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WO2019208110A1 - Composition de bouillie électrolytique, procédé de production de feuille d'électrolyte et procédé de production de batterie secondaire - Google Patents

Composition de bouillie électrolytique, procédé de production de feuille d'électrolyte et procédé de production de batterie secondaire Download PDF

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Publication number
WO2019208110A1
WO2019208110A1 PCT/JP2019/014214 JP2019014214W WO2019208110A1 WO 2019208110 A1 WO2019208110 A1 WO 2019208110A1 JP 2019014214 W JP2019014214 W JP 2019014214W WO 2019208110 A1 WO2019208110 A1 WO 2019208110A1
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Prior art keywords
electrolyte
slurry composition
positive electrode
negative electrode
mass
Prior art date
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PCT/JP2019/014214
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English (en)
Japanese (ja)
Inventor
紘揮 三國
みゆき 室町
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to JP2020516150A priority Critical patent/JP7423120B2/ja
Publication of WO2019208110A1 publication Critical patent/WO2019208110A1/fr
Anticipated expiration legal-status Critical
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an electrolyte slurry composition, a method for producing an electrolyte sheet, and a method for producing a secondary battery.
  • lithium secondary batteries have been attracting attention as power sources for electric vehicle batteries, power storage batteries, and the like because of their high energy density.
  • lithium secondary batteries as batteries for electric vehicles include zero-emission electric vehicles that are not equipped with engines, hybrid electric vehicles that are equipped with both engines and secondary batteries, and plug-in hybrids that are charged directly from the power system. It is used in electric vehicles such as electric vehicles.
  • lithium secondary batteries as power storage batteries are used in stationary power storage systems that supply power stored in advance in an emergency when the power system is shut off.
  • an electrolyte layer formed from an electrolyte is required to have improved mechanical strength from the viewpoint of reducing the weight and thickness of a lithium secondary battery.
  • the electrolyte layer formed from the gel electrolyte is not sufficient in terms of strength, and there is still room for improvement.
  • the main object of the present invention is to provide an electrolyte slurry composition capable of forming an electrolyte layer having excellent strength.
  • At least one electrolyte salt selected from the group consisting of one or more polymers, oxide particles, lithium salt, sodium salt, calcium salt, and magnesium salt It contains at least one of a compound represented by the following general formula (10) (hereinafter sometimes referred to as “glyme”) and an ionic liquid, and an organic solvent, and the organic solvent has a heating rate of 5 ° C./min.
  • the electrolyte slurry composition has a temperature that causes a mass reduction rate of 95% when heated at (hereinafter, sometimes simply referred to as “mass reduction rate 95% temperature”) of 120 ° C. or less.
  • R A O— (CH 2 CH 2 O) y —R B (10) [In the formula (10), R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms, and y represents an integer of 1 to 6. ]
  • the oxide particles are preferably at least one selected from the group consisting of SiO 2 , Al 2 O 3 , AlOOH, MgO, CaO, ZrO 2 , TiO 2 , Li 7 La 3 Zr 2 O 12 , and BaTiO 3 . Particles.
  • the ionic liquid preferably contains at least one selected from the group consisting of a chain quaternary onium cation, a piperidinium cation, a pyrrolidinium cation, a pyridinium cation, and an imidazolium cation as a cation component.
  • the ionic liquid preferably contains at least one anion component represented by the following general formula (A) as an anion component.
  • A (SO 2 C m F 2m + 1 ) (SO 2 C n F 2n + 1 ) ⁇ (A)
  • m and n each independently represents an integer of 0 to 5.
  • the polymer preferably has a first structural unit selected from the group consisting of ethylene tetrafluoride and vinylidene fluoride.
  • the polymer is preferably a structural unit constituting the polymer, the first structural unit, and a second structural unit selected from the group consisting of hexafluoropropylene, acrylic acid, maleic acid, ethyl methacrylate, and methyl methacrylate. Is included.
  • the electrolyte salt is preferably an imide lithium salt.
  • the compound represented by the general formula (10) preferably contains tetraethylene glycol dimethyl ether.
  • the second aspect of the present invention includes a step of disposing the above-described electrolyte slurry composition on a substrate, a step of removing an organic solvent from the disposed electrolyte slurry composition, and forming an electrolyte layer on the substrate.
  • a method for producing an electrolyte sheet includes a step of disposing the above-described electrolyte slurry composition on a substrate, a step of removing an organic solvent from the disposed electrolyte slurry composition, and forming an electrolyte layer on the substrate.
  • the third aspect of the present invention includes a step of obtaining a positive electrode by forming a positive electrode mixture layer on a positive electrode current collector, a step of obtaining a negative electrode by forming a negative electrode mixture layer on the negative electrode current collector, And a step of disposing an electrolyte layer of an electrolyte sheet obtained by the manufacturing method described above between a positive electrode and a negative electrode.
  • an electrolyte slurry composition capable of forming an electrolyte layer having excellent strength can be provided.
  • the manufacturing method of the electrolyte sheet using such an electrolyte slurry composition can be provided.
  • the manufacturing method of a secondary battery using the electrolyte sheet manufactured from an electrolyte slurry composition can be provided.
  • FIG. 1 is a perspective view showing a secondary battery according to a first embodiment. It is a disassembled perspective view which shows one Embodiment of the electrode group in the secondary battery shown in FIG.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment of an electrode group in the secondary battery shown in FIG. 1.
  • A) is a schematic cross section which shows the electrolyte sheet which concerns on one Embodiment
  • (b) is a schematic cross section which shows the electrolyte sheet which concerns on other embodiment.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value described in another stepwise description.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • FIG. 1 is a perspective view showing the secondary battery according to the first embodiment.
  • the secondary battery 1 includes an electrode group 2 composed of a positive electrode, a negative electrode, and an electrolyte layer, and a bag-shaped battery outer package 3 that houses the electrode group 2.
  • a positive electrode current collecting tab 4 and a negative electrode current collecting tab 5 are provided on the positive electrode and the negative electrode, respectively.
  • the positive electrode current collecting tab 4 and the negative electrode current collecting tab 5 protrude from the inside of the battery outer package 3 to the outside so that the positive electrode and the negative electrode can be electrically connected to the outside of the secondary battery 1, respectively.
  • the battery outer package 3 may be formed of, for example, a laminate film.
  • the laminate film may be a laminate film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper, and stainless steel, and a sealant layer such as polypropylene are laminated in this order.
  • PET polyethylene terephthalate
  • metal foil such as aluminum, copper, and stainless steel
  • sealant layer such as polypropylene
  • FIG. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the secondary battery 1 shown in FIG.
  • FIG. 3 is a schematic cross-sectional view showing an embodiment of the electrode group 2 in the secondary battery 1 shown in FIG.
