WO2016063868A1 - Bloc-batterie en film et module de batterie le comprenant - Google Patents

Bloc-batterie en film et module de batterie le comprenant Download PDF

Info

Publication number
WO2016063868A1
WO2016063868A1 PCT/JP2015/079572 JP2015079572W WO2016063868A1 WO 2016063868 A1 WO2016063868 A1 WO 2016063868A1 JP 2015079572 W JP2015079572 W JP 2015079572W WO 2016063868 A1 WO2016063868 A1 WO 2016063868A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
film
clad
solvent
separator
Prior art date
Application number
PCT/JP2015/079572
Other languages
English (en)
Japanese (ja)
Inventor
志村　健一
井上　和彦
登 吉田
Original Assignee
日本電気株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気株式会社 filed Critical 日本電気株式会社
Priority to JP2016555229A priority Critical patent/JP6601410B2/ja
Publication of WO2016063868A1 publication Critical patent/WO2016063868A1/fr

Links

Images

Classifications

    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/211—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for pouch cells
    • 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
    • H01M50/30—Arrangements for facilitating escape of gases
    • 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

Definitions

  • the present invention relates to a film-clad battery and the like, and more particularly, to a film-clad battery and the like with improved safety during overcharge.
  • Non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries have already been put to practical use as batteries for notebook computers and mobile phones due to their advantages such as high energy density, low self-discharge, and excellent long-term reliability. Yes.
  • electronic devices have been enhanced in functionality and used in electric vehicles, and development of lithium ion secondary batteries with higher energy density has been demanded.
  • charging may proceed beyond a predetermined voltage due to an abnormality in the control system, etc., and the battery may generate heat, or a large current may be released due to a short circuit outside the battery and generate heat. is there.
  • the separator when exposed to an abnormally high temperature due to a fire or the like, the separator may be damaged by heat, and the electrodes may be short-circuited to generate smoke or rupture, and further, the cathode active material may be thermally collapsed.
  • Patent Document 1 discloses a secondary battery having a constant voltage element for the purpose of preventing overcharge.
  • Patent Document 2 discloses a battery in which a positive electrode and a negative electrode are short-circuited at a temperature equal to or lower than the thermal runaway temperature of the battery by a short-circuit mechanism when heat is generated, and the battery is forcibly discharged.
  • JP 2012-74401 A Japanese Patent No. 5123624
  • Patent Document 1 it is effective to prevent the charging current from flowing through the battery body by bypassing the charging current with a constant voltage element that operates when the voltage increases during overcharging. .
  • Patent Document 2 it is also effective to short-circuit the positive electrode terminal and the negative electrode terminal using a high temperature during overcharge as a trigger.
  • the present invention prevents the deformation of the separator due to heat, and can improve safety against overcharge, discharge due to an excessively large current due to a short circuit of an external terminal, or external abnormal high temperature.
  • An object is to provide an external battery or the like.
  • a battery according to an embodiment of the present invention is as follows: A battery element having a laminate of a positive electrode, a negative electrode, and a separator; A film outer package containing the battery element together with an electrolyte solution; A film-clad battery comprising: a: The separator has a melting point or decomposition temperature of 180 ° C. or higher, b: The electrolytic solution contains three or more non-aqueous solvents each having a boiling point of 180 ° C. or less, and is a fluorine-containing compound as at least one of the non-aqueous solvents or as another non-aqueous solvent. A film-clad battery containing a non-aqueous solvent.
  • Film-clad battery refers to a battery in which a battery element is accommodated in a film-clad body together with an electrolytic solution, and generally has a flat shape as a whole.
  • a battery for an electric vehicle is required to have a large capacity, a low internal resistance, a high heat dissipation, and the like, and a film-covered battery is advantageous in these respects.
  • One film-clad battery may be referred to as a “battery cell” or simply a “cell”.
  • the “film outer package” means an outer package made of a flexible film and containing a battery element.
  • the film element is hermetically sealed by arranging two films facing each other and welding them together. Alternatively, the battery element may be sealed by folding a single film and welding the opposed surfaces.
  • the present invention it is possible to provide a film-clad battery with improved safety against overcharge, discharge due to an excessively large current due to a short circuit of an external terminal, and abnormally high temperatures in the external environment.
  • FIG. 1 It is a perspective view which shows the basic structure of the film-clad battery of one form of this invention. It is sectional drawing which shows a part of cross section of the battery of FIG. It is a top view which shows typically the internal structure of the film-clad battery of one form of this invention. It is sectional drawing which shows typically the internal structure of the film-clad battery of one form of this invention. It is a schematic diagram (front view) of the battery module which accommodated the film exterior battery in the module container. It is a schematic diagram (side view) of the battery module which accommodated the film exterior battery in the module container. It is a figure which shows typically the mechanism which applies a pressure with respect to a film-clad battery. It is a figure for demonstrating that a nonaqueous solvent vaporizes in order.
  • FIGS. 1 and 2 Basic structure of film-clad battery A basic structure of a film-clad battery 50 according to an embodiment of the present invention will be described with reference to FIGS.
  • the film-clad battery 50 according to this embodiment includes a gas release mechanism as will be described later. However, only the basic configuration of the battery is shown in FIGS. 1 and 2, and other drawings are shown for the gas release mechanism. It will be described with reference to it.
  • a film-clad battery 50 includes a battery element 20, a film-clad body 10 that accommodates it together with a nonaqueous electrolyte, and a battery element 20 that is connected to the outside of the film-clad body 10.
  • a positive electrode tab 21 and a negative electrode tab 25 are provided.
  • the battery element 20 is formed by alternately laminating a plurality of positive electrodes and a plurality of negative electrodes made of metal foils each coated with an electrode material on both sides of a separator.
