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WO2013108841A1 - Cellule secondaire à électrolyte non aqueux contenant un épurateur - Google Patents

Cellule secondaire à électrolyte non aqueux contenant un épurateur Download PDF

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Publication number
WO2013108841A1
WO2013108841A1 PCT/JP2013/050818 JP2013050818W WO2013108841A1 WO 2013108841 A1 WO2013108841 A1 WO 2013108841A1 JP 2013050818 W JP2013050818 W JP 2013050818W WO 2013108841 A1 WO2013108841 A1 WO 2013108841A1
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Prior art keywords
negative electrode
positive electrode
secondary battery
electrolyte secondary
aqueous electrolyte
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PCT/JP2013/050818
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English (en)
Japanese (ja)
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充康 今▲崎▼
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株式会社カネカ
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Publication of WO2013108841A1 publication Critical patent/WO2013108841A1/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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel 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
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a nonaqueous electrolyte secondary battery, and more particularly to improvement of charge / discharge cycle characteristics of the nonaqueous electrolyte secondary battery.
  • lithium ion secondary batteries are now widely used as power sources for mobile devices.
  • lithium ion secondary batteries have higher energy density than existing nickel-cadmium storage batteries and nickel-hydrogen storage batteries, and are therefore expected to be used for large power supplies such as electric vehicles and power storage. Since a lithium ion secondary battery is discharged with use, it must be charged after discharging. In this way, the lithium ion secondary battery is repeatedly charged and discharged during use. There is a property that the battery capacity decreases with this charge / discharge cycle, which is referred to as deterioration of the “charge / discharge cycle characteristics”. This tendency is particularly remarkable at high temperatures.
  • Patent Document 1 in order to suppress deterioration of charge / discharge cycle characteristics at high temperatures, a trapping substance that captures impurity ions such as cations and fluoride ions other than lithium ions generated inside the battery is used as a separator. By holding on the surface, the surface of the positive electrode or the negative electrode or the inside thereof, the cation or fluoride ion causing the battery deterioration is prevented from adhering to the negative electrode active material particles.
  • the trapping substance Patent Document 1 mentions activated carbon having a specific surface area of 1000 m 2 / g or a pore volume of 0.1 cc / g or more, and also includes an alkaline earth metal oxide.
  • the electrode material has a higher potential than carbon (hereinafter, when the potential is “high, low”, it is called “high” when it increases in the positive potential direction, and in the negative potential direction.
  • a negative electrode active material that operates at a low level is called “low”, even if the aforementioned trapping material is used, the trapping material is used before impurity ions such as cations or fluoride ions reach the negative electrode. There is a problem that it is difficult to obtain the captured effect.
  • the present inventor has found that a non-aqueous electrolyte secondary battery excellent in charge / discharge cycle characteristics can be obtained by making a capture body made of metal that operates at a specific potential exist in the battery.
  • the present invention has been completed. Furthermore, the present invention has been completed by finding the effect of suppressing gas generation due to the presence of the trapping body.
  • the nonaqueous electrolyte secondary battery of the present invention includes a positive electrode, a negative electrode, and a nonaqueous electrolyte layer interposed between the positive electrode and the negative electrode.
  • the positive electrode and the negative electrode are interposed between the positive electrode and the negative electrode.
  • a trapping body containing a metal, an intermetallic compound, or an alloy having a redox potential equal to or lower than the negative electrode operating potential in a state where it is not in contact with any of the above and in contact with a nonaqueous electrolyte is interposed.
  • an alkali metal, an alkali intermetallic compound, or an alloy is preferable to select an alkali metal, an alkali intermetallic compound, or an alloy as the metal contained in the capturing body.
  • the redox potential of the alkali metal is a large value of about ⁇ 3 V, and the above-described impurity ion trapping effect can be obtained efficiently.
  • the alkali metal may be lithium or sodium.
  • an alkaline earth metal, an alkaline earth intermetallic compound, or an alloy may be selected.
  • the redox potential of the alkaline earth metal is also a value close to ⁇ 3 V, and the impurity ion trapping effect described above is easily obtained.
