WO2023162485A1 - 固体電解質用組成物および非水電解質二次電池 - Google Patents

固体電解質用組成物および非水電解質二次電池 Download PDF

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WO2023162485A1
WO2023162485A1 PCT/JP2023/000181 JP2023000181W WO2023162485A1 WO 2023162485 A1 WO2023162485 A1 WO 2023162485A1 JP 2023000181 W JP2023000181 W JP 2023000181W WO 2023162485 A1 WO2023162485 A1 WO 2023162485A1
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solid electrolyte
positive electrode
polymer
negative electrode
electrode
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English (en)
French (fr)
Japanese (ja)
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恒平 原
光宏 日比野
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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 EP23759491.6A priority Critical patent/EP4489029A4/en
Priority to JP2024502888A priority patent/JPWO2023162485A1/ja
Priority to CN202380022880.XA priority patent/CN118742975A/zh
Priority to US18/840,631 priority patent/US20250183368A1/en
Publication of WO2023162485A1 publication Critical patent/WO2023162485A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic 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
    • H01M4/13—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
    • H01M4/52—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
    • 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 solid electrolyte composition and a non-aqueous electrolyte secondary battery using the composition.
  • Non-aqueous electrolyte secondary batteries such as lithium-ion batteries are widely used for applications that require high capacity, such as in-vehicle applications and power storage applications.
  • a non-aqueous electrolyte secondary battery generally includes an electrode body in which a positive electrode and a negative electrode are laminated or wound with a separator interposed therebetween, and a non-aqueous electrolyte.
  • batteries using a solid electrolyte instead of an electrolytic solution have been actively studied.
  • Patent Document 1 discloses a solid electrolyte material composed of Li, M, and X, wherein M is at least one element selected from the group consisting of metal elements other than Li and metalloid elements, X is at least one element selected from the group consisting of F, Cl, Br, and I, and has a predetermined X-ray diffraction pattern.
  • Patent Document 2 discloses a lithium ion secondary battery electrode in which a porous film containing an ionic liquid, an electrolyte, and cellulose is formed on a positive electrode or negative electrode.
  • Patent Literature 2 describes an effect that the permeation of the electrolyte into the entire battery can be promoted, and the time required for stabilization of the battery performance is shortened.
  • solid electrolytes used in non-aqueous electrolyte secondary batteries such as lithium-ion batteries are required to have high conductivity and transport number for ions involved in battery reactions. Solid electrolytes are also expected to improve battery performance by suppressing side reactions. However, conventional non-aqueous electrolyte secondary batteries using solid electrolytes have not yet achieved sufficient performance, and there is considerable room for improvement.
  • a solid electrolyte composition according to the present disclosure includes a first polymer having an acidic functional group having an alkali metal ion attached to its main chain, and a second polymer having an electron-donating polar group. Characterized by
  • a non-aqueous electrolyte secondary battery is a non-aqueous electrolyte secondary battery including an electrode and a non-aqueous electrolyte, wherein the film composed of the solid electrolyte composition is formed on the surface of the electrode and It is characterized by being formed on at least a part of the surface of the particles of the active material forming the electrode.
  • solid electrolyte composition according to the present disclosure, it is possible to provide a solid electrolyte having high ionic conductivity and transference number.
  • a non-aqueous electrolyte secondary battery in which the composition for a solid electrolyte according to the present disclosure is applied to a positive electrode or a negative electrode has, for example, less side reactions and excellent storage characteristics.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery according to a first embodiment
  • FIG. It is a figure which shows the particle
  • FIG. 4 is a cross-sectional view of a non-aqueous electrolyte secondary battery according to a second embodiment;
  • the present inventors have made intensive studies to develop a solid electrolyte that contributes to improving the performance of non-aqueous electrolyte secondary batteries.
  • a second polymer having an electron-donating polar group have high ionic conductivity and transference number for ions involved in battery reactions, such as lithium ions.
  • anions that serve as scaffolds for lithium ions are fixed to the main chain of the first polymer. Then, the lithium ions received from the first polymer move smoothly due to the segmental motion of the second polymer. Such a mechanism is thought to realize ionic conduction with a high transport number.
  • FIG. 1 is a diagram schematically showing an axial cross-section of a non-aqueous electrolyte secondary battery 10 of the first embodiment.
