WO2023053591A1 - 二次電池用電極、二次電池用電極の製造方法、及び二次電池 - Google Patents

二次電池用電極、二次電池用電極の製造方法、及び二次電池 Download PDF

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WO2023053591A1
WO2023053591A1 PCT/JP2022/023963 JP2022023963W WO2023053591A1 WO 2023053591 A1 WO2023053591 A1 WO 2023053591A1 JP 2022023963 W JP2022023963 W JP 2022023963W WO 2023053591 A1 WO2023053591 A1 WO 2023053591A1
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secondary battery
polysaccharide
electrode
active material
electrode active
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English (en)
French (fr)
Japanese (ja)
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正悟 江崎
竜一 夏井
健祐 名倉
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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 EP22875470.1A priority Critical patent/EP4411852A4/en
Priority to US18/694,558 priority patent/US20250006895A1/en
Priority to CN202280064250.4A priority patent/CN117981100A/zh
Priority to JP2023551071A priority patent/JPWO2023053591A1/ja
Publication of WO2023053591A1 publication Critical patent/WO2023053591A1/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
    • H01M4/364—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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 secondary battery electrode, a method for manufacturing a secondary battery electrode, and a secondary battery.
  • Secondary batteries such as lithium-ion secondary batteries are used as drive power sources for mobile information terminals such as mobile phones and laptop computers, and as drive power sources for electric vehicles (EV), hybrid electric vehicles (HEV), etc. are doing.
  • EV electric vehicles
  • HEV hybrid electric vehicles
  • Li-containing transition metal oxides containing transition metals such as nickel, cobalt, and manganese are used as positive electrode active materials for lithium-ion secondary batteries.
  • Carbon materials and the like are generally used as negative electrode active materials for lithium ion secondary batteries, but metal-containing compounds such as lithium titanate may be used in some cases.
  • the transition metal in the positive electrode active material may be eluted and deposited on the negative electrode, or may be deposited on the separator between the positive electrode and the negative electrode.
  • the metal in the metal-containing compound may be eluted and deposited on the negative electrode or the separator. In this way, the elution of the metal component from the electrode active material containing the metal element may lead to deterioration in charge-discharge cycle characteristics of the secondary battery.
  • an object of the present disclosure is to provide a secondary battery electrode, a method for manufacturing a secondary battery electrode, and a secondary battery that can suppress deterioration in the charge-discharge cycle characteristics of the secondary battery. .
  • a secondary battery electrode includes a current collector and a mixture layer provided on the current collector, wherein the mixture layer includes an electrode active material containing a metal element, a non- A water-soluble additive and a water-soluble additive are included, the water-soluble additive includes a polysaccharide, and the particle size of the polysaccharide is larger than the particle size of the electrode active material.
  • a method for manufacturing a secondary battery electrode which is one aspect of the present disclosure, includes a water-soluble electrode active material containing a metal element, a water-insoluble additive, and a polysaccharide having a larger particle size than the electrode active material.
  • the method is characterized by comprising a step of kneading an additive in a non-aqueous solvent to prepare a paste, and a step of applying the paste onto a current collector to form a mixture layer.
  • a secondary battery according to one aspect of the present disclosure includes a positive electrode and a negative electrode, and at least one of the positive electrode and the negative electrode is the secondary battery electrode.
  • FIG. 1 is a cross-sectional view of a secondary battery that is an example of an embodiment
  • FIG. 4 shows an SEM image of the surface of the positive electrode used in Example 2.
  • FIG. 4 is an SEM image showing the dried product of Comparative Example 2.
  • FIG. 1 is a cross-sectional view of a secondary battery that is an example of an embodiment.
  • the secondary battery 10 shown in FIG. A battery case having plates 18 and 19 and a case main body 16 and a sealing member 17 for accommodating the above members is provided.
  • the wound electrode body 14 another form of electrode body such as a stacked electrode body in which positive and negative electrodes are alternately stacked via a separator may be applied.
