WO2015132845A1 - Batterie tout solide - Google Patents

Batterie tout solide Download PDF

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Publication number
WO2015132845A1
WO2015132845A1 PCT/JP2014/055217 JP2014055217W WO2015132845A1 WO 2015132845 A1 WO2015132845 A1 WO 2015132845A1 JP 2014055217 W JP2014055217 W JP 2014055217W WO 2015132845 A1 WO2015132845 A1 WO 2015132845A1
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Prior art keywords
negative electrode
lithium ion
active material
conductive polymer
lithium
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PCT/JP2014/055217
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English (en)
Japanese (ja)
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恵理奈 横山
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株式会社日立製作所
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Priority to PCT/JP2014/055217 priority Critical patent/WO2015132845A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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 all solid state battery.
  • the all-solid secondary battery using the non-combustible or flame-retardant solid electrolyte can have high heat resistance and can be made safe, so that module costs can be reduced and high energy density can be achieved.
  • the solid electrolyte has a problem that the conductivity of lithium ions is lower than that of a liquid electrolyte (electrolyte solution), and it is difficult to achieve high output of the battery.
  • Patent Document 1 discloses a technique of adding an ion conductive polymer such as polyethylene oxide (PEO) and polypropylene oxide (PPO) to an active material layer.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • Patent Document 2 discloses a negative electrode using polyethylene oxide as a binder in an active material mixture layer and using an organic electrolytic solution and a solid electrolyte as an electrolyte.
  • the porosity of the electrode containing the negative electrode material is adjusted to 10% or more and 60% or less for the purpose of improving cycle performance and discharge capacity.
  • Patent Document 1 when a solid electrolyte is used as the electrolyte, since there is no electrolytic solution in the active material mixture, even if an ion conductive polymer is added, particles such as active material particles and ion conductive polymer can be used. An air gap occurs. For this reason, it is difficult to improve the lithium ion conductivity in the active material mixture.
  • Patent Document 2 when a solid electrolyte is used as the electrolyte, many pores are present in the inside of the negative electrode layer in the range of the disclosed porosity, so the contact area between the negative electrode active material is small and lithium ions There is a disadvantage that the number of conduction paths is reduced and the internal resistance of the negative electrode mixture is large.
  • An object of the present invention is to provide a high output lithium ion battery in which the lithium ion conductivity in the negative electrode active material is improved even when a solid electrolyte is used as the electrolyte.
  • the negative electrode mixture layer includes a negative electrode active material and a lithium ion conductive polymer provided between the negative electrode active materials, and the porosity of the negative electrode mixture layer is 10% or less
  • the lithium ion secondary battery wherein the ratio of the lithium ion conductive polymer to the negative electrode mixture layer is 5 wt% or more.
  • the above polymer is added to the negative electrode active material mixture, and the battery is manufactured with a porosity of 0.01% or more and 10% or less, thereby reducing the pores in the negative electrode layer, and the lithium ion conduction path. It is possible to provide a high power battery with improved.
  • FIG. 1 is a cross-sectional view of an all-solid secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of the main part of the all-solid-state secondary battery according to an embodiment of the present invention.
  • the all solid secondary battery 100 includes a positive electrode current collector 10, a negative electrode current collector 20, a battery case 30, a positive electrode mixture layer 40, a solid electrolyte 50, and a negative electrode mixture layer 60.
  • the positive electrode 70 in FIG. 1 has a positive electrode current collector 10 and a positive electrode mixture layer 40.
  • the negative electrode 80 in FIG. 1 has a negative electrode current collector 20 and a negative electrode mixture layer 60.
  • an aluminum foil having a thickness of 10 to 100 ⁇ m, a perforated aluminum foil having a thickness of 10 to 100 ⁇ m and a hole diameter of 0.1 to 10 mm, an expanded metal, a foam metal plate or the like is used.
  • aluminum, materials such as stainless steel and titanium are also applicable.
