WO2013042176A1 - Accumulateur au lithium-ion - Google Patents

Accumulateur au lithium-ion Download PDF

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Publication number
WO2013042176A1
WO2013042176A1 PCT/JP2011/071296 JP2011071296W WO2013042176A1 WO 2013042176 A1 WO2013042176 A1 WO 2013042176A1 JP 2011071296 W JP2011071296 W JP 2011071296W WO 2013042176 A1 WO2013042176 A1 WO 2013042176A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
battery
ion battery
negative electrode
lithium ion
Prior art date
Application number
PCT/JP2011/071296
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English (en)
Japanese (ja)
Inventor
誠之 廣岡
Original Assignee
日立ビークルエナジー株式会社
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Publication date
Application filed by 日立ビークルエナジー株式会社 filed Critical 日立ビークルエナジー株式会社
Priority to JP2013534466A priority Critical patent/JP5727023B2/ja
Priority to PCT/JP2011/071296 priority patent/WO2013042176A1/fr
Publication of WO2013042176A1 publication Critical patent/WO2013042176A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/342—Non-re-sealable arrangements
    • H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 high-output and high-capacity lithium ion battery used for in-vehicle applications.
  • High-power and high-capacity lithium ion batteries used for in-vehicle applications etc. are desired to maintain high safety.
  • Patent Document 1 discloses a general formula Li 1 + x M 1-xy M ′ y O 2 ⁇ (where M is an element of Mn, Co, or Ni, or a combination of two or more thereof) M ′ is a transition element existing between a group 3 element and a group 11 element in the periodic table, or an element composed of a combination of two or more thereof. It is described that the output can be increased by using a metal oxide for the positive electrode.
  • In-vehicle lithium-ion batteries require high safety in addition to high output and high capacity. These characteristics are closely related to the physical properties of the positive electrode material, and particularly high output, high capacity, and safety are incompatible with each other. For example, when the output is increased using the positive electrode material described in Patent Document 1, capacity reduction and safety reduction occur. In addition, for example, the positive electrode material described in Patent Document 2 is lithium cobalt oxide, so that safety can be maintained. However, if the Ni content is increased at the Co site for higher capacity, the safety of the battery is significantly reduced. Is expected to.
  • in-vehicle lithium ion batteries need to secure a gas exhaust path in the event of abnormal heat generation and prevent a sudden increase in internal pressure in the battery can.
  • the present invention aims to simultaneously improve three characteristics of a high capacity, high output, and high safety in a lithium ion battery.
  • the present invention is characterized in that a sub-peak of heat generation appears in a temperature range of 150 to 230 ° C. in a differential thermal scanning calorimetry profile measured by combining a positive electrode mixture constituting a positive electrode in a charged state with an electrolyte. Adopt a lithium ion battery.
  • the total heat generation amount in the case of abnormal heat generation of the battery is reduced, and in the case of abnormal heat generation of the battery, the electrolyte in the battery is decomposed by the heat generation of the positive electrode mixture at an early stage to generate gas. It is possible to promote gas escape from the inside of the battery can and prevent a sudden increase in internal pressure.
  • FIG. 3 is a partially developed perspective view schematically showing the configuration of an electrode winding group used in the lithium ion battery of Example 1.
  • FIG. 1 is a perspective view showing a configuration of an assembly part of a lithium ion battery of Example 1.
  • FIG. 1 is a perspective view showing a configuration of an assembly part of a lithium ion battery of Example 1.
  • FIG. 1 is a perspective view showing an external appearance of a lithium ion battery of Example 1.
  • FIG. It is a graph which shows the profile of differential thermal scanning calorimetry (DSC) in Example 1 and a comparative example.
  • DSC differential thermal scanning calorimetry
  • 6 is a partially developed perspective view schematically showing the configuration of an electrode winding group used in the lithium ion battery of Example 2.
  • FIG. 6 is a developed perspective view showing a lithium ion battery of Example 2.
  • FIG. 1 is a perspective view showing a configuration of an assembly part of a lithium ion battery of Example 1.
  • FIG. 1 is a perspective view
  • FIG. 3 is a cross-sectional view showing a lithium ion battery of Example 2.
  • FIG. 3 is a cross-sectional view showing a lithium ion battery of Example 2.
  • FIG. 6 is a partial perspective view illustrating an assembly process of a current collector of a lithium ion battery according to Embodiment 2.
  • FIG. 6 is a partial perspective view illustrating an assembly process of a current collector of a lithium ion battery according to Embodiment 2.
