WO2014156891A1 - Batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion Download PDF

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Publication number
WO2014156891A1
WO2014156891A1 PCT/JP2014/057555 JP2014057555W WO2014156891A1 WO 2014156891 A1 WO2014156891 A1 WO 2014156891A1 JP 2014057555 W JP2014057555 W JP 2014057555W WO 2014156891 A1 WO2014156891 A1 WO 2014156891A1
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WIPO (PCT)
Prior art keywords
metal
electrode plate
resin separator
lithium ion
ion secondary
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PCT/JP2014/057555
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English (en)
Japanese (ja)
Inventor
和香奈 村田
奥村　壮文
学 落田
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新神戸電機株式会社
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Publication of WO2014156891A1 publication Critical patent/WO2014156891A1/fr

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Classifications

    • 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
    • H01M10/05—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
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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 lithium ion secondary battery including an electrode plate group in which a positive electrode plate and a negative electrode plate are laminated via a resin separator.
  • Lithium ion secondary batteries are mainly used as power sources for portable devices such as notebook computers and mobile phones, taking advantage of the high energy density.
  • the inside of a cylindrical lithium ion secondary battery has a strip shape in which both the positive electrode and the negative electrode are coated with an active material on a metal foil, and the cross section is such that these electrodes are not in direct contact with a resin separator in between. It has a wound structure in which a wound group is formed in which a spiral is wound. And this winding group is accommodated in the cylindrical battery can used as a battery container, and is sealed after electrolyte solution injection.
  • the external dimensions of a general cylindrical lithium ion secondary battery are widely used as a small-sized consumer lithium ion secondary battery having a diameter of 18 mm and a height of 65 mm, which is called 18650 type.
  • this 18650 type lithium ion secondary battery lithium cobalt oxide characterized by high capacity and long life is mainly used as a positive electrode active material.
  • the battery capacity of the 18650 type lithium ion secondary battery is about 1.0 Ah to 2.5 Ah (3.7 Wh to 9.3 Wh).
  • lithium-ion secondary batteries are expected to be used not only for consumer applications but also for large-scale power storage systems for natural energy such as solar power and wind power generation.
  • the amount of electric power per system is required to be several MWh.
  • a large amount (about 1 million) of lithium ion secondary batteries are required.
  • a cell controller is attached to each battery, and the battery state is detected. For this reason, in a system that requires a large amount of batteries, a large amount of necessary cell controllers are also required, resulting in a significant increase in cost. Therefore, it is necessary to increase the capacity per battery to reduce the number of batteries and the number of cell controllers required for the system.
  • a high-capacity battery has a problem that, unlike a conventional 18650 battery, energy stored in the battery becomes high, so that it is difficult to ensure safety during unsteady times. Therefore, as shown in Patent Document 1, a method of manufacturing a separator for a lithium ion secondary battery in which an electron beam irradiation treatment is performed on the separator to prevent an internal short circuit due to the shrinkage of the separator during high temperature storage is known.
  • a metal or metal compound may be mixed as a foreign substance for some reason.
  • the inventors of the present invention have found that the possibility of occurrence of an internal short circuit of the battery is increased, starting from the metal or metal compound present in the battery as such a foreign substance.
  • a resin separator with a film thickness of 15 ⁇ m to 50 ⁇ m is used, there is a risk of internal short circuit when metal or metal compound particles having a particle size of 20 ⁇ m or more are present in the cell. Found out that it would be expensive.
  • the metal or metal compound particles mixed in the battery as a foreign substance grow as a dendrite in the battery in the process of repeated charge / discharge of the lithium ion secondary battery, thereby generating an internal short circuit.
  • the internal short circuit caused by the dendrite is generally generated by the following mechanisms (1) to (3).
  • (1) The metal or metal compound is oxidized and dissolved on the positive electrode side (M ⁇ M x + + xe ⁇ ), passes through the separator in the form of metal ions, is reduced on the negative electrode side, and is deposited on the surface of the negative electrode plate ( M x + + xe ⁇ ⁇ M).