  • the electrode group 2 ⁇ / b> A includes a positive electrode 6, an electrolyte layer 7, and a negative electrode 8 in this order.
  • the positive electrode 6 includes a positive electrode current collector 9 and a positive electrode mixture layer 10 provided on the positive electrode current collector 9.
  • the positive electrode current collector 9 is provided with a positive electrode current collector tab 4.
  • the negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12 provided on the negative electrode current collector 11.
  • the negative electrode current collector 11 is provided with a negative electrode current collector tab 5.
  • the positive electrode current collector 9 may be formed of aluminum, stainless steel, titanium, or the like. Specifically, the positive electrode current collector 9 may be, for example, an aluminum perforated foil having a hole diameter of 0.1 to 10 mm, an expanded metal, a foamed metal plate, or the like. In addition to the above, the positive electrode current collector 9 may be formed of any material as long as it does not cause changes such as dissolution and oxidation during use of the battery, and its shape, manufacturing method, etc. Not limited.
  • the thickness of the positive electrode current collector 9 may be 10 ⁇ m or more and 100 ⁇ m or less, and is preferably 10 ⁇ m or more and 50 ⁇ m or less from the viewpoint of reducing the volume of the entire positive electrode, and the positive electrode current collector 9 has a small curvature when forming a battery. From the viewpoint of turning, it is more preferably 10 ⁇ m or more and 20 ⁇ m or less.
  • the positive electrode mixture layer 10 contains a positive electrode active material, a conductive agent, and a binder.
  • the positive electrode active material may be a lithium transition metal compound such as a lithium transition metal oxide or a lithium transition metal phosphate.
  • the lithium transition metal oxide may be, for example, lithium manganate, lithium nickelate, lithium cobaltate, or the like.
  • Lithium transition metal oxide is a part of transition metals such as Mn, Ni, Co, etc. contained in lithium manganate, lithium nickelate, lithium cobaltate, etc., one or more other transition metals, or A lithium transition metal oxide substituted with a metal element (typical element) such as Mg or Al may also be used. That is, the lithium transition metal oxide may be a compound represented by LiM 1 O 2 or LiM 1 2 O 4 (M 1 includes at least one transition metal).
  • lithium transition metal oxides are Li (Co 1/3 Ni 1/3 Mn 1/3 ) O 2 , LiNi 1/2 Mn 1/2 O 2 , LiNi 1/2 Mn 3/2 O. It may be 4 mag.
  • the lithium transition metal oxide is preferably a compound represented by the following formula (1).
  • Lithium transition metal phosphates are LiFePO 4 , LiMnPO 4 , LiMn x M 3 1-x PO 4 (0.3 ⁇ x ⁇ 1, M 3 is Fe, Ni, Co, Ti, Cu, Zn, Mg, and Or at least one element selected from the group consisting of Zr).
  • the positive electrode active material may be primary particles that are not granulated, or may be secondary particles that are granulated.
  • the particle diameter of the positive electrode active material is adjusted to be equal to or less than the thickness of the positive electrode mixture layer 10.
  • the coarse particles are removed in advance by sieving classification, wind classification, etc.
  • a positive electrode active material having a diameter is selected.
  • the average particle diameter of the positive electrode active material is 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. Moreover, Preferably it is 30 micrometers or less, More preferably, it is 25 micrometers or less.
  • the average particle diameter of the positive electrode active material is the particle diameter (D50) when the ratio (volume fraction) to the volume of the entire positive electrode active material is 50%.
  • the average particle diameter (D50) of the positive electrode active material is obtained by measuring a suspension obtained by suspending the positive electrode active material in water by a laser scattering method using a laser scattering particle size measuring device (for example, Microtrac). It is obtained with.
  • the content of the positive electrode active material may be 70% by mass or more, 80% by mass or more, or 85% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the positive electrode active material may be 95% by mass or less, 92% by mass or less, or 90% by mass or less based on the total amount of the positive electrode mixture layer.
  • the conductive agent is not particularly limited, and may be a carbon material such as graphite, acetylene black, carbon black, carbon fiber, and carbon nanotube.
  • the conductive agent may be a mixture of two or more carbon materials described above.
  • the content of the conductive agent may be 0.1% by mass or more, 1% by mass or more, or 3% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the conductive agent is preferably 15% by mass or less, more preferably, based on the total amount of the positive electrode mixture layer, from the viewpoint of suppressing the increase in the volume of the positive electrode 6 and the accompanying decrease in the energy density of the secondary battery 1. It is 10 mass% or less, More preferably, it is 8 mass% or less.
  • the binder is not limited as long as it does not decompose on the surface of the positive electrode 6, but selected from the group consisting of ethylene tetrafluoride, vinylidene fluoride, hexafluoropropylene, acrylic acid, maleic acid, ethyl methacrylate, and methyl methacrylate. It may be a polymer containing at least one of these as a monomer unit, rubber such as styrene-butadiene rubber, isoprene rubber, acrylic rubber, and the like.
  • the binder is preferably a copolymer containing ethylene tetrafluoride and vinylidene fluoride as structural units.
  • the content of the binder may be 0.5% by mass or more, 1% by mass or more, or 3% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the binder may be 20% by mass or less, 15% by mass or less, or 10% by mass or less based on the total amount of the positive electrode mixture layer.
  • the positive electrode mixture layer 10 may further contain an ionic liquid.
  • an ionic liquid used in an electrolyte slurry composition described later can be used.
  • the content of the ionic liquid contained in the positive electrode mixture layer 10 is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the ionic liquid contained in the positive electrode mixture layer 10 is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the total amount of the positive electrode mixture layer.
  • An electrolyte salt may be dissolved in the ionic liquid contained in the positive electrode mixture layer 10.
  • an electrolyte salt used in an electrolyte slurry composition described later can be used.
  • the thickness of the positive electrode mixture layer 10 is a thickness that is equal to or greater than the average particle diameter of the positive electrode active material, specifically, 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more. Good.
  • the thickness of the positive electrode mixture layer 10 may be 100 ⁇ m or less, 80 ⁇ m or less, or 70 ⁇ m or less.
  • the negative electrode current collector 11 may be a metal such as aluminum, copper, nickel, stainless steel, or an alloy thereof. Since the negative electrode current collector 11 is light and has a high weight energy density, it is preferably aluminum or an alloy thereof. The negative electrode current collector 11 is preferably copper from the viewpoint of ease of processing into a thin film and cost.
  • the thickness of the negative electrode current collector 11 may be 10 ⁇ m or more and 100 ⁇ m or less, and is preferably 10 ⁇ m or more and 50 ⁇ m or less from the viewpoint of reducing the volume of the entire negative electrode, and the negative electrode current collector 11 has a small curvature when forming a battery. From the viewpoint of turning, it is more preferably 10 ⁇ m or more and 20 ⁇ m or less.