  • FIG. It is a front view which shows the gas discharge path
  • the lithium ion battery includes an electrode winding group formed by winding a positive electrode, a negative electrode, and a separator sandwiched between them, a battery can containing the electrode winding group and an electrolyte, and the battery can sealed
  • the differential thermal scanning calorimetry profile of the battery including the lid and the cleavage valve provided on the lid and measured by combining the positive electrode mixture constituting the charged positive electrode with the electrolyte is 150. It has an exothermic sub-peak in a temperature range of ⁇ 230 ° C.
  • the positive electrode mixture is represented by the chemical formula Li 1 + x M 1-y Mo y O 2 (wherein M is one or more metal elements selected from the group consisting of Ni, Mn, and Co).
  • X is preferably from 0 to 0.20, and y is preferably from 0.025 to 0.055).
  • the positive electrode active material is preferably a layered lithium transition metal oxide, and the (003) plane crystallite size is preferably 30 to 80 nm.
  • the lid is preferably disposed on a surface orthogonal to the winding axis of the electrode winding group.
  • lithium ion batteries lithium ion secondary batteries
  • a lithium ion battery capable of preventing an increase in internal pressure of the battery by releasing gas generated when abnormal heat generation occurs at an early stage will be described.
  • FIG. 1 is a partially developed perspective view schematically showing the configuration of an electrode winding group used in a lithium ion battery.
  • the electrode winding group 102 includes a strip-like positive electrode 401 in which a positive electrode mixture is applied to both surfaces of an aluminum foil base material, and a strip-like negative electrode 402 in which a negative electrode mixture is applied to both surfaces of a copper foil base material. Are overlapped via two separators 403 and wound around a plate-like core 404.
  • the electrode winding group 102 has a rounded rectangular shape (so-called race track shape) when viewed from the winding axis direction of the winding core 404.
  • the core 404 is not particularly limited as long as it has electrical insulation and heat resistance, but is preferably produced by resin molding from the viewpoint of weight reduction, for example, a thermoplastic resin such as polypropylene or polyphenylene sulfide.
  • Thermosetting resins such as phenol resins, melamine resins, and unsaturated polyesters are preferably used.
  • the positive electrode mixture is not applied to one end of the positive electrode 401 in the winding axis direction (foil width direction), and the aluminum foil base material is exposed.
  • the negative electrode mixture is not applied to one end of the negative electrode 402 in the winding axis direction (the width direction of the foil), and the copper foil base material is exposed.
  • FIG. 2 shows the lid and electrode winding group before assembling the lithium ion battery.
  • FIG. 3 shows a state before the combination of the lid and the electrode winding group is inserted into the battery outer case.
  • FIG. 4 shows the appearance of the assembled lithium ion battery.
  • the positive current collector disposed at the end of the electrode winding group 102 is formed on the aluminum plate 12, and the negative current collector disposed on the opposite end of the positive electrode is formed on the copper plate 11. These are joined by ultrasonic welding.
  • this joining is performed by ultrasonic welding, but there is no particular limitation as long as it can be joined electrically and thermally by resistance welding or other joining methods.
  • the negative electrode external terminal 71, the positive electrode external terminal 73, the negative electrode connection plate 72, and the positive electrode connection plate 74 are electrically connected to the lid 75.
  • the lid 75 is made of aluminum and has a liquid injection port 76 and a gas discharge valve 77.
  • the negative electrode connection plate 72 and the positive electrode connection plate 74 were electrically connected to the copper plate 11 and the aluminum plate 12 joined to the current collector of the electrode winding group 102, respectively.
  • this connection is performed by ultrasonic welding.
  • the connection is not particularly limited as long as it can be electrically connected by resistance welding, bonding by screws, or other bonding methods.
  • the heat inside the electrode winding group 102 is transmitted from the aluminum plate 112 and the copper plate 11 to which the current collector is connected to the positive electrode connection plate 74 and the negative electrode connection plate 72, respectively, and protrudes from the lid 75. Heat is dissipated from the positive external terminal 73 and the negative external terminal 71 installed.
  • the electrode winding group 102 and the lid 75 integrated as shown in FIG. 3 were inserted into an aluminum battery outer casing 78 (battery can).
  • An insulating sheet 79 is provided on the inner wall of the battery outer casing 78 so that insulation from the electrode winding group 102 is maintained.
  • the battery 70 shown in FIG. 4 was produced by sealing the lid
  • Ni + Mn + Co 96 mol%
  • Mo 4 mol%
  • the slurry was pulverized with a zirconia bead mill until the average particle size became 0.2 ⁇ m.
