WO2012132153A1 - Batterie secondaire - Google Patents

Batterie secondaire Download PDF

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Publication number
WO2012132153A1
WO2012132153A1 PCT/JP2011/079986 JP2011079986W WO2012132153A1 WO 2012132153 A1 WO2012132153 A1 WO 2012132153A1 JP 2011079986 W JP2011079986 W JP 2011079986W WO 2012132153 A1 WO2012132153 A1 WO 2012132153A1
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WO
WIPO (PCT)
Prior art keywords
negative electrode
secondary battery
active material
metal
battery according
Prior art date
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PCT/JP2011/079986
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English (en)
Japanese (ja)
Inventor
川崎　大輔
井上　和彦
竜一 笠原
入山　次郎
Original Assignee
日本電気株式会社
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Application filed by 日本電気株式会社 filed Critical 日本電気株式会社
Priority to JP2013507076A priority Critical patent/JP6060897B2/ja
Publication of WO2012132153A1 publication Critical patent/WO2012132153A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 secondary battery.
  • Patent Document 1 describes that an oxide or silicate of silicon containing lithium is used as a negative electrode active material of a non-aqueous electrolyte secondary battery.
  • Patent Document 2 discloses carbon material particles (for example, graphite) capable of absorbing and releasing lithium ions, metal particles capable of alloying with lithium (for example, silicon, aluminum, tin, indium, zinc), and oxidation capable of absorbing and releasing lithium ions.
  • a negative electrode for a secondary battery is described which includes an active material layer containing metal particles (eg, silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, phosphoric acid compound, boric acid compound).
  • Patent Document 3 describes a negative electrode material for a non-aqueous electrolyte secondary battery using a conductive silicon composite in which the surface of a particle having a structure in which silicon microcrystals are dispersed in a silicon compound is coated with carbon.
  • Patent Document 4 describes an active material particle containing silicon and / or silicon alloy having a specific average particle diameter and particle size distribution, and a negative electrode for a lithium secondary battery containing polyimide as a binder.
  • Patent Document 5 describes a negative electrode for a non-aqueous electrolyte secondary battery containing an active material containing Si, polyimide and polyacrylic acid as a binder, and a carbon material as a conductive material.
  • Patent Document 6 discloses a non-aqueous electrolyte secondary battery including active material particles in which a mixture of single silicon and silicon oxide is coated with carbon (a mixture of amorphous carbon and graphite) and a thermosetting resin as a binder. A negative electrode is described. And as this binder, polyimide, polyamide, polyamide imide, polyacrylic acid type resin are illustrated, and about polyimide and polyacrylic acid type resin, the battery using these is produced and the evaluation is performed.
  • Patent Document 7 in a negative electrode for a non-aqueous electrolyte secondary battery formed by forming a coating film comprising an electrode active material carrier and a binder component on the surface of a metal foil, the ratio of the adhesion area of the coating film to the metal foil surface is While being prescribed, including a polyamide imide resin as a binder component is described.
  • Patent Document 8 discloses a polyamideimide having excellent adhesion, which contains 4,4'-diaminodiphenyl ether residue and m-phenylenediamine residue in a specific ratio, and has a specific amount of remaining carboxyl group and gelation activity.
  • the resin is described and can be used as a binder for Li-ion secondary batteries.
  • Patent documents 9 and 10 describe a resin containing a specific aramid structural unit and a specific amidimide structural unit. Further, Patent Document 9 has a structural unit in which a carboxyl group is left without imide ring closure in addition to these structural units, and by having a specific copolymerization composition, it is excellent in adhesiveness, and volume expansion by charge and discharge. It is described that it is possible to provide a resin for a lithium ion secondary battery electrode binder which is excellent in the retention of the negative electrode active material having a large shrinkage.
  • Patent Document 11 an oxide in which the surface of a compound containing Si and O is coated with carbon is used as a negative electrode active material, and a polyimide, a polyamide imide or a polyamide is used as a binder.
  • a lithium secondary battery is described in which at least one of the agent layers is adhered to the separator. In practice, only batteries using polyimide as a binder are manufactured and a charging test is conducted.
  • Patent Document 12 has an active material layer containing particles of an active material containing Si or Sn, and the surface of the active material layer is a polymer film having a large number of pores containing polyvinylidene fluoride or polyamideimide. A coated negative electrode for a non-aqueous electrolyte secondary battery is described.
  • Japanese Patent Laid-Open No. 6-325765 JP 2003-123740 A Japanese Patent Laid-Open No. 2004-47404 Unexamined-Japanese-Patent No. 2004-22433 Japanese Patent Application Publication No. 2007-95670 JP 2008-153117 A JP 2000-149921 A JP 2007-246680 A WO 2008/105036 JP 2007-84808 A JP, 2009-152037, A JP, 2009-176703, A
  • the negative electrode for secondary batteries described in Patent Document 2 has an effect of relieving stress and strain accompanying volume change accompanying absorption and release of lithium, the characteristics of secondary batteries using such negative electrodes are sufficient. It was not a thing.
  • the negative electrode material for secondary batteries described in patent document 3 has an effect which suppresses the volume change accompanying insertion and extraction of lithium, the characteristic of the secondary battery using such a negative electrode material is sufficient. It was not.
  • the negative electrode for secondary battery described in Patent Document 4 and Patent Document 5 uses a silicon-based active material and also uses polyimide as a binder, but the characteristics of a secondary battery using such a negative electrode are sufficient It was not a thing.
  • Patent Documents 7 to 10 describe that polyamide imide is used as a binder, but further improvement is required for a secondary battery using such a binder.
  • a silicon-based active material is used for the negative electrode, and a polyimide is used as a binder, and the separator is further attached to at least one of the negative electrode mixture layer and the positive electrode mixture layer.
  • the negative electrode described in Patent Document 12 covers the surface of the active material layer containing Si-based active material particles with a film having a large number of pores to prevent the active material from falling off, and there is still room for improvement. there were.
  • the present inventors in a laminate type lithium ion secondary battery using a metal capable of alloying with lithium such as silicon as a negative electrode active material, in addition to the problem due to the volume change of the negative electrode active material accompanying charge and discharge, We found a problem that the secondary battery itself would swell when charged and discharged in a high temperature environment, and we conducted intensive studies to solve these problems.
  • An object of the present invention is to provide a secondary battery with good cycle characteristics.
  • a secondary battery includes a positive electrode, a separator, a negative electrode disposed opposite to the positive electrode with the separator interposed therebetween, an electrolytic solution, and an outer package including the above.