  • the battery case include cylindrical, square, coin-shaped, button-shaped metal cases, and resin cases formed by laminating resin sheets (so-called laminated type).
  • the case body 16 is, for example, a bottomed cylindrical metal container.
  • a gasket 28 is provided between the case body 16 and the sealing member 17 to ensure hermeticity inside the battery.
  • the case main body 16 has an overhanging portion 22 that supports the sealing member 17, for example, a portion of the side surface overhanging inward.
  • the projecting portion 22 is preferably annularly formed along the circumferential direction of the case body 16 and supports the sealing member 17 on the upper surface thereof.
  • the sealing body 17 has a structure in which a filter 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are layered in order from the electrode body 14 side.
  • Each member constituting the sealing member 17 has, for example, a disk shape or a ring shape, and each member other than the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected to each other at their central portions, and an insulating member 25 is interposed between their peripheral edge portions.
  • the lower valve body 24 deforms and breaks so as to push the upper valve body 26 upward toward the cap 27 side, breaking the lower valve body 24 and the upper valve body 26 .
  • the current path between is interrupted.
  • the upper valve body 26 is broken and the gas is discharged from the opening of the cap 27 .
  • the positive electrode lead 20 attached to the positive electrode 11 extends through the through hole of the insulating plate 18 toward the sealing member 17
  • the negative electrode lead 21 attached to the negative electrode 12 extends through the insulating plate 19 . It extends to the bottom side of the case body 16 through the outside.
  • the positive electrode lead 20 is connected to the lower surface of the filter 23, which is the bottom plate of the sealing member 17, by welding or the like, and the cap 27, which is the top plate of the sealing member 17 electrically connected to the filter 23, serves as a positive electrode terminal.
  • the negative lead 21 is connected to the inner surface of the bottom of the case body 16 by welding or the like, and the case body 16 serves as a negative terminal.
  • the electrolytic solution may be an aqueous electrolytic solution, but is preferably a non-aqueous electrolytic solution containing a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents include esters, ethers, nitriles, amides, and mixed solvents of two or more thereof.
  • the non-aqueous solvent may contain a halogen-substituted product obtained by substituting at least part of the hydrogen atoms of these solvents with halogen atoms such as fluorine.
  • a lithium salt such as LiPF 6 is used as the electrolyte salt.
  • a porous sheet having ion permeability and insulation is used for the separator 13.
  • porous sheets include microporous thin films, woven fabrics, and non-woven fabrics.
  • polyolefins such as polyethylene and polypropylene, cellulose, and the like are suitable.
  • the separator 13 may have either a single layer structure or a laminated structure. A heat-resistant layer or the like may be formed on the surface of the separator.
  • the secondary battery electrode according to this embodiment will be described below.
  • the secondary battery electrode according to this embodiment is applied to at least one of the positive electrode 11 and the negative electrode 12 .
  • a secondary battery electrode has a current collector and a composite material layer provided on the current collector.
  • the current collector is, for example, a foil of a metal such as aluminum that is stable in the potential range of the positive electrode 11, or a positive electrode current collector such as a film in which the metal is arranged on the surface layer. is the body.
  • the current collector is, for example, a metal foil stable in the potential range of the negative electrode 12 such as copper, or a negative electrode such as a film in which the metal is arranged on the surface layer. It is a current collector.
  • the composite material layer of the secondary battery electrode includes an electrode active material having a metal element, a water-insoluble additive, and a water-soluble additive.
  • the composite material layer contains a conductive material or the like, if necessary.
  • the water-insoluble additive includes, for example, a water-insoluble binder that is used for binding particles such as active materials and conductive agents, and for bonding between a composite layer and a current collector.
  • water-insoluble binders include fluorine-based resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide, acrylic resins, and polyolefins.
  • the water-insoluble binder is preferably a fluororesin, more preferably polyvinylidene fluoride (PVdF), in terms of binding properties.