  • a polyvinyl alcohol (PVA) solution was added to the slurry in an amount of 1 wt% in terms of the solid content ratio, and further mixed for 1 hour, and then dried by a spray dryer and granulated.
  • PVA polyvinyl alcohol
  • lithium hydroxide and lithium carbonate were added to form a powder so that the ratio of Li to transition metal was 1.0: 1 to 1.1: 1.
  • the obtained powder was fired at 750 ° C. for 10 hours to form crystals having a layered structure. Thereafter, this crystal was crushed to obtain a positive electrode active material. Then, after removing coarse particles having a particle diameter of 30 ⁇ m or more by classification, a positive electrode was produced using this positive electrode active material.
  • the compounding ratio of the above elements is an example, and a chemical formula Li 1 + x M 1-y Mo y O 2 (wherein M is one or more metal elements selected from the group consisting of Ni, Mn, and Co). x is 0 to 0.20, and y is 0.025 to 0.055).
  • Table 1 shows the compositions of the positive electrode active material 1 according to Example 1, the positive electrode active materials 2 to 8 according to other examples, and the positive electrode active material 9 according to Comparative Examples described later.
  • the Ni ratio is preferably 5-9.
  • the method for producing the positive electrode active material is not limited to the above method, and other methods such as a coprecipitation method may be used.
  • the obtained positive electrode active material was measured by X-ray diffraction (XRD), resulting from diffraction lines appearing at 2 ⁇ 18 degrees (003).
  • XRD X-ray diffraction
  • a material having a surface crystallite size in the range of 30 to 80 nm according to Scherrer's formula was selected as a positive electrode material.
  • a slurry was prepared by mixing a positive electrode active material with a conductive material and a PVDF binder.
  • the environment for the production is desirably a temperature of 30 ° C. or less and a relative humidity of 50% or less.
  • PVDF is an abbreviation for polyvinylidene fluoride.
  • the positive electrode active material and the conductive material were weighed to a mass ratio of 86:11 and mixed with a mixer.
  • This mixed material and PVDF-based binder were weighed so as to have a mass ratio of 97: 3, N-methylpyrrolidone (NMP) was added and kneaded, and finally defoamed to obtain a slurry.
  • NMP N-methylpyrrolidone
  • the obtained slurry was spread on the surface of an aluminum foil, coated on both sides using an applicator, and dried to obtain a positive electrode.
  • DSC differential scanning calorimetry
  • FIG. 5 shows the result.
  • the horizontal axis represents temperature, and the vertical axis represents heat flow per unit mass.
  • a solid line indicates the present embodiment, and a broken line indicates a comparative example described later.
  • the DSC profile of Example 1 indicated by the solid line has lower temperature dependency of the heat flow rate and higher thermal stability than the comparative example. Moreover, heat generation starts from about 150 ° C. and continues to around 350 ° C. It can be seen that the DSC profile of Example 1 has a main peak near 280 ° C. and a sub-peak near 190 ° C. On the other hand, the DSC profile of the comparative example has a steep main peak near 280 ° C.
  • the positive electrode showing the DSC profile as shown by the solid line in FIG. 5 By applying the positive electrode showing the DSC profile as shown by the solid line in FIG. 5 to the battery, the total amount of heat generated during battery overheating or abnormal heat generation due to an internal short circuit can be reduced.
  • the relatively early heat generation of the positive electrode derived from the DSC profile sub-peak ( ⁇ 190 ° C.) promotes the decomposition of the electrolyte solution present between the positive electrode and the negative electrode, and promotes outgassing in the battery can. And a sudden rise in internal pressure of the battery can be prevented.
  • the point at which the heat flow rate reaches the maximum value when heat generation at a heat flow rate of 0.5 W / g or more occurs from the baseline of the DSC profile is defined as “sub-peak”.
  • the point at which the heat flow rate reaches the maximum value is defined as the “main peak”.
  • the case where the sub-peak is about 190 ° C. is shown as an example, but the appropriate sub-peak range is 150 to 230 ° C. A more desirable sub-peak range is 180 to 220 ° C.
  • DSC differential thermal scanning calorimetry
  • FIG. 6 is a partially developed perspective view schematically showing the configuration of the electrode winding group used in the lithium ion battery.
  • the positive electrode tab 405 and the negative electrode tab 406 are formed on opposite sides. Each of the positive electrode tab 405 and the negative electrode tab 406 preferably has a width of 2 to 10 mm and a length of 15 to 50 mm.