  • any current collector can be used without being limited to the material, shape, manufacturing method and the like.
  • the negative electrode current collector 20 a copper foil having a thickness of 10 to 100 ⁇ m, a perforated copper foil having a thickness of 10 to 100 ⁇ m and a hole diameter of 0.1 to 10 mm, an expanded metal, a foam metal plate or the like is used. Besides copper, materials such as stainless steel, titanium or nickel are also applicable. In the present invention, any current collector can be used without being limited to the material, shape, manufacturing method and the like.
  • the battery case 30 accommodates the positive electrode current collector 10, the negative electrode current collector 20, the positive electrode mixture layer 40, the solid electrolyte layer 50, and the negative electrode mixture layer 60.
  • the shape of the battery case 30 conforms to the shape of the electrode group configured of the positive electrode mixture layer 40, the solid electrolyte layer 50, and the negative electrode mixture layer 60, and has a cylindrical, flat oval, flat oval, square, etc. shape. May be selected.
  • the material of the battery case 30 is selected from materials having corrosion resistance to the non-aqueous electrolyte, such as aluminum, stainless steel, nickel plated steel, and the like.
  • the positive electrode mixture layer 40 has a positive electrode active material, an optional positive electrode conductive agent, and an optional positive electrode binder.
  • the above materials may be contained singly or in combination of two or more as the positive electrode active material.
  • the positive electrode active material lithium ions are desorbed in the charging process, and lithium ions desorbed from the negative electrode active material in the negative electrode mixture layer 60 are inserted in the discharging process.
  • the particle size of the positive electrode active material is usually defined to be equal to or less than the thickness of the positive electrode mixture layer 40.
  • the powder of the positive electrode active material contains coarse particles having a size equal to or larger than the mixture layer thickness, the coarse particles are removed in advance by sieve classification, air flow classification, etc. to produce particles of the mixed layer thickness or less. preferable.
  • the positive electrode active material is generally oxide-based and has high electrical resistance
  • a positive electrode conductive agent made of carbon powder is used to compensate for the electrical conductivity. Since both the positive electrode active material and the positive electrode conductive agent are usually powders, the powders can be mixed with a binder to bond the powders together and to be bonded to the positive electrode current collector 10 at the same time.
  • the positive electrode mixture layer 40 contains a positive electrode conductive agent or a positive electrode binder
  • the positive electrode conductive agent include acetylene black, carbon black, and carbon materials such as graphite or amorphous carbon.
  • positive electrode binders include styrene-butadiene rubber, carboxymethylcellulose and polyvinylidene fluoride (PVDF), and mixtures thereof.
  • FIG. 2 is a schematic cross-sectional view of the negative electrode mixture layer 60 applied to the negative electrode current collector and the solid electrolyte layer 50 provided on the negative electrode mixture layer 60.
  • the negative electrode mixture layer 60 has a negative electrode active material 62, a lithium conductive polymer 63, an optional negative electrode conductive agent 64, and an optional negative electrode binder.
  • a lithium conductive polymer 63 is filled between the negative electrode active material 62 particles. By filling the gaps between the particles, the mobility of lithium ions can be increased, and the resistance of the negative electrode mixture layer 60 can be lowered. By filling the voids inside the negative electrode layer with the lithium conductive polymer, the conduction path of lithium ions can be improved and high output can be realized.
  • a battery using a liquid for the electrolyte requires a certain amount of gaps for the electrolyte to permeate, but when using a solid electrolyte as in the present invention, the gaps are considered to be a factor in the decrease in lithium ion conductivity. Is preferably as small as possible.
  • the porosity of the inside of the negative electrode mixture layer 60 is preferably 10% or less. More preferably, it is 5% or less. When the porosity is larger than the above range, a sufficient lithium ion conduction path is not formed between the negative electrode active materials, and the output of the battery is reduced.