  • the negative electrode mixture layer 12 contains a negative electrode active material and a binder.
  • the negative electrode active material those commonly used in the field of energy devices can be used.
  • the negative electrode active material include metal lithium, lithium titanate (Li 4 Ti 5 O 12 ), a lithium alloy or other metal compound, a carbon material, a metal complex, and an organic polymer compound.
  • the negative electrode active material may be one of these alone or a mixture of two or more.
  • Carbon materials include natural graphite (flaky graphite, etc.), graphite such as artificial graphite, amorphous carbon, carbon fiber, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black And carbon black. From the viewpoint of obtaining a larger theoretical capacity (for example, 500 to 1500 Ah / kg), the negative electrode active material may be silicon, tin, or a compound containing these elements (oxide, nitride, alloy with other metals). Good.
  • the average particle diameter (D 50 ) of the negative electrode active material is preferably 1 ⁇ m or more from the viewpoint of obtaining a well-balanced negative electrode that suppresses an increase in irreversible capacity associated with a decrease in particle diameter and has enhanced electrolyte salt retention ability. More preferably, it is 5 ⁇ m or more, more preferably 10 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the average particle diameter (D 50 ) of the negative electrode active material is measured by the same method as the average particle diameter (D 50 ) of the positive electrode active material described above.
  • the content of the negative electrode active material may be 60% by mass or more, 65% by mass or more, or 70% by mass or more based on the total amount of the negative electrode mixture layer.
  • the content of the negative electrode active material may be 99% by mass or less, 95% by mass or less, or 90% by mass or less based on the total amount of the negative electrode mixture layer.
  • the binder and its content may be the same as the binder and its content in the positive electrode mixture layer 10 described above.
  • the negative electrode mixture layer 12 may further contain a conductive agent from the viewpoint of further reducing the resistance of the negative electrode 8.
  • the conductive agent and its content may be the same as the conductive agent and its content in the positive electrode mixture layer 10 described above.
  • the negative electrode mixture layer 12 may further contain an ionic liquid.
  • an ionic liquid used in an electrolyte slurry composition described later can be used.
  • the content of the ionic liquid contained in the negative electrode mixture layer 12 is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more based on the total amount of the negative electrode mixture layer.
  • the content of the ionic liquid contained in the negative electrode mixture layer 12 is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the total amount of the negative electrode mixture layer.
  • an electrolyte salt similar to the electrolyte salt that can be used for the positive electrode mixture layer 10 described above may be dissolved.
  • the thickness of the negative electrode mixture layer 12 may be 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more.
  • the thickness of the negative electrode mixture layer 12 may be 100 ⁇ m or less, 80 ⁇ m or less, or 70 ⁇ m or less.
  • the electrolyte layer 7 is formed by producing an electrolyte sheet using an electrolyte slurry composition on a substrate.
  • the electrolyte slurry composition includes one or more polymers, oxide particles, at least one electrolyte salt selected from the group consisting of lithium salts, sodium salts, calcium salts, and magnesium salts, and a general formula (10 ) And at least one of an ionic liquid and an organic solvent.
  • the temperature at which the organic solvent has a mass reduction rate of 95% when heated at a heating rate of 5 ° C./min is 120 ° C. or lower.
  • the electrolyte slurry composition contains one or more polymers.
  • the polymer preferably has a first structural unit selected from the group consisting of ethylene tetrafluoride and vinylidene fluoride.
  • the structural unit constituting the polymer includes the first structural unit and a second structural unit selected from the group consisting of hexafluoropropylene, acrylic acid, maleic acid, ethyl methacrylate, and methyl methacrylate. It may be. That is, the first structural unit and the second structural unit may be included in one kind of polymer to form a copolymer, and each of the first structural unit and the second structural unit may be included in another polymer and have the first structural unit. And at least two types of polymers, the second polymer having the second structural unit.
  • the polymer may be polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, or the like.
  • the content of the polymer is preferably 3% by mass or more based on the total amount of components excluding the organic solvent of the electrolyte slurry composition.
  • the content of the polymer is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total amount of components excluding the organic solvent of the electrolyte slurry composition.
  • the content of the polymer is preferably 3 to 50% by mass, more preferably 3 to 40% by mass, based on the total amount of components excluding the organic solvent of the electrolyte slurry composition.
  • the polymer according to the present embodiment is excellent in affinity with the ionic liquid contained in the electrolyte slurry composition, the electrolyte in the glyme or ionic liquid is retained when the electrolyte layer 7 is formed. Thereby, the leakage of the glyme or ionic liquid when a load is applied to the electrolyte layer 7 is suppressed.
  • the electrolyte slurry composition contains oxide particles.
  • the oxide particles are, for example, inorganic oxide particles.
  • the inorganic oxide is an inorganic oxide containing, for example, Li, Mg, Al, Si, Ca, Ti, Zr, La, Na, K, Ba, Sr, V, Nb, B, Ge and the like as constituent elements. Good.
  • the oxide particles are preferably at least one selected from the group consisting of SiO 2 , Al 2 O 3 , AlOOH, MgO, CaO, ZrO 2 , TiO 2 , Li 7 La 3 Zr 2 O 12 , and BaTiO 3 . Particles. Since the oxide particles have polarity, it is possible to promote dissociation of the electrolyte in the electrolyte layer 7 and improve battery characteristics.
  • oxide particles are classified into primary particles (particles that do not constitute secondary particles) integrally forming a single particle and a plurality of primary particles as judged from an apparent geometric form. Secondary particles formed by agglomeration.
  • the specific surface area of the oxide particles is 2 to 380 m 2 / g, and may be 5 to 100 m 2 / g, 10 to 80 m 2 / g, or 15 to 60 m 2 / g.
  • the specific surface area of the oxide particles may be 5 m 2 / g or more, 10 m 2 / g or more, or 15 m 2 / g or more, 100 m 2 / g or less, 80 m 2 / g or less, or It may be 60 m 2 / g or less.
  • the specific surface area of the oxide particles means the specific surface area of the whole oxide particles including primary particles and secondary particles, and is measured by the BET method.
  • the average primary particle size of the oxide particles is preferably 0.005 ⁇ m (5 nm) or more, more preferably 0.01 ⁇ m (10 nm) or more from the viewpoint of further improving the electrical conductivity. More preferably 0.015 ⁇ m (15 nm) or more. From the viewpoint of making the electrolyte layer 7 thin, the average primary particle size of the oxide particles is preferably 1 ⁇ m or less, more preferably 0.1 ⁇ m or less, and even more preferably 0.05 ⁇ m or less.