  • the negative electrode contains a metal (a) that can be alloyed with lithium as a negative electrode active material, and a resin component,
  • the resin component contains a polyamideimide resin,
  • the polyamideimide resin contains an amidoimide structural unit derived from trimellitic acid or a derivative thereof and an aromatic diamine or a derivative thereof.
  • a secondary battery with good cycle characteristics can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a structure of a laminate type secondary battery according to an embodiment of the present invention.
  • the secondary battery according to the present embodiment includes an electrode stack including a positive electrode, a separator, and a negative electrode disposed opposite to the positive electrode with the separator interposed therebetween, an electrolyte, and an outer package including the electrolyte.
  • the electrode laminate may include one electrode pair of a positive electrode and a negative electrode, or may include two or more electrode pairs in one container made of the outer package.
  • FIG. 1 is a schematic cross-sectional view showing an example of an electrode laminate of such a laminated secondary battery.
  • the exterior body is omitted in FIG.
  • the positive electrode 3 and the negative electrode 1 are alternately stacked via the separator 2.
  • the positive electrode current collectors 5 included in the respective positive electrodes 3 are mutually welded and electrically connected at an end portion not covered with the positive electrode active material, and the positive electrode terminal 6 is further welded to the welded portion.
  • the negative electrode current collectors 4 of the respective negative electrodes 1 are mutually welded and electrically connected at the end not covered with the negative electrode active material, and the negative electrode terminal 7 is further welded to the welded portion.
  • the electrode laminate is accommodated in a container formed of a laminate film as an outer package, and an electrolytic solution is injected and sealed.
  • a laminate type battery using an electrode laminate having such a planar laminate structure has a small R (for example, a coil having a smaller R than a wound battery having an electrode laminate having a wound structure. Since there is no region close to the winding core of the structure or the folded region of the flat wound structure, there is an advantage that it is unlikely to be adversely affected by the volume change of the electrode accompanying charge and discharge. At that time, it is desirable that the separator and the electrode are not fixed to each other by adhesion or the like, and the stress due to the volume change of the electrode can be relaxed with respect to the case where the separator and the electrode are fixed. On the other hand, in the wound type battery, since the electrode is curved, when the volume change occurs in the electrode, the structure is easily distorted.
  • a laminate type battery is suitable when an active material having a large volume change due to charge and discharge is used.
  • a planar lamination structure is that each laminated electrode is a sheet-like body, and lamination arrangement is carried out with planar shape (lamination is carried out with the outer peripheral edge of a sheet-like body being a peripheral end). , And is distinguished from the structure in which the electrode stack is bent and the structure in which the electrode stack is wound.
  • such a laminated laminate type battery has a problem that when the gas is generated between the electrodes, the generated gas tends to stay between the electrodes. This is because in the wound type battery, the distance between the electrodes is difficult to expand because tension is applied to the electrodes, but in the laminate type battery, the distance between the electrodes is easily expanded. This problem is particularly noticeable when the outer package is an aluminum laminate film.
  • the electrolytic solution contains a carbonic acid ester solvent or a carboxylic acid ester solvent, this problem becomes more pronounced.
  • the negative electrode in the present embodiment contains a negative electrode active material and a resin component, and the resin component contains a polyamideimide resin as a main component.
  • the negative electrode active material is preferably coated with the resin component.
  • the negative electrode can further include a current collector, and a negative electrode active material layer containing the negative electrode active material and the resin component can be provided on the current collector.
  • the negative electrode active material can be bound to the current collector by the resin component.
  • this resin component can bind particles of the negative electrode active material contained in the negative electrode active material layer.
  • the negative electrode active material in the present embodiment contains a metal (a) that can be alloyed with lithium.
  • the negative electrode active material can further include a metal oxide (b) or a carbon material (c) capable of inserting and extracting lithium.
  • the negative electrode active material in the present embodiment preferably contains a metal (a) and a metal oxide (b), and includes a metal (a), a metal oxide (b) and a carbon material (c). More preferable.
  • metal (a) Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, or an alloy containing two or more of these may be used. it can.
  • silicon (Si) or a silicon-containing metal is preferable as the metal (a), and silicon is more preferable.
  • the content of the metal (a) in the negative electrode active material is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, from the viewpoint of charge and discharge capacity etc. From the point of cycle life etc., 90 mass% or less is preferable, 80 mass% or less is more preferable, and 50 mass% or less is more preferable.
  • silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, or a composite oxide containing two or more of these can be used.
  • silicon oxide is relatively stable and less likely to react with other compounds.
  • one or two or more elements selected from nitrogen, boron and sulfur can be added to the metal oxide (b), for example, 0.1 to 5% by mass. By this, the electrical conductivity of the metal oxide (b) can be improved.
  • the content of the metal oxide (b) in the negative electrode active material is preferably 5% by mass or more, more preferably 15% by mass or more, and still more preferably 45% by mass or more from the viewpoint of improvement of charge / discharge cycle life etc. Moreover, from the viewpoint of current collection and the like, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is more preferable.
  • the metal oxide (b) has an amorphous structure.
  • the metal oxide (b) having an amorphous structure has a large effect of suppressing the volume expansion of the carbon material (c) and the metal (a) which are other negative electrode active material components. Further, the metal oxide (b) having an amorphous structure is considered to contribute relatively little to nonuniformity such as grain boundaries and defects. The fact that all or part of the metal oxide (b) has an amorphous structure can be confirmed by X-ray diffraction measurement (general XRD measurement).
  • the metal oxide (b) does not have an amorphous structure, a peak unique to the metal oxide (b) is observed, but all or part of the metal oxide (b) is amorphous. When it has a structure, a peak specific to the metal oxide (b) is observed as a broad peak.
  • all or part of the metal (a) is preferably dispersed.
  • the metal (a) can be dispersed in the amorphous metal oxide (b). By dispersing at least a part of the metal (a) in the metal oxide (b), the volume expansion of the whole negative electrode can be further suppressed.
  • the fact that all or part of the metal (a) is dispersed in the metal oxide (b) is determined by transmission electron microscopy (general TEM observation) and energy dispersive X-ray spectroscopy (general) This can be confirmed by using the Specifically, the cross section of the sample containing the metal (a) is observed, the oxygen concentration of the particles dispersed in the metal oxide (b) is measured, and the metal (a) constituting the particles is oxidized. It can be confirmed that it is not a thing.
  • the metal oxide (b) is preferably an oxide of the same metal as the metal (a).