  • the capturing body As a form in which the capturing body is disposed in the non-aqueous electrolyte secondary battery, it may be dispersed in the non-aqueous electrolyte solution. Further, when a porous film serving as a separator is interposed between the positive electrode and the negative electrode, the capturing body may be present in the porous film. You may arrange
  • the positive electrode current collector 2 and the negative electrode current collector 4 face each other and are arranged so as to overlap in plan view.
  • a positive electrode active material 5 is formed on a surface of the positive electrode current collector 2 facing the negative electrode current collector 4, and a negative electrode active material is formed on the surface of the negative electrode current collector 4 facing the positive electrode current collector 2.
  • Substance 6 is formed.
  • An aggregate of the positive electrode current collector 2 and the positive electrode active material 5 is referred to as a “positive electrode”
  • an aggregate of the negative electrode current collector 4 and the negative electrode active material 6 is referred to as a “negative electrode”.
  • porous membrane separators 7a and 7b are interposed in a two-stage configuration.
  • the inside of the separators 7a and 7b, the gap between the separator 7a and the positive electrode active material 5, and the gap between the separator 7b and the negative electrode active material 6 are impregnated with a non-aqueous electrolyte solution responsible for ion conduction such as lithium ions. is doing.
  • a frame is formed so as to close between the peripheral part of the positive electrode current collector 2 and the peripheral part of the negative electrode current collector 4. Insulating sealing material 8 is formed.
  • the positive electrode current collector 2 and the negative electrode current collector 4 are not in contact with either the positive electrode current collector 2 or the negative electrode current collector 4.
  • an alkali metal, an alkali intermetallic compound or alloy, or an alkaline earth metal, alkaline earth intermetallic compound or alkaline earth metal alloy is interposed in contact with the nonaqueous electrolyte.
  • This alkali metal, alkali metal intermetallic compound or alloy, or alkaline earth metal, alkaline earth intermetallic compound, or alkaline earth metal alloy is referred to as “capturing body” 9 in this specification.
  • the alkali metal include lithium, sodium, and potassium.
  • alkaline earth metals include magnesium and calcium.
  • the structure for providing the capturing body 9 of the present invention in the nonaqueous electrolyte secondary battery 1 is not limited.
  • the capturing body 9 may be formed as a plurality of particles and dispersed in the nonaqueous electrolyte solution. In this way, when the capturing body 9 is formed as a plurality of particles and dispersed in the nonaqueous electrolyte solution, one particle must not contact both electrodes simultaneously.
  • each particle may be a sphere, ellipsoid, cylinder, needle, cuboid, polyhedron, or the like. Since the dimensional ratio is not limited in the case of a rectangular parallelepiped, the shape may be a plate piece or a foil piece.
  • the volume density of the particles is preferably in the range of 2 to 20 parts by volume with respect to 100 parts by volume of the nonaqueous electrolyte solution. If it exceeds this range, the movement of the electrolyte solution and ions will be inhibited, and if it falls below this range, the function of trapping impurities will be reduced, which is not preferable.
  • FIG. 4 is a perspective view showing the structure of the capturing body 9 formed in a mesh shape.
  • the mesh shape in this case is not limited, and may be a mesh obtained by knitting a vertical capturing body 9 and a horizontal capturing body 9 at right angles as shown in FIG. It may be knitted.
  • the shape of each bar or elongated body constituting the lattice or mesh may be a circle, an ellipse, a rectangle, or a polygon. Since the dimensional ratio is not limited when the cross section is rectangular, it may be plate-shaped or foil-shaped. However, if the thickness t of the rod or the elongated body is too thick, further rolling of the battery occurs due to compression from above and below during battery formation. Therefore, in order to prevent this rolling, the thickness t is preferably 100 ⁇ m or less.
  • the material of the frame 10 needs to be a substance that does not react with the non-aqueous electrolyte solution, but the material is arbitrary as long as it is satisfied.
  • a frame made by molding a strong material such as stainless steel
  • a frame made by molding the alloy If stainless steel or the like is used, the strength can be easily secured and the handling becomes convenient. If produced using an alkali metal or alkaline earth metal, the frame itself can have the same trapping action as the trap 9.
  • an alkali metal, an alkali intermetallic compound or alloy, or an alkaline earth metal an alkaline earth intermetallic compound or alloy is formed into a plate having a thickness t.
  • a hole such as a circle, an ellipse, a triangle, a rectangle, or a polygon may be punched in the hole.