  • the metal or metal compound reduced on the negative electrode side also precipitates in the voids of the separator.
  • the battery capacity is assumed to be about 10 Ah to 300 Ah, and the energy stored in the battery becomes high, so it is necessary to further ensure safety.
  • An object of the present invention is to provide a highly safe lithium ion secondary battery that prevents an internal short circuit even when a metal or a metal compound is mixed as a foreign substance in the battery.
  • a lithium ion secondary battery to be improved by the present invention includes an electrode plate group having a resin separator having a thickness of 15 to 50 ⁇ m, and a positive electrode plate and a negative electrode plate laminated with the resin separator interposed therebetween.
  • the “resin separator” includes both a resin separator constituted by a single resin separator sheet and a resin separator constituted by laminating a plurality of resin separator sheets.
  • the “metal or metal compound particles” do not constitute a positive electrode active material or a negative electrode active material.
  • the “metal or metal compound particles” are expected to be present in the battery as foreign matter generated by welding of electrodes and terminals in the battery manufacturing process. Examples of the “particles” include granular, flaky, spherical, columnar, and irregular shapes.
  • the granular shape is not an irregular shape but a shape having almost equal dimensions (JIS Z2500: 2000).
  • the flake shape is a plate-like shape (JIS Z2500: 2000) and is also called a scaly shape because it is thin like a scale.
  • the aspect ratio is 2 to 100 in the form of a piece.
  • the particle diameter a here is defined as the square root of the area S when the flaky particles are viewed in plan, and this is the particle diameter of the present application.
  • the “spherical shape” is a shape almost similar to a sphere (see JIS Z2500: 2000).
  • the spherical shape is not necessarily required, and the ratio of the major axis (DL) to the minor axis (DS) of the particle (DL) / (DS) (sometimes referred to as spherical coefficient or sphericity) is 1.0 to 1. .2 and the particle size in the present application refers to the major axis (DL).
  • the columnar shape includes a substantially cylindrical column, a substantially polygonal column, and the like, and the particle size in the present application refers to the height of the column.
  • the “particle size” can be measured under the conditions of a magnification of 100 to 1000 times with a microscope or 1000 to 10,000 times with a scanning electron microscope.
  • the reason why the particle size is limited to a metal or metal compound having a particle size of 20 ⁇ m or more is that if it is a metal or metal compound particle having a particle size of less than 20 ⁇ m, it is less likely to cause an internal short circuit even if it exists as a foreign substance in the battery. It is.
  • the maximum particle size of the metal or metal compound mixed in the battery manufacturing process is about 150 ⁇ m.
  • the volume of the metal or metal compound is in the range of about 4.19 ⁇ 10 3 to 1.77 ⁇ 10 6 ⁇ m 3 .
  • the metal which may be mixed in the battery in the manufacturing process is at least one metal selected from copper, iron, nickel, aluminum, manganese, and chromium.
  • the metal compound that may be mixed in the battery during the manufacturing process is an oxide of at least one metal among copper, iron, nickel, aluminum, manganese, and chromium.
  • V1 and V2 are represented by the following formula (1). It is adjusted to meet.
  • the volume V1 of the metal or metal compound particles is calculated from the mass and density of the metal or metal compound.
  • grains of a metal or a metal compound are spherical, you may calculate from ⁇ particle size (micrometer) x (1/2) ⁇ 3 * 4/3 (pi).
  • the “pore volume V2 per 1 ⁇ m 2 of the resin separator” is calculated by multiplying the volume calculated by multiplying the thickness of the resin separator and the unit area (1 ⁇ m 2 ) by the porosity of the resin separator.
  • V1 / V2 means that the volume V1 of the metal or metal compound particles is divided by the pore volume V2 of the resin separator.
  • V1 / V2 ⁇ 2250 means that the value of V1 / V2 is smaller than 2250.
  • the reduction-precipitated metal or metal compound dendrite is transferred from the surface of the negative electrode plate to the resin. It stays in the separator and can be prevented from reaching the positive electrode plate through the resin separator. As a result, a short circuit between the positive electrode and the negative electrode due to dendrites is prevented, and an internal short circuit of the battery can be prevented.