  • the metal (a) is a metal containing silicon
  • the metal oxide (b) contains a silicon oxide
  • the metal (a) is single silicon (Si)
  • the metal oxide (b) is In the case of silicon oxide
  • the metal (a) is an alloy of silicon and tin (Sn)
  • the metal oxide (b) is a silicon oxide or a composite oxide of silicon and tin.
  • the metal (a) is single silicon and the metal oxide (b) is silicon oxide.
  • the mass ratio (a / b) of the metal (a) to the metal oxide (b) in the negative electrode active material is not particularly limited, but is preferably set in the range of 5/95 to 90/10, 10 It is more preferable to set in the range of / 90 to 80/20, and can be set in the range of 30/70 to 60/40.
  • the carbon material (c) graphite, amorphous carbon, diamond-like carbon, carbon nanotubes, or a composite containing two or more of these can be used.
  • highly crystalline graphite has high electrical conductivity, and is excellent in adhesion to a positive electrode current collector made of a metal such as copper and voltage flatness.
  • amorphous carbon having low crystallinity has a relatively small volume expansion, so the effect of alleviating the volume expansion of the entire negative electrode is high, and deterioration due to nonuniformity such as grain boundaries and defects hardly occurs.
  • the content of the carbon material (c) in the negative electrode active material is preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of improvement in conductivity, charge / discharge cycle life, etc., and charge / discharge capacity Or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the metal (a), the metal oxide (b) and the carbon material (c) contained in the negative electrode active material are not particularly limited, but may each be in the form of particles.
  • the negative electrode active material By making the negative electrode active material into an aggregate of particles, it is possible to maintain an appropriate binding force between different material particles, thereby suppressing the occurrence of residual stress and residual strain caused by differences in volume change associated with charge and discharge. be able to.
  • the average particle size of the metal (a) is preferably smaller than the average particle size of the carbon material (c) and the average particle size of the metal oxide (b). In this way, the metal (a) having a large volume change during charging and discharging becomes relatively small in particle diameter, and the metal oxide (b) and the carbon material (c) having a relatively small volume change are relatively large.
  • the average particle diameter of the metal (a) may be, for example, 20 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and may be 5 ⁇ m or less.
  • the average particle diameter is a 50% cumulative diameter D 50 (median diameter) obtained by particle size distribution measurement by a laser diffraction scattering method.
  • a negative electrode containing particles of metal (a), particles of metal oxide (b) and particles of carbon material (c) as a negative electrode active material comprises these particles, a polyamideimide resin (optionally a binder resin) and a solvent. It can be formed by preparing a slurry containing it, applying it on a current collector, and drying and compressing it.
  • Composite particles A can be formed by mechanical milling particles of metal (a), particles of metal oxide (b), and particles of carbon material (c) as the negative electrode active material.
  • a slurry containing the composite particles A (negative electrode active material particles), a polyamideimide resin (optionally a binder resin) and a solvent is prepared, this is applied on a current collector, dried and compressed to form a negative electrode.
  • the surface of this composite particle can also be coated with a carbon material.
  • the negative electrode active material can include composite particles B containing a metal (a) and a metal oxide (b), and a carbon material.
  • the negative electrode active material containing the composite particles B and the carbon material can be obtained by mechanical milling of the composite particles B and the particles of the carbon material, or can be obtained by coating the composite particles B with the carbon material it can.
  • the method of coating composite particle B with carbon includes a method of mixing and firing an organic compound and composite particle B, or thermal CVD (thermal chemical vapor deposition) by introducing composite particle B under a gas atmosphere of an organic compound such as methane. How to do it.
  • Composite particles B containing metal (a) and metal oxide (b) can be obtained, for example, by sintering metal (a) and metal oxide (b) under high temperature reduced pressure. Moreover, it can obtain by carrying out mechanical milling of a metal (a) and a metal oxide (b).
  • the composite particle B containing the metal (a) and the metal oxide (b) all or part of the metal oxide (b) has an amorphous structure, and all or part of the metal (a) is oxidized It can be in the form of being dispersed in the substance (b).
  • the negative electrode active material in which the composite particles B in such a form are coated with a carbon material can be produced, for example, by the method described in Patent Document 3 (Japanese Patent Laid-Open No. 2004-47404). Specifically, for example, the metal oxide (b) is disproportionated at 900 to 1400 ° C. in a gas atmosphere of an organic compound such as methane, and thermal CVD is performed.
  • the metal element in the metal oxide (b) is nanoclustered in the metal oxide (b) to form the composite particle B, and the surface of the composite particle B is coated with the carbon material (c) .
  • it can be obtained by mechanical milling a metal (a) and an amorphous metal oxide (b).
  • the specific surface area (as measured by a general BET specific surface area measurement) as the whole of the negative electrode active material is 2.0 m 2 / g or more but more preferably, and is preferably 9.0 m 2 / g or less, more preferably 8.0 m 2 / g or less, more preferably 7.0 m 2 / g or less.
  • the average particle diameter of the negative electrode active material is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 0.2 ⁇ m or more, and preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less. It is preferable to set in such a range from the viewpoint of the handling property at the time of manufacture, the easiness of film formation, the battery characteristic after manufacture, and the like.
  • the average particle diameter is a 50% cumulative diameter D 50 (median diameter) obtained by particle size distribution measurement by a laser diffraction scattering method.
  • the polyamideimide resin contained in the negative electrode contains an amideimide structural unit derived from trimellitic acid or a derivative thereof and an aromatic diamine or a derivative thereof.
  • Such a polyamideimide resin is excellent in electrolytic solution resistance and heat resistance, and has excellent properties as a binder, and can have a function of suppressing gas generation due to the solvent of the negative electrode active material and the electrolytic solution.
  • Such a polyamidoimide resin is composed of trimellitic acid or its derivative (such as trimellitic anhydride or its acid chloride) (hereinafter, these are collectively referred to as "aromatic tricarboxylic acid component"), aromatic diamine or It can be obtained by the reaction with its derivatives (aromatic diisocyanate, substituted products having a substituent on the aromatic ring, etc.) (hereinafter, these are generically called “aromatic diamine component”). For example, it can be obtained by the reaction of trimellitic anhydride and aromatic diamine, the reaction of trimellitic anhydride and aromatic diisocyanate, and the reaction of trimellitic anhydride chloride and aromatic diamine.
  • the acid component and the diamine component are usually mixed in equal molar amounts, but if necessary, one component may be mixed in excess.