  • the average primary particle diameter of the oxide particles is preferably 0.005 to 1 ⁇ m, 0.01 to 0.01% from the viewpoint of thinning the electrolyte layer 7 and suppressing the protrusion of the oxide particles from the surface of the electrolyte layer 7. 0.1 ⁇ m, or 0.015 to 0.05 ⁇ m.
  • the average primary particle size of the oxide particles can be measured by observing the oxide particles with a transmission electron microscope or the like.
  • the average particle diameter of the oxide particles is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and further preferably 0.03 ⁇ m or more.
  • the average particle diameter of the oxide particles is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 1 ⁇ m or less.
  • the average particle diameter of the oxide particles is measured by a laser diffraction method, and corresponds to the particle diameter at which the volume accumulation is 50% when the volume accumulation particle size distribution curve is drawn from the small particle diameter side.
  • the shape of the oxide particles may be, for example, a block shape or a substantially spherical shape.
  • the aspect ratio of the oxide particles is preferably 10 or less, more preferably 5 or less, and even more preferably 2 or less, from the viewpoint of facilitating thinning of the electrolyte layer 7.
  • the aspect ratio is calculated from the scanning electron micrograph of the oxide particles.
  • the length of the particles in the long axis direction (maximum length of the particles) and the length of the particles in the short axis direction (minimum length of the particles) Defined as the ratio of The length of the particles is obtained by statistically calculating the above photograph using a commercially available image processing ft (for example, image analysis software manufactured by Asahi Kasei Engineering Co., Ltd., Image A (registered trademark)).
  • the oxide particles may be surface-treated with a surface treatment agent.
  • the surface treatment agent include silicon-containing compounds. Silicon-containing compounds are methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydiphenylsilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyl Alkoxysilanes such as diethoxysilane and n-propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Epoxy group-containing silanes such as 3-glycidoxypropylmethyldiethoxysilane
  • oxide particles surface-treated with the surface treatment agent those produced by a known method may be used, or commercially available products may be used as they are.
  • the content of the oxide particles is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably, based on the total amount of components excluding the organic solvent of the electrolyte slurry composition. It is 20% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
  • the electrolyte slurry composition contains an electrolyte salt.
  • the electrolyte salt is at least one selected from the group consisting of a lithium salt, a sodium salt, a calcium salt, and a magnesium salt.
  • the electrolyte salt is a compound used to exchange cations between the positive electrode 6 and the negative electrode 8.
  • the above electrolyte salt is preferable in that it has a low degree of dissociation at a low temperature and easily diffuses in glyme or ionic liquid, and does not thermally decompose at a high temperature, so that the environmental temperature at which the secondary battery can be used is wide.
  • the electrolyte salt may be an electrolyte salt used in a fluorine ion battery.
  • the anion component of the electrolyte salt includes halide ions (I ⁇ , Cl ⁇ , Br ⁇ etc.), SCN ⁇ , BF 4 ⁇ , BF 3 (CF 3 ) ⁇ , BF 3 (C 2 F 5 ) ⁇ , PF 6 ⁇ .
  • the anion component of the electrolyte salt is preferably an anion represented by the formula (A) exemplified by anion components of the ionic liquid described later such as N (SO 2 F) 2 ⁇ , N (SO 2 CF 3 ) 2 —, etc.
  • the component is PF 6 ⁇ , BF 4 ⁇ , B (O 2 C 2 O 2 ) 2 ⁇ , or ClO 4 ⁇ .
  • [FSI] ⁇ N (SO 2 F) 2 ⁇ , bis (fluorosulfonyl) imide anion [TFSI] ⁇ : N (SO 2 CF 3 ) 2 ⁇ , bis (trifluoromethanesulfonyl) imide anion [BOB] ⁇ : B (O 2 C 2 O 2 ) 2 ⁇ , bisoxalate borate anion [f3C] ⁇ : C (SO 2 F) 3 ⁇ , tris (fluorosulfonyl) carbanion
  • Lithium salts include LiPF 6 , LiBF 4 , Li [FSI], Li [TFSI], Li [f 3 C], Li [BOB], LiClO 4 , LiBF 3 (CF 3 ), LiBF 3 (C 2 F 5 ), LiBF 3 (C 3 F 7 ), LiBF 3 (C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , CF 3 SO 2 OLi, CF 3 COOLi, and R′COOLi (R ′ has 1 to 4 carbon atoms) An alkyl group, a phenyl group, or a naphthyl group).
  • Sodium salts include NaPF 6 , NaBF 4 , Na [FSI], Na [TFSI], Na [f 3 C], Na [BOB], NaClO 4 , NaBF 3 (CF 3 ), NaBF 3 (C 2 F 5 ), NaBF 3 (C 3 F 7 ), NaBF 3 (C 4 F 9 ), NaC (SO 2 CF 3 ) 3 , CF 3 SO 2 ONa, CF 3 COONa, and R′COONa (R ′ has 1 to 4 carbon atoms) An alkyl group, a phenyl group, or a naphthyl group).
  • the calcium salts are Ca (PF 6 ) 2 , Ca (BF 4 ) 2 , Ca [FSI] 2 , Ca [TFSI] 2 , Ca [f3C] 2 , Ca [BOB] 2 , Ca (ClO 4 ) 2 , Ca [BF 3 (CF 3 )] 2 , Ca [BF 3 (C 2 F 5 )] 2 , Ca [BF 3 (C 3 F 7 )] 2 , Ca [BF 3 (C 4 F 9 )] 2 , Ca [C (SO 2 CF 3 ) 3 ] 2 , (CF 3 SO 2 O) 2 Ca, (CF 3 COO) 2 Ca, and (R′COO) 2 Ca (R ′ is an alkyl having 1 to 4 carbon atoms) A group, a phenyl group, or a naphthyl group).
  • Magnesium salts are Mg (PF 6 ) 2 , Mg (BF 4 ) 2 , Mg [FSI] 2 , Mg [TFSI] 2 , Mg [f 3 C] 2 , Mg [BOB] 2 , Na (ClO 4 ) 2 , Mg [BF 3 (CF 3 )] 2 , Mg [BF 3 (C 2 F 5 )] 2 , Mg [BF 3 (C 3 F 7 )] 2 , Mg [BF 3 (C 4 F 9 )] 2 , Mg [C (SO 2 CF 3 ) 3 ] 2 , (CF 3 SO 3 ) 2 Mg, (CF 3 COO) 2 Mg, and (R′COO) 2 Mg (R ′ is an alkyl group having 1 to 4 carbon atoms. , A phenyl group, or a naphthyl group).
  • the electrolyte salt is preferably one selected from the group consisting of an imide lithium salt, an imide sodium salt, an imide calcium salt, and an imide magnesium salt, and more preferably an imide lithium salt.
  • the imide-based lithium salt may be Li [TFSI], Li [FSI], or the like.
