WO2017038327A1 - Pile rechargeable - Google Patents

Pile rechargeable Download PDF

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Publication number
WO2017038327A1
WO2017038327A1 PCT/JP2016/072099 JP2016072099W WO2017038327A1 WO 2017038327 A1 WO2017038327 A1 WO 2017038327A1 JP 2016072099 W JP2016072099 W JP 2016072099W WO 2017038327 A1 WO2017038327 A1 WO 2017038327A1
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WIPO (PCT)
Prior art keywords
negative electrode
positive electrode
protective layer
inorganic filler
secondary battery
Prior art date
Application number
PCT/JP2016/072099
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English (en)
Japanese (ja)
Inventor
稔之 有賀
拓郎 綱木
三木　健
佐々木　寛文
Original Assignee
日立オートモティブシステムズ株式会社
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Application filed by 日立オートモティブシステムズ株式会社 filed Critical 日立オートモティブシステムズ株式会社
Priority to JP2017537666A priority Critical patent/JP6586169B2/ja
Publication of WO2017038327A1 publication Critical patent/WO2017038327A1/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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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 discloses that a protective layer made of organic particles and inorganic particles is provided on at least one electrode of a sealed battery, and the organic particles in the protective layer are melted when abnormal heat is generated. A technology that improves safety by providing a shutdown function that closes holes is published.
  • the present invention has been made in view of the above problems, and its purpose is to provide a protective layer between the positive electrode and the negative electrode even when the secondary battery falls into a high temperature state, so that the positive electrode and the negative electrode It is intended to provide a secondary battery that can avoid the secondary short circuit between them and improve safety.
  • the present invention includes a plurality of means for solving the above problems.
  • the secondary battery includes an electrode group in which a positive electrode and a negative electrode are stacked with a separator interposed therebetween.
  • the melting point is higher than the melting point of the separator.
  • the negative electrode protective layer provided on the surface of the negative electrode mixture layer has an inorganic filler, a resin filler having a melting point higher than that of the separator, and a binder, abnormal heat generation above the melting point of the separator.
  • the resin filler of the protective layer softens and develops adhesive strength, binds the inorganic filler, and can suppress the outflow of the protective layer. Therefore, even if the separator shrinks due to heat, the protective layer can suppress a secondary short circuit between the positive electrode and the negative electrode. Therefore, a highly safe battery can be provided.
  • the external appearance perspective view of a square secondary battery The disassembled perspective view of a square secondary battery.
  • the perspective view of a winding group The figure explaining the structure of a positive electrode.
  • the figure explaining the structure of a negative electrode Sectional drawing of the winding group in a present Example.
  • the cross-sectional image figure which shows an example of a negative electrode protective layer The cross-sectional image figure which shows the other example of a negative electrode protective layer.
  • the present invention provides an inorganic filler and a resin filler that have ionic conductivity on the negative electrode active material layer and avoid direct contact between the positive electrode uncoated portion and the negative electrode coated portion due to separator contraction when abnormal heat is generated due to an internal short circuit or the like.
  • the present invention relates to a sealed secondary battery including a layer made of
  • the present invention is applied to a prismatic lithium ion secondary battery having a flat wound electrode group.
  • the present invention is limited to the configurations of these examples.
  • the present invention can also be applied to secondary batteries having other types of electrode groups such as a stacked type in which a plurality of positive electrodes and negative electrodes are alternately stacked.
  • FIG. 1 is an external perspective view of a prismatic secondary battery
  • FIG. 2 is an exploded perspective view of the prismatic secondary battery.
  • the prismatic secondary battery 100 includes a battery can 1 and a battery lid 6.
  • the battery can 1 has a side surface and a bottom surface 1d having a pair of opposed wide side surfaces 1b having a relatively large area and a pair of opposed narrow side surfaces 1c having a relatively small area, and an opening 1a above the side surface 1d.
  • the wound group 3 is accommodated in the battery can 1, and the opening 1 a of the battery can 1 is sealed by the battery lid 6.
  • the battery lid 6 is a substantially rectangular flat plate that closes the opening 1 a and is welded to the battery can 1 to form a battery container in cooperation with the battery can 1.
  • the battery lid 6 is provided with a positive external terminal 14 and a negative external terminal 12.