  • FIG. 7 shows an exploded view of a lithium ion battery.
  • FIG. 8A shows a cross section of the lithium ion battery in a plane parallel to the wide surface of the core (the flat surface of the battery).
  • FIG. 8B shows a cross section of the lithium ion battery on a plane parallel to the thickness direction of the core (a plane perpendicular to the flat surface of the battery).
  • FIG. 9A shows the assembly process (joining process) of the current collector of the lithium ion battery.
  • FIG. 9B shows an assembly process (bending process) of the current collector of the lithium ion battery.
  • the lithium ion battery 100 includes a battery container (a cylindrical battery can 101 (container body) having a rounded rectangular cross section) at both end portions of a positive electrode side sealing plate 116 and a negative electrode side sealing plate 103.
  • the electrode winding group 102 (details are shown in FIG. 6) is accommodated together with the electrolytic solution inside (sealed by the container lid).
  • aluminum or stainless steel is preferably used as the material for the battery container. That is, in the present embodiment, unlike the first embodiment, the positive electrode terminal 109 and the negative electrode terminal 110 are arranged on the container lids on the opposite sides.
  • the battery can 101 may have a rectangular cross-sectional shape.
  • the positive electrode tab 405 and the negative electrode tab 406 of the electrode winding group 102 are welded to the positive electrode current collector plate 104 and the negative electrode current collector plate 105, respectively. Then, the current collector plate protrusion 603 is fitted into the groove 407 of the winding core 404 wound around the electrode winding group 102. Thereby, the positive electrode current collecting plate 104 and the negative electrode current collecting plate 105 are disposed in a flange shape at both ends of the core 404.
  • a positive electrode terminal 109 and a negative electrode terminal 110 are connected to the positive current collector 104 and the negative current collector 105 by welding or the like, respectively.
  • the positive electrode current collector plate 104 and the negative electrode current collector plate 105 are provided with openings 602 (positive electrode openings and negative electrode openings), which serve as an exhaust path when the internal pressure of the cell increases.
  • the insulating cover 111 produced by resin molding is put on the positive electrode current collector plate 104 and the negative electrode current collector plate 105, and the electrode winding group 102, the positive electrode current collector plate 104, the negative electrode current collector plate 105, and the insulating cover 111 are formed.
  • the integrated unit is inserted into the battery can 101.
  • the insulating cover 111 includes an electrode opening 303 and a gas discharge opening 302.
  • the gasket 112 (made of resin) of the positive electrode terminal 109 is attached inside the positive electrode side sealing plate 116, and the positive electrode side sealing plate 116 is welded to the end of the battery can 101.
  • the gasket 112 (made of resin) of the negative electrode terminal 110 is attached to the inside of the negative electrode side sealing plate 103, and the negative electrode side sealing plate 103 is welded to the end of the battery can 101. Welding is performed by an electron beam or a laser.
  • Each of the positive electrode side sealing plate 116 and the negative electrode side sealing plate 103 includes an electrode terminal opening 304, and a central portion thereof includes a cleavage valve 108.
  • the positive electrode side sealing plate 116 also includes a liquid injection hole 301 for injecting an electrolytic solution.
  • the gasket 115 is attached to the outside of the positive electrode side sealing plate 116 and the negative electrode side sealing plate 103 and fixed by the nut 113.
  • the positive electrode current collector plate 104 and the negative electrode current collector plate 105 are fitted to a cylindrical or plate-like core 404 to which the electrode winding group 102 is attached.
  • the core 404 is made by resin molding, and if it is a thermoplastic resin, polypropylene or polyphenylene sulfide is used, and if it is a thermosetting resin, a phenol resin, a melamine resin, an unsaturated polyester, or the like is used, If it has electrical insulation and heat resistance, it will not specifically limit.
  • a cleavage valve 108 is provided at the center of the negative electrode side sealing plate 103.
  • the positive side sealing plate 116 is provided with a liquid injection stopper 107 in addition to the cleavage valve 108.
  • a resin gasket 112 is provided inside the positive electrode terminal 109 and the negative electrode terminal 110 (inside the battery can 101), and a gasket 115 is provided outside the positive electrode terminal 109 and the negative electrode terminal 110 (outside the battery can 101). Is provided. These gaskets 112 and 115 are fixed from the outside of the positive side sealing plate 116 and the negative side sealing plate 103 by nuts 113.
  • the insulating cover 111 and the two types of gaskets 112 and 115 are preferably produced by resin molding.