  • the direct current resistance value of the negative electrode mixture layer 60 is preferably 10 ⁇ or less. More preferably, it is 6 ⁇ , 5 ⁇ or less, and it is considered that this value can be obtained if the porosity in the negative electrode mixture layer 60 is 4 to 5% or less.
  • the porosity is a volume ratio of a space or void generated between particles of a negative electrode active material or the like with respect to the volume of the negative electrode mixture, and can be determined, for example, by mercury porosimetry.
  • the lithium conductive polymer 63 one having high lithium ion conductivity and being stable in each process of electrode preparation, such as a process of preparing a negative electrode mixture with a binder and a solvent, and a subsequent kneading process of the negative electrode mixture Those which are stable with respect to the solvent and do not cause elution or peeling can be used. In addition, it is desirable to use one that is chemically and electrochemically stable even during operation of the secondary battery.
  • fluorine-based resins such as polyvinylidene fluoride and polytetrafluoroethylene
  • polymer compounds used for solid electrolytes such as polyethylene oxide, polypropylene oxide and polyacrylonitrile
  • polyvinyl alcohol polyethylene glycol, polypropylene glycol
  • polyvinyl pyrrolidone Water-soluble polymer compounds such as styrene-maleic anhydride copolymer, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, crosslinkable polymer compounds such as styrene-butadiene rubber, olefin polymers such as polyethylene and polypropylene Compounds, polymeric amine compounds and the like can be used.
  • it may be a hydrolyzate of these polymers, a cross-linked product, a variety of reactants such as an acid-modified product, or a modified product, or a salt such as a neutralized salt of an acid or a base or a metal salt.
  • R 1 is hydrogen, an alkyl group or an alkyl group having oxygen.
  • n is the number of repeating units. It is believed that lithium ion transfer takes place via oxygen in the structure.
  • the branched polyethylene oxide is a structure in which polyethylene oxide of Formula 1 is further branched from R 1 in Formula 1, which is higher in hardness and higher in mechanical strength than linear polyethylene oxide.
  • R 2 is a functional group having at least one of elements C, N, S, O, and H. It is believed that lithium ion transfer takes place via oxygen in the structure.
  • R 2 preferably has a structure such as —COOR—, —CO—, NH, and a sulfo group having a high degree of lithium ion conductivity.
  • x and y are composition ratios of copolymerization, and can appropriately take a value of 0 ⁇ y / (x + y) ⁇ 1.
  • R 3 and R 4 are functional groups having at least one of elements C, N, S, O, and H. R 3 and R 4 may be the same or different. n is the number of repeating units.
  • the lithium conductive polymer 6 is lower in hardness and softer than the negative electrode active material and the conductive material particles, so that a slurry containing the negative electrode active material, the lithium conductive polymer 6 and the conductive material is applied to the current collector and pressure is applied.
  • the lithium conductive polymer 6 can be deformed and filled so as to enter between the negative electrode active material and the conductive material. Since the contact area between the negative electrode active material and the lithium conductive polymer 6 is increased by being deformed and filled, high lithium ion conductivity can be realized even with a negative electrode active material mixture that does not use a liquid electrolyte. Can.
  • the average molecular weight of the lithium conductive polymer 6 is preferably 1,000 to 400,000. More preferably, it is 5,000 to 100,000, and particularly preferably 10,000 to 50,000.
  • the average molecular weight is smaller than the lower limit value of the above range, the polymers are aggregated at the time of preparation of the electrode, and a good electron conduction path is not formed, and the output of the battery is reduced.
  • the value is larger than the upper limit value, it is considered that since the polymer becomes hard, it gets into the voids of the negative electrode active material and it becomes difficult to fill the voids.
  • the negative electrode active material can be flexibly deformed even with respect to the expansion and contraction of the negative electrode active material, and a gap can be hardly generated between the negative electrode active material and the polymer.
  • a carbon material capable of reversibly inserting and desorbing lithium ions such as artificial graphite, natural graphite, and coke can be used.