  • the wound group 3 is charged through the positive external terminal 14 and the negative external terminal 12, and power is supplied to the external load.
  • the battery cover 6 is integrally provided with a gas discharge valve 10, and when the pressure in the battery container rises to a preset value or more, the gas discharge valve 10 is opened and gas is discharged from the inside, so that the inside of the battery container The pressure of is reduced. Thereby, the safety of the prismatic secondary battery 100 is ensured.
  • the wound group 3 is accommodated in an insulating protective film 2. Since the wound group 3 is wound in a flat shape, the wound group 3 has a pair of curved surface portions facing each other and having a semicircular cross section, and a flat surface portion formed continuously between the pair of curved surface portions. ing.
  • the winding group 3 is inserted into the battery can 1 from one curved surface portion side so that the winding axis direction is along the lateral width direction of the battery can 1, and the other curved surface portion side is disposed on the opening 1a side.
  • the positive electrode metal foil exposed portion 34 b of the winding group 3 is electrically connected to the positive electrode external terminal 14 provided on the battery lid 6 via the positive electrode current collector plate 44. Further, the negative electrode metal foil exposed portion 32 b of the wound group 3 is electrically connected to the negative electrode external terminal 12 provided on the battery lid 6 via the negative electrode current collector plate 24. Thereby, electric power is supplied from the winding group 3 to the external load via the positive electrode current collecting plate 44 and the negative electrode current collecting plate 24, and externally supplied to the wound group 3 via the positive electrode current collecting plate 44 and the negative electrode current collecting plate 24. The generated power is supplied and charged.
  • a gasket 5 and an insulating plate 7 are provided on the battery lid 6. It has been.
  • the material for forming the positive electrode external terminal 14 and the positive electrode current collector plate 44 include an aluminum alloy
  • examples of the material for forming the negative electrode external terminal 12 and the negative electrode current collector plate 24 include a copper alloy.
  • the material for forming the insulating plate 7 and the gasket 5 include resin materials having insulating properties such as polybutylene terephthalate, polyphenylene sulfide, and perfluoroalkoxy fluororesin.
  • the battery lid 6 is provided with a liquid injection port 9 for injecting the electrolytic solution into the battery container.
  • the liquid injection port 9 is injected by the liquid injection plug 11 after the electrolytic solution is injected into the battery container. Sealed.
  • the liquid injection plug 11 is joined to the battery lid 6 by laser welding to seal the liquid injection port 9 and seal the rectangular secondary battery 100.
  • a nonaqueous electrolytic solution in which a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) is dissolved in an organic carbonate-based organic solvent such as ethylene carbonate is used as the electrolytic solution injected into the battery container. Can do.
  • the positive electrode connecting portion 14 a and the negative electrode connecting portion 12 a have a cylindrical shape that protrudes from the lower surface of the positive electrode external terminal 14 and the negative electrode external terminal 12 and can be inserted into the positive electrode side through hole 46 and the negative electrode side through hole 26 of the battery lid 6. Have.
  • the positive electrode connecting portion 14 a and the negative electrode connecting portion 12 a penetrate the battery lid 6 and are more inside the battery can 1 than the positive electrode current collector plate 44, the positive electrode current collector plate base 41 of the negative electrode current collector plate 24, and the negative electrode current collector plate base 21.
  • the positive electrode external terminal 14, the negative electrode external terminal 12, the positive electrode current collector plate 44, and the negative electrode current collector plate 24 are integrally fixed to the battery lid 6.
  • a gasket 5 is interposed between the positive electrode external terminal 14 and the negative electrode external terminal 12 and the battery cover 6, and an insulating plate is interposed between the positive electrode current collector plate 44, the negative electrode current collector plate 24 and the battery cover 6. 7 is interposed.
  • the positive electrode current collector plate 44 and the negative electrode current collector plate 24 are a rectangular plate-shaped positive electrode current collector plate base 41, a negative electrode current collector plate base 21, and a positive electrode current collector plate base 41 that are arranged to face the lower surface of the battery lid 6.
  • the negative electrode current collector plate base 21 is bent at the side end and extends toward the bottom surface along the wide surface of the battery can 1, and the positive electrode metal foil exposed portion 34 b and the negative electrode metal foil exposed portion of the wound group 3. It has the positive electrode side connection end part 42 and the negative electrode side connection end part 22 which are connected in the state which overlapped facing 32b.