  • a non-aqueous electrolyte secondary battery 10 includes a wound electrode body 14, an electrolyte, and an outer can 16 that accommodates the electrode body 14 and the non-aqueous electrolyte.
  • the electrode body 14 has a positive electrode 11, a negative electrode 12, and a separator 13, and has a wound structure in which the positive electrode 11 and the negative electrode 12 are spirally wound with the separator 13 interposed therebetween.
  • the outer can 16 is a bottomed cylindrical metal container that is open at one end in the axial direction.
  • the side of the sealing member 17 of the battery will be referred to as the upper side
  • the bottom side of the outer can 16 will be referred to as the lower side.
  • the solid electrolyte composition is applied to the positive electrode 11 . Specifically, it is applied as the coating 32 formed on the particle surface of the lithium-containing composite oxide 31 constituting the positive electrode active material 30 . Due to the effect of the coating 32 of the solid electrolyte, the side reaction in the positive electrode 11 is sufficiently suppressed, and the oxidation current resulting from the side reaction can be effectively reduced.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents include esters, ethers, nitriles, amides, and mixed solvents of two or more thereof.
  • the non-aqueous solvent may contain a halogen-substituted product obtained by substituting at least part of the hydrogen atoms of these solvents with halogen atoms such as fluorine.
  • non-aqueous solvents include ethylene carbonate (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), mixed solvents thereof, and the like.
  • Lithium salts such as LiPF 6 are used, for example, as electrolyte salts.
  • the positive electrode 11, the negative electrode 12, and the separator 13, which constitute the electrode assembly 14, are all strip-shaped elongated bodies, and are alternately laminated in the radial direction of the electrode assembly 14 by being spirally wound.
  • the negative electrode 12 is formed with a size one size larger than that of the positive electrode 11 in order to prevent deposition of lithium. That is, the negative electrode 12 is formed longer than the positive electrode 11 in the longitudinal direction and the width direction (transverse direction).
  • the separator 13 is at least one size larger than the positive electrode 11 and, for example, two separators 13 are arranged so as to sandwich the positive electrode 11 .
  • 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.
  • the first embodiment exemplifies a cylindrical battery in which an electrode body 14 having a wound structure is housed in a cylindrical outer can 16 with a bottom. It may also be a laminated electrode body in which the electrodes are alternately laminated via the electrodes. Moreover, the shape of the battery is not limited to a cylindrical one, and may be a prismatic battery, a laminate battery, a coin-shaped battery, or the like.
  • the positive electrode 11 has a positive electrode core and a positive electrode mixture layer formed on the positive electrode core.
  • a foil of a metal such as aluminum or an aluminum alloy that is stable in the potential range of the positive electrode 11, a film having the metal on the surface layer, or the like can be used.
  • the positive electrode material mixture layer contains a positive electrode active material, a conductive agent, and a binder, and is preferably formed on both surfaces of the positive electrode core excluding the exposed portion to which the positive electrode lead 20 is welded.
  • a positive electrode slurry containing a positive electrode active material, a conductive agent, a binder, and the like is applied onto a positive electrode core, the coating is dried, and then compressed to form a positive electrode mixture layer on the positive electrode core.
  • a positive electrode slurry containing a positive electrode active material, a conductive agent, a binder, and the like is applied onto a positive electrode core, the coating is dried, and then compressed to form a positive electrode mixture layer on the positive electrode core.
  • Examples of the conductive agent contained in the positive electrode mixture layer include carbon black such as acetylene black and Ketjen black, graphite, carbon nanotubes (CNT), carbon nanofiber, and carbon materials such as graphene.
  • Examples of the binder contained in the positive electrode mixture layer include fluorine-containing resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimides, acrylic resins, and polyolefins. Further, these resins may be used in combination with carboxymethyl cellulose (CMC) or salts thereof, polyethylene oxide (PEO), and the like.
  • the negative electrode 12 has a negative electrode core and a negative electrode mixture layer formed on the negative electrode core.
  • a foil of a metal such as copper or a copper alloy that is stable in the potential range of the negative electrode 12, a film having the metal on the surface layer, or the like can be used.
