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WO2018135011A1 - Batterie de type à enroulement - Google Patents

Batterie de type à enroulement Download PDF

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Publication number
WO2018135011A1
WO2018135011A1 PCT/JP2017/010543 JP2017010543W WO2018135011A1 WO 2018135011 A1 WO2018135011 A1 WO 2018135011A1 JP 2017010543 W JP2017010543 W JP 2017010543W WO 2018135011 A1 WO2018135011 A1 WO 2018135011A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
electrode
positive electrode
wound
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/010543
Other languages
English (en)
Japanese (ja)
Inventor
阿部　敏浩
山中　英明
拓磨 森下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maxell Ltd
Original Assignee
Maxell Holdings Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maxell Holdings Ltd filed Critical Maxell Holdings Ltd
Priority to JP2017517145A priority Critical patent/JPWO2018135011A1/ja
Publication of WO2018135011A1 publication Critical patent/WO2018135011A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H01M50/595—Tapes
    • 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
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a wound battery having an electrode body formed by winding a positive electrode, a negative electrode, and a separator, each formed in a strip shape, in an overlapped state.
  • Patent Document 1 discloses a cylindrical type by winding a positive electrode plate, a negative electrode plate, and a separator interposed between the electrode plates using a winding core. A method of obtaining a flat spiral electrode body by producing an electrode body and pressing the electrode body is disclosed.
  • Patent Document 2 discloses that an alloy of lithium and aluminum, lead, zinc, tin or the like is used as the negative electrode active material. Patent Document 2 also discloses that when such a lithium alloy is used as a negative electrode active material, dendrites are generated in the lithium alloy and become fine powder as the battery is charged and discharged. .
  • Patent Document 2 when a lithium alloy is used as the negative electrode active material, there is a possibility that the lithium alloy of the negative electrode is pulverized by charging and discharging of the battery. If it does so, a part of micronized lithium alloy may fall out from a negative electrode within a battery.
  • the end of the negative electrode winding end of the negative electrode in the electrode body means the end of the negative electrode in the longitudinal direction and the portion located on the outermost periphery of the negative electrode in the electrode body.
  • the dropped part affects the electrical characteristics of the negative electrode. Therefore, the battery characteristics of the wound battery may be deteriorated.
  • An object of the present invention is to provide a wound battery including an electrode body formed by winding a positive electrode, a negative electrode, and a separator, each formed in a strip shape, and the negative electrode contains a metal alloyed with Li. It is to prevent the end portion of the negative electrode from being wound down and falling off due to charge / discharge.
  • a positive electrode, a negative electrode, and a separator each formed in a strip shape are wound so that the separator is positioned between the positive electrode and the negative electrode,
  • An extending columnar electrode body is provided.
  • the negative electrode includes an element that can be alloyed with Li.
  • the end of winding of the negative electrode in the electrode body is covered with a protective member.
  • the electrode body has a columnar shape wound so that the separator is positioned between the positive electrode and the negative electrode.
  • the negative electrode includes an element that can be alloyed with Li, and a winding end portion of the negative electrode in the electrode body is covered with a protective member.
  • FIG. 1 is a perspective view illustrating a schematic configuration of the wound battery according to the embodiment.
  • FIG. 2 is a cross-sectional view showing the configuration of the wound battery along the line II-II in FIG.
  • FIG. 3 is a diagram schematically showing the arrangement of the positive electrode, the negative electrode, and the separator.
  • FIG. 4 is a diagram schematically illustrating a state where the positive electrode, the negative electrode, and the separator are wound in a state where they are stacked in the thickness direction.
  • FIG. 7 is a perspective view showing a schematic configuration of a wound battery according to another embodiment.
  • a positive electrode, a negative electrode, and a separator each formed in a strip shape are wound so that the separator is positioned between the positive electrode and the negative electrode,
  • An extending columnar electrode body is provided.
  • the negative electrode includes an element that can be alloyed with Li.
  • the end of winding of the negative electrode in the electrode body is covered with a protective member (first configuration).
  • the negative electrode containing an element that can be alloyed with Li an alloy with Li is generated when the battery is charged. Therefore, in the said negative electrode, micronization may arise by charging / discharging of a battery.
  • the end of winding of the negative electrode in the electrode body is covered with a protective member, so that an alloy with Li is not generated in the portion covered with the protective member. Therefore, in the part covered with the said protection member, pulverization does not arise by charging / discharging of a battery.
  • the end of winding end of the negative electrode in the electrode body means the end of the negative electrode in the longitudinal direction and the portion located on the outermost periphery of the negative electrode in the electrode body.
  • the end of the negative electrode in the electrode body is covered with a protective member, so that the separator can be prevented from being damaged by the end.
  • the protective member is provided so as to cover the end of winding of the negative electrode from one end to the other end in the short direction of the negative electrode (second). Configuration).
  • the above configuration can more reliably prevent the separator from being damaged by the winding end portion of the negative electrode.
  • the protective member is provided so as to cover a winding end end portion of the negative electrode and a portion within a predetermined range from the winding end end portion in the short-side end portion of the negative electrode. (Third configuration).
  • the separator can be prevented from being damaged by the winding end side of the negative electrode. Therefore, it is possible to more reliably prevent the separator from being damaged by the negative electrode.
  • the positive electrode includes a positive electrode active material layer.
  • the protective member is provided in a portion of the winding end portion of the negative electrode that overlaps the positive electrode active material layer with the separator interposed therebetween in a radial direction of the electrode body (fourth configuration).
  • the negative electrode and the positive electrode active material layer may come into contact with each other to cause a short circuit.
  • a protective member in the portion as described above it is possible to prevent the negative electrode and the positive electrode active material layer from being short-circuited due to damage to the separator by the negative electrode.