  • the imide-based sodium salt may be Na [TFSI], Na [FSI] or the like.
  • the imide-based calcium salt may be Ca [TFSI] 2 , Ca [FSI] 2 or the like.
  • the imide-based magnesium salt may be Mg [TFSI] 2 , Mg [FSI] 2 or the like.
  • the electrolyte slurry composition contains at least one of a compound (glyme) represented by the general formula (10) and an ionic liquid. Glyme and ionic liquid are not included in the organic solvent.
  • the electrolyte slurry composition preferably contains an ionic liquid from the viewpoints of ionic conductivity and discharge characteristics.
  • Glyme is a compound represented by the general formula (10).
  • R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms, and y represents an integer of 1 to 6.
  • the alkyl group as R A and R B may be a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group or the like.
  • the alkyl group is preferably a methyl group or an ethyl group.
  • glyme examples include triethylene glycol dimethyl ether (sometimes referred to as “triglyme” or “G3”), tetraethylene glycol dimethyl ether (sometimes referred to as “tetraglyme” or “G4”), pentaethylene glycol dimethyl ether (“penta”). And may be referred to as “glyme” or “G5”), hexaethylene glycol dimethyl ether (sometimes referred to as “hexalime” or “G6”), and the like. You may use these individually by 1 type or in combination of 2 or more types. Among these, glyme is preferably triglyme or tetraglyme, more preferably tetraglyme. These glymes tend to have a temperature at which the mass reduction rate becomes 95% when the temperature is raised at a temperature elevation rate of 5 ° C./min (mass reduction rate 95% temperature) exceeds 120 ° C.
  • the ionic liquid contains the following anion component and cation component.
  • the ionic liquid in the present embodiment is a liquid material at ⁇ 20 ° C. or higher. It is known that an ionic liquid has almost no vapor pressure unlike molecular liquids such as water and organic solvents due to a strong electrostatic interaction that acts between constituent cations and anions. Therefore, the temperature at which the ionic liquid has a mass reduction rate of 95% when heated at a temperature rising rate of 5 ° C./min tends to exceed 120 ° C.
  • the anion component of the ionic liquid is not particularly limited, but is an anion of a halogen such as Cl ⁇ , Br ⁇ and I ⁇ , an inorganic anion such as BF 4 ⁇ and N (SO 2 F) 2 — , B (C 6 H 5 ) 4 ⁇ , CH 3 SO 2 O ⁇ , CF 3 SO 2 O ⁇ , N (SO 2 C 4 F 9 ) 2 ⁇ , N (SO 2 CF 3 ) 2 ⁇ , N (SO 2 C 2 F 5 ) 2 ⁇ Or an organic anion.
  • a halogen such as Cl ⁇ , Br ⁇ and I ⁇
  • an inorganic anion such as BF 4 ⁇ and N (SO 2 F) 2 — , B (C 6 H 5 ) 4 ⁇ , CH 3 SO 2 O ⁇ , CF 3 SO 2 O ⁇ , N (SO 2 C 4 F 9 ) 2 ⁇ , N (SO 2 CF 3 ) 2 ⁇
  • the anionic component of the ionic liquid preferably contains at least one anionic component represented by the following general formula (A). N (SO 2 C m F 2m + 1 ) (SO 2 C n F 2n + 1 ) ⁇ (A)
  • m and n each independently represents an integer of 0 to 5.
  • m and n may be the same as or different from each other, and are preferably the same as each other.
  • Examples of the anion component represented by the formula (A) include N (SO 2 C 4 F 9 ) 2 ⁇ , N (SO 2 F) 2 ⁇ , N (SO 2 CF 3 ) 2 ⁇ , and N (SO 2 C 2 F 5 ) 2 — .
  • the anionic component of the ionic liquid is more preferably N (SO 2 C 4 F 9 ) 2 ⁇ , CF 3 SO from the viewpoint of further improving the ionic conductivity with a relatively low viscosity and further improving the charge / discharge characteristics.
  • the cation component of the ionic liquid is not particularly limited, but is preferably at least one selected from the group consisting of a chain quaternary onium cation, a piperidinium cation, a pyrrolidinium cation, a pyridinium cation, and an imidazolium cation.
  • the chain quaternary onium cation is, for example, a compound represented by the following general formula (2).
  • R 1 to R 4 each independently represents a chain alkyl group having 1 to 20 carbon atoms, or a chain alkoxyalkyl group represented by R—O— (CH 2 ) n —.
  • R represents a methyl group or an ethyl group, and n represents an integer of 1 to 4
  • X represents a nitrogen atom or a phosphorus atom.
  • the number of carbon atoms of the alkyl group represented by R 1 to R 4 is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the piperidinium cation is, for example, a nitrogen-containing six-membered cyclic compound represented by the following general formula (3).
  • R 5 and R 6 are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group represented by R—O— (CH 2 ) n — (R is methyl And n represents an integer of 1 to 4.
  • the number of carbon atoms of the alkyl group represented by R 5 and R 6 is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the pyrrolidinium cation is, for example, a five-membered cyclic compound represented by the following general formula (4).
  • R 7 and R 8 are each independently an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group represented by R—O— (CH 2 ) n — (R is methyl And n represents an integer of 1 to 4.
  • the carbon number of the alkyl group represented by R 7 and R 8 is preferably 1-20, more preferably 1-10, and still more preferably 1-5.
  • a pyridinium cation is a compound shown, for example by General formula (5).
  • R 9 to R 13 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group represented by R—O— (CH 2 ) n — (R represents a methyl group) Or an ethyl group, and n represents an integer of 1 to 4), or a hydrogen atom.
  • the number of carbon atoms of the alkyl group represented by R 9 to R 13 is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the imidazolium cation is, for example, a compound represented by the general formula (6).
  • R 14 to R 18 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group represented by R—O— (CH 2 ) n — (R is a methyl group) Or an ethyl group, and n represents an integer of 1 to 4), or a hydrogen atom.
  • the number of carbon atoms of the alkyl group represented by R 14 to R 18 is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the total content of glyme and ionic liquid may be 10% by mass or more and 80% by mass based on the total amount of components excluding the organic solvent of the electrolyte slurry composition from the viewpoint of suitably producing the electrolyte layer 7. It may be the following.
  • the content of the ionic liquid is preferably 20% by mass or more based on the total amount of components excluding the organic solvent of the electrolyte slurry composition from the viewpoint of enabling charging and discharging of the lithium secondary battery at a high load factor. Yes, more preferably 30% by mass or more.
  • the concentration of the electrolyte salt per unit volume of the total of glyme and ionic liquid in the electrolyte layer 7 is preferably 0.5 mol / L or more, more preferably 0.7 mol / L or more, from the viewpoint of further improving the charge / discharge characteristics. More preferably, it is 1.0 mol / L or more, preferably 3.0 mol / L or less, more preferably 2.5 mol / L or less, and still more preferably 2.3 mol / L or less.