  • the positive electrode current collector plate base 41 and the negative electrode current collector plate base 21 are respectively formed with a positive electrode side opening hole 43 and a negative electrode side opening hole 23 through which the positive electrode connection part 14a and the negative electrode connection part 12a are inserted.
  • FIG. 3 is an exploded perspective view showing a state in which a part of the wound group is developed.
  • the winding group 3 is configured by winding the negative electrode 32 and the positive electrode 34 in a flat shape with separators 33 and 35 interposed therebetween.
  • the outermost electrode is the negative electrode 32, and the separators 33 and 35 are wound outside thereof.
  • the separators 33 and 35 have a role of insulating between the positive electrode 34 and the negative electrode 32.
  • the separators 33 and 35 are provided with a plurality of fine holes through which the electrolytic solution can pass.
  • the negative electrode mixture layer 32a of the negative electrode 32 (see FIG. 5B) is larger in the width direction than the positive electrode mixture layer 34a of the positive electrode 34, and the positive electrode mixture layer 34a is always the negative electrode mixture layer 32a. It is configured to be sandwiched between them.
  • the positive electrode metal foil exposed portion 34b and the negative electrode metal foil exposed portion 32b are respectively bundled at a plane portion and connected to the positive electrode current collector plate 44 and the negative electrode current collector plate 24 by welding or the like.
  • the separators 33 and 35 are wider than the negative electrode mixture layer 32a in the width direction, the separators 33 and 35 are wound at positions where the metal foil surface at the end is exposed at the positive metal foil exposed portion 34b and the negative metal foil exposed portion 32b. , It does not hinder bundled welding. Moreover, it is also possible to arrange
  • the shaft core for example, a material obtained by winding a resin sheet having higher bending rigidity than any of the positive electrode metal foil, the negative electrode metal foil, and the separators 33 and 35 can be used.
  • polyolefin separators are used as the separators 33 and 35.
  • a polyolefin multilayer separator made of polypropylene (melting point: about 130 ° C.) and polyethylene (melting point: about 100 ° C.) is used.
  • the configuration of the separator is not limited to the polyolefin-based multilayer separator, but may be a single-layer separator made of polypropylene or polyethylene or a heat-resistant separator made of aramid.
  • the heat resistant coating layer which consists of an inorganic filler in the at least single side
  • this inorganic filler the same inorganic filler as the negative electrode protective layer 32c can be used.
  • the desired place of the present invention is that the melting point of the resin filler mixed in the negative electrode protective layer 32c disposed in the negative electrode 32 described later is higher than that of the separator.
  • the separator also has a shutdown function from the viewpoint of improving safety.
  • FIG. 4A and 4B are diagrams for explaining the configuration of the positive electrode in this example.
  • FIG. 4A is a front view showing a part of the positive electrode, and
  • FIG. It is A sectional view.
  • the positive electrode 34 has a positive electrode mixture layer 34a in which a positive electrode mixture is applied to both surfaces of a positive electrode metal foil that is a positive electrode current collector, and a positive electrode mixture is provided at one end in the width direction of the positive electrode metal foil.
  • An exposed positive metal foil exposed portion 34b is provided.
  • the positive electrode metal foil exposed portion 34b is a region where the metal surface of the positive electrode metal foil is exposed, and is wound so as to be disposed at one position in the winding axis direction.
  • the positive electrode 34 10 parts by weight of flaky graphite as a conductive material and 10 parts by weight of PVDF as a binder are added to 100 parts by weight of lithium manganate (chemical formula LiMn 2 O 4 ) as a positive electrode active material. Then, NMP was added as a dispersion solvent and kneaded to prepare a slurry-like positive electrode mixture. This slurry-like positive electrode mixture was applied on both sides of an aluminum foil (positive metal foil) having a thickness of 20 ⁇ m, leaving a positive metal foil exposed portion 34b (positive electrode uncoated portion) as a welded portion. Then, the positive electrode 34 with a thickness of 90 ⁇ m of the positive electrode mixture layer 34a not including the aluminum foil was obtained through drying, pressing, and cutting processes.
  • LiMn 2 O 4 lithium manganate
  • NMP was added as a dispersion solvent and kneaded to prepare a slurry-like positive electrode mixture.