  • Water-insoluble additives include fillers and the like in addition to water-insoluble binders.
  • the water-soluble additive contains polysaccharides.
  • the polysaccharide can capture metal components eluted from the electrode active material due to repeated charging and discharging of the secondary battery.
  • Polysaccharides include, for example, xanthan gum, gum arabic, polysaccharides having a carboxy group such as carboxymethylcellulose and pectin, polysaccharides having a sulfone group such as carrageenan, guar gum, tamarind seed gum, locust bean gum, pullulan, psyllium, and hyaluron. acid, chitosan, and the like.
  • guar gum, locust bean gum, polysaccharides having a carboxyl group, and polysaccharides having a sulfone group are preferred in terms of, for example, a high ability to trap metal components eluted from the electrode active material. and more preferably polysaccharides having a carboxyl group and polysaccharides having a sulfone group, particularly gum arabic and carrageenan.
  • Guar gum (GG) has a skeleton having two molecules of mannose linked in a straight chain and one molecule of galactose as a side chain, and is represented by the following structural formula.
  • Locust bean gum has a skeleton having 4 molecules of mannose bonded in a straight chain and a side chain of 1 molecule of galactose, and is represented by the following structural formula.
  • Xanthan gum (XG) consists of 2 molecules of glucose, 2 molecules of mannose, and repeating units of gluconic acid, and is represented by the following structural formula.
  • Gum arabic (GA) is represented by the following structural formula.
  • Carboxymethyl cellulose includes, for example, ammonium salt type carboxymethyl cellulose and the like, and is represented by the following structural formula.
  • carrageenan examples include kappa-type carrageenan (k-Car), iota-type carrageenan (i-Car), and the like, and are represented by the following structural formulas. kappa carrageenan iota-type carrageenan
  • the particle size of the polysaccharide is larger than that of the electrode active material.
  • the particle size of the polysaccharide is, for example, 1 ⁇ m or more and 100 ⁇ m or less in that it can effectively capture the metal component eluted from the electrode active material and effectively suppress the deterioration of the charge-discharge cycle characteristics of the secondary battery. and more preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the particle size of polysaccharides is obtained as follows.
  • the surface of the secondary battery electrode is observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • 30 polysaccharide particles are randomly selected from the SEM image of the cross section of the electrode.
  • the major diameter (longest diameter) of each of the 30 particles is determined, and the average value thereof is taken as the particle diameter of the polysaccharide.
  • the polysaccharide constitutes the secondary particles, the above particles are replaced with the secondary particles.
  • the content of the polysaccharide is, for example, 0.1% by mass or more and 2% by mass or less with respect to the mass of the composite layer excluding the polysaccharide, in order to further suppress the deterioration of the charge-discharge cycle characteristics of the secondary battery. preferably 0.1% by mass or more and 1% by mass or less.
  • the electrode active material i.e., positive electrode active material
  • a metal element constituting the composite layer i.e., positive electrode composite layer
  • the electrode active material is, for example, a Li-containing transition metal An oxide or the like.
  • Metal elements contained in the Li-containing transition metal oxide include Ni, Co, Mn, Al, B, Mg, Ti, V, Cr, Fe, Cu, Zn, Ga, Sr, Zr, Nb, In, Sn , Ta, W, and the like. Among them, it is preferable to contain at least one of Ni, Co, and Mn.
  • Li-containing transition metal oxides for example, have a layered structure in that they can increase the capacity of secondary batteries, and the number of moles of Li relative to the total number of moles of metal elements other than Li (A) (B ) is 1 or more, and the ratio of the number of moles (C) of Ni to the total number of moles (A) of metal elements other than Li is 0.5 or more. is preferred.
  • the layered structure of the Li-containing transition metal oxide include a layered structure belonging to the space group R-3m and a layered structure belonging to the space group C2/m. Among these, a layered structure belonging to the space group R-3m is preferable from the viewpoints of high capacity, stability of the layered structure, and the like.