  • a binder may be used to facilitate the forming.
  • the binder is not particularly limited, and for example, at least one selected from the group consisting of polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polyimide, and derivatives thereof can be used.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • styrene-butadiene rubber polyimide, and derivatives thereof can be used.
  • the capturing body 9 of the present invention may be a “single unit” of an alkali metal, an alkali intermetallic compound or alloy, or an alkaline earth metal, an alkaline earth intermetallic compound or alloy.
  • the following structure may be used. That is, particles, lattices, nets, plates before punching, etc. are composed of a substrate of a different metal or a different material, and on the surface of the different metal or different material substrate, an alkali metal, an alkali intermetallic compound or alloy, or An alkaline earth metal, an alkaline earth intermetallic compound or alloy may be formed into a thin film by a technique such as coating, plating, vapor deposition, or sputtering.
  • the nonaqueous electrolyte secondary battery 1 it is not always necessary to use the independent separators 7a and 7b unless the positive electrode and the negative electrode are in direct contact. That is, a structure without the separators 7a and 7b is also conceivable.
  • a gel-like material may be used as the nonaqueous electrolyte in order to prevent contact between the positive electrode and the negative electrode.
  • a gel-like nonaqueous electrolyte when using a gel-like nonaqueous electrolyte, when forming the capturing body 9 of the present invention as a plurality of particles, it is dispersedly arranged inside the gel-like nonaqueous electrolyte. Further, when the planar capturing body 9 is inserted and arranged, it is inserted and arranged in the gel-like nonaqueous electrolyte so as not to contact either the positive electrode or the negative electrode.
  • the negative electrode used in the nonaqueous electrolyte secondary battery of the present invention is composed of at least a negative electrode active material or a negative electrode active material and a current collector.
  • the negative electrode active material may contain a conductive additive and a binder as necessary. It is preferable to use a material that operates at ⁇ 2.7 V or more and ⁇ 1.0 V or less with respect to a standard hydrogen electrode as the negative electrode active material.
  • transition metal-containing oxides such as molybdenum oxide, niobium oxide, manganese oxide, lithium manganese oxide, titanium oxide, lithium titanium oxide, nickel nitride, manganese nitride, iron nitride, etc.
  • a binder may be used to form the negative electrode of the present invention.
  • the binder is not particularly limited, and for example, at least one selected from the group consisting of polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polyimide, and derivatives thereof can be used.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • styrene-butadiene rubber polyimide, and derivatives thereof
  • the binder is preferably dissolved or dispersed in a non-aqueous solvent or water from the viewpoint of easy production of the negative electrode.
  • the amount of the binder contained in the negative electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the negative electrode active material. If it is this range, the adhesiveness of a negative electrode active material and a conductive support material will be maintained, and adhesiveness with a collector can fully be acquired.
  • the negative electrode of the present invention may contain a conductive additive as necessary. Although it does not specifically limit as a conductive support material, A carbon material and / or a metal microparticle are preferable.
  • Examples of the carbon material include natural graphite, artificial graphite, vapor-grown carbon fiber, carbon nanotube, acetylene black, ketjen black, and furnace black.
  • Examples of the metal fine particles include copper, aluminum, nickel, and an alloy containing at least one of these. Further, the fine particles of inorganic material may be plated. These carbon materials and metal fine particles may be used alone or in combination of two or more.
  • the amount of the conductive additive contained in the negative electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the negative electrode active material. . If it is a range, the electroconductivity of a negative electrode will be ensured.
  • the material of the current collector used for the negative electrode of the nonaqueous electrolyte secondary battery of the present invention include copper, aluminum, nickel, an alloy containing at least one of these, or a conductive polymer.
  • the shape include a foil shape, a mesh shape, a punching shape, an expanded shape, and a foam structure.
  • the mesh shape is a woven or unemployed cloth made of metal or conductive polymer fibers.
  • the thickness of the fiber is preferably 50 ⁇ m or more and 2000 ⁇ m or less. When the thickness is less than 50 ⁇ m, the strength of the current collector is weak. Therefore, when the active material mixture is supported on the current collector, the current collector tends to be easily broken. On the other hand, when a fiber thicker than 2000 ⁇ m is used, the opening becomes too large to make the porosity described later, and it tends to be difficult to hold the active material mixture by the mesh.