  • the negative electrode mixture layer contains a negative electrode active material, a binder, and optionally a conductive agent, and is preferably formed on both surfaces of the negative electrode core excluding the exposed portion to which the negative electrode lead 21 is welded.
  • a negative electrode active material, a negative electrode slurry containing a binder, etc. is applied to the surface of the negative electrode core, the coating film is dried, and then compressed to form negative electrode mixture layers on both sides of the negative electrode core. It can be produced by
  • the negative electrode mixture layer generally contains a carbon material that reversibly absorbs and releases lithium ions as a negative electrode active material.
  • a carbon material is natural graphite such as flake graphite, massive graphite, and earthy graphite, artificial graphite such as massive artificial graphite (MAG), and graphitized mesophase carbon microbeads (MCMB).
  • an active material containing at least one of an element that alloys with Li, such as Si and Sn, and a material containing the element may be used as the negative electrode active material.
  • an active material containing at least one of an element that alloys with Li, such as Si and Sn, and a material containing the element may be used as the negative electrode active material.
  • a suitable example of the active material is a Si-containing material in which Si fine particles are dispersed in a SiO 2 phase, a silicate phase such as lithium silicate, or an amorphous carbon phase.
  • Graphite and a Si-containing material may be used in combination
  • the binder contained in the negative electrode mixture layer may be fluororesin, PAN, polyimide, acrylic resin, polyolefin, or the like, but preferably styrene-butadiene rubber (SBR). use.
  • the negative electrode mixture layer preferably contains CMC or its salt, polyacrylic acid (PAA) or its salt, polyvinyl alcohol (PVA), or the like. Among them, it is preferable to use SBR together with CMC or a salt thereof and PAA or a salt thereof.
  • the negative electrode mixture layer may contain a conductive agent such as CNT.
  • 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 a single layer structure or a multilayer structure.
  • a resin layer having high heat resistance such as aramid resin may be formed on the surface of the separator 13 .
  • a filler layer containing an inorganic filler may be formed at the interface between the separator 13 and at least one of the positive electrode 11 and the negative electrode 12 .
  • Insulating plates 18 and 19 are arranged above and below the electrode body 14, respectively.
  • the positive electrode lead 20 extends through the through hole of the insulating plate 18 toward the sealing member 17
  • the negative electrode lead 21 extends through the outside of the insulating plate 19 toward the bottom of the outer can 16 .
  • the positive electrode lead 20 is connected to the lower surface of the internal terminal plate 23 of the sealing body 17 by welding or the like, and the cap 27, which is the top plate of the sealing body 17 electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner surface of the bottom of the outer can 16 by welding or the like, and the outer can 16 serves as a negative electrode terminal.
  • a gasket 28 is provided between the outer can 16 and the sealing body 17 to ensure hermeticity inside the battery.
  • the outer can 16 is formed with a grooved portion 22 that supports the sealing member 17 and has a portion of the side surface projecting inward.
  • the grooved portion 22 is preferably annularly formed along the circumferential direction of the outer can 16 and supports the sealing member 17 on its upper surface.
  • the sealing member 17 is fixed to the upper portion of the outer can 16 by the grooved portion 22 and the open end of the outer can 16 that is crimped to the sealing member 17 .
  • the sealing body 17 has a structure in which an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are layered in order from the electrode body 14 side.
  • Each member constituting the sealing member 17 has, for example, a disk shape or a ring shape, and each member except for the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at their central portions, and an insulating member 25 is interposed between their peripheral edge portions.
  • the positive electrode active material 30, particularly the coating 32 formed on the particle surface of the positive electrode active material 30, and the solid electrolyte composition forming the coating 32 will be described in detail.
  • FIG. 2 is a diagram schematically showing a particle cross section of the positive electrode active material 30 contained in the mixture layer of the positive electrode 11.
  • the positive electrode active material 30 has particulate lithium-containing composite oxides 31 and coatings 32 formed on the particle surfaces of the lithium-containing composite oxides 31 .
  • Coating 32 is a coating of a solid electrolyte, and preferably covers substantially the entire particle surface of lithium-containing composite oxide 31 .
  • the lithium-containing composite oxide 31 has, for example, a layered crystal structure. Specific examples include a layered structure belonging to the space group R-3m or a layered structure belonging to the space group C2/m.