  • polyamide imide resin those having a number average molecular weight (Mn) in the range of, for example, 5,000 to 100,000 can be used, those in the range of 5,000 to 70000 are preferable, and those in the range of 10,000 to 70000 are more preferable. preferable.
  • Mn number average molecular weight
  • the number average molecular weight can be measured by gel permeation chromatography (GPC). When the molecular weight is too low, the film forming property and the binding ability become low, and when the molecular weight is too large, film formation processing of the active material layer becomes difficult, or it becomes difficult to form a homogeneous active material layer.
  • the unit of the aromatic tricarboxylic acid component of this polyamideimide resin is, in part, pyromellitic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, diphenylmethane-3,3', 4,4 ' -Tetracarboxylic acid, diphenylether-3,3 ', 4,4'-tetracarboxylic acid, diphenylthioether-3,3', 4,4'-tetracarboxylic acid, benzophenone-3,3 ', 4,4'- It may be replaced by a unit of an aromatic polyvalent carboxylic acid component such as tetracarboxylic acid (including acid anhydrides, acid chlorides, and derivatives such as substituents having a substituent on the aromatic ring).
  • an aromatic polyvalent carboxylic acid component such as tetracarboxylic acid (including acid anhydrides, acid chlorides, and derivatives such as substituents having a substituent on the aromatic
  • this substituent examples include alkyl groups having 1 to 4 carbon atoms, such as methyl and ethyl.
  • These aromatic polyvalent carboxylic acid components can be used alone or in combination of two or more.
  • the replacement ratio of the aromatic polycarboxylic acid component unit to the aromatic tricarboxylic acid component unit of the polyamideimide resin before replacement is preferably less than 40 mol%, from the viewpoint of not impairing the desired properties. Less than mol% is more preferable, and less than 20 mol% is more preferable.
  • the ratio of the unit of the aromatic tricarboxylic acid component to the unit of the total acid component is preferably 60 mol% or more, more preferably 70 mol% or more. Preferably, 80 mol% or more is more preferable.
  • a part of the unit of the aromatic tricarboxylic acid component is a polyvalent carboxylic acid other than the above-mentioned aromatic polyvalent carboxylic acid component, as long as the desired properties are not impaired. You may replace with the unit of an ingredient.
  • aliphatic dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid (or their acid anhydrides and acid chlorides); aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid (or their acids Anhydrides, acid chlorides); aliphatic polyvalent carboxylic acids such as butane-1,2,3,4-tetracarboxylic acid (or acid anhydrides thereof, acid chlorides) can be mentioned.
  • the replacement ratio of the unit of the other polyvalent carboxylic acid component to the unit of the aromatic tricarboxylic acid component of the polyamideimide resin before replacement is preferably less than 10 mol%, Less than mol% is more preferred.
  • aromatic carboxylic acid components are preferable.
  • Unit of aromatic tricarboxylic acid component in unit of total acid component (sum of aromatic tricarboxylic acid component, aromatic polyvalent carboxylic acid component and other polyvalent carboxylic acid component) contained in the polyamideimide resin in the present embodiment 60 mol% or more is preferable, 70 mol% or more is more preferable, and 80 mol% or more is further more preferable. That is, the ratio of the amidimide structural unit of the aromatic tricarboxylic acid component and the aromatic diamine component is preferably 60 mol% or more, more preferably 70 mol% or more, with respect to the entire condensation structural unit of the acid component and the diamine component. 80 mol% or more is more preferable.
  • it is particularly preferable that all the units of the acid component are units of the aromatic carboxylic acid component.
  • aromatic diamine component used for the polyamideimide resin in the present embodiment examples include phenylenediamines such as 1,3-phenylenediamine and 1,4-phenylenediamine; biphenyl-4,4′-diamine, biphenyl-3,4 ′ Biphenyldiamine (diaminobiphenyl) such as -diamine, biphenyl-3,3'-diamine, biphenyl-2,2'-diamine; 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether such as diaminodiphenyl ether; Diaminodiphenylmethane such as 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane; 4,4'-diaminodipheny
  • the aromatic ring of these aromatic diamine components may have a substituent, and examples of the substituent include alkyl groups having 1 to 4 carbon atoms such as methyl and ethyl. Moreover, the diisocyanate which substituted the amino group of these aromatic diamine components by the isocyanate group is mentioned.
  • aromatic diamines selected from phenylenediamine, biphenyldiamine (diaminobiphenyl), diaminodiphenylmethane, diaminodiphenylether, diaminobenzophenone, diaminodiphenylthioether and bisaminophenoxybenzene are preferable, and phenylenediamine, biphenyldiamine, diaminodiphenylmethane, diamino
  • An aromatic diamine selected from diphenyl ether, diaminobenzophenone and diaminodiphenylthioether is more preferable, and an aromatic diamine selected from phenylenediamine, biphenyldiamine, diaminodiphenylmethane, diaminodiphenylether and diaminobenzophenone is more preferable, phenylenediamine, biphenyldiamine, diaminodiphenyl Meta , Aromatic diamines selected from diamine
  • a part of the units of the aromatic diamine component may be replaced with the units of the other diamine component, as long as the desired properties are not impaired.
  • less than 10 mol% is preferable, and less than 5 mol% is more preferable as the replacement ratio of the unit of the other diamine component to the unit of the aromatic diamine component of the polyamideimide resin before replacement. That is, 90 mol% or more is preferable and, as for the ratio of the unit of the aromatic diamine component to the unit of all the diamine components contained in the polyamide resin in this embodiment, 95 mol% or more is more preferable.
  • the polyamideimide resin in the present embodiment it is particularly preferable that all of the units of the diamine component are units of the aromatic diamine component. That is, in the polyamide imide resin in the present embodiment, the content ratio of the aromatic condensation unit (including the above-mentioned amidoimide structural unit) derived from the aromatic polyvalent carboxylic acid component and the aromatic diamine component is preferably 90 mol% or more 95 mol% or more is more preferable, and 100 mol% is further more preferable.
  • a metal (a) such as silicon is used as the negative electrode active material
  • a gas is generated from the negative electrode by charge and discharge cycles, and in the case of the laminated type secondary battery, in particular, the gas is accumulated between the electrodes and the whole battery is expanded.
  • the capacity is reduced due to poor contact or the like.
  • By uniformly distributing the negative electrode active material causing such a problem in the negative electrode so as to cover with the polyamideimide it is possible to suppress the generation of gas such as CO 2 due to the reductive decomposition of the electrolytic solution.