  • an oxide that intercalates and releases lithium such as an oxide containing Si, Sn, and Ti can be used.
  • a silicon-based material Si, SiO, a tin-based material, lithium titanate with or without a substitution element, lithium vanadium complex oxide can be used.
  • various alloys for example, an alloy of lithium and tin, aluminum, antimony or the like can be used.
  • the carbon material natural graphite, composite carbonaceous material obtained by forming a film on natural graphite by dry CVD method or wet spray method, resin material such as epoxy and phenol, or pitch material obtained from petroleum or coal As artificial graphite manufactured by baking, a non-graphitizable carbon material, etc. are mentioned.
  • the above materials may be contained singly or in combination as the negative electrode active material 62. In the negative electrode active material 62, insertion and desorption reactions or conversion reactions of lithium ions proceed in the charge and discharge process.
  • the particle size of the negative electrode active material 62 is usually defined to be equal to or less than the thickness of the negative electrode mixture layer 60. If the powder of the negative electrode active material 62 has coarse particles having a size equal to or larger than the mixture layer thickness, the coarse particles are removed in advance by sieve classification, air flow classification or the like, and particles of a thickness of the negative electrode mixture layer 60 or less It is preferable to make it.
  • a negative electrode conductive agent 64 and a negative electrode binder can be added to the negative electrode mixture layer 60.
  • acetylene black, carbon black, and carbon materials such as graphite or amorphous carbon can be used.
  • the negative electrode binder styrene-butadiene rubber, carboxymethyl cellulose and polyvinylidene fluoride (PVDF), or a mixture of two or more of them can be used.
  • the negative electrode mixture layer 60 is formed of a negative electrode active material 62, a lithium conductive polymer 63, a negative electrode conductive agent, a negative electrode binder, and an organic solvent mixed negative electrode slurry by a doctor blade method, a dipping method, a spray method or the like. After adhering to the current collector 20, the organic solvent can be dried and pressure-formed by a roll press.
  • the negative electrode active material 62 and the particles of the lithium conductive polymer 63 make it possible to obtain a negative electrode mixture having a higher density and a lower porosity than when the voids are filled.
  • a large press pressure is required.
  • the ratio of the lithium conductive polymer 63 in the negative electrode slurry without changing the amount of the negative electrode active material 62 as in (2).
  • the void between the negative electrode active material 63 can be filled with the lithium conductive polymer 63, and the porosity can be lowered.
  • the lithium conductive polymer 63 can be inserted between the negative electrode active materials by pressing, and thus does not require a pressing pressure as large as (1).
  • the porosity can be lowered by increasing the proportion of the negative electrode active material 63 or the conductive material, but it is preferable to increase the proportion of the lithium conductive polymer 63. Since the negative electrode active material 63 and the conductive material are hard materials as compared with the lithium conductive polymer 63, a large pressing pressure is required to fill the voids. Also, from the viewpoint of lithium ion conductivity, it is preferable to fill the voids with the lithium conductive polymer 63 rather than the conductive material.
  • lithium ion conduction to the negative electrode mixture is performed.
  • the proportion of the polymer is preferably 1 to 20 wt%.
  • the porosity is 5% or less, it is preferably 10 to 20 wt%.
  • the electrode is pressed at a predetermined pressure in order to set the porosity to a preferable range and to form a conductive path of ions or electrons.
  • a known method capable of uniformly pressing the electrode mixture layer can be selected according to the electrode area.
  • an apparatus capable of pressing a large area such as a uniaxial press when the electrode area is small, or a roll press when the electrode area is large can be suitably used.
  • the pressing pressure can be set arbitrarily, but the pressure or pressure at which the lithium conductive polymer forms a sufficient contact surface with the negative electrode active material, and the negative electrode active material loses the lithium ion storage capacity, and so on.
  • the pressure be less than or equal to the pressure that causes structural change such as shaking.