  • the lithium-containing composite oxide 31 may be secondary particles formed by aggregation of many primary particles.
  • the coating 32 is formed, for example, on the secondary particle surface of the lithium-containing composite oxide 31 .
  • the volume-based median diameter (D50) of the lithium-containing composite oxide 31 is, for example, 3 to 30 ⁇ m, preferably 5 to 25 ⁇ m.
  • the D50 of the composite oxide means the D50 of the secondary particles.
  • D50 means a particle size at which the cumulative frequency is 50% from the smaller particle size in the volume-based particle size distribution, and is also called median diameter.
  • the particle size distribution of the composite oxide can be measured using a laser diffraction particle size distribution analyzer (eg MT3000II manufactured by Microtrack Bell Co., Ltd.) using water as a dispersion medium.
  • the lithium-containing composite oxide 31 is a composite oxide containing metal elements such as Co, Mn, Ni, and Al in addition to Li.
  • Metal elements contained in the lithium-containing composite oxide 31 include, for example, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Sn , Sb, W, Pb, and Bi. Among them, it is preferable to contain at least one selected from Co, Ni, and Mn.
  • suitable composite oxides include composite oxides containing Ni, Co and Mn and composite oxides containing Ni, Co and Al.
  • the coating 32 is preferably composed of the solid electrolyte composition and preferably formed with a uniform thickness over the entire particle surface of the lithium-containing composite oxide 31 .
  • the thickness of the coating 32 is, for example, 5-200 nm, preferably 10-100 nm. If the thickness of the coating 32 is within this range, side reactions can be suppressed more effectively while ensuring smooth movement of lithium ions.
  • the thickness of the coating 32 is obtained by forming a particle cross section of the positive electrode active material 30 with a cross section polisher (CP) and observing the particle cross section with a scanning electron microscope (SEM).
  • the coating 32 is formed on the particle surface of the lithium-containing composite oxide 31 by, for example, spray-drying a raw material liquid in which the lithium-containing composite oxide 31 is dispersed and the solid electrolyte composition is dissolved. Detailed conditions for spray drying will be described later. As a method other than spray drying, there is a method of spraying the solution of the solid electrolyte composition onto the powder of the lithium-containing composite oxide 31, and the powder of the lithium-containing composite oxide 31 is added to the solution of the solid electrolyte composition. A method of immersion and the like can be mentioned.
  • the solid electrolyte composition forming the coating 32 includes a first polymer having an acidic functional group having alkali metal ions bonded to its main chain and a second polymer having an electron-donating polar group.
  • the solid electrolyte composition may contain components other than the first and second polymers within a range that does not impair the purpose of the present disclosure, but contains 50% by mass or more of the first and second polymers. is preferred.
  • the solid electrolyte composition may be substantially composed of only the first and second polymers.
  • the mixing ratio of the first polymer and the second polymer is determined, for example, by considering the molar ratio between the alkali metal ions of the first polymer and the electron-donating polar groups of the second polymer. be done.
  • two types of polymers are blended so that the molar ratio of alkali metal ions and polar groups is 1:5 to 1:100, preferably 1:10 to 1:50. In this case, the effect of improving the conductivity of metal ions becomes more pronounced.
  • Two types of polymers can be combined, for example, by mixing them in the form of an aqueous solution.
  • the first polymer may be any polymer containing an acidic functional group that captures alkali metal ions, and has a weight average molecular weight (Mw) of 500 or more.
  • Mw weight average molecular weight
  • a polymer means a molecule with an Mw of 500 or more, unless otherwise specified.
  • Mw is preferably 100,000 or more, more preferably 300,000 or more.
  • Alkali metal ions captured by the acidic functional groups may be sodium ions (Na + ), potassium ions (K + ), etc., but are preferably lithium ions (Li + ).
  • the main chain of the first polymer may have a molecular structure that is electrochemically stable and that can realize a composition that can be easily applied to the electrode surface and the active material particle surface.
  • main chains include polysaccharides such as polyethylene glycol, polyethylene oxide, polyvinyl alcohol, and cellulose. Among them, cellulose or derivatives thereof (for example, CMC, etc.) are preferred.