  • the relational expression between V1 and V2 is 2250 or more, precipitates such as dendrite easily reach the positive electrode from the resin separator, and a short circuit between the positive electrode and the negative electrode is likely to occur.
  • the relationship between the volume V1 of the metal or metal compound particles and the pore volume V2 of the resin separator is preferably adjusted to satisfy the relationship of the following equation (2).
  • the relational expression “150 ⁇ V1 / V2 ⁇ 2250” means that the value of V1 / V2 is larger than 150 in addition to the value of V1 / V2 being smaller than 2250. Even if the value of V1 / V2 is smaller than 2250, if the value of V1 / V2 is 150 or less, the pore volume V2 of the resin separator is relative to the volume V1 of the metal or metal compound particles. Becomes significantly larger. When the pore volume of the resin separator becomes relatively large, precipitates such as dendrites tend to penetrate the resin separator, and a short circuit between the positive electrode and the negative electrode is likely to occur. Therefore, it is preferable to adjust the value of V1 / V2 to be larger than 150 as described above.
  • the relationship between the volume V1 of the metal or metal compound particles and the pore volume V2 of the resin separator is more preferably adjusted to satisfy the relationship of the following formula (3).
  • V1 / V2 When the value of V1 / V2 is adjusted to be smaller than 2220 and larger than 165, when the particle size of the metal or metal compound exists between the resin separator and the positive electrode plate (the internal short circuit of the battery is Even in an environment in which it is likely to occur, deposits such as dendrites extending from the surface of the negative electrode plate tend to stay in the resin separator, and the short circuit between the positive electrode and the negative electrode can be reliably prevented.
  • a resin separator having a porosity adjusted to 30 to 50% is preferable to use as the resin separator.
  • the value of V1 / V2 is reduced to a value in which an internal short circuit is unlikely to occur even when metal or metal compound particles having a particle size of 20 ⁇ m or more are mixed in the battery. Easy to adjust.
  • a resin separator containing a polyolefin made of at least one of polypropylene and polyethylene is preferable to use as a material for the resin separator.
  • the present embodiment is directed to a stacked lithium ion secondary battery in which a positive electrode plate and a negative electrode plate are stacked via a resin separator
  • the present invention includes a positive electrode plate and a negative electrode plate stacked via a resin separator.
  • the present invention can also be applied to a wound lithium ion battery in which a laminated body is wound.
  • a positive electrode plate is produced by forming a positive electrode active material layer containing a positive electrode active material and a binder on a positive electrode current collector. Specifically, a positive electrode active material and a binder, and if necessary, a conductive material and a thickener mixed in a dry form into a sheet form are pressure-bonded to the positive electrode current collector, or these The material is dissolved and dispersed in a liquid medium, applied as a slurry to the positive electrode current collector, and dried to form a positive electrode active material layer on the positive electrode current collector.
  • a known lithium and transition metal composite oxide capable of inserting, desorbing and dissolving lithium can be used alone or in combination of two or more.
  • the composite oxide of lithium metal and transition metal include lithium manganate, lithium nickelate, lithium cobaltate, and lithium iron phosphate. These composite oxides may be of a single phase, a transition metal partially substituted with a different element, or a surface coated with an oxide or carbon.
  • the positive electrode conductive material a known conductive material can be arbitrarily used. Specific examples include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; and carbonaceous materials such as amorphous carbon such as needle coke. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the binder used for manufacturing the positive electrode active material layer is not particularly limited, and in the case of a coating method, any material that dissolves or disperses in the liquid medium used during electrode manufacturing may be used.
  • the binder include resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene) Rubber) Rubber-like polymers such as rubber, fluoro rubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber; ), Thermoplastic elastomeric polymers such as styrene / ethylene / butadiene / ethylene copolymers, styrene / isoprene / styrene block copolymers, or hydrogenated products thereof; syndiotactic-1, 2-polybuta
  • these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
  • a fluorine-based polymer such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene / vinylidene fluoride copolymer is preferable.