  • the electrode active material (that is, the negative electrode active material) containing the metal element that constitutes the mixture layer (that is, the negative electrode mixture layer) is, for example, lithium titanate ( Li-containing metal oxides such as Li 4 Ti 5 O 12 , etc.), Li-containing nitrides such as lithium cobalt nitride, lithium iron nitride, and lithium manganese nitride.
  • lithium titanate Li-containing metal oxides such as Li 4 Ti 5 O 12 , etc.
  • Li-containing nitrides such as lithium cobalt nitride, lithium iron nitride, and lithium manganese nitride.
  • metal elution from the negative electrode active material is almost unthinkable.
  • Examples of negative electrode active materials that do not contain metal elements include carbon materials such as artificial graphite, natural graphite, hard carbon, soft carbon, carbon nanotubes, and activated carbon.
  • the particle size of the electrode active material may be smaller than the particle size of the polysaccharide.
  • the particle size of the negative electrode active material is preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 3 ⁇ m or more and 20 ⁇ m or less.
  • the particle size of the electrode active material is measured by the same method as the measurement of the polysaccharide particle size.
  • the mixture layer may contain a conductive material, and examples of the conductive material include carbon materials such as carbon black, acetylene black, ketjen black, graphite, and carbon nanotubes.
  • the particle size of the conductive material is preferably smaller than that of the polysaccharide in terms of, for example, ensuring conductive paths within the electrode.
  • the particle size of the conductive material is, for example, 1 nm or more and 1000 nm or less.
  • the particle size of the conductive material is measured by the same method as the measurement of the polysaccharide particle size.
  • a secondary battery electrode is prepared by kneading an electrode active material containing a metal element, a water-insoluble additive, and a water-soluble additive containing a polysaccharide having a larger particle size than the electrode active material in a non-aqueous solvent. and a first step of forming a paste, and a second step of applying the paste to a current collector to form a composite material layer.
  • a polysaccharide as a binder by dissolving it in an aqueous solvent.
  • the polysaccharide does not function as a binder.
  • non-aqueous solvents used in obtaining the paste examples include N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • kneading of raw materials when obtaining a paste can be done, for example, by a cutter mill, a pin mill, a bead mill, a fine particle compounding device (a device that generates a shearing force between a specially shaped rotor that rotates at high speed inside a tank and a collision plate), It is carried out by a kneader such as a granulator, a twin-screw extruder kneader, or a planetary mixer.
  • a kneader such as a granulator, a twin-screw extruder kneader, or a planetary mixer.
  • a slit die coater for example, a slit die coater, reverse roll coater, lip coater, blade coater, knife coater, gravure coater, and dip coater are used.
  • the second step it is preferable to heat and dry the mixture layer after the paste is applied to the current collector. Moreover, it is preferable to roll the mixture layer with a rolling roller or the like.
  • a rolling roller or the like For the rolling of the composite layer, for example, a roll press machine or the like is used.
  • Example 1 [Preparation of positive electrode]
  • NMP N-methyl-2-pyrrolidone
  • the mass ratio of Li-containing transition metal oxide represented by LiNi 0.5 Mn 0.5 O 2 : acetylene black: polyvinylidene fluoride: gum arabic (GA) , 92:5:3:0.5 to prepare a positive electrode paste.
  • This positive electrode paste was applied to an aluminum foil, the coating film was dried, and then the coating film was rolled by rolling rollers to produce a positive electrode in which a positive electrode mixture layer was formed on a positive electrode current collector.
  • LiPF 6 was dissolved at a concentration of 1 mol/L in a mixed solvent in which fluoroethylene carbonate (FEC), ethylene carbonate (EC), and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1:3:6. to prepare a non-aqueous electrolyte.