  • Such a gas generation suppression effect can not be observed in the case of using an ordinary polyimide or a polyamic acid which is a precursor of the polyimide.
  • Polyamides having no imide group have low solubility in solvents such as water and N-methylpyrrolidone, and it is difficult to produce a negative electrode.
  • polyamideimide has high solubility in solvents such as water and N-methylpyrrolidone, and can easily form a negative electrode in which polyamideimide is uniformly distributed in the negative electrode.
  • polyamide imide can also function as a binder because it has high mechanical strength like polyimide. Therefore, the gas generation suppression effect can be obtained without significantly increasing the amount of the resin component in the negative electrode (that is, without significantly reducing the energy density).
  • the hydrogen atom present in the amide bond functions as a negative catalyst at the time of reductive decomposition of the electrolytic solution.
  • a negative electrode active material particularly containing silicon is used as the metal (a)
  • silicon (or silicon-containing metal) of metal (a), silicon oxide of metal oxide (b), and silicon oxide of metal (a) rather than using silicon that is metal (a) alone as the negative electrode active material
  • the carbon material (c) is preferable to use the carbon material (c) from the viewpoint of suppressing gas generation.
  • all or part of the metal oxide (b) amorphous from the viewpoint of suppressing gas generation. Furthermore, it is preferable that all or part of the metal (a) be dispersed in the metal oxide (b) from the viewpoint of gas generation suppression.
  • the mass ratio of the resin component containing the polyamideimide resin to the negative electrode active material is preferably 7/100 or more 8/100 or more is more preferable, 11/100 or more is further preferable, 25/100 or less is preferable, 20/100 or less is more preferable, and 15/100 or less is more preferable. If the amount of the resin component is too small, the resin is distributed unevenly, so that a sufficient gas generation suppressing effect can not be obtained, and the binding effect is also reduced. When the amount of the resin component is too large, the energy density is lowered.
  • the resin component in the negative electrode can contain another resin other than the polyamideimide resin.
  • a common negative electrode binder can be used.
  • polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide and the like can be used.
  • polyimide As a resin component other than polyamideimide in the negative electrode, polyimide is preferable, and aromatic polyimide is more preferable, from the viewpoint of suppressing a decrease in cycle characteristics caused by a volume change of the negative electrode.
  • aromatic polyimide what is comprised from the imide structural unit derived from aromatic tetracarboxylic acid and aromatic diamine is preferable.
  • aromatic tetracarboxylic acid pyromellitic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, diphenylmethane-3,3', 4,4'-tetracarboxylic acid, diphenyl ether-3,3 ', 4,4'-tetracarboxylic acid, diphenylthioether-3,3', 4,4'-tetracarboxylic acid, benzophenone-3,3 ', 4,4'-tetracarboxylic acid
  • the above can be used.
  • aromatic diamine the aromatic diamine component used for the above-mentioned polyamidoimide resin can be used.
  • one or more aromatic diamines selected from phenylenediamine, biphenyldiamine (diaminobiphenyl), diaminodiphenylmethane, diaminodiphenylether, diaminobenzophenone, diaminodiphenylthioether and bisaminophenoxybenzene can be used.
  • the proportion of the polyamideimide resin can be 100% by mass, and even in this case, sufficient binding property can be secured.
  • the polyamide imide resin and the polyimide resin as another resin are used in combination, it is possible to obtain both of the gas generation suppressing effect and the preventing effect of the cycle characteristic decrease due to the volume change of the negative electrode at high level.
  • it is preferable to increase the amount of the polyamideimide resin, and the mass ratio (PAI / PI) of the polyamideimide resin (PAI) to the polyimide resin (PI) is 60/40 to 90 /. It can be set in the range of 10.
  • the negative electrode current collector it is preferable to use a material selected from aluminum, nickel, copper, silver, and an alloy thereof from the viewpoint of electrochemical stability.
  • a material selected from aluminum, nickel, copper, silver, and an alloy thereof from the viewpoint of electrochemical stability.
  • shape, foil, flat form, mesh form is mentioned.
  • copper foil is preferable as the negative electrode current collector.
  • the negative electrode can be formed, for example, as follows.
  • a negative electrode slurry is prepared including a negative electrode active material, a polyamideimide resin, another resin (binder) as needed, and a solvent, and the negative electrode slurry is applied on a negative electrode current collector and dried to obtain a negative electrode current collector.
  • a negative electrode active material layer can be formed on the body.
  • the obtained electrode can be compressed by a method such as a roll press to adjust to an appropriate density.
  • polar solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, water, aromatic hydrocarbons such as xylene, ketones such as cyclohexanone can be used, and N-methyl-2-pyrrolidone, water Is preferred.
  • a doctor blade method, a die coater method, a dip coating method and the like can be mentioned.
  • a metal thin film of aluminum, nickel or an alloy thereof may be formed on the negative electrode active material layer by a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • the viscosity of the negative electrode slurry is preferably in the range of 1000 to 20000 mPa ⁇ s (cP) as a measurement value at a rotor rotational speed of 10 rpm using a rotary viscometer. At that time, it is preferable to use a negative electrode active material having a BET specific surface area in the range of 0.2 to 9.0 m 2 / g.
  • a negative electrode active material having a BET specific surface area in the range of 0.2 to 9.0 m 2 / g.
  • the viscosity of the negative electrode slurry was measured by attaching a UL adapter using a Brookfield Digital Viscometer III Ultra (LVDV-III Ultra, RVDV-III Ultra, HADV-III Ultra, HBDV-III Ultra) manufactured by USA at room temperature. can do.
  • a positive electrode can be used in which a positive electrode active material layer containing a positive electrode active material and a binder is provided on a positive electrode current collector.
  • lithium manganate having a layered structure or spinel structure such as LiMnO 2 or Li x Mn 2 O 4 (0 ⁇ x ⁇ 2); manganese Lithium metal oxide in which a part of Mn of lithium oxide is replaced by another metal; LiCoO 2 , LiNiO 2 , lithium metal oxide in which a part of these transition metals (Co, Ni) is replaced by other metal; LiNi Lithium transition metal oxides in which specific transition metals such as 1/3 Co 1/3 Mn 1/3 O 2 do not exceed half of the total transition metals (atomic ratio); Stoichiometric composition in these lithium metal oxides And lithium metal oxides containing an excessive amount of Li.
  • ⁇ can be set to 0.1
  • ⁇ can be set to 0.01.
  • the positive electrode active materials can be used alone or in combination of two or more.
