WO2018221668A1 - Composition d'électrolyte et batterie rechargeable - Google Patents

Composition d'électrolyte et batterie rechargeable Download PDF

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Publication number
WO2018221668A1
WO2018221668A1 PCT/JP2018/021002 JP2018021002W WO2018221668A1 WO 2018221668 A1 WO2018221668 A1 WO 2018221668A1 JP 2018021002 W JP2018021002 W JP 2018021002W WO 2018221668 A1 WO2018221668 A1 WO 2018221668A1
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Prior art keywords
electrolyte
positive electrode
negative electrode
salt
electrolyte composition
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PCT/JP2018/021002
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English (en)
Japanese (ja)
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西村　拓也
紘揮 三國
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日立化成株式会社
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Priority to JP2019521305A priority Critical patent/JPWO2018221668A1/ja
Publication of WO2018221668A1 publication Critical patent/WO2018221668A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte composition and 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.
  • lithium secondary battery having a higher energy density is required and has been developed.
  • lithium secondary batteries for electric vehicles require high safety in addition to high input / output characteristics and high energy density, more advanced technology for ensuring safety is required.
  • the gel electrolyte has an ionic conductivity equivalent to that of the electrolyte solution used in the conventional lithium secondary battery, so that it is released without deteriorating the battery performance by changing the electrolyte solution to the gel electrolyte.
  • Patent Document 1 discloses a gel electrolyte layer containing a plasticizer containing a lithium salt, a matrix polymer in which the plasticizer is dispersed, and a fibrous insoluble material.
  • the fibrous insoluble matter contained in the gel electrolyte in an amount of 0.1 wt% to 50 wt% has a ratio of fiber length to fiber diameter of 10 to 3000, fiber length of 10 ⁇ m to 1 cm, and fiber diameter.
  • Patent Document 2 discloses a gel electrolyte and a gel electrolyte battery.
  • the gel electrolyte layer is formed by swelling a matrix polymer with an electrolytic solution and contains a large amount of a low viscosity solvent having a low boiling point.
  • a gel electrolyte containing a large amount of a low-boiling low-viscosity solvent By using a gel electrolyte containing a large amount of a low-boiling low-viscosity solvent, a gel electrolyte battery excellent in temperature characteristics, current characteristics, capacity, and charge / discharge characteristics at low temperatures is provided.
  • the electrical conductivity of the conventional gel electrolyte as described above is insufficient.
  • the discharge characteristics of the secondary battery may be remarkably deteriorated.
  • the main object of the present invention is to provide an electrolyte composition capable of producing a secondary battery having excellent discharge characteristics.
  • 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, An electrolyte composition, wherein the oxide particles have a specific surface area of 2 to 380 m 2 / g.
  • 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.
  • a second aspect of the present invention is a secondary battery including a positive electrode, a negative electrode, and an electrolyte layer made of an electrolyte composition provided between the positive electrode and the negative electrode.
  • an electrolyte composition capable of producing a secondary battery having excellent discharge characteristics can be provided.
  • the secondary battery using such an electrolyte 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 including 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, for example, a laminated 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
  • a 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 Mg Or a lithium transition metal oxide substituted with a metal element (typical element) such as Al. That is, the lithium transition metal oxide may be a compound represented by LiM 1 O 2 or LiM 1 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 preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 30 ⁇ m or less, more preferably 25 ⁇ m 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 by.
  • 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, or 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.
  • the polymer may contain at least one selected from the group consisting of a monomer, a rubber such as styrene-butadiene rubber, isoprene rubber, and acrylic rubber.
  • 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.
  • 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 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.
  • the negative electrode active material is silicon, tin, or a compound containing these elements (oxide, nitride, alloy with other metals) from the viewpoint of obtaining a larger theoretical capacity (for example, 500 to 1500 Ah / kg). May be.
  • 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.
  • 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, for example, by producing an electrolyte sheet using an electrolyte composition.