  • the overall external shape of the battery element 20 is not particularly limited, in this example, it is a flat and substantially rectangular parallelepiped. Details of each part constituting the battery element 20 will be described later.
  • any material may be used as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
  • a laminate film of aluminum and resin as the outer package.
  • An exterior body may be comprised with a single member and may be comprised combining several members.
  • the film exterior body 10 is comprised with the 1st film 11 and the 2nd film 12 arrange
  • the cup portion may be formed on one film 11 and the cup portion may not be formed on the other film 12, or the cup portions may be formed on both films 11 and 12. It is good also as a structure (not shown).
  • the outline shape of the film outer package 10 is not particularly limited, but may be a quadrangle, which is a rectangle in this example. Both the films 11 and 12 are heat-welded to each other around the battery element 20 and joined. Thereby, the peripheral part of the film exterior body 10 becomes the heat welding part 15. A positive electrode tab 21 and a negative electrode tab 25 are drawn from one side of the short side of the heat-welded portion 15. Various materials can be adopted as the electrode tabs 21 and 25. As an example, the positive electrode tab 21 is aluminum or an aluminum alloy, and the negative electrode tab 25 is copper or nickel. When the material of the negative electrode tab 25 is copper, the surface may be nickel-plated.
  • the tab may be pulled out from one side of the long side.
  • the positive electrode tab 21 and the negative electrode tab 25 may be pulled out from different sides. As this example, a configuration in which the positive electrode tab 21 and the negative electrode tab 25 are drawn in opposite directions from the opposite sides can be given.
  • Each of the positive electrode and the negative electrode has an extension part protruding partially at a part of the outer periphery (see reference numerals 31a and 35a in FIG. 3).
  • the positive electrode extension part and the negative electrode extension part are formed by laminating the positive electrode and the negative electrode. The positions are staggered so as not to interfere with each other.
  • the current collector 31a is formed by stacking and connecting the extension portions of the positive electrode, and the positive electrode tab 21 is connected to the current collector 31a.
  • the extension portions are stacked and connected to each other to form the current collecting portion 35a, and the negative electrode tab 25 is connected to the current collecting portion 35a.
  • the connection between the electrode tab and the current collector may be performed by welding, for example.
  • Gas release mechanism 18 A part of the film outer package 10 is provided with a gas release mechanism 18 that releases the internal gas by opening in preference to the other welded portions when the gas pressure inside the battery exceeds a predetermined value. Yes.
  • a gas release mechanism 18 as shown in FIG. 3 may be used. This gas release mechanism 18 is preferentially peeled off by partially narrowing the seal width of the heat-welded part between the films. It is a part configured to do. More specifically, the gas release mechanism 18 may be configured such that stress concentration occurs in the portion during expansion, thereby preferentially peeling the film.
  • the seal width may be partially narrowed as shown in FIG. 3 or may be the same as other seal portions.
  • the position where the gas release mechanism 18 is formed is not particularly limited, and the gas release mechanism 18 can be provided at an arbitrary position in the heat fusion part 15 of the film outer package 10.
  • One or two or more gas release mechanisms 18 may be provided.
  • the gas release mechanism 18 is formed on the side opposite to the drawing position of the electrode tabs 21 and 25. Of course, any of the other three sides may be formed.
  • the gas release mechanism is not limited to the above-described principle, and for example, a valve that is opened when the pressure exceeds a predetermined value may be used.
  • a valve may be provided in the welding part 15 of films, or may be provided in parts other than the welding part 15 among films.
  • a valve member prepared as a separate member from the film may be provided in the heat fusion portion 15 (one example).
  • the separator in this embodiment has a high temperature of heat melting or thermal decomposition exceeding 180 ° C. and high air permeability.
  • the separator preferably has a Gurley value (sec / 100 cc) of 100 or less, more preferably 50 or less, and even more preferably 20 or less.
  • a minimum of the Gurley value of a separator it is preferable that it is 0.5 or more by an example.
  • polymer materials include polyethylene terephthalate (PET), cellulose, aramid, polyimide, polyphenylene sulfide (PPS), and the like.
  • PET polyethylene terephthalate
  • cellulose cellulose
  • aramid polyimide
  • PPS polyphenylene sulfide
  • glass fiber is mentioned with an inorganic material.
  • a high air permeability separator made of a porous film, a woven fabric, or a nonwoven fabric made of these materials can be suitably used in the present invention.
  • a separator made of woven fabric or nonwoven fabric is particularly preferable because of high air permeability.
  • Specific examples include aramid fibers, polyimide fibers, PPS fibers, and the like.
  • the porous membrane has a lower air permeability than woven fabrics and nonwoven fabrics, but unlike woven fabrics and nonwoven fabrics, there is no restriction due to the diameter of the fiber. Is suitable.
  • FIG. 4 is a schematic diagram of a cross section of a film-clad battery, in which a positive electrode 31 and a negative electrode 35 are stacked with a separator 38 interposed therebetween.
  • a separator 38 interposed therebetween.
  • the separator may have a coat layer made of a material having higher heat resistance than the base material.
  • a material for the coating layer a high heat resistant resin, an oxide such as aluminum, silicon, titanium, or a nitride can be used.
  • the thickness of the separator is preferably 50 ⁇ m or less, particularly preferably 25 ⁇ m or less so as not to impair the charge / discharge rate characteristics and energy density.
  • the negative electrode has a negative electrode current collector formed of a metal foil, and a negative electrode active material coated on both surfaces of the negative electrode current collector.
  • the negative electrode active material is bound so as to cover the negative electrode current collector with a negative electrode binder.
  • the negative electrode current collector is formed to have an extension connected to the negative electrode terminal, and the negative electrode active material is not applied to the extension.
  • the negative electrode active material in the present embodiment is not particularly limited.
  • a carbon material that can occlude and release lithium ions a metal that can be alloyed with lithium, a metal oxide that can occlude and release lithium ions, and the like. Is mentioned.
  • Examples of the carbon material include carbon, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof.