  • the positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material.
  • the material for the positive electrode current collector is not particularly limited, and any known material can be used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbonaceous materials such as soot carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.
  • the form of the positive electrode current collector is not particularly limited, and a known form can be arbitrarily used.
  • the metal material include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal.
  • a carbonaceous material a carbon plate, a carbon thin film, a carbon cylinder, etc. are mentioned. Of these, metal thin films are preferred.
  • the thickness of the thin film is arbitrary, but is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and usually 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. If the thin film is thinner than this range, the strength required for the current collector may be insufficient. Conversely, if the thin film is thicker than this range, the handleability may be impaired.
  • the negative electrode compound material containing the negative electrode active material which can electrochemically occlude / release lithium ion is apply
  • the negative electrode active material include carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, metals that can form alloys with lithium such as tin and silicon, etc. Is mentioned. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Among these, it is preferable from the viewpoint of safety to use a carbonaceous material or a lithium composite oxide.
  • the metal composite oxide is not particularly limited as long as it can occlude and release lithium, but it contains titanium and / or lithium as a constituent component in view of high current density charge / discharge characteristics. To preferred.
  • Carbonaceous materials include amorphous carbon, natural graphite, composite carbonaceous materials in which a film formed by dry CVD (Chemical Vapor Deposition) method or wet spray method is formed on natural graphite, resins such as epoxy and phenol Lithium that can occlude and release lithium by forming a carbonaceous material such as artificial graphite and amorphous carbon material that is made by firing from raw materials or pitch-based materials obtained from petroleum or coal, or by forming a compound with lithium
  • An oxide or nitride of a group 14 element such as silicon, germanium, tin, or the like, which forms a compound with metal, lithium, and is inserted into a crystal gap to absorb and release lithium, can be used.
  • the negative electrode mixture may contain two or more carbonaceous materials having different properties as a conductive material.
  • the negative electrode current collector a known one can be arbitrarily used.
  • the current collector for the negative electrode include copper, nickel, stainless steel, nickel-plated steel, and the like. Among these, copper is preferable from the viewpoint of ease of processing and cost.
  • the shape of the negative electrode current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punching metal, and foam metal when the current collector is a metal material. Among these, a metal thin film is preferable, and a copper foil is more preferable.
  • a rolled copper foil obtained by a rolling method and an electrolytic copper foil obtained by an electrolytic method can be used as the negative electrode current collector. When the thickness of the copper foil is less than 25 ⁇ m, a copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.) having higher strength than pure copper can be used.
  • the binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used during electrode production.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose; SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluorine rubber, NBR ( Acrylonitrile-butadiene rubber), rubber-like polymers such as ethylene-propylene rubber; styrene / butadiene / styrene block copolymer or hydrogenated product thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene ⁇ Thermoplastic elastomeric polymers such as butadiene / styrene copolymer, styrene /
  • the resin separator has a predetermined mechanical strength that electrically insulates both electrodes, has a high ion permeability, and is resistant to oxidation on the side in contact with the positive electrode and reducibility on the negative electrode side.
  • a resin having both is used.
  • An olefin polymer is used as such a resin.
  • a porous sheet containing at least one of polypropylene and polyethylene as a material. .
  • the resin separator As the form of the resin separator, a microporous film having a thin film shape, a pore diameter of 0.01 to 1 ⁇ m, and a thickness of 15 to 50 ⁇ m is preferably used. Further, the porosity of the resin separator is preferably 30 to 50%, more preferably 35 to 45%. Note that the resin separator of this example (a resin separator having a thickness of 15 to 50 ⁇ m) may be constituted by a single separator or may be constituted by stacking two or more separators.
  • the metal or metal compound used in this example has a particle size of 20 ⁇ m or more.
  • the metal include copper, iron, nickel, manganese, and chromium.
  • the metal compound include oxides such as copper, iron, nickel, manganese and chromium, and compounds containing two or more of these.