  • the pressing pressure depends on the amount of lithium conductive polymer added and the composition of the electrode. In order to reduce the porosity in the negative electrode mixture, a larger press pressure is required than when the amount of lithium conductive polymer added is increased. The relationship between the pressing pressure and the porosity can be confirmed by observing the cross section of the negative electrode mixture by SEM after pressing.
  • the negative electrode mixture of the present invention in which the porosity is kept low is higher in density than the conventional negative electrode mixture.
  • the electrode density after pressing solid content The density
  • the density is in the range of 1.0 to 2.5 g / cm.sup.- 3 .
  • the density is more preferably in the range of 1.2 to 2.3 g / cm.sup.- 3 , further preferably 1.5 to 2.0 g / cm.sup.- 3 .
  • the solid electrolyte layer 50 has solid electrolyte particles 52 and an optional binder.
  • the solid electrolyte particle is not particularly limited as long as it is a solid material which conducts lithium ions, but from the viewpoint of safety, it is desirable to contain a nonflammable inorganic solid electrolyte.
  • an oxide glass represented by Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 , LiAlGe (PO 4 ) 3 , Li 3.4 V 0.6 Si 0.4 O 4 , Li 2 P 2 O 6 or the like, Li 0.34 Perovskite-type oxides represented by La 0.51 TiO 2.94 etc., garnet-type oxides represented by LiLaZrO 2, etc. can be used.
  • the oxide conductor may contain a lithium halide such as LiCl or LiI.
  • a lithium halide such as LiCl or LiI.
  • sulfide-based inorganic solid electrolytes and polymer electrolytes can also be suitably used.
  • the above solid electrolytes can be used alone or in combination of two or more.
  • the binder is not particularly limited, and examples thereof include lithium ion conductive crystals such as Li 3 BO 3 .
  • the coating amount of the negative electrode active material on the electrode foil is adjusted to be substantially constant at 8 mg / m 2 ⁇ 0.5 mg, and the ratio of lithium conductive polymer type and lithium conductive polymer, and the press pressure are changed.
  • the porosity was adjusted by
  • the application amount of the negative electrode active material to the electrode foil is not limited to this value.
  • the amount can be appropriately adjusted in the range of about 1 to 20 mg / m 2 .
  • the lithium conductive polymer represented by the following formula (4) was dissolved in NMP, and allowed to stand at 70 ° C. for 3 hours to prepare a 10 wt% uniform polymer solution.
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the positive electrode active material LiCoO 2 is 90 wt%
  • a conductive auxiliary agent of acetylene black (AB) is 5 wt%
  • PVDF is 5% by weight solids ratio
  • LiCoO 2 AB powder having an average particle diameter of 10 [mu] m, in NMP
  • the dissolved PVDF and lithium conductive polymer solution were mixed in an agate mortar to make a slurry.
  • the slurry was applied on a 20 ⁇ m thick aluminum foil.
  • the coated electrode was allowed to stand still in a dryer maintained at 80 ° C. to distill off NMP, punched into a circle with a diameter of 15 mm, and uniaxially pressed from above and below to obtain a positive electrode.
  • ⁇ Production of resistance evaluation cell> The cell for resistance measurement was measured in a glove box purged with argon gas with a dew point of ⁇ 80 ° C. or less.
  • the negative electrode layer of the prepared electrode was made to face the polymer sheet, and the positive electrode was further laminated in the form of a polymer sheet. The laminate was inserted into the aluminate pack.
  • the polymer sheet was prepared by dissolving branched PEO and lithium salt LiFSI in acetonitrile and drying at 80 ° C. ⁇ Evaluation of resistance> Charge / discharge was performed at 0.01 C at a voltage range of 4.2 to 2.5 V, and direct current resistance was measured when discharged at SOC 50% for 10 seconds.
  • an all solid secondary battery was manufactured using a lithium conductive polymer represented by the following formula (5).