  • the binder for the positive electrode the same one as a conventional binder for the negative electrode can be used.
  • polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
  • the amount of the positive electrode binder to be used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoint of the binding effect and energy density in a trade-off relationship.
  • the same one as the negative electrode current collector can be used as long as it is stable in terms of potential, and aluminum foil is particularly preferable.
  • a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing the impedance.
  • the conductive auxiliary include carbonaceous fine particles such as graphite, carbon black and acetylene black.
  • the positive electrode can be formed, for example, as follows. A positive electrode slurry containing a positive electrode active material, a binder, a solvent, and optionally a conductive auxiliary agent is prepared, this positive electrode slurry is applied on a positive electrode current collector, and dried to obtain a positive electrode active material on the positive electrode current collector. Layers can be formed. The obtained electrode can be compressed by a method such as a roll press to adjust to an appropriate density.
  • the solvent for example, N-methyl-2-pyrrolidone can be used.
  • Electrolyte Solution A non-aqueous electrolyte solution containing a lithium salt (supporting salt) and a non-aqueous solvent capable of dissolving the supporting salt can be used as the electrolytic solution used in the present embodiment.
  • non-protic organic solvents such as carbonates (chain or cyclic carbonates), carboxylic esters (chain or cyclic carboxylic esters) and the like can be used.
  • cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), etc .; dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), linear carbonates such as dipropyl carbonate (DPC); and propylene carbonate derivatives.
  • carboxylic acid ester solvents examples include aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate; and lactones such as ⁇ -butyrolactone.
  • ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (MEC), dipropyl carbonate Carbonates (cyclic or linear carbonates) such as (DPC) are preferred.
  • the non-aqueous solvents can be used alone or in combination of two or more.
  • the non-aqueous electrolyte preferably further contains a fluorinated ether compound.
  • the fluorinated ether compound has high affinity with metal (a) (especially Si), and can improve cycle characteristics (particularly capacity retention).
  • the fluorinated ether compound may be a fluorinated chain ether compound in which a part of hydrogen of the non-fluorinated chain ether compound is substituted with fluorine, or a part of the hydrogen of the non-fluorinated cyclic ether compound is fluorine It may be a substituted fluorinated cyclic ether compound.
  • fluorinated chain ether compounds having higher stability are preferable.
  • the fluorinated chain ether compound As the fluorinated chain ether compound, the following formula (1): H- (CX 1 X 2 -CX 3 X 4) n -CH 2 O-CX 5 X 6 -CX 7 X 8 -H (1) (Wherein, n is 1, 2, 3 or 4 and X 1 to X 8 are each independently a fluorine atom or a hydrogen atom, provided that at least one of X 1 to X 4 is a fluorine atom, At least one of X 5 to X 8 is a fluorine atom The atomic ratio of the fluorine atom to the hydrogen atom bonded to the present fluorinated chain ether compound (total number of fluorine atoms / total number of hydrogen atoms) 11 .) The compound represented by is preferable, and the following formula (2): H- (CF 2 -CF 2) n -CH 2 O-CF 2 -CF 2 -H (2) (Wherein n is 1 or 2) The compound represented
  • the content of such a fluorinated ether compound is preferably 10 vol% or more, and 15 vol% or more with respect to the whole (100 vol%) of the non-aqueous solvent, from the viewpoint of obtaining sufficient addition effect within the range that does not impair battery characteristics. Is more preferable, 75 vol% or less is preferable, 70 vol% or less is more preferable, and 50 vol% or less is more preferable.
  • the supporting salt in the present embodiment includes LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 , LiN ( Lithium salts usable for ordinary lithium ion batteries such as CF 3 SO 2 ) 2 can be used.
  • the supporting salts can be used alone or in combination of two or more.
  • separator in the present embodiment, a porous film or non-woven fabric made of polyolefin such as polypropylene and polyethylene, or fluorocarbon resin can be used. Moreover, what laminated
  • Exterior Body As the exterior body in the present embodiment, a laminate film which is stable to the electrolytic solution and has sufficient water vapor barrier properties can be used.
  • a laminated film of aluminum, silica coated polypropylene, polyethylene or the like can be used as such an outer package.
  • an aluminum laminate film is preferably used from the viewpoint of suppressing volume expansion.
  • the distortion of the electrode becomes much larger than that of a secondary battery using a metal can as an outer package. This is because the laminate film is more easily deformed by the internal pressure of the secondary battery than the metal can. Furthermore, when sealing a secondary battery using a laminate film as an outer package, usually, the internal pressure of the battery is made lower than the atmospheric pressure, and there is no extra space inside, so when gas is generated inside the battery. It is easy for the volume change of the battery and the deformation of the electrode to occur immediately. According to the present embodiment, since the gas generation in the battery can be suppressed, such a problem can be solved.
  • a laminated type lithium ion secondary battery is excellent in heat dissipation, can be provided at low cost, has a high degree of freedom in designing the cell capacity (the cell capacity can be changed according to the number of laminations), and a winding type using metal cans Although it has various advantageous features with respect to the battery, it is possible to improve the cycle characteristics of such a laminate type lithium ion secondary battery.
  • the secondary battery according to the present embodiment can be manufactured according to a usual method.
  • a laminate type lithium ion secondary battery can be produced as follows.
  • a positive electrode in which a positive electrode active material layer is provided on a positive electrode current collector and a negative electrode in which a negative electrode active material layer is provided on a negative electrode current collector are produced.
  • the positive electrode and the negative electrode are disposed to face each other with the separator interposed therebetween to form an electrode pair, thereby forming an electrode stack of the number of laminations corresponding to a predetermined capacity.
  • This electrode laminate has a positive electrode terminal connected to the positive electrode current collector and a negative electrode terminal connected to the negative electrode current collector.
  • this electrode laminate is housed in an outer package (container), a non-aqueous electrolyte is injected, and then sealed.
  • Example 1 30 parts by mass of Si—Sn alloy particles having an average particle diameter of 2 ⁇ m as metal (a), 65 parts by mass of SiO 2 particles having an average particle diameter of 6 ⁇ m as metal oxide (b), and an average as carbon material (c)
  • Five parts by mass of graphite having a particle diameter of 0.1 ⁇ m are mixed by mechanical milling for 24 hours to form a negative electrode active material.
  • the average particle diameter D 50 of this negative electrode active material is 5 ⁇ m, and the BET specific surface area is 5 m 2 / g.