  • the electrolyte slurry composition contains an organic solvent. However, the above-mentioned glyme and ionic liquid are not included in the organic solvent.
  • the organic solvent has a temperature at which the mass reduction rate becomes 95% when the temperature is raised at a temperature elevation rate of 5 ° C./min (mass reduction rate of 95% temperature) is 120 ° C. or less.
  • the organic solvent can be used without particular limitation as long as the mass reduction rate is 95% and the temperature is 120 ° C. or lower.
  • An organic solvent may be used individually by 1 type, and may be used as a mixed solvent combining 2 or more types.
  • the mass reduction rate 95% temperature can be adjusted to a desired range by adjusting the ratio of two or more organic solvents having different mass reduction rates of 95%. Therefore, even if this condition is not satisfied with a single organic solvent, this condition may be satisfied by combining two or more types into a mixed solvent.
  • the mass reduction rate of 95% can be determined by measuring the temperature when the mass reduction rate reaches 95% by using a thermogravimetric measuring device to raise the temperature at a rate of temperature increase of 5 ° C./min. .
  • the temperature is 120 ° C. or lower, preferably 115 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 105 ° C. or lower. If the temperature of the organic solvent is 95%, the electrolyte layer 7 formed from the electrolyte slurry composition tends to have excellent strength. The reason for this is not necessarily clear, but it is considered that the organic solvent is easily volatilized, so that the drying rate is improved and a dense layer (film) is formed.
  • the lower limit of the 95% mass reduction rate of the organic solvent is not particularly limited, it is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably 70 ° C. or higher. If the temperature at which the organic solvent is reduced by 95% is 50 ° C. or higher, the drying rate can be easily controlled, and a uniform film tends to be obtained.
  • the electrolyte slurry composition may contain other components.
  • other components include cellulose fiber, resin fiber, and glass fiber.
  • the content of other components may be 0.1 to 20% by mass based on the total amount of components excluding the organic solvent of the electrolyte slurry composition.
  • the concentration of the component contained in the electrolyte slurry composition may be 5 to 70% by mass based on the total mass of the electrolyte slurry composition.
  • the electrolyte slurry composition is at least one electrolyte salt selected from the group consisting of one or more polymers, oxide particles, lithium salt, sodium salt, calcium salt and magnesium salt, represented by the general formula (10). It can be prepared by mixing and kneading at least one of the compound and ionic liquid, an organic solvent, and other components. Mixing and kneading can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, a ball mill, and a bead mill.
  • dispersers such as a normal stirrer, a raking machine, a triple roll, a ball mill, and a bead mill.
  • the electrolyte sheet used as the electrolyte layer 7 includes the step of disposing the above-described electrolyte slurry composition on the substrate, and removing the organic solvent from the disposed electrolyte slurry composition to form the electrolyte layer on the substrate. And a manufacturing method comprising the steps.
  • FIG. 4A is a schematic cross-sectional view showing an electrolyte sheet according to an embodiment. As shown in FIG. 4A, the electrolyte sheet 13 ⁇ / b> A includes a base material 14 and an electrolyte layer 7 provided on the base material 14.
  • the electrolyte layer 7 can be composed of components obtained by removing the organic solvent from the electrolyte slurry composition.
  • the method of disposing the electrolyte slurry composition on the substrate is not particularly limited, and examples thereof include application by a doctor blade method, a dipping method, a spray method, and the like.
  • the method for removing the organic solvent from the electrolyte slurry composition is not particularly limited, and examples thereof include a method of volatilizing the organic solvent by heating the electrolyte slurry composition.
  • the heating temperature can be appropriately set according to the organic solvent used.
  • the substrate 14 is not limited as long as it has heat resistance capable of withstanding heating when volatilizing the organic solvent, does not react with the electrolyte slurry composition, and does not swell with the electrolyte slurry composition.
  • the base material 14 may be a film made of a resin (general-purpose engineer plastic) such as polyethylene terephthalate, polytetrafluoroethylene, polyimide, polyethersulfone, or polyetherketone.
  • the substrate 14 only needs to have a heat-resistant temperature that can withstand the processing temperature for volatilizing the organic solvent in the process of manufacturing the electrolyte layer.
  • the heat-resistant temperature is a lower temperature of the softening point (temperature at which plastic deformation starts) or the melting point of the base material 14.
  • the heat-resistant temperature of the base material 14 is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, further preferably 150 ° C. or higher, from the viewpoint of adaptability with the glyme and ionic liquid used in the electrolyte layer 7. Yes, for example, it may be 400 ° C. or lower. If the base material which has said heat-resistant temperature is used, the above organic solvents can be used conveniently.
  • the thickness of the base material 14 is preferably as thin as possible while maintaining the strength that can withstand the tensile force of the coating apparatus.
  • the thickness of the base material 14 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m from the viewpoint of securing strength when the electrolyte slurry composition is applied to the base material 14 while reducing the volume of the entire electrolyte sheet 13A. It is above, More preferably, it is 25 micrometers or more, Preferably it is 100 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 40 micrometers or less.
  • the electrolyte sheet can be continuously produced while being wound into a roll.
  • the electrolyte layer 7 may be damaged by the surface of the electrolyte layer 7 coming into contact with the back surface of the substrate 14 and a part of the electrolyte layer 7 sticking to the substrate 14.
  • the electrolyte sheet may be provided with a protective material on the opposite side of the electrolyte layer 7 from the substrate 14 as another embodiment.
  • FIG. 4B is a schematic cross-sectional view showing an electrolyte sheet according to another embodiment. As shown in FIG. 4B, the electrolyte sheet 13 ⁇ / b> B further includes a protective material 15 on the opposite side of the electrolyte layer 7 from the base material 14.
  • the protective material 15 may be any material that can be easily peeled off from the electrolyte layer 7, and is preferably a nonpolar resin film such as polyethylene, polypropylene, or polytetrafluoroethylene. When a nonpolar resin film is used, the electrolyte layer 7 and the protective material 15 do not stick to each other, and the protective material 15 can be easily peeled off.
  • a nonpolar resin film such as polyethylene, polypropylene, or polytetrafluoroethylene.
  • the thickness of the protective material 15 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m, more preferably 100 ⁇ m or less, from the viewpoint of securing strength while reducing the volume of the entire electrolyte sheet 13B. Preferably it is 50 micrometers or less, More preferably, it is 30 micrometers or less.
  • the heat resistant temperature of the protective material 15 is preferably ⁇ 30 ° C. or higher, more preferably 0 ° C. or higher, from the viewpoint of suppressing deterioration in a low temperature environment and suppressing softening in a high temperature environment. Preferably it is 100 degrees C or less, More preferably, it is 50 degrees C or less.