  • carbon with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a negative electrode current collector made of a metal such as copper.
  • amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
  • a negative electrode containing a metal or metal oxide is preferable in that it can improve the energy density and increase the capacity per unit weight or unit volume of the battery.
  • the metal examples include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and alloys of two or more thereof. Moreover, you may use these metals or alloys in mixture of 2 or more types. These metals or alloys may contain one or more non-metallic elements.
  • the metal oxide examples include silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, and composites thereof.
  • tin oxide or silicon oxide is included as a negative electrode active material, and it is more preferable that silicon oxide is included. This is because silicon oxide is relatively stable and hardly causes a reaction with other compounds.
  • one or more elements selected from nitrogen, boron and sulfur may be added to the metal oxide, for example, 0.1 to 5% by mass. By carrying out like this, the electrical conductivity of a metal oxide can be improved.
  • the negative electrode active material can be used by mixing a plurality of materials without using a single material.
  • the same kind of materials such as graphite and amorphous carbon may be mixed, or different kinds of materials such as graphite and silicon may be mixed.
  • the binder for the negative electrode is not particularly limited.
  • polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide, polyacrylic acid, or the like can be used.
  • the amount of the binder for the negative electrode used is 0.5 to 25 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. Is preferred.
  • the negative electrode current collector aluminum, nickel, stainless steel, chromium, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • the shape include foil, flat plate, and mesh.
  • the positive electrode has a positive electrode current collector formed of a metal foil, and a positive electrode active material coated on both surfaces of the positive electrode current collector.
  • the positive electrode active material is bound so as to cover the positive electrode current collector with a positive electrode binder.
  • the positive electrode current collector is formed to have an extension connected to the positive electrode terminal, and the positive electrode active material is not applied to the extension.
  • the positive electrode active material has a layered structure such as LiMnO 2 , LixMn 2 O 4 (0 ⁇ x ⁇ 2), Li 2 MnO 3 , Li x Mn 1.5 Ni 0.5 O 4 (0 ⁇ x ⁇ 2).
  • Lithium transition metal oxides whose specific transition metals are less than half, those in which these lithium transition metal oxides have an excess of Li over the stoichiometric composition, those having an olivine structure such as LiFePO 4 , etc. It is done.
  • these metal oxides were partially substituted with Al, Fe, P, Ti, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, etc. Materials can also be used.
  • NCM532 or NCM523 and NCM433 are within a range of 9: 1 to 1: 9 (typically 2: 1). It is also preferable to use a mixture.
  • a material having a high Ni content (x is 0.4 or less) and a material having a Ni content not exceeding 0.5 (x is 0.5 or more, for example NCM433 ) Can be combined to form a battery with high capacity and high thermal stability.
  • the positive electrode active materials can be used singly or in combination of two or more.
  • radical materials or the like can be used as the positive electrode active material.
  • the positive electrode binder the same as the negative electrode binder can be used.
  • the amount of the positive electrode binder to be used is preferably 2 to 15 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
  • the positive electrode current collector for example, aluminum, nickel, silver, or an alloy thereof can be used.
  • the shape of the positive electrode current collector include a foil, a flat plate, and a mesh.
  • an aluminum foil can be suitably used.
  • a conductive auxiliary material may be added to the positive electrode active material coating layer for the purpose of reducing impedance.
  • the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
  • the electrolytic solution in the present embodiment is a non-aqueous electrolytic solution including a lithium salt (supporting salt) and a plurality of non-aqueous solvents that dissolve the supporting salt, and non-aqueous solutions having different boiling points of 180 ° C. or less at normal pressure.
  • a non-aqueous electrolytic solution including a lithium salt (supporting salt) and a plurality of non-aqueous solvents that dissolve the supporting salt, and non-aqueous solutions having different boiling points of 180 ° C. or less at normal pressure.
  • the nonaqueous solvent having a boiling point of 180 ° C. or lower at normal pressure includes at least one set of nonaqueous solvents having a boiling point difference of 10 ° C. or higher and 40 ° C. or lower.
  • the electrolytic solution contains at least one non-aqueous solvent based on a compound containing at least fluorine.
  • the non-aqueous solvent includes at least a first solvent, a second solvent, and a third solvent in order of increasing boiling point, and the difference in boiling point between the first solvent and the second solvent is 10 ° C. or more and 40 ° C. or less. Furthermore, the difference in boiling point between the second solvent and the third solvent may be 10 ° C. or more and 40 ° C. or less. Furthermore, when the fourth solvent is not included, similarly, the difference in boiling point between the third solvent and the fourth solvent may be 10 ° C. or more and 40 ° C. or less. The same applies to the fifth and subsequent solvents.
  • the ratio of the first solvent is preferably 50% or less, more preferably 20% or less by volume ratio with respect to the whole non-aqueous solvent having a boiling point of 180 ° C. or less at normal pressure. Furthermore, the ratio of the first solvent is preferably 5% or more by volume ratio with respect to the whole non-aqueous solvent having a boiling point of 180 ° C. or less at normal pressure.
  • an aprotic organic solvent such as carbonate ester (chain or cyclic carbonate), carboxylic acid ester (chain or cyclic carboxylic acid ester), and phosphate ester can be used.
  • carbonate solvents examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate. (EMC), chain carbonates such as dipropyl carbonate (DPC); and propylene carbonate derivatives.
  • PC propylene carbonate
  • EC ethylene carbonate
  • BC butylene carbonate
  • VVC vinylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DPC dipropyl carbonate
  • propylene carbonate derivatives examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate
  • carboxylic acid ester solvent examples include aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate; and lactones such as ⁇ -butyrolactone.
  • phosphate ester examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trioctyl phosphate, triphenyl phosphate, and the like.