  • the main chain of the first polymer may be at least partially composed of cellulose or a derivative thereof, and substantially entirely composed of cellulose or a derivative thereof.
  • the acidic functional groups of the first polymer are anionic groups that pair with alkali metal ions such as Li + and are attached to the main chain. That is, since the anionic group is fixed to the main chain and does not move, high transport number alkali metal ion conduction can be achieved. Any acidic functional group can be used as long as it can bind to the main chain and trap alkali metal ions.
  • acidic functional groups include carboxylic acid groups, sulfonic acid groups, and phosphorous acid groups. Among them, a phosphite group is preferable from the viewpoint of flame retardancy and the like.
  • An example of a suitable first polymer is a polymer represented by the following formula 1 in which a phosphorous acid group that traps Li + is introduced into the main chain of cellulose.
  • (Formula 1) In the first polymer represented by formula 1, it is preferable that 20% to 60%, or 30% to 50% of the OH groups of the cellulose are substituted with phosphite groups.
  • the first polymer can be synthesized, for example, by introducing an acidic functional group into the main chain and exchanging the counter cation of the acidic functional group with an alkali metal ion.
  • an acid imidazolium salt imidazolium phosphate, etc.
  • the imidazolium cation is removed using an ion-exchange resin, and the counter cation of the acidic functional group is exchanged for a lithium ion by neutralizing the acidic polymer with lithium hydroxide or the like.
  • a detailed method for synthesizing the first polymer will be described later.
  • the second polymer may be any polymer containing an electron-donating polar group.
  • the molecular weight of the second polymer can be appropriately changed depending on the method of application to the battery and the like.
  • the second polymer receives alkali metal ions from the acidic functional groups of the first polymer and moves the ions by segmental motion of the molecules, as shown in FIG. 3 described later.
  • the solid electrolyte of this embodiment is considered to have high ionic conductivity.
  • the electron-donating polar group coordinates and captures the alkali metal ion.
  • the second polymer examples include polypropylene oxide, polyacrylonitrile, polyvinyl chloride, polyethylene glycol (PEG), and polyethylene oxide (PEO).
  • the second polymer preferably contains at least one of PEG and PEO, and may consist essentially of PEG or PEO.
  • PEG and PEO have similar molecular structures, but in general, PEG is defined as having an Mn of 20,000 or less, and PEO is defined as having an Mn of more than 20,000.
  • the molecular weight of PEG applied to the second polymer is, for example, Mn of 500-20,000.
  • the molecular weight of PEO is, for example, Mn of 30,000 to 5,000,000.
  • FIG. 3 is a diagram schematically showing a cross section of a main part of a non-aqueous electrolyte secondary battery according to a second embodiment.
  • the non-aqueous electrolyte secondary battery of the second embodiment includes a positive electrode 51, a negative electrode 52, and a solid electrolyte membrane 53.
  • the positive electrode 51 and the negative electrode 52 are arranged to face each other with the solid electrolyte membrane 53 interposed therebetween.
  • the solid electrolyte membrane 53 is a thin film made of the solid electrolyte composition, and has a thickness of, for example, about 10 to 20 ⁇ m.
  • the solid electrolyte membrane 53 is composed of a first polymer containing a counter anion (acidic functional group) fixed to its main chain, and a second polymer receiving and transferring alkali metal ions from the first polymer. , has high ionic conductivity and transference number.
  • the solid electrolyte membrane 53 is formed on the surface of the positive electrode 51 or the negative electrode 52, for example. That is, it is integrated with the positive electrode 51 or the negative electrode 52 .
  • a solid electrolyte film 53 (solid electrolyte layer) can be formed on the surface of the positive electrode 51 or the negative electrode 52 by applying a solution of the solid electrolyte composition to the surface of the positive electrode 51 or the negative electrode 52 and drying the coating film.
  • the solid electrolyte membrane 53 functions as an electrolyte having alkali metal ion conductivity, and also functions as a separator that prevents electrical contact between the positive electrode 51 and the negative electrode 52 .
  • the coating composed of the solid electrolyte composition according to the present disclosure is formed on the surface of the electrode and at least a part of the surface of the active material particles constituting the electrode, thereby forming a non-aqueous electrolyte secondary.
  • the coating may be formed on the electrode surface or the active material particle surface, or may be formed on both the electrode surface and the active material particle surface.