  • FEC fluoroethylene carbonate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • test cell An electrode body in which a positive electrode and a lithium metal negative electrode are laminated so as to face each other via a separator, and the non-aqueous electrolyte are housed in a coin-shaped case body, and the coin-shaped case body is formed by a gasket and a sealing member. The opening was sealed to prepare a test cell.
  • Example 2 In N-methyl-2-pyrrolidone (NMP), the mass ratio of Li-containing transition metal oxide represented by LiNi 0.5 Mn 0.5 O 2 : acetylene black: polyvinylidene fluoride: gum arabic (GA) , 92:5:3:1, and a test cell was prepared in the same manner as in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • Example 3 A test cell was prepared in the same manner as in Example 1, except that gum arabic (GA) was changed to guar gum (GG).
  • Example 4 A test cell was prepared in the same manner as in Example 1, except that gum arabic (GA) was changed to carboxymethylcellulose ammonium (CMC).
  • GA gum arabic
  • CMC carboxymethylcellulose ammonium
  • Example 5 Li-containing transition metal oxide represented by LiNi 0.5 Mn 0.5 O 2 in N-methyl-2-pyrrolidone (NMP): acetylene black: polyvinylidene fluoride: gum arabic (GA), xanthan gum (XG ) were kneaded at a mass ratio of 92:5:3:0.25:0.25 to prepare a test cell in the same manner as in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • acetylene black polyvinylidene fluoride: gum arabic (GA), xanthan gum (XG ) were kneaded at a mass ratio of 92:5:3:0.25:0.25 to prepare a test cell in the same manner as in Example 1.
  • Example 6 A test cell was prepared in the same manner as in Example 5, except that xanthan gum (XG) was changed to guar gum (GG).
  • Example 7 A test cell was prepared in the same manner as in Example 1, except that gum arabic (GA) was changed to kappa-type carrageenan (k-Car).
  • Example 8 A test cell was prepared in the same manner as in Example 1, except that gum arabic (GA) was changed to iota-type carrageenan (i-Car).
  • Example 1 A test cell was prepared as in Example 1, except that no gum arabic (GA) was used.
  • a SEM image of the surface of the positive electrode used in Example 2 is shown in FIG. As shown in FIG. 2, it was confirmed that the particle size of gum arabic is larger than the particle size of the positive electrode active material. Although not shown in the drawings, it was confirmed by SEM images that the particle size of the polysaccharide was larger than that of the positive electrode active material in other examples as well.
  • Examples 1 to 8 suppressed the metal elution amount more than Comparative Example 1. From these results, it can be said that Examples 1 to 8 containing a polysaccharide larger than the particle size of the positive electrode active material can suppress the metal elution amount more than Comparative Example 1 containing no polysaccharide.
  • Example 9-1 In N-methyl-2-pyrrolidone (NMP), the mass ratio of Li-containing transition metal oxide represented by LiNi 0.5 Mn 0.5 O 2 : acetylene black: polyvinylidene fluoride: guar gum (GG) is A test cell was prepared in the same manner as in Example 1, except that these were kneaded so as to have a ratio of 92:5:3:0.1.
  • NMP N-methyl-2-pyrrolidone
  • Examples 9-2 to 9-7 use guar gum (GG) of Example 9-1, xanthan gum (XG), locust bean gum (LBG), gum arabic (GA), carboxymethylcellulose ammonium (CMC), kappa type A test cell was prepared in the same manner as in Example 9-1, except that carrageenan (k-Car) and iota-type carrageenan (i-Car) were used.
  • GG guar gum
  • XG xanthan gum
  • LBG locust bean gum
  • GA gum arabic
  • CMC carboxymethylcellulose ammonium
  • kappa type A test cell was prepared in the same manner as in Example 9-1, except that carrageenan (k-Car) and iota-type carrageenan (i-Car) were used.
  • Example 10-1 to 10-3 gum arabic in Example 1 was changed to carboxymethylcellulose ammonium (CMC), kappa-type carrageenan (k-Car), and iota-type carrageenan (i-Car).