  • solvents that can be contained in the non-aqueous electrolyte include, for example, ethylene sulfite (ES), propane sultone (PS), butane sultone (BS), dioxathilane-2,2-dioxide (DD), and sulfolene.
  • ES ethylene sulfite
  • PS propane sultone
  • BS butane sultone
  • DD dioxathilane-2,2-dioxide
  • sulfolene sulfolene
  • non-aqueous solvent containing fluorine examples include a fluorinated carbonate compound, a fluorinated carboxylic acid ester compound, and a chain fluorinated ether compound.
  • the fluorinated carbonate is represented by the formula (1).
  • R 1 and R 2 each independently represents an alkyl group or a fluorine-substituted alkyl group, and at least one of R 1 and R 2 Is a fluorine-substituted alkyl group.
  • fluorinated carboxylic acid ester examples include, for example, ethyl pentafluoropropionate, ethyl 3,3,3-trifluoropropionate, methyl 2,2,3,3-tetrafluoropropionate, acetic acid 2, 2-difluoroethyl, methyl heptafluoroisobutyrate, methyl 2,3,3,3-tetrafluoropropionate, methyl pentafluoropropionate, methyl 2- (trifluoromethyl) -3,3,3-trifluoropropionate , Ethyl heptafluorobutyrate, methyl 3,3,3-trifluoropropionate, 2,2,2-trifluoroethyl acetate, isopropyl trifluoroacetate, tert-butyl trifluoroacetate, 4,4,4-trifluorobutyric acid Ethyl, methyl 4,4,4-trifluorobutyrate, 2,2-
  • the chain fluorinated ether compound is represented by the formula (2).
  • R a and R b each independently represents an alkyl group or a fluorine-substituted alkyl group, and at least one of Ra and Rb Is a fluorine-substituted alkyl group.
  • LiPF 6 LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiN ( CF 3 SO 2) 2 normal lithium salt which can be used in lithium ion batteries or the like can be used.
  • the supporting salt can be used alone or in combination of two or more.
  • FIG. 5 shows an example of a battery module using the film-exterior battery of the present embodiment.
  • the battery module 1 includes a plurality of film-clad batteries 50 and a module container 71 that accommodates them.
  • the module container 71 may be configured as a hard case, and the material may be any of resin, metal, a combination thereof, and the like.
  • the module container 71 may be made of a nonflammable material.
  • the module container 71 may be configured as an incombustible container such as an aluminum alloy.
  • the arrangement of the film-clad battery 50 in the container is not particularly limited, and various arrangements can be made.
  • the film-clad batteries 50 may be arranged in a plane as shown in FIG. 5 and arranged in a single layer state as shown in FIG.
  • the film-clad batteries 50 may be arranged in a plane and arranged in a stacked state as shown in FIG.
  • the orientation of the battery module 1 may be set so that the film-covered battery 50 is substantially horizontal (horizontal placement), or the orientation (vertical placement) is substantially vertical. ), An inclined direction, or a combination thereof.
  • Fig. 5 and Fig. 6 show the vertical mode.
  • the film-clad battery 50 is arranged in such an orientation that the electrode tabs 21 and 25 are on the upper side and the gas release mechanism 18 is on the lower side.
  • the gas release mechanism 18 since the gas release mechanism 18 is located below, when the gas release mechanism 18 is opened to release the internal gas, the discharge of the electrolyte in the battery is promoted by gravity, and only the gas is discharged.
  • the internal electrolyte can be discharged well, and the function of the battery can be stopped more reliably.
  • the absorbent material 73 plays a role of absorbing the electrolyte discharged through the gas release mechanism 18. Any material and shape may be used as long as they have such a function, but a material having good absorbability such as glass wool or a porous material is preferable. Moreover, it is also preferable that it is a nonflammable material.
  • the absorbent 73 may contain a chemical substance that neutralizes the acid generated when the electrolytic solution reacts with moisture. In the example of FIG.
  • one absorbent material 73 is arranged for one film-covered battery 50, but a common absorbent material 73 is used for two or more or all film-covered batteries 50 of the module container 71. It may be arranged. More specifically, the absorbent material 73 may be spread in the module container 71.
  • the electrolyte solution can be absorbed and held by the member, and therefore the electrolyte solution is contained in the module container. Can prevent spreading.
  • the absorbent 73 is not necessarily arranged near the opening of the gas release mechanism 18 as long as the absorbent 73 has the effect of absorbing and holding the electrolytic solution.
  • the module container 71 may have a substantially sealed structure so that the discharged electrolytic solution does not leak to the outside.
  • the gas discharged from the film-clad battery 50 can be released to the outside, but the electrolyte solution may not be leaked to the outside.
  • the battery module 1 includes pressing members 61 and 62 (see FIG. 6A) for pressing the battery in the thickness direction in order to prevent the film-clad battery 50 from expanding. It may be a thing.
  • the holding members 61 and 62 may have any size and shape as long as they have a pressing surface for pressing at least a part of the outer surface of the film-clad battery 50.
  • the pressing surface may be entirely in contact with the outer surface of the film-clad battery 50 (precisely, the flat surface of the raised portion corresponding to the shape of the battery element).
  • the pressing surface may be formed flat.
  • the pressing members 61 and 62 may be plate members. As an embodiment, the pressing surface may be formed in an uneven shape.
  • the pressing members 61 and 62 do not necessarily have to be pressed against the film-clad battery 50 (biased by a biasing member such as a spring). In the initial state, the pressing members 61 and 62 are simply in contact with or close to the film-clad battery 50, and when the film-clad battery 50 begins to expand, they are in close contact to prevent further deformation of the battery. If it is.
  • one pressing member 62 may be disposed between the film-clad batteries 50, and the pressing members 61 and 63 may be disposed on both sides thereof.
  • the shape and the like of the pressing member 63 may be the same as those of the pressing members 61 and 62 described above.
  • 1 is formed in a size that can press the plurality of film-clad batteries 50 arranged as shown in FIG. It is good also as one member (a plate-shaped member in an example).
  • the side surfaces of the film outer package battery 50 are at least when the expansion of the film outer package starts due to the vaporization of the nonaqueous solvent. This prevents deformation of the film outer package and the electrode laminate inside the battery.
  • the film-clad body 10 can be freely expanded, and the internal pressure of the gas release mechanism is increased even though a large amount of gas is generated.
  • the operating pressure may not be reached and the gas release mechanism may not operate.
  • the internal pressure of the battery gradually increases as the gas is generated. Therefore, the gas release mechanism can be opened at a desired timing and condition.