  • the average molecular weight of the lithium conductive polymer is 15,000.
  • the other preparation conditions are the same as in Example 1.
  • an all solid secondary battery was manufactured using a lithium conductive polymer represented by the following formula (6).
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the other preparation conditions are the same as in Example 1.
  • an all solid secondary battery was manufactured using the lithium conductive polymer represented by the formula (5).
  • the average molecular weight of the lithium conductive polymer is 15,000.
  • the other preparation conditions are the same as in Example 2.
  • an all solid secondary battery was produced using the lithium conductive polymer represented by the formula (4).
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the other preparation conditions are the same as in Example 1.
  • an all solid secondary battery was produced using the lithium conductive polymer represented by the formula (4).
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the other preparation conditions are the same as in Example 1.
  • an all solid secondary battery was produced using the lithium conductive polymer represented by the formula (4).
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the other preparation conditions are the same as in Example 1.
  • an all solid secondary battery was produced without using a lithium conductive polymer.
  • the other preparation conditions are the same as in Example 1.
  • an all solid secondary battery was manufactured using the lithium conductive polymer represented by the formula (6).
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the other preparation conditions are the same as in Example 1.
  • the porosity was confirmed by SEM, it was 10.7%. Due to the high porosity, the DC resistance value showed a high value of 12.1 ⁇ .
  • an all solid secondary battery was produced using the lithium conductive polymer represented by the formula (4).
  • the average molecular weight of the lithium conductive polymer is 10000.
  • the other preparation conditions are the same as in Example 1.
  • the porosity was confirmed by SEM, it was 10.1%. Due to the high porosity, the DC resistance value showed a high value of 11.4 ⁇ .
  • Table 1 shows the porosity and the output characteristics of the all-solid secondary batteries produced in Examples 1 to 5 and Comparative Examples 1 to 5.
  • Positive electrode current collector 10 Negative electrode current collector 20 Battery case 30 Positive electrode mixture layer 40 Solid electrolyte layer 50 Solid electrolyte particles 52 Negative electrode mixture layer 60 Negative electrode active material 62 Lithium conductive polymer 63 Negative electrode conductive agent 64 Positive electrode 70 Negative electrode 80 All solid secondary battery 100

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Abstract

La présente invention concerne une batterie lithium-ion à haut rendement qui présente une meilleure conductivité du lithium-ion dans un matériau actif d'électrode négative, même dans les cas où un électrolyte solide est utilisé en tant qu'électrolyte. Une batterie secondaire lithium-ion qui comprend : une électrode positive, une couche de mélange d'électrode positive étant disposée sur la surface d'un collecteur d'électrode positive ; une électrode négative, une couche de mélange d'électrode négative étant disposée sur la surface d'un collecteur d'électrode négative ; et un électrolyte solide qui est disposé entre l'électrode positive et l'électrode négative. La couche de mélange d'électrode négative contient un matériau actif d'électrode négative et un polymère conducteur lithium-ion qui est disposé parmi le matériau actif d'électrode négative. La couche de mélange d'électrode négative présente une fraction de vide inférieure ou égale à 10 %. Le rapport entre le polymère conducteur lithium-ion et la couche de mélange d'électrode négative est supérieur ou égal à 5 % en poids.