  • CMC carboxymethylcellulose ammonium
  • k-Car kappa-type carrageenan
  • i-Car iota-type carrageenan
  • Example 11-1 to 11-3 gum arabic in Example 2 was changed to carboxymethylcellulose ammonium (CMC), kappa-type carrageenan (k-Car), and iota-type carrageenan (i-Car).
  • CMC carboxymethylcellulose ammonium
  • k-Car kappa-type carrageenan
  • i-Car iota-type carrageenan
  • Example 1 For Example 1, Example 2, Examples 9-1 to 9-7, Examples 10-1 to 10-3, Examples 11-1 to 11-3 and Comparative Example 1, the charge-discharge cycle test A was performed, and the capacity retention rate was calculated. The results are summarized in Table 2.
  • Capacity retention rate (%) (discharge capacity at 53rd cycle/discharge capacity at 1st cycle) x 100
  • GA gum arabic
  • FIG. 3 is an SEM image showing the dried product of Comparative Example 2. As shown in FIG. 3, it was confirmed that gum arabic having a particle size smaller than that of the positive electrode active material adhered to the particle surface of the positive electrode active material.
  • a test cell was produced in the same manner as in Example 1, except that this positive electrode paste was used.
  • Example 12 Li-containing transition metal oxide represented by LiNi 0.5 Co 0.2 Mn 0.3 O 2 in N-methyl-2-pyrrolidone (NMP): acetylene black: polyvinylidene fluoride: gum arabic (GA)
  • NMP N-methyl-2-pyrrolidone
  • acetylene black polyvinylidene fluoride: gum arabic
  • a test cell was prepared in the same manner as in Example 1, except that these were kneaded so that the mass ratio of 1 was 92:5:3:0.25.
  • the particle size of gum arabic was larger than the particle size of the positive electrode active material.
  • Example 12 The capacity retention rate of the test cell of Example 12 was 95.6%. On the other hand, the capacity retention rate of the test cell of Comparative Example 2 was 94.4%. From these results, Example 12, which contains a polysaccharide larger than the particle size of the positive electrode active material, suppresses deterioration in charge-discharge cycle characteristics more than Comparative Example 2, which contains a polysaccharide smaller than the particle size of the positive electrode active material. It can be said that
  • Comparative Examples 3 and 4 were charged and discharged for 53 cycles under the conditions of the charge-discharge cycle test A described above. When the capacity retention rate at that time was obtained, Comparative Example 3 was 88.1%, and Comparative Example 4 was 89.9%. Here, looking at the results of the capacity retention rate of Examples 1 and 2 and Comparative Examples 1, 3, and 4, Examples 1 and 2 containing gum arabic larger than the particle size of the positive electrode active material are the highest, followed by the positive electrode. Comparative Examples 3 and 4 containing gum arabic smaller than the particle size of the active material, and Comparative Example 1 containing no gum arabic was the lowest.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • Example 15 In N-methyl-2-pyrrolidone (NMP), the mass ratio of Li-containing transition metal oxide represented by LiNi 0.8 Mn 0.2 O 2 : acetylene black: polyvinylidene fluoride: gum arabic (GA) , 92:5:3:1, and a test cell was prepared in the same manner as in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • Capacity retention rate (%) (discharge capacity at 27th cycle/discharge capacity at 1st cycle) x 100
  • Example 13 The capacity retention rate of Example 13 was 96.3%, the capacity retention rate of Example 14 was 96.3%, the capacity retention rate of Example 15 was 95.7%, and the capacity retention rate of Comparative Example 5 was 96.3%.
  • the retention rate was 94.4%. From these results, it can be said that the examples containing polysaccharides having a particle size larger than that of the positive electrode active material can suppress deterioration of the charge-discharge cycle characteristics more than the comparative examples containing no polysaccharides.

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