  • PAI polyamideimide resin
  • a resin composed of an amideimide structural unit derived from trimellitic acid and 1,4-phenylenediamine is used as the polyamideimide resin (PAI).
  • the mass ratio Mb / Mc of the amount Mb of the polyamideimide resin (PAI) to the amount Mc (100 parts by mass) of the negative electrode active material is 12/100.
  • the negative electrode slurry is applied to a copper foil having a thickness of 15 ⁇ m and then dried, and heat treatment is further performed at 300 ° C. in a nitrogen atmosphere to form a negative electrode.
  • the positive electrode slurry is applied to an aluminum foil with a thickness of 20 ⁇ m, dried, and pressed to form a positive electrode.
  • Three layers of the positive electrode and four layers of the negative electrode are alternately laminated via a polypropylene porous film as a separator to form an electrode laminate.
  • the end portions of the positive electrode current collector not covered with the positive electrode active material are welded, the aluminum positive electrode terminal is welded to the welded portion, and the end portions of the negative electrode current collector not covered with the negative electrode active material Welding is performed, and a nickel negative electrode terminal is welded to the welding portion.
  • total resin amount indicates the mass ratio of the total resin component to the negative electrode active material (the ratio of the mass part of the total resin component to 100 parts by mass of the negative electrode active material), and the “PAI ratio” is the total resin The mass ratio of PAI in a component is shown.
  • Example 2 A secondary battery is fabricated in the same manner as Example 1, except that biphenyl-4,4'-diamine is used in place of phenylenediamine. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 3 A secondary battery is fabricated in the same manner as Example 1, except that 4,4'-diaminodiphenyl ether is used in place of phenylenediamine. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 4 A secondary battery is fabricated in the same manner as Example 1, except that 4,4'-diaminodiphenylmethane is used in place of phenylenediamine. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 5 A secondary battery is fabricated in the same manner as in Example 1, except that 4,4'-diaminodiphenyl thioether is used in place of phenylenediamine. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 6 A secondary battery is fabricated in the same manner as Example 1, except that biphenyl-4,4'-diamine is used in addition to phenylenediamine.
  • the molar ratio of these monomers is 1/1.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 7 A secondary battery is fabricated in the same manner as Example 1, except that 4,4'-diaminodiphenyl ether is used in addition to phenylenediamine.
  • the molar ratio of these monomers is 1/1.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 8 A secondary battery is fabricated in the same manner as Example 1, except that 4,4'-diaminodiphenylmethane is used in addition to phenylenediamine.
  • the molar ratio (phenylenediamine / diaminodiphenylmethane) of these monomers is 1/1.
  • Example 9 A secondary battery is fabricated in the same manner as Example 1, except that 4,4'-diaminodiphenyl thioether is used in addition to phenylenediamine.
  • the molar ratio of these monomers is 1/1.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 10 A secondary battery is fabricated in the same manner as in Example 1, except that 4,4'-diaminodiphenylmethane and biphenyl-4,4'-diamine are used in place of phenylenediamine.
  • the molar ratio of these monomers is 1/1.
  • Example 11 A secondary battery is fabricated in the same manner as in Example 1, except that 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylether are used instead of phenylenediamine.
  • the molar ratio of these monomers (diaminodiphenylmethane / diaminodiphenyl ether) is 1/1.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 12 A secondary battery is fabricated in the same manner as in Example 1, except that 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylthioether are used instead of phenylenediamine.
  • the molar ratio of these monomers is 1/1.
  • Example 13 to 24 Secondary batteries are produced in the same manner as in Examples 1 to 12, respectively, except that silicon particles are used instead of Si—Sn alloy particles. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Examples 25 to 36 30 parts by mass of silicon particles having an average particle diameter of 2 ⁇ m as the metal (a) and 65 mass of amorphous silicon oxide particles (SiO x , 0 ⁇ x ⁇ 2) having an average particle diameter of 6 ⁇ m as the metal oxide (b) Parts and 5 parts by mass of graphite having an average particle diameter of 0.1 ⁇ m as the carbon material (c) are mixed by mechanical milling for 24 hours to form a negative electrode active material.
  • the average particle diameter D 50 of this negative electrode active material is 5 ⁇ m, and the BET specific surface area is 5 m 2 / g.
  • silicon is dispersed in amorphous silicon oxide.
  • Secondary batteries are produced in the same manner as in Examples 1 to 12 except that the above-mentioned negative electrode active material is used. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 37 Using a negative electrode active material similar to that used in Examples 25 to 36, using a portion of trimellitic acid as biphenyl-3,3 ', 4,4'-tetracarboxylic acid (BP-TCA) A secondary battery is fabricated in the same manner as in Example 1 except for replacing and using 4,4'-diaminodiphenylmethane instead of phenylenediamine.
  • the molar ratio (trimellitic acid / BP-TCA) of the monomer of these acid components is 10/5.
  • Example 38 A secondary battery is fabricated in the same manner as in Example 37 except that trimellitic acid and diphenylmethane-3,3 ', 4,4'-tetracarboxylic acid (DPM-TCA) are used as the acid component.
  • the molar ratio of these monomers is 10/5.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 39 A secondary battery is fabricated in the same manner as in Example 37 except that trimellitic acid and diphenylether-3,3 ', 4,4'-tetracarboxylic acid (DPE-TCA) are used as the acid component.
  • the molar ratio of these monomers is 10/5.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 40 A secondary battery is fabricated in the same manner as in Example 37 except that trimellitic acid and benzophenone-3,3 ', 4,4'-tetracarboxylic acid (BZP-TCA) are used as the acid component.
  • the molar ratio of these monomers is 10/5.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 41 A secondary battery is fabricated in the same manner as in Example 37 except that trimellitic acid and diphenylthioether-3,3 ', 4,4'-tetracarboxylic acid (DPTE-TCA) are used as the acid component.
  • the molar ratio of these monomers is 10/5.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 42 30 parts by mass of Si—Sn alloy particles having an average particle diameter of 2 ⁇ m as metal (a), 65 parts by mass of SiO 2 particles having an average particle diameter of 6 ⁇ m as metal oxide (b), and an average as carbon material (c)
  • Five parts by mass of graphite having a particle diameter of 0.1 ⁇ m are mixed by mechanical milling for 24 hours to form a negative electrode active material.
  • the average particle diameter D 50 of this negative electrode active material is 5 ⁇ m, and the BET specific surface area is 5 m 2 / g.
  • PAI polyamideimide resin
  • Mb / Mc of the amount Mb of the total resin component (the sum of PAI and PI) to the amount Mc (100 parts by mass) of the negative electrode active material is 12/100.