  • the shape of the metal or metal compound include granular shapes, flake shapes, spherical shapes, needle shapes, irregular shapes, and the like.
  • the aspect ratio (particle diameter a / average thickness t) of the particle when analyzed from the result of SEM observation is in the range of 2 to 100, and the particle diameter a at this time (the particle is viewed in plan view)
  • the square root of the area S) was defined as the particle size.
  • the ratio (DL) / (DS) of the major axis (DL) and minor axis (DS) of the particle (sometimes referred to as a spherical coefficient or sphericity) is 1.0 to 1.2.
  • the major axis (DL) at this time was defined as the particle size.
  • the height of the column is defined as the particle size.
  • metals or metal compounds are mainly mixed from manufacturing equipment and manufacturing processes. It is preferable that a metal or a metal compound having a particle size of 20 ⁇ m or more is not included in the battery, but it is difficult to prevent a metal or a metal compound having a particle size of 20 ⁇ m or more from being included in the battery in the manufacturing process. It is.
  • the lower limit of the particle size of the metal or metal compound is 20 ⁇ m, and if it is smaller than this particle size, the problem of short circuit does not occur.
  • the upper limit is not particularly limited, but the metal or metal compound that may be mixed in the manufacturing process is assumed to be 150 ⁇ m or less.
  • V1 is calculated from the mass and density of the metal or metal compound particles, or ⁇ the particle size of the metal or metal compound ⁇ (1/2) ⁇ 3 when the metal or metal compound particles are spherical. It can be calculated from x4 / 3 ⁇ .
  • V2 is obtained by multiplying the volume calculated by multiplying the thickness and unit area (1 ⁇ m 2 ) of the resin separator by the porosity of the resin separator.
  • V1 and V2 satisfy the relationship of V1 / V2 ⁇ 2220. Further, from the practical viewpoint, the relationship 150 ⁇ V1 / V2 ⁇ 2250 may be satisfied, and more preferably the relationship 165 ⁇ V1 / V2 ⁇ 2220 is satisfied.
  • the resin separator has pores inside to hold and replace the electrolyte.
  • a metal or metal compound having a particle diameter of 20 ⁇ m or more is easily oxidized and dissolved during the operation of the lithium ion secondary battery, particularly when it is present between the resin separator and the positive electrode plate. It diffuses and migrates in the voids of the separator and is reduced and deposited on the negative electrode surface. When the reduction deposition continues, the metal or metal compound is deposited not only on the negative electrode surface but also in the separator gap. When this deposit reaches the positive electrode, it is considered that the positive electrode and the negative electrode are slightly short-circuited and an internal short circuit occurs in the battery. Note that a resin separator having a thinnest film thickness of 15 ⁇ m or more, which is generally applied, does not short-circuit when a metal or a metal compound having a particle size of less than 20 ⁇ m is included.
  • Electrolytic Solution used in the lithium ion secondary battery of this example is composed of a lithium salt and a non-aqueous solvent that dissolves the lithium salt, and may further contain an additive.
  • a known lithium salt is used as an electrolyte of a non-aqueous electrolyte for a lithium ion secondary battery, and examples thereof include the following.
  • Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 .
  • Fluorine-containing organic lithium salt perfluoroalkane sulfonate such as F 3 SO 3 ; LiN (CF 3 SO 2 ) 2 , LiN (CF 3 CF 2 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 Perfluoroalkanesulfonylimide salts such as F 9 SO 2 ); perfluoroalkanesulfonylmethide salts such as LiC (CF 3 SO 2 ) 3 ; Li [PF 5 (CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 3 ) 2 ], Li [PF 3 (CF 2 CF 2 CF 3 ) 3 ], Li [PF 5 (CF 2 CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 3 ) 2 ], Li [PF 3 (CF 2 CF 2 CF 3 ) 3 ], Li [PF 3 (CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2
  • Oxalatoborate salts lithium bis (oxalato) borate, lithium difluorooxalatoborate, etc. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios. Among these, lithium hexafluorophosphate (LiPF 6 ) is preferable when comprehensively judging solubility in a solvent, charge / discharge characteristics when used in a secondary battery, output characteristics, cycle characteristics, and the like.