  • a coating may be formed on the electrode surface by disposing an active material having a coating on the particle surface on the electrode surface.
  • the composition for solid electrolyte may be formed into a film to form a single solid electrolyte film, which may be interposed between the positive electrode and the negative electrode.
  • reaction solution is diluted with water and purified with ultrapure water using a dialysis membrane (Slide-A-lyzer, MWCO: 20K, manufactured by Thermo Fisher).
  • MWCO dialysis membrane
  • IR124(H)-HG manufactured by Organo
  • An aqueous solution of lithium hydroxide is added to the acidified aqueous solution to neutralize it and lithify the end of the phosphite group.
  • aqueous solution is concentrated by an evaporator, and the concentrated solution is placed in a flat petri dish made of PFA and air-dried.
  • (9) Vacuum-dry the film obtained on the Petri dish at 100° C. to obtain lithium ion-containing phosphite cellulose.
  • (10) Lithium ion-containing phosphite cellulose and PEO with Mn of 300,000 were mixed so that the molar ratio of Li and EO was 1:20, and this was dissolved in water to form an aqueous solution (each may be prepared and mixed).
  • An aqueous solution of the solid electrolyte composition was obtained through the above steps.
  • the lithium-containing composite oxide As the lithium-containing composite oxide, a composite oxide represented by LiNi 0.5 Co 0.2 Mn 0.3 O 2 with a D50 of 6 ⁇ m was used. A lithium-containing composite oxide is added to the aqueous solution of the solid electrolyte composition so that the solid content concentration is 7.4% by mass, and dispersion treatment is performed with ultrasonic waves for 20 minutes to obtain a raw material solution for spray drying. got The raw material solution is supplied to a spray drying device (SD-1010, manufactured by Tokyo Rikakikai Co., Ltd.) and spray-dried under the following conditions to form a coating composed of the composition for a solid electrolyte of about 20 nm on the particle surface of the lithium-containing composite oxide. A positive electrode active material having a thickness of . (Spray drying conditions) Inlet temperature: about 160°C Outlet temperature: about 90°C Atomizing pressure: 100 kPa Blower air volume: 0.6 m 3 /min
  • NMP N-methyl-2-pyrrolidone
  • PVdF positive electrode active material
  • acetylene black at a mass ratio of 91.5:3.0:5.5 and stirred.
  • the positive electrode slurry is applied to the surface of the positive electrode core made of aluminum foil, and after the coating film is dried, it is rolled and coated on one side of the aluminum foil with a thickness of 40 to 43 ⁇ m and a density of 3.0 g/cm 3 .
  • a positive electrode having a positive electrode mixture layer formed thereon was produced.
  • LiPF 6 was added to a solvent obtained by mixing ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) at a volume ratio of 20:75:5 (25° C.) at a concentration of 1.3 mol/L. to prepare a non-aqueous electrolyte.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • test cell The positive electrode and the lithium metal negative electrode were arranged opposite to each other with a laminate of separator/non-woven fabric/separator interposed therebetween, and housed in an exterior body (UFO cell) made of SUS. Subsequently, the above non-aqueous electrolyte was injected into the exterior body, and the exterior body was sealed to obtain a test cell with a design capacity of 2.5 to 2.6 mAh.
  • Example 2 A test cell was prepared in the same manner as in Experimental Example 1, except that the solid electrolyte composition was not added to the raw material liquid supplied to the spray drying apparatus in the preparation of the positive electrode active material.
  • the test cell of Experimental Example 1 has a smaller accumulated amount of electricity in the trickle test than the test cell of Experimental Example 2. That is, it is considered that the use of the positive electrode active material having the solid electrolyte film suppresses the side reaction at the positive electrode, and as a result, the oxidation current derived from the side reaction is reduced.
  • Example 3 The lithium ion-containing phosphite cellulose synthesized in Experimental Example 1 and PEG having an Mn of 1000 were mixed so that the molar ratio of Li to EO was 1:20, and then dissolved in water to form an aqueous solution ( Each aqueous solution may be prepared and mixed), the aqueous solution was applied to a glass substrate, and the dried solid was molded into a film to obtain a solid electrolyte film having a thickness of 250 ⁇ m. A non-blocking electrode in which this solid electrolyte membrane was sandwiched between lithium metals was placed in a measurement cell, and the direct current resistance and the alternating current resistance were measured.