  • the proportion of PAI in the total resin component is 67% by mass.
  • the negative electrode slurry is applied to a copper foil having a thickness of 15 ⁇ m and then dried, and heat treatment is further performed at 300 ° C. in a nitrogen atmosphere to form a negative electrode.
  • the positive electrode slurry is applied to an aluminum foil with a thickness of 20 ⁇ m, dried, and pressed to form a positive electrode.
  • Three layers of the positive electrode and four layers of the negative electrode are alternately laminated via a polypropylene porous film as a separator to form an electrode laminate.
  • the end portions of the positive electrode current collector not covered with the positive electrode active material are welded, the aluminum positive electrode terminal is welded to the welded portion, and the end portions of the negative electrode current collector not covered with the negative electrode active material And weld the negative electrode terminal made of nickel to the welding point.
  • the above-described electrode laminate is wrapped with an aluminum laminate film as an exterior body, an electrolytic solution is injected into the inside, and then the battery is sealed while decompressing to fabricate a secondary battery.
  • the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • total resin amount indicates the mass ratio of the total resin component to the negative electrode active material (the ratio of the mass part of the total resin component to 100 parts by mass of the negative electrode active material), and the “PAI ratio” is the total resin The mass ratio of PAI in a component is shown.
  • Example 43 to 46 A secondary battery is fabricated in the same manner as Example 42, except that the total resin component amount and the PAI ratio are as shown in the table. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 47 A secondary battery is fabricated in the same manner as Example 42, except that the BET specific surface area of the negative electrode active material is 1.0 m 2 / g. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 48 A secondary battery is fabricated in the same manner as Example 42, except that the BET specific surface area of the negative electrode active material is 8.0 m 2 / g. With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • Example 1 A secondary battery is manufactured in the same manner as Example 1, except that polyimide (trade name: U Varnish A, manufactured by Ube Industries, Ltd.) is used in place of the polyamideimide resin (PAI). With respect to the secondary battery thus obtained, the capacity retention rate and the swelling rate after charge and discharge cycles obtained by the measurement method described later are shown in the table.
  • polyimide trade name: U Varnish A, manufactured by Ube Industries, Ltd.
  • PAI polyamideimide resin
  • the ratio of the discharge capacity at the 50th cycle to the initial discharge capacity is calculated as a capacity retention rate (%). Further, the ratio of the volume increase amount at the 50th cycle to the volume of the battery before the start of charge and discharge is calculated as a swelling ratio (%) (volume change ratio). This volume increase is measured by the Archimedes method. The volume can be calculated from the mass loss when the battery is suspended on a scale and submerged in deionized water.
  • the secondary battery according to the present embodiment can be used in any industrial fields requiring a power source, and in the industrial fields related to transport, storage and supply of electrical energy.
  • power supplies for mobile devices such as mobile phones and laptops
  • power supplies for mobile vehicles such as electric vehicles, hybrid cars, electric bikes, electrically assisted bicycles, and electric vehicles such as trains, satellites, submarines, etc.
  • Backup power supply such as UPS (Uninterruptible Power Supply); It can be used for storage equipment etc. which stores electric power generated by solar power generation, wind power generation etc.
  • UPS Uninterruptible Power Supply

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  • Secondary Cells (AREA)

Abstract

Une batterie secondaire comprend une électrode positive, un séparateur, une électrode négative placée face à l'électrode positive et possédant le séparateur entre elles, un électrolyte, et un logement externe dans lequel ces éléments sont logés. L'électrode négative comprend: un métal (a) capable de s'allier au lithium en tant que matériau actif d'électrode négative; et un composant de résine. Le composant de résine comprend une résine polyamide-imide, et cette résine comprend une unité structurelle amide-imide dérivée d'un trimellitate ou d'un dérivé de celui-ci et d'une diamine aromatique ou d'un dérivé de celle-ci.
PCT/JP2011/079986 2011-03-28 2011-12-26 Batterie secondaire WO2012132153A1 (fr)

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JP2014086218A (ja) * 2012-10-22 2014-05-12 Toyota Motor Corp 全固体電池システム
CN103855402A (zh) * 2012-12-04 2014-06-11 三星Sdi株式会社 负极、其制备方法和包括其的可再充电锂电池
JP2015065163A (ja) * 2013-08-30 2015-04-09 Tdk株式会社 リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池
JP2016027561A (ja) * 2014-06-30 2016-02-18 Tdk株式会社 リチウムイオン二次電池用負極バインダー、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JPWO2015111187A1 (ja) * 2014-01-24 2017-03-23 日産自動車株式会社 電気デバイス
KR101815710B1 (ko) * 2012-12-04 2018-01-05 삼성에스디아이 주식회사 리튬 이차 전지용 음극, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
JP2018041702A (ja) * 2016-09-09 2018-03-15 日産自動車株式会社 非水電解質二次電池用負極及びこれを用いた非水電解質二次電池

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JP2009037842A (ja) * 2007-08-01 2009-02-19 Sony Corp 負極、電池およびそれらの製造方法
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Cited By (9)

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Publication number Priority date Publication date Assignee Title
JP2014086218A (ja) * 2012-10-22 2014-05-12 Toyota Motor Corp 全固体電池システム
CN103855402A (zh) * 2012-12-04 2014-06-11 三星Sdi株式会社 负极、其制备方法和包括其的可再充电锂电池
EP2741352A3 (fr) * 2012-12-04 2015-10-14 Samsung SDI Co., Ltd. Électrode positive pour batterie au lithium rechargeable, procédé de préparation de celle-ci et batterie au lithium rechargeable le comprenant
US9437872B2 (en) 2012-12-04 2016-09-06 Samsung Sdi Co., Ltd. Negative electrode for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same
KR101815710B1 (ko) * 2012-12-04 2018-01-05 삼성에스디아이 주식회사 리튬 이차 전지용 음극, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
JP2015065163A (ja) * 2013-08-30 2015-04-09 Tdk株式会社 リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池
JPWO2015111187A1 (ja) * 2014-01-24 2017-03-23 日産自動車株式会社 電気デバイス
JP2016027561A (ja) * 2014-06-30 2016-02-18 Tdk株式会社 リチウムイオン二次電池用負極バインダー、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JP2018041702A (ja) * 2016-09-09 2018-03-15 日産自動車株式会社 非水電解質二次電池用負極及びこれを用いた非水電解質二次電池

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