  • the punching shape is a plate in which holes such as a circle, a rectangle, or a hexagon are formed, and a metal made of metal is punching metal.
  • the porosity corresponds to the hole area ratio, which is determined by the hole diameter and bone ratio, hole shape, and hole arrangement.
  • the shape of the hole is not particularly limited, but from the viewpoint of increasing the open area ratio, a round hole 60 ° staggered type and a square hole staggered / parallel type are preferable.
  • the expanded shape is a staggered cut made on a plate and stretched to form a mesh. Expanded metal is made of metal.
  • the porosity corresponds to the hole area ratio, which is determined by the hole diameter and bone ratio, the hole shape, and the hole arrangement.
  • the foam structure has a three-dimensional network structure like a sponge and has continuous pores.
  • the structure is determined by the pore size and porosity.
  • the shape and diameter of the continuous holes are not particularly limited, but a structure having a high specific surface area is preferable.
  • the metal used in the current collector of the present invention may be stable between negative electrode operating voltages, preferably copper and its alloys when the operating potential is ⁇ 2.3 V or lower, and aluminum and its alloys when ⁇ 2.3 V or higher. Is preferred.
  • the negative electrode of the present invention is produced by, for example, supporting a negative electrode mixture comprising a negative electrode active material, a conductive additive, and a binder on a current collector. It is preferable to prepare a negative electrode by preparing a slurry with a binder and a solvent, filling and applying the obtained slurry to the pores of the current collector and the outer surface thereof, and then removing the solvent. Alternatively, the mixture of the negative electrode active material, the conductive additive and the binder may be supported on the current collector as it is without being dispersed in the solvent.
  • the slurry is not particularly limited, but it is preferable to use a ball mill, a planetary mixer, a jet mill, or a thin film swirling mixer because the negative electrode active material, the conductive additive, the binder, and the solvent can be mixed uniformly.
  • the production of the slurry is not particularly limited, it may be produced by mixing the negative electrode active material, the conductive additive, and the binder and then adding a solvent, or the negative electrode active material, the conductive additive, the binder, and the solvent together. You may mix and produce.
  • the solid content concentration of the slurry is preferably 30 wt% or more and 80 wt% or less. If it is less than 30 wt%, the viscosity of the slurry tends to be too low, whereas if it is higher than 80 wt%, the viscosity of the slurry tends to be too high, and it may be difficult to form an electrode described later.
  • the solvent used for the slurry is preferably a non-aqueous solvent or water.
  • the non-aqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, ethyl acetate, and tetrahydrofuran. Moreover, you may add a dispersing agent and a thickener to these.
  • the method for supporting the negative electrode mixture on the current collector is not particularly limited, but for example, a method of removing the solvent after applying the slurry with a doctor blade, die coater, comma coater or the like, or a method of removing the solvent after adhering to the current collector by spraying.
  • a removal method and a method of removing the solvent after impregnating the current collector in the slurry are preferable.
  • the method for removing the solvent is preferable because it is easy to dry using an oven or a vacuum oven. Examples of the atmosphere include room temperature or high temperature air, an inert gas, and a vacuum state.
  • the negative electrode may be formed before or after forming the positive electrode described later.
  • the negative electrode active material, conductive additive and binder When the negative electrode active material, conductive additive and binder are not dispersed in the solvent, the negative electrode active material, conductive additive and binder can be mixed uniformly, so use a ball mill, planetary mixer, jet mill, or thin film swirl mixer. After preparing the mixture, it is preferable to carry the mixture on the current collector.
  • the method of supporting the mixture on the current collector is not particularly limited, and a method of pressing the mixture after it is packed on the current collector is preferable.
  • the press may be heated.
  • the electrode may be compressed before or after the above-described positive electrode is formed.
  • the positive electrode used in the nonaqueous electrolyte secondary battery of the present invention is composed of at least a positive electrode mixture, or a positive electrode mixture and a current collector.
  • a positive electrode mixture contains a positive electrode active material and a binder at least, and a conductive support material as needed.
  • the positive electrode active material is not particularly limited, but a composite oxide, composite nitride, composite containing an alkali metal and / or an alkaline earth metal having an operating potential of ⁇ 0.2 V to 2.2 V with respect to a standard hydrogen electrode. At least one selected from the group consisting of fluoride, composite sulfide, composite selenide and the like can be used.