  • thermoplastic resin polypropylene or polyphenylene sulfide
  • thermosetting resin a phenol resin, Melamine resins, unsaturated polyesters, and the like
  • unsaturated polyesters and the like are used, but they are not particularly limited as long as they have electrical insulation and heat resistance.
  • the positive electrode tab 405 and the negative electrode tab 406 are formed in groups, and protrude from both ends of the flat electrode winding group 102, respectively.
  • the positive electrode tab 405 and the negative electrode tab 406 are bundled and welded to the positive electrode current collector plate 104 and the negative electrode current collector plate 105, respectively.
  • the positive electrode tab 405 and the negative electrode tab 406 are provided on the flat portion of the electrode winding group 102 that is opposite to the winding core (core 404 in FIG. 7) of the electrode winding group 102. And welded so as to be arranged on the opposite side (opposite side) with respect to the core. As a result, the positive electrode tab 405 and the negative electrode tab 406 respectively block half of the positive electrode current collector plate 104 side and the negative electrode current collector plate 105 side of the electrode winding group 102.
  • gas discharge paths 114 (positive gas discharge path and negative gas discharge path) indicated by broken lines in FIG. 8B are provided on both sides of the core, and when gas is generated in the battery due to battery abnormality. Even when the battery can 101 is deformed, the gas discharge path 114 can be secured.
  • the positive electrode side will be mainly described with reference to FIGS. 9A and 9B, but the same applies to the negative electrode side.
  • the positive electrode current collector plate 104 is a plate-like member having a thickness of 0.5 to 5 mm, and has a rounded rectangular shape (a shape in which a curved region consisting of a substantially semicircular shape is coupled to both ends of a linear region consisting of a rectangle, so-called race track shape). It has the external shape.
  • the outer shape of the positive electrode current collector plate 104 is larger than the outer shape of the end surface of the winding core 404 and slightly smaller than the outer shape of the end surface of the electrode winding group 102 (rounded rectangle).
  • a positive electrode terminal 109 is integrally fixed to the end of the positive electrode current collector plate 104 by welding or the like.
  • an opening 602 for smoothly discharging gas generated due to abnormal heat generation is provided at the center of the positive electrode current collector plate 104.
  • the negative electrode current collector plate 105 has the same outer shape as the positive electrode current collector plate 104. Further, the negative electrode current collector plate 105 is provided with a negative electrode terminal 110 and an opening 602.
  • the group of positive electrode tabs 405 is pressed against the tab joint portion 601 disposed on the surface of the positive electrode current collector plate 104 on the electrode winding group 102 side, and joined together by welding or the like in a close contact state.
  • the positive electrode current collector plate 104 is flanged at the end of the core 404 (that is, the flange surface of the positive electrode current collector 104 and the winding axis direction of the core 404 are orthogonal to each other). Arranged).
  • connection is fixed by fitting the current collector plate convex portions 603 disposed outside both ends of the opening 602 of the positive electrode current collector plate 104 and the groove 407 (core concave portion) of the core 404. Shows when to do.
  • This fixing method has an advantage of not increasing the number of parts.
  • the group of negative electrode tabs 406 is joined to the negative electrode current collector plate 105, and the current collector plate convex portion 603 of the negative electrode current collector plate 105 and the groove 407 of the core 404 are fitted.
  • the present invention is not limited to the fixing method shown in the figure.
  • a fitting recess or fitting hole is formed on the positive electrode current collector plate 104 side, and a fitting projection is formed on the core 404 side.
  • the formed combination may be used, or the positive electrode current collector plate 104 and the core 404 may be fixed with screws.
  • the group of the positive electrode tabs 405 is drawn long, but the positive electrode tabs 405 are within a range not impeding workability when fixing the positive electrode current collector plate 104 and the core 404.
  • the length of is preferably as short as possible.
  • the positive electrode tab 405 and the negative electrode tab 406 protrude from both ends of the electrode winding group 102 and are arranged on opposite sides of the winding core 404. As shown in FIG. 8B, the positive electrode tab 405 and the negative electrode tab 406 are welded, so that a gas discharge path 114 without an obstacle can be secured on the opposite sides of the core 404. As a result, even under abnormal circumstances, even if gas generation locations are unevenly distributed within the electrode winding group 102, gas discharge is kept good.
  • the positive electrode current collector plate 104 and the negative electrode current collector plate 105 are each covered with an insulating cover 111 produced by resin molding.
  • the insulating cover 111 is formed with an electrode opening 303 through which the positive terminal 109 or the negative terminal 110 is inserted, and a gas discharge opening 302 having the same position and the same size as the opening 602.