  • the concentration of these electrolytes in the nonaqueous electrolytic solution is not particularly limited, but is usually 0.5 mol / L or more, preferably 0.6 mol / L or more, more preferably 0.7 mol / L or more. Moreover, the upper limit is 2 mol / L or less normally, Preferably it is 1.8 mol / L or less, More preferably, it is 1.7 mol / L or less. If the concentration is too low, the electrical conductivity of the electrolyte solution may be insufficient. On the other hand, if the concentration is too high, the electrical conductivity may decrease due to an increase in viscosity, and the performance of the lithium ion secondary battery may be reduced. May decrease.
  • non-aqueous solvent a known non-aqueous solvent is used as an electrolyte of a non-aqueous electrolyte for a lithium ion secondary battery, and examples thereof include the following.
  • Cyclic carbonate The alkylene group constituting the cyclic carbonate preferably has 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms. Specific examples include ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Of these, ethylene carbonate and propylene carbonate are preferable.
  • Chain carbonate As the chain carbonate, dialkyl carbonate is preferable, and the number of carbon atoms of the alkyl group is preferably 1 to 5%, particularly preferably 1 to 4. Specifically, for example, symmetrical chain carbonates such as dimethyl carbonate, diethyl carbonate, and di-n-propyl carbonate; asymmetric chain carbonates such as ethyl methyl carbonate, methyl-n-propyl carbonate, and ethyl-n-propyl carbonate And dialkyl carbonates. Of these, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable.
  • Chain ester methyl acetate, ethyl acetate, propyl acetate, methyl propionate, etc. are mentioned.
  • Cyclic ether Tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran and the like.
  • the additive is not particularly limited as long as it is known to be used as an additive for a non-aqueous electrolyte solution for a lithium ion secondary battery, and examples thereof include the following.
  • a heterocyclic compound containing nitrogen and / or sulfur or sulfur is not particularly limited, but includes 1-methyl-2-pyrrolidinone, 1,3-dimethyl- 2-pyrrolidinone, Pyrrolidinones such as 1,5-dimethyl-2-pyrrolidinone, 1-ethyl-2-pyrrolidinone, 1-cyclohexyl-2-pyrrolidinone; 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, 3-cyclohexyl- Oxazolidinones such as 2-oxazolidinone; piperidones such as 1-methyl-2-piperidone and 1-ethyl-2-piperidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidi Imidazolidinones such as non-sulfones; sulfolane, 2-methylsulfolane, 3-methylsulfolane,
  • Sulfolanes Sulfolenes; sulfites such as ethylene sulfite and propylene sulfite; 1,3-propane sultone, 1-methyl-1,3-propane sultone, 3-methyl-1,3-propane sultone, 1,4 -Sultone such as butane sultone, 1,3-propene sultone, 1,4-butene sultone, and the like.
  • Cyclic carboxylic acid ester is not particularly limited, but ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone , ⁇ -undecalactone, ⁇ -dodecalactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -ethyl- ⁇ -butyrolactone, ⁇ -propyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -ethyl- ⁇ -Valerolactone, ⁇ , ⁇ -dimethyl- ⁇ -butyrolactone, ⁇ , ⁇ -dimethyl- ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -nonalactone, ⁇ -buty
  • Fluorine-containing cyclic carbonate is not particularly limited, and examples thereof include fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, and trifluoropropylene carbonate.
  • aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, etc .; 2-fluoro Partially fluorinated products of the above aromatic compounds such as biphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3,5-difluoro Examples thereof include fluorine-containing anisole compounds such as anisole.
  • examples of the negative electrode film forming material include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, and the like.
  • succinic anhydride and maleic anhydride are used. Two or more of these may be used in combination.
  • methyl methanesulfonate, busulfan, and dimethylsulfone are used. Two or more of these may be used in combination.