  • a binder may be used for the positive electrode active material. What was illustrated by the binder used for the negative electrode mixture mentioned above is applicable similarly.
  • the binder is preferably dissolved or dispersed in a non-aqueous solvent or water from the viewpoint of easy production of the positive electrode.
  • a non-aqueous solvent those exemplified above for the non-aqueous solvent can be similarly applied. You may add a dispersing agent and a thickener to these.
  • the positive electrode of the present invention may contain a conductive additive as necessary. Although it does not specifically limit as a conductive support material, A carbon material or a metal microparticle is preferable. Examples of the carbon material include the same carbon materials that can be contained in the negative electrode. Examples of the metal fine particles include aluminum and aluminum alloys. Further, the fine particles of inorganic material may be plated. These carbon materials and metal fine particles may be used alone or in combination of two or more.
  • the amount of the conductive additive contained in the positive electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the positive electrode active material. . If it is a range, the electroconductivity of a positive electrode will be ensured. Moreover, adhesiveness with a binder is maintained and sufficient adhesiveness with a collector can be obtained. On the other hand, when a larger amount of conductive aid than 30 parts by weight is used, the volume occupied by the conductive aid increases and the energy density tends to decrease.
  • A shows the electric capacity per 1 cm ⁇ 2> of positive electrodes
  • B shows the electric capacity per 1 cm ⁇ 2> of negative electrodes.
  • B / A is less than 0.7
  • the potential of the negative electrode may become the deposition potential of alkali metal and / or alkaline earth metal during overcharge, while B / A is greater than 1.3.
  • Side reactions may occur because there are many negative electrode active materials not involved in the battery reaction.
  • control of the area of a positive electrode and a negative electrode is not specifically limited, For example, in the case of slurry coating, it can carry out by controlling the coating width.
  • the thickness of the separator is preferably 1 to 500 ⁇ m. If it is less than 1 ⁇ m, it tends to break due to insufficient mechanical strength of the separator and cause an internal short circuit. On the other hand, when it is thicker than 500 ⁇ m, the load characteristics of the battery tend to be reduced due to the increase in the internal resistance of the battery and the distance between the positive and negative electrodes. A more preferred thickness is 10 to 50 ⁇ m.
  • the area ratio between the separator and the negative electrode used in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but preferably satisfies the following formula (3).
  • dimethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, tetrahydrofuran, ⁇ -butyrolactone, 1,2-dimethoxyethane, Sulfolane, dioxolane, methyl propionate and the like can be used.
  • These solvents may be used alone or as a mixture of two or more. However, in view of the ease of dissolving the solute described below and the high conductivity of lithium ions, a mixture of two or more of these solvents. Is preferably used.
  • a gel electrolyte in which an electrolyte is impregnated in a polymer can also be used.
  • the solute is not particularly limited.
  • lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiBOB (Lithium Bis (Oxalato) Borate), LiN (SO 2 CF 3 ) 2
  • Sodium salts such as NaClO 4 , NaBF 4 and NaPF 6 and magnesium salts such as Mg [AlCl 2 (C 4 H 9 ) (C 2 H 5 )] 2 , C 6 H 5 MgCl and C 6 H 5 MgBr are used as solvents. It is preferable because it is easily dissolved.
  • the concentration of the solute contained in the electrolytic solution is preferably 0.5 mol / L or more and 2.0 mol / L or less. If it is less than 0.5 mol / L, the desired ionic conductivity may not be exhibited. On the other hand, if it is higher than 2.0 mol / L, the solute may not be dissolved any more, and the viscosity increases and the load characteristic decreases. To do.
  • the non-aqueous electrolyte solution may contain a trace amount of a flame retardant, a stabilizer and the like.
  • Li 4 Ti 5 O 12 / Li 1.1 Al 0.1 Mn 1.8 O 4 battery was produced as follows. (Preparation of negative electrode)
  • the negative electrode active material Li 4 Ti 5 O 12 can be found in the literature ("Zero-Strain Insertion Material of Li [Li1 / 3Ti5 / 3] O4 for Rechargeable Lithium Cells" J. Electrochem. Soc., Volume 142, Issue 5, pp. 1431-1435 (1995)).