  • This slurry-like positive electrode mixture was applied on both
  • lithium manganate is used as the positive electrode active material
  • other lithium manganate having a spinel crystal structure or a lithium manganese composite oxide or layered in which a part is substituted or doped with a metal element A lithium cobalt oxide or lithium titanate having a crystal structure, or a lithium-metal composite oxide obtained by substituting or doping a part thereof with a metal element may be used.
  • PVDF was used as the binder in the positive electrode mixture, but polytetrafluoroethylene (PTFE), polyethylene, polystyrene, polybutadiene, butyl rubber, nitrile rubber, styrene butadiene rubber, and polysulfide rubber.
  • PTFE polytetrafluoroethylene
  • Polymers such as nitrocellulose, cyanoethyl cellulose, various latexes, acrylonitrile, vinyl fluoride, vinylidene fluoride, propylene fluoride, chloroprene fluoride, and acrylic resins, and mixtures thereof can be used.
  • FIG. 5A and 5B are diagrams for explaining the configuration of the negative electrode.
  • FIG. 5A is a front view showing a part of the negative electrode
  • FIG. 5B is a cross-sectional view taken along line AA in FIG. FIG.
  • the negative electrode 32 is provided on the surface of a negative electrode mixture layer 32a provided by applying a negative electrode mixture containing a negative electrode active material on both surfaces of a negative electrode metal foil which is a negative electrode current collector, and the surface of the negative electrode mixture layer 32a. Negative electrode protective layer 32c. And the negative electrode metal foil exposure part 32b in which the negative mix is not apply
  • the negative electrode metal foil exposed portion 32b is a region where the metal surface of the negative electrode metal foil is exposed, and is wound so as to be disposed at the position on the other side in the winding axis direction.
  • styrene butadiene rubber 1 part by weight of styrene butadiene rubber (hereinafter referred to as SBR) is added as a binder to 100 parts by weight of graphite powder as a negative electrode active material, and carboxymethyl cellulose (CMC) as a thickener. Was added thereto, and H 2 O was added thereto as a dispersion solvent and kneaded to prepare a negative electrode mixture.
  • SBR styrene butadiene rubber
  • the negative electrode mixture was applied to both sides of a 10 ⁇ m thick copper foil (negative electrode metal foil) leaving the negative electrode metal foil exposed portion 32b (negative electrode uncoated portion) as a welded portion, dried and pressed, and then protected for negative electrode
  • the slurry of the layer 32c was apply
  • the negative electrode mixture is applied, dried and pressed, and then the slurry for the negative electrode protective layer 32c is applied onto the negative electrode mixture layer 32a.
  • the present invention is not limited to this.
  • the negative electrode 32 may be produced by pressing and cutting.
  • graphite is used as the negative electrode active material, but the present invention is not limited to this.
  • Carbonaceous materials, amorphous carbon, compounds such as Si and Sn (for example, SiO, TiSi 2 etc.), or composite materials thereof may be used, and the particle shape may be scale-like, spherical, fibrous, massive, etc. There is no particular limitation.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • polyethylene polystyrene
  • polybutadiene butyl rubber
  • nitrile rubber polysulfide Polymers such as rubber, nitrocellulose, cyanoethyl cellulose, various latexes, acrylonitrile, vinyl fluoride, vinylidene fluoride, propylene fluoride, chloroprene fluoride, and acrylic resins, and mixtures thereof can be used.
  • H 2 O is used as a dispersion solvent for the coated portion of the negative electrode, not limited thereto, it may be used such as polyvinylidene fluoride (NMP) solvent.
  • NMP polyvinylidene fluoride
  • FIG. 6 is a cross-sectional view of the wound group in the first embodiment.
  • the negative electrode 32 has a negative electrode mixture layer 32a facing the positive electrode mixture layer 34a and wider than the positive electrode mixture layer 34a.
  • the negative electrode protective layer 32c has a width that covers the negative electrode mixture layer 32a, and has a size that covers the negative electrode mixture layer 32a so that the negative electrode mixture layer 32a is not exposed particularly at a portion facing the positive electrode metal foil exposed portion 34b via the separator. Is a requirement.