  • the solid electrolyte composition used in Experimental Example 3 has, for example, a practical level of ionic conductivity and Li + transference number as an electrode coating agent having a thickness of several tens of nanometers.
  • non-aqueous electrolyte secondary battery 11,51 positive electrode 12,52 negative electrode 13 separator 14 electrode body 16 outer can 17 sealing body 18,19 insulating plate 20 positive electrode lead 21 negative electrode lead 22 grooved portion , 23 internal terminal plate, 24 lower valve body, 25 insulating member, 26 upper valve body, 27 cap, 28 gasket, 30 positive electrode active material, 31 lithium-containing composite oxide, 32 coating, 53 solid electrolyte membrane

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01186767A (ja) * 1988-01-18 1989-07-26 Tokuyama Soda Co Ltd 電池
JP2011228114A (ja) 2010-04-20 2011-11-10 Konica Minolta Holdings Inc 二次電池用電極、その製造方法及び二次電池
JP2016222780A (ja) * 2015-05-28 2016-12-28 公立大学法人兵庫県立大学 プロトン伝導性高分子ゲル電解質
JP2019059912A (ja) * 2017-06-28 2019-04-18 フンダシオン セントロ デ インベスティガシオン コオペラティバ デ エネルヒアス アルテルナティバス セイセ エネルヒグネ フンダツィオアＦｕｎｄａｃｉｏｎ Ｃｅｎｔｒｏ Ｄｅ Ｉｎｖｅｓｔｉｇａｃｉｏｎ Ｃｏｏｐｅｒａｔｉｖａ Ｄｅ Ｅｎｅｒｇｉａｓ Ａｌｔｅｒｎａｔｉｖａｓ Ｃｉｃ Ｅｎｅｒｇｉｇｕｎｅ Ｆｕｎｄａｚｉｏａ 改質セルロースをベースとする固体ポリマー電解質、及びリチウム又はナトリウム二次電池におけるその使用
JP2020109047A (ja) 2018-12-28 2020-07-16 パナソニックＩｐマネジメント株式会社 固体電解質材料、およびそれを用いた電池

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
JP7395132B2 (ja) * 2019-09-27 2023-12-11 愛媛県 水性塗料と陶磁器類と絵付け方法
EP4270525A4 (en) * 2020-12-28 2025-02-19 Panasonic Intellectual Property Management Co., Ltd. ALKALI METAL ION CONDUCTING SOLID ELECTROLYTE, MANUFACTURING METHOD THEREFOR, SEPARATOR FOR SECONDARY BATTERIES WITH ANHYDROUS ELECTROLYTE, METHOD FOR MANUFACTURING

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01186767A (ja) * 1988-01-18 1989-07-26 Tokuyama Soda Co Ltd 電池
JP2011228114A (ja) 2010-04-20 2011-11-10 Konica Minolta Holdings Inc 二次電池用電極、その製造方法及び二次電池
JP2016222780A (ja) * 2015-05-28 2016-12-28 公立大学法人兵庫県立大学 プロトン伝導性高分子ゲル電解質
JP2019059912A (ja) * 2017-06-28 2019-04-18 フンダシオン セントロ デ インベスティガシオン コオペラティバ デ エネルヒアス アルテルナティバス セイセ エネルヒグネ フンダツィオアＦｕｎｄａｃｉｏｎ Ｃｅｎｔｒｏ Ｄｅ Ｉｎｖｅｓｔｉｇａｃｉｏｎ Ｃｏｏｐｅｒａｔｉｖａ Ｄｅ Ｅｎｅｒｇｉａｓ Ａｌｔｅｒｎａｔｉｖａｓ Ｃｉｃ Ｅｎｅｒｇｉｇｕｎｅ Ｆｕｎｄａｚｉｏａ 改質セルロースをベースとする固体ポリマー電解質、及びリチウム又はナトリウム二次電池におけるその使用
JP2020109047A (ja) 2018-12-28 2020-07-16 パナソニックＩｐマネジメント株式会社 固体電解質材料、およびそれを用いた電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4489029A4

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