  • lithium manganate which is an active material
  • scale-like graphite average particle size: 20 ⁇ m
  • polyvinylidene fluoride as a binder
  • NMP N-methyl-2-pyrrolidone
  • the kneaded slurry was substantially evenly and evenly formed on both surfaces of an aluminum foil (positive electrode current collector) as a current collector having a thickness of 20 ⁇ m.
  • a predetermined amount was applied uniformly. Thereafter, it was dried, pressed to a predetermined density, and further cut to a width of 30 mm ⁇ 45 mm to obtain a positive electrode plate.
  • the prepared positive electrode plate and negative electrode plate are opposed to each other through a polyethylene resin separator made of a microporous film made by Asahi Kasei E-materials, and metal particles (Cu or Ni) are placed between the positive electrode plate and the resin separator.
  • metal particles Cu or Ni
  • the metal particles used were spherical. Although one metal particle is used in this example, it is considered that one or more metals or metal compounds may actually be mixed.
  • the laminate bag After pouring 1 mL of electrolyte containing 1 mol / L of lithium hexafluorophosphate as an electrolyte into a solvent in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 1: 2, the laminate bag was vacuumed with a vacuum welding device. Then, the other end of the bag was thermally welded and sealed to produce a lithium ion secondary battery with a design capacity of 40 mAh.
  • the resistance of the internal short circuit of the lithium ion secondary battery thus produced was evaluated by the method shown below.
  • species, and the particle size of the metal was charged in 25 degreeC environment.
  • a constant current and constant voltage method was adopted as a charging method. After constant current charging at 20 mA, switching to constant voltage charging was performed when the battery voltage reached 4.2 V, and charging was performed for a total of 5 hours.
  • a battery having a current value higher than 0.1 mA (compared to a battery into which no metal was introduced) at the time of constant voltage charging after 5 hours was defined as “with short circuit”.
  • the volume of the metal particles (V1) and the pore volume of the resin separator (V2) were calculated as follows.
  • Metal particle volume (V1) (1/2 of metal particle size) 3 ⁇ 4 ⁇ / 3
  • Resin separator pore volume (V2) (1 ⁇ m 2 ) ⁇ (resin separator thickness) ⁇ (separator porosity)
  • the particle size of the metal particles was measured using a microscope (manufactured by Keyence, VHX-2000) at a magnification of 1000 times.
  • a battery was manufactured by introducing one metal particle (copper and nickel) having a different particle size (particle size) on the positive electrode plate by changing the thickness of the separator, the metal species, and the particle size of the metal. did.
  • the evaluation results are shown in Table 1.
  • Example 1 and Comparative Examples 1 to 3 a resin separator having a thickness of 16 ⁇ m was used.
  • Examples 4 to 6 and Comparative Example 6 a separator having a thickness of 36 ⁇ m was used.
  • Examples 7 to 9 and Comparative Example 7 a separator having a thickness of 40 ⁇ m was used.
  • the porosity of the resin separator is in the range of 30 to 50%, and the pore volume of the resin separator obtained from these porosity is 4.19 ⁇ 10 3 to 3.35 ⁇ 10.
  • the range is 4 ⁇ m (the pore volume per 1 ⁇ m 2 is 6.2 to 16.8 ⁇ m 3 ).
  • Examples 1 to 9 spherical Cu metal having a particle size of 20 to 40 ⁇ m was used, and in Examples 10 and 11, spherical Ni metal having a particle size of 20 to 40 ⁇ m was used.
  • the volume of the metal particles is included in the range of 4.19 ⁇ 10 3 to 3.35 ⁇ 10 4 ⁇ m 3 . Note that the range of the particle diameter is only required to satisfy the above-described relationship between the volume V1 of the metal or metal compound particles and the pore volume V2 per 1 ⁇ m 2 of the resin separator. It has been confirmed that the effect can be obtained.