  • the negative electrode protective layer 32c in the present embodiment will be described with reference to a cross-sectional image diagram of the negative electrode protective layer 32c in FIG. Note that the cross-sectional image diagram of FIG. 7 is a structure inspired by Example 1-2 described later.
  • the negative electrode protective layer 32c is a mixture of an inorganic filler 32c1 and a resin filler 32c2 having a melting point higher than that of the separator as a protective material, SBR as a binder 32c3, and CMC (not shown) as a thickener. And including. H 2 O is added to these mixtures as a dispersion solvent and kneaded to produce a slurry-like mixture, which is applied to the desired location, dried, and evaporated to a thickness of about 5 ⁇ m. A negative electrode protective layer 32c having the same was formed.
  • the case where SBR is included as the binder of the negative electrode protective layer 32c and CMC is included as the thickener is exemplified, but the present invention is not limited thereto, and PVDF or acrylic is used as the binder. NMP may be used as a solvent.
  • the inorganic filler 32c1 is, for example, at least iron oxide, silica (SiO 2 ), alumina (Al 2 O 3 ), boehmite (Al 2 O 3 hydrate), titanium oxide (TiO 2 ), or barium titanate (BaTiO 2 ). Have one.
  • boehmite was used for the inorganic filler 32c1, and a battery in which the presence or absence of the resin filler, the material, and the composition ratio were changed was manufactured and the effect was verified.
  • a nail penetration test was conducted in which the battery was completely penetrated with a SUS nail having a diameter of 3 mm. The set SOC was set in increments of 5%, and the highest SOC that did not lead to smoke or ignition in the nail penetration test was used as an effect index.
  • the mechanism of heat generation by the nail penetration test is not clear, but as an example of a hypothesis, the penetration portion by the nail penetration is not only indirect short circuit through the nail, but also by the electrode breakage by the nail, the positive electrode 34 It is considered that a part of the negative electrode 32 and a part of the negative electrode 32 are in contact and directly short-circuited. In general, the greater the area of the part that is directly short-circuited, and the higher the SOC, the greater the amount of heat generated during the short-circuit. These heat generations promote the shrinkage of the separators 33 and 35, and reduce the binding force of the binder (SBR) 32c3 constituting the negative electrode protective layer 32c.
  • SBR binder
  • the separators 33 and 35 are shrunk, and the binding force of the binding material 32c3 of the constituent material of the negative electrode protection layer 32c becomes insufficient, and the resin filler 32c2 of the negative electrode protection layer 32c is melted. If it flows out between the positive electrode 34 and the negative electrode 32, the positive electrode metal foil exposed portion 34b and the negative electrode mixture layer 32a come into contact with each other, a secondary short circuit occurs, and eventually, ignition and smoke are caused. Is considered.
  • the negative electrode protective layer 32c can maintain sufficient insulation, it is possible to avoid a short circuit due to contact between the positive electrode 34 and the negative electrode 32 due to nail penetration and to suppress heat generation. In addition, since the heat generation is higher in the high SOC state, the separators 33 and 35 are likely to shrink. However, if the insulating property of the negative electrode protective layer 32c is sufficient, the positive metal foil exposed portion 34b and the negative electrode 32 A secondary short circuit can be avoided and safety can be ensured.
  • the binder (SBR in this embodiment) 32c3 of the negative electrode protective layer 32c is: In the case of an abnormal heat generation state, the function as a binder is decreased by melting, but at the same time, the resin filler 32c2 is softened to exhibit tackiness and exhibit a function as a second adhesive. In addition, the movement of the inorganic filler 32c1 is suppressed, and at the same time, the pores are closed and the insulating properties are improved. Therefore, a secondary short circuit in which the positive electrode 34 and the negative electrode 32 are directly short-circuited can be avoided, and safety can be improved.
  • Table 1 shows examples and comparative examples in which the composition of the negative electrode protective layer 32c was studied and the effects thereof.
  • Comparative Example 1-1 shown in Table 1 was prepared without the negative electrode protective layer 32c shown in FIGS. 5 and 6, and Comparative Example 1-2 was a resin applied to the negative electrode protective layer 32c.
  • the filler 32c2 was not mixed and it was produced using only the inorganic filler 32c1 and the binder 32c3.
  • polyethylene (PE) having a melting point substantially equal to that of the separators 33 and 35 is used for the resin filler of the comparative example
  • polyphenylene sulfide (PPS) having a melting point higher than that of the separators 33 and 35 is used for the resin filler of the example.