  • FIG. 7 schematically shows a mechanism for applying pressure to the film-clad battery 50.
  • the film-clad battery 50 is disposed on the first member 65, and the second member 69 that holds the battery is disposed on the film-clad battery 50.
  • the film-clad battery 50 is placed horizontally.
  • whether the battery is placed horizontally or vertically is not an essential difference. Whether pressing or energizing is a more important point.
  • the member corresponding to the first member 65 for example, a module container, another laminated film-clad battery, or a base member constituting a part of a device on which the battery is mounted may be used.
  • stacked, the pressing member which presses a film-clad battery, etc. may be sufficient, for example, it is a film using together biasing means, such as a spring. It is also preferable that the outer battery is pressed.
  • stacking a film-clad battery since a lower film-clad battery will be pressed by the dead weight of a battery, it may not be necessary to use an urging means together.
  • the expansion of the film-clad battery 50 be restricted by the first member 65 and the second member 69 in that the gas release mechanism can be opened at a desired timing and condition.
  • first member 65 and the second member 69 various members can be used.
  • the thermal decomposition temperature of the positive electrode active material decreases due to the extraction of Li, if the positive electrode exceeds the thermal decomposition temperature due to overheating, the positive electrode active material may run out of heat.
  • the film-clad battery of this embodiment boiles in order from a non-aqueous solvent having a low boiling point when the internal temperature of the battery becomes higher than the assumed temperature, and gas is generated.
  • the gas release mechanism is opened and the nonaqueous solvent gas inside the battery is released outside the battery.
  • the heat welding portion is peeled off in the gas release mechanism 18 so that this portion is opened, and the internal gas is released to the outside through the portion.
  • the electrolyte is also pushed out of the battery by the gas released from the battery.
  • the loss of the electrolyte increases, the Li ion conductivity between the positive electrode and the negative electrode is lost, so that the battery is safely stopped.
  • the melting point or decomposition temperature of the separator is 180 ° C. or higher, which is higher than the boiling points of at least three nonaqueous solvents. Therefore, before the separator is broken by heat, the non-aqueous solvent is vaporized and the battery loses its function. Moreover, if it is up to 180 degreeC, unless overcharge progresses abnormally, thermal decomposition of a positive electrode active material will not arise.
  • the separator of the present embodiment has high air permeability, as described above with reference to FIG. 4, bubbles due to the gas of the nonaqueous solvent generated at the electrode are likely to enter the separator. Bubbles that have entered the separator efficiently discharge the electrolyte solution from the laminate to the outside and block the conduction of Li ions between the positive electrode and the negative electrode.
  • the electrolyte can be discharged out of the battery.
  • the separator having a low air permeability the bubbles in which the nonaqueous solvent is vaporized pass through the boundary between the electrode and the separator and come out of the laminated body, so that the effect of eliminating the electrolyte solution in the separator is small.
  • the electrolytic solution includes at least three nonaqueous solvents having different boiling points of 180 ° C. or less at normal pressure.
  • the nonaqueous solvent is gasified in order from the one having the lowest boiling point (see FIG. 8; temperatures t1 to t3 indicate the boiling point of the nonaqueous solvent). It is possible to gradually increase the internal pressure of the battery while avoiding a rapid increase.
  • the boiling point at normal pressure is 180 ° C. or less and the difference in boiling points is 10
  • a set of non-aqueous solvents at a temperature between 0 ° C and 40 ° C.
  • the electrolytic solution preferably further contains at least one non-aqueous solvent of a fluorine-containing compound. Since the compound containing fluorine is a flame retardant compound, the electrolyte extruded outside the battery is prevented from igniting.
  • the heat dissipation of the film-clad battery is too high, for example, the battery temperature will not rise to a predetermined temperature unless the voltage during overcharging is increased to some extent. While the voltage is relatively low (in other words, in a safer state), it may be preferable from the viewpoint of safety to raise the battery temperature to a predetermined temperature and operate a desired safety mechanism. Based on such a concept, it is also preferable to design the heat dissipation of the film-clad battery relatively low.
  • the surface area per volume of the battery may be 5000 mm 2 / Ah or less, preferably 4000 mm 2 / Ah or less, and more preferably 2500 mm 2 / Ah.
  • both the gas and the electrolytic solution are discharged from the gas releasing mechanism, but a mechanism for discharging the electrolytic solution is provided separately from the mechanism for discharging the gas. It may be provided.
  • a leak valve that is opened when the internal pressure of the battery becomes equal to or higher than a predetermined value may be provided, and the electrolytic solution may be discharged through the leak valve.
  • the leak valve is an example, and is preferably provided at a position that is downward in the battery use posture.
  • a battery element having a laminate of a positive electrode, a negative electrode, and a separator; A film outer package containing the battery element together with an electrolyte solution; A film-clad battery comprising: a: The separator has a melting point or decomposition temperature of 180 ° C. or higher, b: The electrolytic solution contains three or more non-aqueous solvents each having a boiling point of 180 ° C. or less, and is a fluorine-containing compound as at least one of the non-aqueous solvents or as another non-aqueous solvent.
  • a film-clad battery comprising (at least one) a non-aqueous solvent from
  • the electrolyte solution contains “three or more non-aqueous solvents each having a boiling point of 180 ° C. or lower” does not exclude that a non-aqueous solvent having a boiling point of higher than 180 ° C. is included. Therefore, the electrolyte solution may contain one or more nonaqueous solvents having a boiling point exceeding 180 ° C.
  • the non-aqueous solvent includes at least a first solvent, a second solvent, and a third solvent in order of increasing boiling point, and the difference in boiling point between the first solvent and the second solvent is 10 ° C. to 40 ° C.
  • a battery module comprising the plurality of film-clad batteries according to any one of the above and a module container that houses the film-clad batteries (may be expressed as “assembled battery” or the like).
  • the pressing member may be a member whose pressing surface is in contact with the entire outer surface (maximum area surface) of the film exterior body.