  • Example 3 A non-aqueous electrolyte secondary battery (Li 4 Ti 5 O 12 / NaNi 0.5 Mn 0.5 O 2 ) was used in the same manner as in Example 5 except that the trapping body (lithium metal pressed onto the stainless steel frame) was not inserted in Example 5. Battery).
  • the constant current I was set to a current value at which discharge was completed in just one hour by discharging the cell having the capacity measured in the above ⁇ Measurement of negative electrode and positive electrode capacities> (referred to as “1 hour Rate current value)). In this way, charge / discharge was repeated a predetermined number of times to measure how much the battery capacity had decreased.
  • Battery capacity refers to a value “TI” obtained by multiplying current I by time T from the start of discharge of the battery to the end of discharge. At the beginning of the cycle, the internal resistance of the cell is small and the battery capacity (TI value) is large, but when the cycle is repeated, the battery capacity decreases and the discharge ends in a short time. Since the value of the current I is constant, the battery capacity may be considered to be proportional to the discharge time T.
  • Example 6 Comparative Examples 1 to 2, and Comparative Example 4
  • the battery capacity retention rate after repeating charge / discharge 250 times using a charge / discharge test apparatus HJ1005SD8; manufactured by Hokuto Denko Co., Ltd.
  • HJ1005SD8 a charge / discharge test apparatus
  • Example 5 since the battery capacity maintenance factor after repeating charging / discharging 100 times was measured, it shows in Table 1.
  • the “battery capacity maintenance rate” is a numerical value (unit%) obtained by dividing “battery capacity after repeated charging / discharging a predetermined number of times” by “battery capacity in the first cycle of charging / discharging cycle test”.
  • the cell was immersed in ethylene carbonate before and after the measurement, and the increased volume difference was measured, and this was taken as the gas generation amount.
  • the measurement results of the gas generation amount are listed together in Table 1 (unit: mL).
  • the nonaqueous electrolyte secondary battery (Li 4 Ti 5 O 12 / Li 1.1 Al 0.1 Mn 1.8 O 4 battery) of Comparative Example 1 has a current value of 60 ° C., upper limit voltage 3.4 V, lower limit voltage 0 V, and 1 hour rate.
  • a 250 cycle test was conducted. The battery capacity gradually decreased with each cycle, and the capacity retention rate at 250 cycles was 89% of the initial stage. The amount of gas generated depending on the charge / discharge cycle was 8.76 mL.
  • a 250 cycle test was conducted at a lower limit voltage of 0 V and a current value of 1 hour rate.
  • the battery capacity gradually decreased with each cycle, and the capacity retention rates at 250 cycles were 94% and 92% of the initial values, respectively.
  • the amounts of gas generated depending on the charge / discharge cycle were 4.30 mL and 5.44 mL, respectively.
  • the non-aqueous electrolyte secondary battery of Example 3 (Li 4 Ti 5 O 12 / Li 1.1 Al 0.1 Mn 1.8 O 4 battery, magnesium metal frame) is also 60 ° C., upper limit voltage 3.4 V, lower limit voltage 0 V, 1 hour rate
  • a 250 cycle test was conducted at a current value of. The capacity gradually decreased with each cycle, and the capacity retention rate at 250 cycles was 91% of the initial stage. The amount of gas generated due to the charge / discharge cycle was 6.22 mL. From this, it can be seen that by arranging the alkaline earth metal in the cell, the charge / discharge cycle characteristics are improved and gas generation is suppressed.
  • the nonaqueous electrolyte secondary battery (TiO 2 (B) / Li 1.1 Al 0.1 Mn 1.8 O4 battery) of Comparative Example 2 is 250 cycles at 60 ° C., upper limit voltage 3.4 V, lower limit voltage 0 V, and current value of 1 hour rate. A test was conducted. The capacity decreased with each cycle, and the capacity retention rate at 250 cycles was 66% of the initial stage. Moreover, the gas generation amount resulting from a charging / discharging cycle was 10.78 mL.
  • the nonaqueous electrolyte secondary battery (Li 4 Ti 5 O 12 / NaNi 0.5 Mn 0.5 O 2 battery) of Comparative Example 3 is 100 cycles at 25 ° C., upper limit voltage 3.4 V, lower limit voltage 0 V, and current value of 1 hour rate. A test was conducted. The capacity retention rate at 100 cycles was 61% of the initial value. Moreover, the gas generation amount resulting from a charging / discharging cycle was 17.78 mL.