  • the effect was confirmed using.
  • a spherical inorganic filler having an aspect ratio of 2 or less was used.
  • the measurement of the particle size was performed using the particle size distribution measuring apparatus by a laser diffraction / scattering method.
  • Comparative Examples 1-3 to 1-5 were equivalent or less, and no improvement effect was observed. This is because in Comparative Examples 1-3 to 1-5, the amount of the inorganic filler was substantially reduced by mixing the resin filler, and the resin filler and the binder were at the same temperature as the melting point of the separator. Therefore, the resin filler and the binder of the protective layer are melted at the same time as the separator, and the inorganic filler fixed by the resin filler and the binder becomes movable, and a part of the negative electrode protective layer 32c is formed. It is thought that it flowed out and became thin and was in a state where sufficient insulation was not obtained.
  • Examples 1-1 to 1-3 Although the inorganic filler 32c1 is substantially reduced by mixing the resin filler 32c2, the heat resistance temperature of the resin filler 32c2 is high, so that the insulating property can be maintained. In addition, the resin filler 32c2 is softened by heat generation and develops an adhesive force, binds the inorganic filler 32c1 with a certain binding force, and exhibits a function as a second binding material. This is thought to be due to the suppression of movement, resulting in increased insulation.
  • Example 1-2 the level (Example 1-2) in which the mixing ratio of the inorganic filler 32c1 and the resin filler 32c2 was 3: 1 was most effective. This is presumed that Example 1-2 was provided with a sufficient amount of the inorganic filler 32c1 capable of ensuring insulation and was suitable for serving as the second binder by the resin filler 32c2.
  • Example 2-1 was more effective and could ensure safety at a high SOC (95%).
  • the particle size of the resin filler 32c2 and the particle size of the inorganic filler 32c1 are made different from each other, so that particles of two types of particle sizes are mixed. This is thought to be due to an increase in insulation and improved insulation.
  • the particle size of the resin filler 32c2 smaller than the particle size of the inorganic filler 32c1, the number of contacts where the inorganic filler 32c1 and the resin filler 32c2 are in contact with each other can be increased.
  • the voids of the negative electrode protective layer 32c are formed by melting the resin filler 32c2. It was estimated that the insulation was further improved.
  • Example 3-1 when Example 3-1 was compared with Example 2-1, Example 3-1 was more effective, and safety at the maximum SOC (100%) could be ensured.
  • the particle shape of the resin filler 32c2 is spherical, whereas the particle shape of the inorganic filler 32c1 is a plate, as shown in the image diagram of FIG.
  • the plate-like inorganic filler 32c1 has an aspect ratio of 5 or more, and in the present embodiment, a filler having a ratio of 5 to 15 was used.
  • the measurement of the particle size was performed using the particle size distribution measuring apparatus by a laser diffraction / scattering method.
  • Table 2 shows the results of the nail penetration test when the material of the inorganic filler 32c1 was changed with respect to Example 3-1.
  • boehmite Al 2 O 3 hydrate
  • alumina Al 2 O 3
  • silica silica
  • TiO 2 titanium oxide in example 4-3
  • TiO 4-4 barium titanate
  • Table 3 shows the results of a nail penetration test when separators 33 and 35 in which inorganic filler (alumina) 32c1 is applied to separators 33 and 35 are used in Example 3-1.
  • the secondary battery was produced so that the coating layer of the separators 33 and 35 might be arrange
  • Example 5-1 had the same maximum SOC as Example 3-1 but the highest temperature reached. This is because the coated layers of the separators 33 and 35 generally have an effect of suppressing the thermal contraction of the separators 33 and 35, so that the contraction of the separators 33 and 35 around the nail is suppressed, and the break due to the nail is short-circuited. It is considered that the maximum temperature reached has decreased due to a decrease in. Therefore, higher safety can be expected by combining the coated separator with improved heat resistance and this example.
  • the protective layer 32c is mixed with the resin filler 32c2 having a melting point higher than that of the separators 33 and 35 and the binder 32c3 of the protective layer 32c.
  • the function as the binder is exhibited to suppress the movement of the inorganic filler 32c1. Accordingly, even if the separators 33 and 35 are shrunk, the secondary short circuit between the positive electrode 34 and the negative electrode 32 can be avoided by the protective layer 32c, and safety can be improved.