  • the insulating cover 111 is preferably made of a thermoplastic resin such as polypropylene or polyphenylene sulfide, or a thermosetting resin such as a phenol resin, a melamine resin, or an unsaturated polyester.
  • the electrode winding group 102, the positive electrode current collector plate 104, the negative electrode current collector plate 105, and the insulating cover 111 are integrated into the battery can 101.
  • the electrode winding group 102, the positive electrode current collector plate 104, the negative electrode current collector plate 105, and the insulating cover 111 are integrated into the battery can 101.
  • a resin gasket 112 (first gasket) is disposed on each electrode terminal.
  • a resin gasket 115 (second gasket) is disposed on each electrode terminal, and each electrode terminal and the battery container are fixed by a nut 113.
  • the first gasket and the second gasket are preferably made of a thermoplastic resin such as polypropylene or polyphenylene sulfide, or a thermosetting resin such as a phenol resin, a melamine resin, or an unsaturated polyester.
  • an electrolyte containing lithium ions is injected from the injection hole 301 in a low humidity environment and sealed with the injection plug 107 to complete the assembly of the lithium ion battery 100.
  • FIG. 10 shows a path through which gas is discharged from a lithium ion battery that has expanded in the event of abnormal heat generation.
  • the positive electrode side will be described as an example.
  • the gas generated in one region (the region above the core 404 in the figure) obtained by dividing the battery can 101 into two parts by a plane parallel to the flat surface 1001 of the battery can 101 passes through the opening 602 of the positive electrode current collector plate 104.
  • the gas passes through the gas discharge opening 302 of the insulating cover 111 and is efficiently discharged from the cleavage valve provided outside the gas discharge opening 302.
  • the gas discharge path 114 is indicated by an arrow.
  • the gas discharge path 114 can be arranged on both sides of the core 404 of the electrode winding group 102, and even when the battery can 101 is deformed, the gas is efficiently discharged. can do.
  • the positive electrode lead and the negative electrode lead are formed using a plurality of lead pieces (tabs), but the present invention is not limited to this, and is parallel to the flat surface 1001 of the electrode winding group 102.
  • an undivided (series) lead piece may be used.

Abstract

La présente invention concerne un accumulateur au lithium-ion comprenant un groupe bobiné d'électrodes formé en bobinant une électrode positive, une électrode négative et un séparateur interposé entre elles, une cuve d'accumulateur qui abrite le groupe bobiné d'électrodes et un électrolyte et un capuchon destiné à fermer la cuve d'accumulateur, le capuchon comprenant une vanne de clivage. Sur cet accumulateur au lithium-ion, un profil de calorimétrie différentielle à balayage mesuré en combinant un mélange d'électrode positive constituant l'électrode positive à l'état chargé et l'électrolyte est conçu de manière à présenter un pic secondaire de production thermique sur la plage de températures de 150 à 230°C. Cela améliore simultanément trois caractéristiques de l'accumulateur au lithium-ion, à savoir une capacité élevée, une production élevée en sortie et une sécurité élevée.
PCT/JP2011/071296 2011-09-20 2011-09-20 Accumulateur au lithium-ion WO2013042176A1 (fr)

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JP2013534466A JP5727023B2 (ja) 2011-09-20 2011-09-20 リチウムイオン電池
PCT/JP2011/071296 WO2013042176A1 (fr) 2011-09-20 2011-09-20 Accumulateur au lithium-ion

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WO2015129187A1 (fr) * 2014-02-28 2015-09-03 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
WO2017071846A1 (fr) * 2015-10-29 2017-05-04 Lithium Energy and Power GmbH & Co. KG Dispositif de stockage d'énergie
CN109037761A (zh) * 2018-07-17 2018-12-18 江苏海基新能源股份有限公司 一种方形铝壳锂离子电池及装配方法
JP2020087821A (ja) * 2018-11-29 2020-06-04 株式会社豊田自動織機 リチウムニッケルコバルトモリブデン酸化物

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CN109037761A (zh) * 2018-07-17 2018-12-18 江苏海基新能源股份有限公司 一种方形铝壳锂离子电池及装配方法
JP2020087821A (ja) * 2018-11-29 2020-06-04 株式会社豊田自動織機 リチウムニッケルコバルトモリブデン酸化物
JP7099286B2 (ja) 2018-11-29 2022-07-12 株式会社豊田自動織機 リチウムニッケルコバルトモリブデン酸化物

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