  • Example 6 Li 4 Ti 5 O 12 / captured dispersion PEO / Li 1.1 Al 0.1 Mn 1.8 O 4 battery
  • 60 ° C. upper limit voltage 3.4 V
  • lower limit voltage 0 V 1
  • a 250 cycle test was conducted at the current value of the time rate.
  • the capacity retention rate at 250 cycles was 89% of the initial stage, and the amount of gas generated due to the charge / discharge cycle was 2.26 mL. Therefore, the charge / discharge cycle characteristics were improved by dispersing the trap in the solid electrolyte. It can be seen that the generation of gas due to the charge / discharge cycle is suppressed.

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Abstract

La présente invention concerne une cellule secondaire à électrolyte non aqueux qui a d'excellentes caractéristiques de cycle de charge-décharge et qui supprime la génération de gaz due à la présence dans la cellule d'un épurateur contenant du métal agissant à un potentiel spécifié. La cellule secondaire à électrolyte non aqueux a une électrode positive, une électrode négative, et une couche d'électrolyte non aqueux interposée entre l'électrode positive et l'électrode négative. L'épurateur est présent entre l'électrode positive et l'électrode négative dans un état n'étant pas en contact ni avec l'électrode positive ni avec l'électrode négative, et en contact avec l'électrolyte non aqueux, et l'épurateur contient un métal alcalin, un métal de terre alcaline ou un autre métal ayant un potentiel d'oxydoréduction inférieur au potentiel d'action négatif d'électrons, ou un composé intermétallique ou un alliage.
PCT/JP2013/050818 2012-01-19 2013-01-17 Cellule secondaire à électrolyte non aqueux contenant un épurateur WO2013108841A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017204452A (ja) * 2016-05-13 2017-11-16 株式会社東芝 非水電解質電池、組電池及びバッテリーシステム
CN108172895A (zh) * 2016-12-07 2018-06-15 松下知识产权经营株式会社 二次电池
US10847774B2 (en) 2016-09-21 2020-11-24 Kabushiki Kaisha Toshiba Assembled battery, battery pack and vehicle
CN112635926A (zh) * 2019-10-07 2021-04-09 株式会社杰士汤浅国际 铅蓄电池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024243888A1 (fr) * 2023-05-31 2024-12-05 宁德时代新能源科技股份有限公司 Séparateur et son procédé de préparation, batterie secondaire et dispositif électrique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11121032A (ja) * 1997-10-13 1999-04-30 Mitsubishi Chemical Corp 非水系電解液二次電池
WO2001063687A1 (fr) * 2000-02-24 2001-08-30 Japan Storage Battery Co., Ltd. Element secondaire a electrolyte non-aqueux
JP2002093463A (ja) * 2000-09-11 2002-03-29 Japan Storage Battery Co Ltd 非水電解質電池
JP2005317551A (ja) * 2004-04-29 2005-11-10 Samsung Sdi Co Ltd リチウム二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11121032A (ja) * 1997-10-13 1999-04-30 Mitsubishi Chemical Corp 非水系電解液二次電池
WO2001063687A1 (fr) * 2000-02-24 2001-08-30 Japan Storage Battery Co., Ltd. Element secondaire a electrolyte non-aqueux
JP2002093463A (ja) * 2000-09-11 2002-03-29 Japan Storage Battery Co Ltd 非水電解質電池
JP2005317551A (ja) * 2004-04-29 2005-11-10 Samsung Sdi Co Ltd リチウム二次電池

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017204452A (ja) * 2016-05-13 2017-11-16 株式会社東芝 非水電解質電池、組電池及びバッテリーシステム
US10847774B2 (en) 2016-09-21 2020-11-24 Kabushiki Kaisha Toshiba Assembled battery, battery pack and vehicle
CN108172895A (zh) * 2016-12-07 2018-06-15 松下知识产权经营株式会社 二次电池
CN108172895B (zh) * 2016-12-07 2022-08-09 松下知识产权经营株式会社 二次电池
CN112635926A (zh) * 2019-10-07 2021-04-09 株式会社杰士汤浅国际 铅蓄电池

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