  • the protective material 15 it is not necessary to increase the heat-resistant temperature because the volatilization step of the dispersion medium described above is not essential.
  • the thickness of the electrolyte layer 7 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of increasing the electrical conductivity and improving the strength. From the viewpoint of suppressing the resistance of the electrolyte layer 7, the thickness of the electrolyte layer 7 is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the manufacturing method of the secondary battery 1 mentioned above includes the first step of forming the positive electrode mixture layer 10 on the positive electrode current collector 9 to obtain the positive electrode 6, and the negative electrode mixture on the negative electrode current collector 11. A second step of forming the layer 12 to obtain the negative electrode 8, and a third step of disposing the electrolyte layer 7 of the electrolyte sheet obtained by the above-described manufacturing method between the positive electrode 6 and the negative electrode 8. .
  • the positive electrode 6 is obtained by, for example, dispersing a material used for the positive electrode mixture layer in a dispersion medium using a kneader, a disperser, or the like to obtain a slurry-like positive electrode mixture, and then the positive electrode mixture. Is applied onto the positive electrode current collector 9 by a doctor blade method, a dipping method, a spray method or the like, and then the dispersion medium is volatilized. After volatilizing the dispersion medium, a compression molding step using a roll press may be provided as necessary.
  • the positive electrode mixture layer 10 may be formed as a positive electrode mixture layer having a multilayer structure by performing the above-described steps from application of the positive electrode mixture to volatilization of the dispersion medium a plurality of times.
  • the dispersion medium used in the first step may be water, 1-methyl-2-pyrrolidone (hereinafter also referred to as NMP), or the like.
  • the dispersion medium is a compound other than the above-mentioned glyme and ionic liquid.
  • the method of forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same method as in the first step described above.
  • the method of disposing the electrolyte layer 7 between the positive electrode 6 and the negative electrode 8 using the electrolyte sheet 13A includes, for example, peeling the base material 14 from the electrolyte sheet 13A, and the positive electrode 6, the electrolyte layer 7, And the secondary battery 1 is obtained by laminating
  • the electrolyte layer 7 is positioned on the positive electrode mixture layer 10 side of the positive electrode 6 and on the negative electrode mixture layer 12 side of the negative electrode 8, that is, the positive electrode current collector 9, the positive electrode mixture layer 10, and the electrolyte layer 7.
  • the negative electrode mixture layer 12 and the negative electrode current collector 11 are laminated so as to be arranged in this order.
  • FIG. 5 is a schematic cross-sectional view showing an embodiment of an electrode group in the secondary battery according to the second embodiment.
  • the secondary battery in the second embodiment is different from the secondary battery in the first embodiment in that the electrode group 2 ⁇ / b> B includes a bipolar electrode 16. That is, the electrode group 2B includes the positive electrode 6, the first electrolyte layer 7, the bipolar electrode 16, the second electrolyte layer 7, and the negative electrode 8 in this order.
  • the bipolar electrode 16 includes a bipolar electrode current collector 17, a positive electrode mixture layer 10 provided on a surface (positive electrode surface) on the negative electrode 8 side of the bipolar electrode current collector 17, and a positive electrode 6 side of the bipolar electrode current collector 17. And a negative electrode mixture layer 12 provided on the surface (negative electrode surface).
  • the positive electrode surface may be preferably formed of a material excellent in oxidation resistance, and may be formed of aluminum, stainless steel, titanium, or the like.
  • the negative electrode surface of the bipolar electrode current collector 17 using graphite or an alloy as the negative electrode active material may be formed of a material that does not form an alloy with lithium, specifically, stainless steel, nickel, iron, titanium, or the like. It may be formed.
  • the bipolar electrode current collector 17 may be a clad material in which different metal foils are laminated.
  • the bipolar electrode current collector 17 may be a single metal foil.
  • the bipolar electrode current collector 17 as a single metal foil may be an aluminum perforated foil having a hole diameter of 0.1 to 10 mm, an expanded metal, a metal foam plate, or the like.
  • the bipolar electrode current collector 17 may be formed of any material as long as it does not cause changes such as dissolution and oxidation during use of the battery, and its shape, manufacturing method, etc. Is not limited.
  • the thickness of the bipolar electrode current collector 17 may be not less than 10 ⁇ m and not more than 100 ⁇ m, and is preferably not less than 10 ⁇ m and not more than 50 ⁇ m from the viewpoint of reducing the volume of the entire positive electrode, and has a small curvature when forming a battery. More preferably, the thickness is 10 ⁇ m or more and 20 ⁇ m or less.
  • the manufacturing method of the secondary battery includes a first step of forming the positive electrode mixture layer 10 on the positive electrode current collector 9 to obtain the positive electrode 6, and the negative electrode mixture layer on the negative electrode current collector 11.
  • a positive electrode mixture layer 10 is formed on one surface of the bipolar electrode current collector 17, and a negative electrode mixture layer 12 is formed on the other surface of the bipolar electrode current collector 17.
  • the first step and the second step may be the same method as the first step and the second step in the first embodiment.
  • the method of forming the positive electrode mixture layer 10 on one surface of the bipolar electrode current collector 17 may be the same method as the first step in the first embodiment.
  • the method of forming the negative electrode mixture layer 12 on the other surface of the bipolar electrode current collector 17 may be the same method as the second step in the first embodiment.
  • the method of disposing the electrolyte layer 7 of the electrolyte sheet obtained by the above production method between the positive electrode 6 and the bipolar electrode 16 in the fourth step and the above production method between the negative electrode 8 and the bipolar electrode 16.
  • the method of disposing the electrolyte layer 7 of the obtained electrolyte sheet may be the same method as the third step in the first embodiment.
  • Example 1 ⁇ Preparation of electrolyte slurry composition> Lithium bis (trifluoromethanesulfonyl) imide (Li [TFSI]) dried under a dry argon atmosphere is used as an electrolyte salt, and the concentration of the electrolyte salt is 2.3 mol / L in tetraethylene glycol dimethyl ether (G4) which is glyme.
  • Li [TFSI] G4 solution was prepared (hereinafter, when describing a glyme solution or ionic liquid solution of an electrolyte salt, “concentration of lithium salt / type of lithium salt / type of glyme or ion May be described as "type of liquid").
  • PVDF-HFP a copolymer of vinylidene fluoride and hexafluoropropylene as a polymer and SiO 2 particles as an oxide particle
  • dimethylacetamide (DMAc, 100% by mass) is added as an organic solvent, and the G4 solution of Li [TFSI] prepared above is added and mixed.