  • the protective layer 32c is formed by mixing the inorganic filler 32c1 and the resin filler 32c2 has been described.
  • at least a part of the inorganic filler 32c1 is made of a resin such as PPS constituting the resin filler 32c2.
  • a coated material or a resin in which the resin constituting the resin filler 32c2 is supported on the inorganic filler 32c1 may be used, and the effect of improving the safety can be obtained similarly.
  • the present invention is not limited to the above-described embodiments, and various designs can be made without departing from the spirit of the present invention described in the claims. It can be changed.
  • the above-described embodiment has been described in detail for easy understanding of the present invention, and is not necessarily limited to one having all the configurations described.
  • a part of the configuration of an embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of an embodiment.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une pile rechargeable dans laquelle une couche protectrice est interposée entre une électrode positive et une électrode négative de sorte que des courts-circuits secondaires entre l'électrode positive et l'électrode négative puissent être évités y compris lorsque la pile rechargeable est dans un état de température élevée, ce qui permet d'améliorer la sécurité. Cette pile rechargeable 100 comprend une couche protectrice 32c d'électrode négative agencée sur une surface d'une couche de mélange 32a d'électrode négative d'une électrode négative 32, la couche protectrice 32c d'électrode négative comprenant une charge inorganique 32c1, une charge de résine 32c2 et un matériau de liaison 32c3. Une résine présentant un point de fusion plus élevé que des séparateurs 33, 35 et que le matériau de liaison 32c3 est utilisée en tant que charge de résine 32c2. Par conséquent, à des moments de génération de chaleur anormale, cette charge de résine 32c2 fonctionne en tant que second matériau de liaison, ce qui permet d'empêcher un mouvement de la charge inorganique 32c1. Par conséquent, même si les séparateurs 33, 35 rétrécissent, des courts-circuits secondaires entre une électrode positive 34 et l'électrode négative 32 peuvent être évités, ce qui permet d'améliorer la sécurité.
PCT/JP2016/072099 2015-09-02 2016-07-28 Pile rechargeable WO2017038327A1 (fr)

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JP2017537666A JP6586169B2 (ja) 2015-09-02 2016-07-28 二次電池

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JP2015-172868 2015-09-02

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WO2019003770A1 (fr) * 2017-06-30 2019-01-03 日立オートモティブシステムズ株式会社 Accumulateur et son procédé de fabrication
CN110364667A (zh) * 2018-04-11 2019-10-22 宁德新能源科技有限公司 多孔膜和锂离子电池
WO2019244401A1 (fr) * 2018-06-19 2019-12-26 日立オートモティブシステムズ株式会社 Batterie secondaire au lithium-ion et son procédé de production
WO2022185580A1 (fr) 2021-03-05 2022-09-09 ビークルエナジージャパン株式会社 Batterie secondaire au lithium-ion et son procédé de production

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JP2005327680A (ja) * 2004-05-17 2005-11-24 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019003770A1 (fr) * 2017-06-30 2019-01-03 日立オートモティブシステムズ株式会社 Accumulateur et son procédé de fabrication
JPWO2019003770A1 (ja) * 2017-06-30 2020-03-19 日立オートモティブシステムズ株式会社 二次電池およびその製造方法
CN110364667A (zh) * 2018-04-11 2019-10-22 宁德新能源科技有限公司 多孔膜和锂离子电池
WO2019244401A1 (fr) * 2018-06-19 2019-12-26 日立オートモティブシステムズ株式会社 Batterie secondaire au lithium-ion et son procédé de production
CN112335088A (zh) * 2018-06-19 2021-02-05 日本汽车能源株式会社 锂离子二次电池及其制造方法
JPWO2019244401A1 (ja) * 2018-06-19 2021-03-11 ビークルエナジージャパン株式会社 リチウムイオン二次電池及びその製造方法
JP7027540B2 (ja) 2018-06-19 2022-03-01 ビークルエナジージャパン株式会社 リチウムイオン二次電池及びその製造方法
WO2022185580A1 (fr) 2021-03-05 2022-09-09 ビークルエナジージャパン株式会社 Batterie secondaire au lithium-ion et son procédé de production

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