  • 50% or more of the outer surface preferably 75 % Or more area may be suppressed.
  • the pressing surface may be an uneven surface.
  • the battery module according to the above further comprising an absorbent material that absorbs and holds the electrolytic solution discharged from the film-clad battery in the module container.
  • Example 1 (Positive electrode) A slurry was prepared by dispersing lithium nickelate (LNO), a carbon conductive agent, and polyvinylidene fluoride as a binder in N-methyl-2-pyrrolidone (NMP) in a weight ratio of 92: 4: 4, and then producing aluminum.
  • the positive electrode active material layer was formed by applying and drying on the current collector foil. Similarly, after forming an active material layer on the back surface of the current collector foil made of aluminum, it was rolled to obtain a positive electrode plate.
  • LNO lithium nickelate
  • NMP N-methyl-2-pyrrolidone
  • Natural graphite, sodium carboxymethyl cellulose as a thickener, and styrene butadiene rubber as a binder are mixed in an aqueous solution at a weight ratio of 98: 1: 1 to prepare a slurry, which is applied to a current collector foil made of copper. It dried and the negative electrode active material layer was formed. Similarly, after forming an active material layer on the back surface of the current collector foil made of copper, a negative electrode plate was obtained by rolling.
  • Non-aqueous solvent of the electrolytic solution a non-aqueous solvent in which EC, DEC, EMC, and fluorinated ether were mixed at a volume ratio of 30: 40: 25: 5 was used.
  • the boiling point of EC is 238 ° C.
  • the boiling point of DEC is 127 ° C.
  • the boiling point of EMC is 108 ° C.
  • H (CF 2 ) 2 CH 2 O (CF 2 ) 2 H having a boiling point of 92 ° C. was used.
  • LiPF 6 was dissolved as a supporting salt to a concentration of 1M.
  • the positive electrode plate was cut to 90 mm ⁇ 100 mm as a dimension excluding the current extraction part, and the negative electrode plate was cut to 94 mm ⁇ 104 mm as a dimension excluding the current extraction part, and laminated via a separator.
  • the capacity of the battery was 10 Ah.
  • the electrode laminate in which the electrode and the separator were laminated was connected to the electrode tab and housed in a film outer package made of a laminate film of an aluminum film and a resin film.
  • a portion where the seal width was narrowed to 2 mm was formed on the opposite side of the electrode tab.
  • the seal width was 5 mm at locations other than the gas release mechanism.
  • the outer package with a laminate film was sealed in a reduced-pressure atmosphere to produce a battery.
  • the overcharge test was conducted at 10A. When the battery voltage was about 6V, the surface temperature of the battery reached 95 ° C., and the gas release mechanism was opened. As charging continued, the voltage of the battery continued to rise, rising to over 12V. The battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 2 A battery was fabricated in the same manner as in Example 1 except that the separator was changed to a polyimide nonwoven fabric having a thickness of 20 ⁇ m.
  • the Gurley value of the used polyimide nonwoven fabric is 1.1 seconds.
  • the thermal decomposition temperature of polyimide exceeded 500 ° C., and the shrinkage rate of the separator at 200 ° C. was less than 1%.
  • the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 3 A battery was produced in the same manner as in Example 1 except that the separator was changed to a cellulose nonwoven fabric having a thickness of 25 ⁇ m.
  • the Gurley value of the used cellulose nonwoven fabric is 2.2 seconds.
  • the thermal decomposition temperature of cellulose was about 300 ° C., and the shrinkage rate of the separator at 200 ° C. was less than 1%.
  • the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 4 A battery was fabricated in the same manner as in Example 1 except that the non-aqueous solvent fluorinated ether of Example 1 was changed to bis (2,2,2-trifluoroethyl) carbonate.
  • Bis (2,2,2-trifluoroethyl) carbonate is obtained by replacing a part of hydrogen of DEC with fluorine and has a boiling point of 93 ° C.
  • the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 5 A battery was fabricated in the same manner as in Example 1 except that the mixing ratio of EC, DEC, EMC, and fluorinated ether in the nonaqueous solvent of the electrolytic solution was 30: 60: 5: 5 by volume.
  • the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 6 A battery was fabricated in the same manner as in Example 1 except that the separator was changed to a 15 ⁇ m thick aramid porous membrane.
  • the Gurley value of the aramid porous film used was 80 seconds.
  • the thermal decomposition starting temperature of the aramid used was 360 ° C., and the shrinkage rate at 200 ° C. of the separator was less than 0.5%.
  • the battery voltage was about 6 V
  • the battery surface temperature reached 95 ° C.
  • the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • a battery was fabricated in the same manner as in Example 1 except that the separator was an aramid porous film having a thickness of 12 ⁇ m.
  • the Gurley value of the aramid porous film used was 50 seconds.
  • the thermal decomposition starting temperature of the aramid used was 360 ° C., and the shrinkage rate at 200 ° C. of the separator was less than 0.5%.
  • the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 8> A battery was fabricated in the same manner as in Example 1 except that the separator was changed to a polyimide porous film having a thickness of 20 ⁇ m.
  • the polyimide porous film used had a Gurley value of 100 seconds.
  • the thermal decomposition starting temperature of the polyimide used was 500 ° C. or higher, and the shrinkage rate at 200 ° C. of the separator was less than 0.5%.
  • the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • This positive electrode active material, a carbon conductive agent, and polyvinylidene fluoride as a binder were dispersed in N-methyl-2-pyrrolidone (NMP) at a weight ratio of 92: 4: 4 to prepare a slurry, which was collected with aluminum.
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode active material layer was formed by applying and drying on an electric foil. Similarly, after forming an active material layer on the back surface of the current collector foil made of aluminum, it was rolled to obtain a positive electrode plate.
  • the negative electrode was prepared by mixing natural graphite, sodium carboxymethyl cellulose as a thickener, and styrene butadiene rubber as a binder in an aqueous solution at a weight ratio of 98: 1: 1.
  • the negative electrode active material layer was formed by applying and drying on a copper current collector foil. Similarly, after forming an active material layer on the back surface of the current collector foil made of copper, a negative electrode plate was obtained by rolling.
  • an aramid nonwoven fabric having a thickness of 20 ⁇ m was used as in Example 1.
  • the Gurley value of this aramid nonwoven fabric is 1.2 seconds.
  • the thermal decomposition temperature of the aramid used was 400 ° C. or higher, and the shrinkage rate at 200 ° C. of the separator was less than 1%.