  • DMAc dimethylacetamide
  • the concentration of the component contained in the electrolyte slurry composition was 45% by mass based on the total mass of the electrolyte slurry composition.
  • the temperature at which the mass reduction rate becomes 95% when the temperature is raised at a rate of temperature increase of 5 ° C./minute is a differential thermal-thermogravimetric measurement device (Hitachi High-Tech Science Co., Ltd. The temperature was increased at a rate of temperature increase of 5 ° C./min using a -6200 type), and the temperature at which the mass reduction rate reached 95% was measured.
  • the obtained electrolyte sheet was cut into a width of 5 mm, sandwiched between chucks, and then fixed to a pedestal with tape so as to have a length of 20 mm. Then, the electrolyte sheet was pulled by using a force gauge (manufactured by Nidec Sympo Co., Ltd., FGP-5), and the strength when the electrolyte sheet broke was measured. The results are shown in Table 1.
  • the obtained electrolyte sheet was punched into ⁇ 10 mm to prepare a sample for measuring ionic conductivity.
  • This sample was placed in a bipolar closed cell (manufactured by Hosen Co., Ltd., HS cell), and measured using an AC impedance measuring device (Solartron, model 1260).
  • the AC impedance was measured in the range of 1 Hz to 10 MHz at 10 mV at room temperature (25 ° C.).
  • the resistance value was calculated from the arc width of the Nyquist plot, and the ionic conductivity was calculated from the resistance value.
  • the sample was placed in the closed cell in a dry room. The results are shown in Table 1.
  • a positive electrode mixture slurry was prepared.
  • This positive electrode mixture slurry is applied on a current collector (aluminum foil having a thickness of 20 ⁇ m) at a coating amount of 147 g / m 2 and dried at 80 ° C., whereby a positive electrode having a mixture density of 2.9 g / cm 3 . A mixture layer was formed. This was punched to 15 mm to make a positive electrode.
  • This negative electrode mixture slurry is applied on a current collector (copper foil having a thickness of 10 ⁇ m) at a coating amount of 68 g / m 2 and dried at 80 ° C., whereby a negative electrode having a mixture density of 1.9 g / cm 3 . A mixture layer was formed. This was punched to ⁇ 16 mm to form a negative electrode.
  • the obtained electrolyte sheet was punched to ⁇ 16 mm, and the substrate was peeled off to obtain an electrolyte layer.
  • An evaluation coin-type battery was fabricated using the positive electrode, the electrolyte layer, and the negative electrode.
  • lithium bis (fluorosulfonyl) imide Li [FSI]
  • Li [FSI] N-methyl-N-propylpyrrolidinium bis (fluorosulfonyl) imide
  • [Py13] [ FSI] N-methyl-N-propylpyrrolidinium bis (fluorosulfonyl) imide
  • the discharge rate characteristic in 25 degreeC was measured on the following charging / discharging conditions using the charging / discharging apparatus (made by Toyo System Co., Ltd.).
  • CCCV constant current constant voltage
  • two cycles of discharging a constant current (CC) to a final voltage of 2.7 V at 0.05 C were performed.
  • C means “current value (A) / battery capacity (Ah)”.
  • CCCV constant current constant voltage
  • CCCV constant current constant voltage
  • one cycle of constant current (CC) discharging to a final voltage of 2.7 V at 0.1 C went.
  • the rate of constant current (CC) discharge was changed to 0.2, 0.3, 0.5, and 1.0 C every cycle, and the discharge rate characteristics were evaluated. The results are shown in Table 1.
  • Example 2 As an organic solvent, instead of DMAc, a mixed solvent in which N-methyl-2-pyrrolidone (NMP) and cyclohexanone (CHN) were mixed at a mass ratio of 1: 1 was used in the same manner as in Example 1. An electrolyte sheet was produced. A 95% mass reduction rate of the mixed solvent of NMP (50% by mass) and CHN (50% by mass) was 87 ° C. Evaluation similar to Example 1 was performed using the produced electrolyte sheet. The results are shown in Table 1.
  • NMP N-methyl-2-pyrrolidone
  • CHN cyclohexanone
  • Example 3 An electrolyte sheet was produced in the same manner as in Example 1 except that a mixed solvent in which NMP and methyl ethyl ketone (MEK) were mixed at a mass ratio of 1: 1 was used instead of DMAc as the organic solvent. A 95% mass reduction rate of the mixed solvent of NMP (50 mass%) and MEK (50 mass%) was 103 ° C. Evaluation similar to Example 1 was performed using the produced electrolyte sheet. The results are shown in Table 1.
  • Example 4 An electrolyte sheet was produced in the same manner as in Example 1 except that a mixed solvent in which NMP and 2-butanol (2-BuOH) were mixed at a mass ratio of 4: 1 was used instead of DMAc as the organic solvent. .
  • the 95% mass reduction rate of the mixed solvent of NMP (80 mass%) and 2-BuOH (20 mass%) was 97 ° C. Evaluation similar to Example 1 was performed using the produced electrolyte sheet. The results are shown in Table 1.
  • Example 5 An electrolyte sheet was produced in the same manner as in Example 4 except that a Li [FSI] solution [Py13] [FSI] was used instead of the Li [TFSI] G4 solution. Evaluation similar to Example 1 was performed using the produced electrolyte sheet. The results are shown in Table 1.
  • the electrolyte sheets of Examples 1 to 5 were superior to the electrolyte sheets of Reference Examples 1 and 2 in terms of the tensile strength of the electrolyte layer. From these results, it was confirmed that the electrolyte slurry composition of the present invention can form an electrolyte layer having excellent strength.

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Abstract

L'invention concerne une composition de bouillie électrolytique contenant une ou deux espèces de polymère ou plus, une particule d'oxyde, au moins une espèce de sel d'électrolyte choisie dans le groupe constitué par le sel de lithium, le sel de sodium, le sel de calcium et le sel de magnésium, un liquide ionique et/ou un composé représenté par la formule générale (10), et un solvant organique, le solvant organique étant tel que, lorsque la température est élevée à une vitesse de 5 °C/minute, la température à laquelle le rapport de réduction de masse atteint 95 % est inférieure ou égale à 120 °C. RAO-(CH2CH2O)y-RB (10) [dans la formule (10), RA et RB représentent chacun indépendamment un groupe alkyle ayant de 1 à 4 atomes de carbone, et y représente un nombre entier allant de 1 à 6.]
PCT/JP2019/014214 2018-04-26 2019-03-29 Composition de bouillie électrolytique, procédé de production de feuille d'électrolyte et procédé de production de batterie secondaire Ceased WO2019208110A1 (fr)

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KR102888310B1 (ko) 2020-08-28 2025-11-18 주식회사 엘지에너지솔루션 리튬 이온 2차 전지, 분리막 및 이들의 제조 방법

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