  • the metal or metal compound particle volume V1 and the pore volume V2 per 1 ⁇ m 2 of the resin separator satisfy the relationship of V1 / V2 ⁇ 2250. Since the pore volume V2 per 1 ⁇ m 2 of the resin separator is adjusted with respect to the volume V1, the dendrite of the reduced metal or metal compound stays in the separator from the surface of the negative electrode plate, penetrates the separator and passes through the positive electrode It can prevent reaching the board. As a result, a short circuit between the positive electrode and the negative electrode due to dendrites is prevented, and an internal short circuit of the battery can be prevented. Therefore, according to the present invention, a highly safe lithium ion secondary battery can be provided.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne une batterie secondaire au lithium-ion hautement sécurisée. Un groupement de plaques d'électrode est configuré pour comprendre : un séparateur en résine ayant une épaisseur de 15 à 50 µm ; et une plaque d'électrode positive et une plaque d'électrode négative, qui sont stratifiées avec le séparateur en résine interposé entre celles-ci. Des particules d'un métal ou d'un composé métallique, qui possèdent des diamètres de particule de 20 µm ou plus, sont présentes entre le séparateur en résine et la plaque d'électrode positive ou la plaque d'électrode négative. Le volume (V1) des particules d'un métal ou d'un composé métallique et le volume de cavités (V2) pour 1 µm² de séparateur en résine satisfont l'expression relationnelle suivante : V1/V2 < 2,250.
PCT/JP2014/057555 2013-03-29 2014-03-19 Batterie secondaire au lithium-ion WO2014156891A1 (fr)

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US9954213B2 (en) 2011-07-11 2018-04-24 California Institute Of Technology Electrochemical systems with at least one electronically and ionically conductive layer
US9991492B2 (en) 2013-11-18 2018-06-05 California Institute Of Technology Separator enclosures for electrodes and electrochemical cells
US10158110B2 (en) 2011-07-11 2018-12-18 California Institute Of Technology Separators for electrochemical systems
US10714724B2 (en) 2013-11-18 2020-07-14 California Institute Of Technology Membranes for electrochemical cells
US11271214B2 (en) 2015-12-02 2022-03-08 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells

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WO2011070710A1 (fr) * 2009-12-11 2011-06-16 パナソニック株式会社 Batterie secondaire à électrolyte non aqueux
WO2012105661A1 (fr) * 2011-02-03 2012-08-09 東レ株式会社 Film de polypropylène poreux, séparateur pour dispositif d'accumulation d'électricité et dispositif d'accumulation d'électricité
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JP2008266457A (ja) * 2007-04-20 2008-11-06 Asahi Kasei Chemicals Corp ポリオレフィン製微多孔膜
JP2009164062A (ja) * 2008-01-10 2009-07-23 Panasonic Corp 非水系二次電池およびその製造装置
JP2009199730A (ja) * 2008-02-19 2009-09-03 Panasonic Corp 非水電解質二次電池
JP2011100694A (ja) * 2009-11-09 2011-05-19 Panasonic Corp 非水電解質二次電池
WO2011070710A1 (fr) * 2009-12-11 2011-06-16 パナソニック株式会社 Batterie secondaire à électrolyte non aqueux
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9954213B2 (en) 2011-07-11 2018-04-24 California Institute Of Technology Electrochemical systems with at least one electronically and ionically conductive layer
US10158110B2 (en) 2011-07-11 2018-12-18 California Institute Of Technology Separators for electrochemical systems
US10693117B2 (en) 2011-07-11 2020-06-23 California Institute Of Technology Electrochemical systems with ionically conductive and electronically insulating separator
US11527802B2 (en) 2011-07-11 2022-12-13 California Institute Of Technology Electrochemical systems with ionically conductive and electronically insulating separator
US9991492B2 (en) 2013-11-18 2018-06-05 California Institute Of Technology Separator enclosures for electrodes and electrochemical cells
US10714724B2 (en) 2013-11-18 2020-07-14 California Institute Of Technology Membranes for electrochemical cells
US11177537B2 (en) 2013-11-18 2021-11-16 California Institute Of Technology Separator enclosures for electrodes and electrochemical cells
US11271214B2 (en) 2015-12-02 2022-03-08 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells
US11894562B2 (en) 2015-12-02 2024-02-06 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells

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