  • the electrolyte solution used was a nonaqueous solvent in which EC, DEC, EMC, and fluorinated ether were mixed at a volume ratio of 30: 40: 25: 5.
  • the fluorinated ether is H (CF 2 ) 2 CH 2 O (CF 2 ) 2 H having a boiling point of 92 ° C.
  • LiPF 6 was dissolved as a supporting salt to a concentration of 1M. Otherwise, the battery was fabricated in the same manner as in Example 1.
  • the battery voltage was about 6 V
  • the battery surface temperature reached 95 ° C.
  • the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 10 A battery was fabricated in the same manner as in Example 9 except that an aramid porous film having a thickness of 15 ⁇ m was used as the separator.
  • the Gurley value of the aramid porous film used was 80 seconds.
  • the thermal decomposition starting temperature of the aramid used was 360 ° C., and the shrinkage rate at 200 ° C. of the separator was less than 0.5%.
  • the battery voltage was about 6 V
  • the battery surface temperature reached 95 ° C.
  • the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • a battery was produced.
  • the battery surface temperature reached 95 ° C. when the voltage of the battery rose to about 6 V, and the gas release mechanism was opened. As charging continued, the voltage of the battery continued to rise, rising to over 12V. The battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 12 A battery was fabricated in the same manner as in Example 11 except that an aramid porous film having a thickness of 15 ⁇ m was used as the separator.
  • the Gurley value of the aramid porous film used was 80 seconds.
  • the thermal decomposition starting temperature of the aramid used was 360 ° C., and the shrinkage rate at 200 ° C. of the separator was less than 0.5%.
  • the battery surface temperature reached 95 ° C. when the voltage of the battery rose to about 6 V, and the gas release mechanism was opened. As charging continued, the voltage of the battery continued to rise, rising to over 12V. The battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • This positive electrode active material, a carbon conductive agent, and polyvinylidene fluoride as a binder were dispersed in N-methyl-2-pyrrolidone (NMP) at a weight ratio of 92: 4: 4 to prepare a slurry, which was collected with aluminum.
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode active material layer was formed by applying and drying on an electric foil. Similarly, after forming an active material layer on the back surface of the current collector foil made of aluminum, it was rolled to obtain a positive electrode plate.
  • the negative electrode was prepared by mixing natural graphite, sodium carboxymethyl cellulose as a thickener, and styrene butadiene rubber as a binder in an aqueous solution at a weight ratio of 98: 1: 1.
  • the negative electrode active material layer was formed by applying and drying on a copper current collector foil. Similarly, after forming an active material layer on the back surface of the current collector foil made of copper, a negative electrode plate was obtained by rolling.
  • an aramid porous membrane having a thickness of 15 ⁇ m was used as in Example 10.
  • the Gurley value of the aramid porous film used was 80 seconds.
  • the thermal decomposition starting temperature of the aramid used was 360 ° C., and the shrinkage rate at 200 ° C. of the separator was less than 0.5%.
  • the electrolyte solution used was a nonaqueous solvent in which EC, DEC, EMC, and fluorinated ether were mixed at a volume ratio of 30: 40: 25: 5.
  • the fluorinated ether is H (CF 2 ) 2 CH 2 O (CF 2 ) 2 H having a boiling point of 92 ° C.
  • LiPF 6 was dissolved as a supporting salt to a concentration of 1M. Otherwise, the battery was fabricated in the same manner as in Example 1.
  • the battery voltage was about 6 V
  • the battery surface temperature reached 95 ° C.
  • the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • a battery was fabricated in the same manner as in Example 13 except that 0.3 O 2 was used.
  • the battery voltage was about 6 V
  • the battery surface temperature reached 95 ° C.
  • the gas release mechanism was opened.
  • the voltage of the battery continued to rise, rising to over 12V.
  • the battery surface temperature started to decrease after reaching about 140 ° C., and there was no battery rupture or smoke generation.
  • Example 1 A battery was prepared and an overcharge test was performed in the same manner as in Example 1 except that the separator of Example 1 was a polypropylene nonwoven fabric.
  • the polypropylene nonwoven fabric had a thickness of 25 ⁇ m and a Gurley value of 1.7 seconds.
  • the melting point of the used polypropylene is about 160 ° C.
  • Example 2 As a result of performing an overcharge test in the same manner as in Example 1, the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened. When charging was continued, the voltage and surface temperature of the battery continued to rise, and when the battery surface temperature reached about 130 ° C., intense smoke was generated from the opening of the gas release mechanism. On the battery surface after the test, a part of the laminate outer package was discolored black.
  • Example 2 A battery was fabricated in the same manner as in Example 1 except that EC and DEC were mixed in a volume ratio of 30:70 as the nonaqueous solvent of the electrolytic solution of Example 1.
  • Example 2 As a result of performing an overcharge test in the same manner as in Example 1, the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened. When charging was continued, the voltage and surface temperature of the battery continued to rise, and when the battery surface temperature reached about 130 ° C., intense smoke was generated from the opening of the gas release mechanism. On the battery surface after the test, a part of the laminate outer package was discolored black.
  • Example 2 As a result of performing an overcharge test in the same manner as in Example 1, the surface temperature of the battery reached 95 ° C. when the battery voltage was about 6 V, and the gas release mechanism was opened. When charging was continued, the voltage and surface temperature of the battery continued to rise, and when the battery surface temperature reached about 130 ° C., intense smoke was generated from the opening of the gas release mechanism. On the battery surface after the test, a part of the laminate outer package was discolored black.
  • the secondary battery according to one embodiment of the present invention can be used in, for example, all industrial fields that require a power source.
  • it can be used as a power source for mobile devices such as mobile phones and laptop computers; it can be used as a power source for electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles; transport for transportation such as trains, satellites, and submarines
  • electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles
  • transport for transportation such as trains, satellites, and submarines
  • It can be used as a power source for mediums; it can be used as a power storage system for storing electric power.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Gas Exhaust Devices For Batteries (AREA)
  • Cell Separators (AREA)
  • Battery Mounting, Suspending (AREA)