  • the electrolyte composition includes one or more polymers, oxide particles, at least one electrolyte salt selected from the group consisting of a lithium salt, a sodium salt, a calcium salt, and a magnesium salt, an ionic liquid, Containing.
  • 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 the electrolyte composition (electrolyte layer).
  • 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 the electrolyte composition.
  • the content of the polymer is preferably 3 to 50% by mass or 3 to 40% by mass based on the total amount of the electrolyte composition.
  • the polymer according to the present embodiment has excellent affinity with the ionic liquid contained in the electrolyte composition, the polymer in the ionic liquid is retained. Thereby, the leakage of the ionic liquid when a load is applied to the electrolyte composition is suppressed.
  • the oxide particles may be, 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.
  • the specific surface area is 2 to 380 m 2 / g, the obtained secondary battery tends to have excellent discharge characteristics.
  • the specific surface area of the oxide particles is 5 m 2 / g or more, 10 m 2 / g or more, 15 m 2 / g or more, 20 m 2 / g or more, 30 m 2 / g or more, 35 m 2 / g or more, 40 m. It may be 2 / g or more, or 45 m 2 / g or more.
  • the specific surface area of the oxide particles is 350 m 2 / g or less, 300 m 2 / g or less, 250 m 2 / g or less, 200 m 2 /. g or less, 180 m 2 / g or less, 150 m 2 / g or less, 130 m 2 / g or less, 100 m 2 / g or less, 80 m 2 / g or less, 60 m 2 / g or less, or 55 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, and still more preferably, from the viewpoint of further improving the electrical conductivity. Is 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 from the viewpoint of thinning the electrolyte composition and suppressing the protrusion of the oxide particles from the surface of the electrolyte composition. .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 a 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 commercially available image processing software (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, and particularly preferably 20% by mass or more, based on the total amount of the electrolyte composition (electrolyte layer). Moreover, it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
  • 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 an 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 ionic liquid contains the following anion component and cation component. Note that the ionic liquid in the present embodiment is a liquid material at ⁇ 20 ° C. or higher.
  • 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 the electrolyte salt and the ionic liquid is 10% by mass or more based on the total amount of the electrolyte composition (electrolyte layer) from the viewpoint of suitably producing the electrolyte layer. It may be 80 mass% or less.
  • the content of the ionic liquid is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the electrolyte composition, from the viewpoint of enabling charging and discharging of the lithium secondary battery at a high load factor. is there.
  • the molar concentration of the ionic liquid in which the electrolyte salt is dissolved is preferably 0.5 mol / L or more, more preferably 0. 0.7 mol / L or more, more preferably 1.0 mol / L or more, preferably 2.0 mol / L or less, more preferably 1.8 mol / L or less, still more preferably 1.6 mol / L or less.
  • the thickness of the electrolyte layer 7 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of increasing electrical conductivity and improving 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 providing the electrolyte layer 7 between the positive electrode 6 and the negative electrode 8 are provided.
  • 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 ionic liquid described above.
  • 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 electrolyte layer 7 is formed by producing an electrolyte sheet using the electrolyte composition.
  • 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 sheet 13A is produced, for example, by dispersing a material used for the electrolyte layer 7 in a dispersion medium to obtain a slurry, and applying the slurry onto the base material 14 and then volatilizing the dispersion medium.
  • the dispersion medium is preferably water, NMP, toluene or the like.
  • the substrate 14 is not limited as long as it has heat resistance that can withstand the heating when the dispersion medium is volatilized, does not react with the electrolyte composition, and does not swell with the electrolyte composition. May be formed.
  • 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 dispersion medium 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 ionic liquid used for the electrolyte layer 7. It may be 400 ° C. or lower. If the base material which has said heat-resistant temperature is used, the above dispersion media (NMP, toluene, etc.) 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 substrate 14 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of securing strength when the electrolyte composition is applied to the substrate 14 while reducing the volume of the entire electrolyte sheet 13A.