PCT/JP2014/055217 2014-03-03 2014-03-03 Batterie tout solide WO2015132845A1 (fr)

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CN108987687A (zh) * 2018-06-22 2018-12-11 中南大学 一种低温锂离子电池石墨负极材料及其制备方法
CN110212157A (zh) * 2019-07-11 2019-09-06 天津市捷威动力工业有限公司 一种锂离子电池极片及其制备方法及锂离子电池
CN111864211A (zh) * 2019-04-25 2020-10-30 本田技研工业株式会社 二次电池用电极及其制造方法、二次电池
WO2023042579A1 (fr) * 2021-09-14 2023-03-23 マクセル株式会社 Batterie

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07312219A (ja) * 1994-03-24 1995-11-28 Fuji Photo Film Co Ltd 非水二次電池と充電法
JPH117942A (ja) * 1997-06-19 1999-01-12 Matsushita Electric Ind Co Ltd 全固体リチウム電池
JPH11273735A (ja) * 1998-03-19 1999-10-08 Yuasa Corp リチウムイオンポリマー２次電池
JP2008140633A (ja) * 2006-11-30 2008-06-19 Nissan Motor Co Ltd 双極型二次電池のモジュール構造
JP2009176484A (ja) * 2008-01-22 2009-08-06 Idemitsu Kosan Co Ltd 全固体リチウム二次電池用正極及び負極、並びに全固体リチウム二次電池
JP2010009951A (ja) * 2008-06-27 2010-01-14 Mitsubishi Chemicals Corp 非水系二次電池用複合黒鉛粒子、それを含有する負極材料、負極及び非水系二次電池
JP2012234665A (ja) * 2011-04-28 2012-11-29 Nippon Zeon Co Ltd リチウム二次電池用負極スラリー組成物、リチウム二次電池用負極の製造方法、リチウム二次電池用負極及びリチウム二次電池
JP2013109881A (ja) * 2011-11-18 2013-06-06 Sumitomo Electric Ind Ltd 非水電解質電池用電極、及び非水電解質電池、並びに電動車両
WO2014020654A1 (fr) * 2012-07-30 2014-02-06 株式会社 日立製作所 Batterie secondaire à ion entièrement solide

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07312219A (ja) * 1994-03-24 1995-11-28 Fuji Photo Film Co Ltd 非水二次電池と充電法
JPH117942A (ja) * 1997-06-19 1999-01-12 Matsushita Electric Ind Co Ltd 全固体リチウム電池
JPH11273735A (ja) * 1998-03-19 1999-10-08 Yuasa Corp リチウムイオンポリマー２次電池
JP2008140633A (ja) * 2006-11-30 2008-06-19 Nissan Motor Co Ltd 双極型二次電池のモジュール構造
JP2009176484A (ja) * 2008-01-22 2009-08-06 Idemitsu Kosan Co Ltd 全固体リチウム二次電池用正極及び負極、並びに全固体リチウム二次電池
JP2010009951A (ja) * 2008-06-27 2010-01-14 Mitsubishi Chemicals Corp 非水系二次電池用複合黒鉛粒子、それを含有する負極材料、負極及び非水系二次電池
JP2012234665A (ja) * 2011-04-28 2012-11-29 Nippon Zeon Co Ltd リチウム二次電池用負極スラリー組成物、リチウム二次電池用負極の製造方法、リチウム二次電池用負極及びリチウム二次電池
JP2013109881A (ja) * 2011-11-18 2013-06-06 Sumitomo Electric Ind Ltd 非水電解質電池用電極、及び非水電解質電池、並びに電動車両
WO2014020654A1 (fr) * 2012-07-30 2014-02-06 株式会社 日立製作所 Batterie secondaire à ion entièrement solide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108987687A (zh) * 2018-06-22 2018-12-11 中南大学 一种低温锂离子电池石墨负极材料及其制备方法
CN108987687B (zh) * 2018-06-22 2021-04-27 中南大学 一种低温锂离子电池石墨负极材料及其制备方法
CN111864211A (zh) * 2019-04-25 2020-10-30 本田技研工业株式会社 二次电池用电极及其制造方法、二次电池
CN111864211B (zh) * 2019-04-25 2024-02-27 本田技研工业株式会社 二次电池用电极及其制造方法、二次电池
CN110212157A (zh) * 2019-07-11 2019-09-06 天津市捷威动力工业有限公司 一种锂离子电池极片及其制备方法及锂离子电池
WO2023042579A1 (fr) * 2021-09-14 2023-03-23 マクセル株式会社 Batterie

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