrode.
  • FIG. 2 shows the coating layer 15 formed on the surface of the negative electrode main body 12 , a coating layer may be formed on the surface of the separator 11 .
  • the negative electrode collector sheet of the negative electrode is electrically connected to the negative electrode terminal 6 provided on the sealing plate 5 via the negative electrode lead 3 .
  • the negative electrode terminal 6 is insulated from the sealing plate 5 by a gasket 7 made of resin.
  • the positive electrode collector sheet of the positive electrode is connected to the rear surface of the sealing plate 5 via the positive electrode lead 2 . That is, the positive lead 2 is electrically connected to the battery case 4 which also serves as a positive terminal.
  • the peripheral edge of the sealing plate 5 is fitted to the open end of the battery case 4, and the fitted portion is laser-welded.
  • the electrolyte injection hole provided in the sealing plate 5 is closed with a sealing plug 8 .
  • Examples 1 to 5>> A non-aqueous electrolyte secondary battery (evaluation cell) was produced and evaluated by the following procedure.
  • Preparation of positive electrode 100 parts by mass of the positive electrode active material, 1 part by mass of AB, 1 part by mass of PVDF, and an appropriate amount of NMP were mixed to obtain a positive electrode slurry. Next, the positive electrode slurry is applied to one side of the aluminum foil, the coating film is dried, and then rolled to form a positive electrode mixture layer (thickness: 95 ⁇ m, density: 3.6 g/cm 3 ) on one side of the aluminum foil. Then, a positive electrode was obtained. LiNi 0.88 Co 0.09 Al 0.03 O 2 was used as the positive electrode active material.
  • Negative electrode slurry was prepared by mixing 98 parts by mass of a negative electrode active material (graphite), 1 part by mass of sodium salt of CMC, 1 part by mass of SBR, and an appropriate amount of water. Next, the negative electrode slurry was applied to one side of a copper foil as a negative electrode collector sheet, and the coating film was dried and then rolled to form a negative electrode mixture layer on one side of the copper foil.
  • a negative electrode active material graphite
  • the amount of the iron cyano complex attached to the surface of the negative electrode was in the range of 0.08 parts by mass to 1.6 parts by mass per 100 parts by mass of the negative electrode active material.
  • the average particle size of the particles of the iron cyano complex adhering to the negative electrode surface determined by the method described above was in the range of 10 ⁇ m to 30 ⁇ m.
  • the concentration of LiPF 6 in the non-aqueous electrolyte was set to 1.0 mol/L.
  • a positive electrode was cut into a predetermined shape to obtain a positive electrode for evaluation.
  • the positive electrode was provided with a 20 mm ⁇ 20 mm region functioning as a positive electrode and a 5 mm ⁇ 5 mm connecting region with a tab lead.
  • the positive electrode material mixture layer formed on the connection region was scraped off to expose the positive electrode current collector sheet.
  • the exposed portion of the positive electrode current collecting sheet was connected to the positive electrode tab lead, and a predetermined region of the outer circumference of the positive electrode tab lead was covered with an insulating tab film.
  • copper powder with a diameter of about 100 ⁇ m was intentionally embedded in the vicinity of the center of the positive electrode mixture layer.
  • a negative electrode was cut into the same shape as the positive electrode to obtain a negative electrode for evaluation.
  • the negative electrode mixture layer formed on the connection region formed in the same manner as the positive electrode was peeled off to expose the negative electrode current collecting sheet. After that, the exposed portion of the negative electrode current collecting sheet was connected to the negative electrode tab lead in the same manner as the positive electrode, and a predetermined region of the outer periphery of the negative electrode tab lead was covered with an insulating tab film.
  • a cell was produced using a positive electrode and a negative electrode for evaluation.
  • the positive electrode and the negative electrode were opposed to each other with the separator interposed therebetween so that the positive electrode mixture layer and the negative electrode mixture layer overlapped to obtain an electrode plate assembly.
  • a polyethylene separator having a thickness of 12 ⁇ m was used as the separator.
  • an Al laminate film (thickness: 100 ⁇ m) cut into a rectangle of 60 ⁇ 90 mm was folded in half, and the end of the long side of 60 mm was heat-sealed at 230° C. to form a cylinder of 60 ⁇ 45 mm.
  • the produced electrode plate group was placed in a cylinder, and heat sealing was performed at 230° C.
  • Example 6 to 10 Evaluation cells of Examples 6 to 10 were prepared in the same manner as in Examples 1 to 5, except that potassium ferricyanide: K 3 [Fe(CN) 6 ] was used instead of potassium ferrocyanide as the iron cyano complex.
  • Charging performed the following 1st charge and 2nd charge. (first charging) In an environment of 25° C., constant current charging was performed at 0.5 C (1 C is a current value for discharging the designed capacity in 1 hour) until the battery voltage reached 3.6 V. The current value and the charging time at that time were measured to obtain the charging capacity C1 (mAh). After that, the evaluation cell was left in an environment of 25° C. for 24 hours.
  • Table 1 shows the evaluation results.
  • the coverage rate indicates the coverage rate of the iron cyano complex on the negative electrode surface (the surface of the negative electrode mixture layer) obtained by the method described above.
  • the discharge capacity ratio (%) indicates the ratio (percentage) of the discharge capacity D of each evaluation cell to the discharge capacity D of the evaluation cell of Comparative Example 1.
  • the potassium ferrocyanide covering the negative electrode surface captured the copper ions eluted from the positive electrode, inhibited the deposition of copper on the negative electrode, and increased the initial charge-discharge efficiency.
  • the evaluation cells of Examples 2 to 4 in which the coverage ratio of potassium ferrocyanide was 10% to 90%, maintained a discharge capacity ratio comparable to that of the evaluation cell of Comparative Example 1, while maintaining high initial charge/discharge efficiency. was gotten.
  • the potassium ferricyanide covering the negative electrode surface captured the copper ions eluted from the positive electrode, inhibited the deposition of copper on the negative electrode, and increased the initial charge/discharge efficiency.
  • the evaluation cells of Examples 7 to 9 in which the coverage ratio of potassium ferricyanide was 10% to 90%, maintained a discharge capacity ratio comparable to that of the evaluation cell of Comparative Example 1, while maintaining high initial charge/discharge efficiency. was gotten.
  • the non-aqueous electrolyte secondary battery according to the present invention is used, for example, as a power source for small devices such as smartphones, a vehicle power source, and the like. While the invention has been described in terms of presently preferred embodiments, such disclosure is not to be construed in a limiting sense. Various alterations and modifications will no doubt become apparent to those skilled in the art to which the invention pertains after reading the above disclosure. Therefore, the appended claims are to be interpreted as covering all variations and modifications without departing from the true spirit and scope of the invention.

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