  • 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 side opposite to the base material 14 of the electrolyte layer 7 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, and preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, from the viewpoint of ensuring strength while reducing the volume of the entire electrolyte sheet 13B. 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, and preferably 100 ° C. from the viewpoint of suppressing deterioration in a low temperature environment and suppressing softening in a high temperature environment. Below, more preferably 50 ° 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 method of providing the electrolyte layer 7 between the positive electrode 6 and the negative electrode 8 using the electrolyte sheet 13A is, for example, by peeling the base material 14 from the electrolyte sheet 13A and laminating the positive electrode 6, the electrolyte layer 7 and the negative electrode 8 by lamination.
  • the secondary battery 1 is obtained by stacking.
  • 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 in this order.
  • the electrolyte layer 7 kneads the material used for the electrolyte layer 7, and sandwiches the obtained kneaded material between resin sheets such as polytetrafluoroethylene (PTFE), It is formed by producing an electrolyte sheet by pressing with a roll press or the like.
  • resin sheets such as polytetrafluoroethylene (PTFE)
  • 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.
  • 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 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. 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. 16 and a fourth step of providing the electrolyte layer 7 between the positive electrode 6 and the bipolar electrode 16 and between the negative electrode 8 and the bipolar electrode 16.
  • 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 electrolyte layer 7 is formed by producing an electrolyte sheet using an electrolyte composition.
  • the manufacturing method of the electrolyte sheet may be the same method as the manufacturing method of the electrolyte sheets 13A and 13B in the first embodiment.
  • the method of providing the electrolyte layer 7 between the negative electrode 8 and the bipolar electrode 16 may be the same method as the method of providing the electrolyte layer 7 between the positive electrode 6 and the bipolar electrode 16 described above. .
  • Example 1 ⁇ Preparation of electrolyte layer> N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium as an ionic liquid using lithium bis (trifluoromethanesulfonyl) imide (Li [TFSI]) dried under a dry argon atmosphere as an electrolyte salt The electrolyte salt was dissolved in bis (trifluoromethanesulfonyl) imide ([DEME] [TFSI]) at a concentration of 1.5 mol / L.
  • Li [TFSI] lithium bis (trifluoromethanesulfonyl) imide
  • [DEME] [TFSI] bis (trifluoromethanesulfonyl) imide
  • composition of the ionic liquid in which the electrolyte salt is dissolved may be expressed as “concentration of electrolyte salt / type of electrolyte salt / type of ionic liquid”).
  • a copolymer (PVDF-HFP) of vinylidene fluoride and hexafluoropropylene as a polymer and SiO 2 particles as an oxide particle product name: AEROSIL OX50, manufactured by Nippon Aerosil Co., Ltd., specific surface area: 50 m 2 / g, average primary particle size: about 30 nm
  • NMP N-methyl-2-pyrrolidone
  • NMP was further added to adjust the viscosity, and this slurry was applied onto a polyethylene terephthalate base material (product name: Teonex R-Q51, manufactured by Teijin DuPont Films, Inc., thickness 38 ⁇ m) using an applicator. .
  • the applied slurry was heated and dried at 80 ° C. for 1 hour to volatilize the dispersion medium and obtain an electrolyte sheet.
  • the obtained electrolyte sheet was punched into ⁇ 16 mm to form an electrolyte layer.
  • acetylene black conductive agent, average particle size 48 nm, product name: HS-100, Denka Co., Ltd.
  • 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 with a mixture density of 2.9 g / cm 3 is obtained. A mixture layer was formed. This was punched to 15 mm to make a positive electrode.
  • This negative electrode mixture slurry was 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.
  • a coin-type battery for evaluation was produced using the positive electrode, the electrolyte layer, and the negative electrode.
  • the positive electrode, the electrolyte layer, and the negative electrode were stacked in this order and placed in a CR2032-type coin cell container, and then the upper part of the battery container was crimped and sealed through an insulating gasket.
  • a coin-type battery was produced in the same manner as in Example 1 except that it was changed to.
  • a coin-type battery was produced in the same manner as in Example 1 except that it was changed to.
  • a coin-type battery was produced in the same manner as in Example 1 except that it was changed to.