Abstract

La présente invention porte sur un bloc-batterie en film qui comprend : un élément de batterie qui comprend un stratifié composé d'une électrode positive, d'une électrode négative et d'un séparateur ; et un boîtier en film qui contient cet élément de batterie conjointement avec une solution électrolytique. a : Le séparateur a un point de fusion ou une température de décomposition de 180 °C ou plus. b : La solution électrolytique contient trois solvants non aqueux ou plus, dont chacun a un point de fusion de 180 °C ou moins, et un solvant non aqueux composé d'un composé contenant du fluor est contenu dans la solution électrolytique sous la forme de l'un des solvants non aqueux ou sous la forme d'un autre solvant non aqueux.
PCT/JP2015/079572 2014-10-21 2015-10-20 Bloc-batterie en film et module de batterie le comprenant WO2016063868A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016555229A JP6601410B2 (ja) 2014-10-21 2015-10-20 フィルム外装電池およびそれを備えた電池モジュール

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014-214490 2014-10-21
JP2014214490 2014-10-21
JP2015-061735 2015-03-24
JP2015061735 2015-03-24

Publications (1)

Publication Number Publication Date
WO2016063868A1 true WO2016063868A1 (fr) 2016-04-28

Family

ID=55760901

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/079572 WO2016063868A1 (fr) 2014-10-21 2015-10-20 Bloc-batterie en film et module de batterie le comprenant

Country Status (2)

Country Link
JP (1) JP6601410B2 (fr)
WO (1) WO2016063868A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021131889A1 (fr) * 2019-12-23 2021-07-01 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux et son procédé de fabrication
KR20220062046A (ko) * 2019-12-03 2022-05-13 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 이차 전지 및 이를 포함하는 장치
JP7501068B2 (ja) 2020-04-16 2024-06-18 マツダ株式会社 車載用二次電池装置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004311387A (ja) * 2003-02-18 2004-11-04 Sony Chem Corp 吸液性シート及び非水電解液電池パック
JP2006269345A (ja) * 2005-03-25 2006-10-05 Nec Lamilion Energy Ltd 過電圧検出方法、装置及びバッテリパック
JP2007173030A (ja) * 2005-12-22 2007-07-05 Toyota Motor Corp 電池
JP2011204378A (ja) * 2010-03-24 2011-10-13 Fuji Heavy Ind Ltd 蓄電デバイス
JP2012009165A (ja) * 2010-06-22 2012-01-12 Teijin Techno Products Ltd 極細径不織布からなるセパレータ
JP2012138368A (ja) * 2012-03-12 2012-07-19 Nec Energy Devices Ltd リチウムイオン電池およびそれを用いた組電池
WO2012132060A1 (fr) * 2011-03-28 2012-10-04 日本電気株式会社 Batterie secondaire et électrolyte

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004311387A (ja) * 2003-02-18 2004-11-04 Sony Chem Corp 吸液性シート及び非水電解液電池パック
JP2006269345A (ja) * 2005-03-25 2006-10-05 Nec Lamilion Energy Ltd 過電圧検出方法、装置及びバッテリパック
JP2007173030A (ja) * 2005-12-22 2007-07-05 Toyota Motor Corp 電池
JP2011204378A (ja) * 2010-03-24 2011-10-13 Fuji Heavy Ind Ltd 蓄電デバイス
JP2012009165A (ja) * 2010-06-22 2012-01-12 Teijin Techno Products Ltd 極細径不織布からなるセパレータ
WO2012132060A1 (fr) * 2011-03-28 2012-10-04 日本電気株式会社 Batterie secondaire et électrolyte
JP2012138368A (ja) * 2012-03-12 2012-07-19 Nec Energy Devices Ltd リチウムイオン電池およびそれを用いた組電池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220062046A (ko) * 2019-12-03 2022-05-13 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 이차 전지 및 이를 포함하는 장치
JP2022550792A (ja) * 2019-12-03 2022-12-05 寧徳時代新能源科技股▲分▼有限公司 二次電池及び該二次電池を備える装置
KR102566396B1 (ko) * 2019-12-03 2023-08-22 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 이차 전지 및 이를 포함하는 장치
JP7332800B2 (ja) 2019-12-03 2023-08-23 寧徳時代新能源科技股▲分▼有限公司 二次電池及び該二次電池を備える装置
WO2021131889A1 (fr) * 2019-12-23 2021-07-01 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux et son procédé de fabrication
JP7501068B2 (ja) 2020-04-16 2024-06-18 マツダ株式会社 車載用二次電池装置

Also Published As

Publication number Publication date
JP6601410B2 (ja) 2019-11-06
JPWO2016063868A1 (ja) 2017-08-03

Similar Documents

Publication Publication Date Title
JP6337777B2 (ja) セパレータ、電極素子、蓄電デバイスおよび前記セパレータの製造方法
US10587002B2 (en) Secondary battery, method for manufacturing secondary battery, electric vehicle and electricity storage system
JP4649502B2 (ja) リチウムイオン二次電池
JP6597630B2 (ja) 二次電池およびその製造方法
US10741879B2 (en) Secondary battery and production method therefor
JP6384477B2 (ja) リチウムイオン二次電池およびその製造方法
US20090226803A1 (en) Battery, battery pack and method of manufacturing connection terminal used therein
KR20140147412A (ko) 부피 팽창성 물질을 포함하는 전기화학소자용 외장재 및 이를 구비한 전기화학소자
JP6547295B2 (ja) 電池およびその製造方法
JP6634671B2 (ja) 二次電池、電動車両、蓄電システム、および製造方法
JP6601410B2 (ja) フィルム外装電池およびそれを備えた電池モジュール
KR101640889B1 (ko) 상변화 물질을 포함하는 리튬이온 이차전지 셀 및 모듈
JP6597631B2 (ja) フィルム外装電池およびそれを備えた電池モジュール
KR101025415B1 (ko) 전기 화학 소자용 외장재, 그 제조방법, 및 이를 구비한전기 화학 소자
JP2010199035A (ja) 非水電解質二次電池
JP5793411B2 (ja) リチウム二次電池
JP6531491B2 (ja) 二次電池
CN114503300B (zh) 一种改善电极组件安全性的极片及包含其的电化学装置、电子装置
JP7459960B2 (ja) 二次電池用電解液および二次電池
JP6634676B2 (ja) 電池およびその製造方法
JP2017139086A (ja) 電池用セパレータ、その製造方法及び二次電池
JP6550732B2 (ja) 二次電池
WO2016088686A1 (fr) Batterie secondaire, véhicule électrique, et système de stockage d'énergie
WO2012073748A1 (fr) Bloc-batterie stratifié et son procédé de fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15853388

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016555229

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15853388

Country of ref document: EP

Kind code of ref document: A1