  • Example 5 In the preparation of the electrolyte layer, in place of the SiO 2 particles used in Example 1, hexamethyldisilazane surface-treated with the SiO 2 particles (product name: AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd., specific surface area: 35m 2 / g, average primary particle size: about 40 nm) was used in the same manner as in Example 1 to produce a coin-type battery.
  • AEROSIL RX50 manufactured by Nippon Aerosil Co., Ltd., specific surface area: 35m 2 / g, average primary particle size: about 40 nm
  • Example 6 In the preparation of the electrolyte layer, in place of the SiO 2 particles used in Example 1, dimethyl silicone oil on the surface-treated SiO 2 particles (product name: AEROSIL RY50, manufactured by Nippon Aerosil Co., Ltd., specific surface area: 30 m 2 / g A coin-type battery was produced in the same manner as in Example 1 except that the average primary particle size was about 40 nm.
  • Example 7 In preparing the electrolyte layer, instead of the SiO 2 particles used in Example 1, TiO 2 particles (product name: AEROXIDE TiO 2 P25, manufactured by Nippon Aerosil Co., Ltd., specific surface area: 50 m 2 / g, average primary particle size: A coin-type battery was produced in the same manner as in Example 1 except that about 21 nm) was used.
  • TiO 2 particles product name: AEROXIDE TiO 2 P25, manufactured by Nippon Aerosil Co., Ltd., specific surface area: 50 m 2 / g, average primary particle size: A coin-type battery was produced in the same manner as in Example 1 except that about 21 nm) was used.
  • Example 8 In preparation of the electrolyte layer, 1.5 mol / L / Li instead of 1.5 mol / L / Li [TFSI] / [DEME] [TFSI] used in Example 1 was used as the ionic liquid in which the electrolyte salt was dissolved.
  • a coin-type battery was fabricated in the same manner as in Example 1 except that [FSI] / [Py13] [FSI] was used.
  • a coin-type battery was produced in the same manner as in Example 8 except that it was changed to.
  • Example 10 A coin-type battery was fabricated in the same manner as in Example 8, except that the molar concentration of the ionic liquid in which the electrolyte salt was dissolved was changed from 1.5 mol / L to 1.0 mol / L.
  • Example 11 A coin-type battery was fabricated in the same manner as in Example 8, except that the molar concentration of the ionic liquid in which the electrolyte salt was dissolved was changed from 1.5 mol / L to 1.2 mol / L.
  • Example 12 In preparation of the electrolyte layer, 1.5 mol / L / Li instead of 1.5 mol / L / Li [TFSI] / [DEME] [TFSI] used in Example 1 was used as the ionic liquid in which the electrolyte salt was dissolved.
  • a coin-type battery was fabricated in the same manner as in Example 1 except that [FSI] / [EMI] [FSI] (1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide) was used.
  • a coin-type battery was produced in the same manner as in Example 12 except that it was changed to.
  • the discharge characteristic (%) was calculated using the following formula. It can be said that the larger the value, the better the discharge characteristics.
  • the case where the discharge characteristic was 95% or more was evaluated as “A”, the case where the discharge characteristic was 80% or more and less than 95% was evaluated as “B”, and the case where the discharge characteristic was less than 80% was evaluated as “C”.
  • the results are shown in Table 1.
  • Discharge characteristics (%) discharge capacity obtained in (2) / discharge capacity obtained in the third cycle of (1) ⁇ 100

Abstract

L'invention concerne une composition d'électrolyte contenant : un ou plusieurs polymères; des particules d'oxyde; un ou plusieurs sels électrolytiques choisis dans un groupe constitué de sels de lithium, de sels de sodium, de sels de calcium et de sels de magnésium; et un liquide ionique. La surface spécifique des particules d'oxyde se situe dans la plage de 2 à 380 m2/g.
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WO2021038862A1 (fr) * 2019-08-30 2021-03-04 昭和電工マテリアルズ株式会社 Feuille d'électrolyte, son procédé de production et batterie secondaire

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