  • the protective member is provided so as to cover both surfaces of the winding end portion of the negative electrode (fifth configuration). Thereby, it can prevent more reliably that the winding end part of the negative electrode in an electrode body pulverizes and a part falls off by charging / discharging of a battery.
  • the protective member is provided so as to partially cover an end surface extending in the thickness direction of the negative electrode (sixth configuration). As a result, when burrs, protrusions, etc. are formed on the end surface extending in the thickness direction at the end of winding of the negative electrode in the electrode body, the end surface is in direct contact with the separator and the separator is damaged. Can be prevented.
  • the protection member is made of an electrically insulating material that does not contribute to the battery reaction (seventh configuration).
  • the protective member provided on the negative electrode can prevent a short circuit from occurring inside the battery and can also prevent the battery characteristics from being affected.
  • the negative electrode includes a Li—Al alloy as a negative electrode active material after charging the battery (eighth configuration).
  • the negative electrode is pulverized by charging and discharging of the battery. Even in the case where the Li—Al alloy is generated in the negative electrode in this way, by applying the first to seventh configurations described above, the winding end portion of the negative electrode in the electrode body is pulverized and partly falls off. This can be effectively suppressed.
  • the negative electrode is a laminate having a metal base layer that is not alloyed with Li and a metal surface layer joined to at least one of the metal base layers in the thickness direction. At least the surface side of the metal surface layer contains the Li—Al alloy after charging the battery (ninth configuration).
  • the negative electrode has a metal base layer and a metal surface layer as in the above-described configuration, the negative electrode has high rigidity. Therefore, in an electrode body wound with the positive electrode, the negative electrode, and the separator being stacked, a force that is displaced in the radial direction of the electrode body is more likely to be generated at the end of winding of the negative electrode. Therefore, there is a high possibility that the winding end portion of the negative electrode in the electrode body will damage the separator.
  • the first to seventh configurations described above are more effective in preventing the separator from being damaged in the electrode body wound using the negative electrode having the configuration described above.
  • FIG. 1 is a perspective view showing a schematic configuration of a wound battery 1 according to an embodiment of the present invention.
  • the wound battery 1 includes a bottomed cylindrical outer can 10, a cover plate 20 that covers an opening of the outer can 10, and an electrode body 30 that is accommodated in the outer can 10.
  • a rectangular parallelepiped battery case 2 (exterior body) having a rectangular parallelepiped space is formed.
  • a non-aqueous electrolyte is also enclosed in the battery case 2.
  • the outer can 10 is a bottomed cylindrical member made of an aluminum alloy, and constitutes the battery case 2 together with the cover plate 20.
  • the outer can 10 is a bottomed cylindrical member having a rectangular bottom surface 11 in a top view.
  • the outer can 10 includes a bottom surface 11 and a flat cylindrical side wall 12. That is, the outer can 10 is formed in a flat shape such that the dimension in the thickness direction corresponding to the short side direction of the bottom surface 11 is smaller than the width direction corresponding to the long side direction of the bottom surface 11.
  • the outer can 10 is joined to a lid plate 20 connected to a positive electrode lead (not shown), it also serves as a positive electrode terminal of the wound battery 1.
  • a positive electrode 31 described later of the electrode body 30 is connected to the lid plate 20 by a positive electrode lead (not shown).
  • the lid plate 20 is joined to the opening of the outer can 10 by welding so as to cover the opening of the outer can 10. Thereby, the upper surface of the battery case 2 is formed by the cover plate 20. Similar to the outer can 10, the lid plate 20 is made of a member made of an aluminum alloy and is formed in a rectangular shape so as to be fitted inside the opening of the outer can 10. Moreover, the through-hole 20a is formed in the center part of the longitudinal direction at the cover board 20 (refer FIG. 2).
  • an insulating packing 21 made of polypropylene and a negative electrode terminal 22 made of stainless steel are inserted into the through hole 20 a of the cover plate 20.
  • a substantially cylindrical insulating packing 21 into which a substantially columnar negative electrode terminal 22 is inserted is fitted to the peripheral edge of the through hole 20a.
  • the negative electrode terminal 22 has a configuration in which flat portions are integrally formed at both ends of a cylindrical shaft portion.
  • the negative electrode terminal 22 is arranged with respect to the insulating packing 21 so that the flat surface portion is exposed to the outside and the shaft portion is positioned in the insulating packing 21.
  • a stainless steel lead plate 27 is connected to the negative terminal 22. Thereby, the negative electrode terminal 22 is electrically connected to the negative electrode 32 of the electrode body 30 via the lead plate 27 and the negative electrode lead 35 described later.
  • An insulator 26 is disposed between the lead plate 27 and the lid plate 20.
  • a resin insulating plate 36 is disposed between the negative electrode terminal 22 attached to the cover plate 20 and the electrode body 30 between the negative electrode terminal 22 attached to the cover plate 20 and the electrode body 30, a resin insulating plate 36 is disposed.
  • a negative electrode lead 35 penetrates the insulating plate 36.
  • a positive electrode lead (not shown) extends to the lid plate 20 through the insulating plate 36 or through the side of the insulating plate 36.
  • a non-aqueous electrolyte inlet 24 is formed in the lid plate 20 along with the negative electrode terminal 22.
  • the injection port 24 is formed in a substantially circular shape in plan view.
  • the injection port 24 has a small diameter portion and a large diameter portion so that the diameter changes in two steps in the thickness direction of the lid plate 20.
  • the injection port 24 is sealed by a sealing plug 25 formed in a step shape corresponding to a change in the diameter of the injection port 24.
  • the outer peripheral portion on the large diameter side of the sealing plug 25 and the peripheral portion of the injection port 24 are joined by laser welding so that no gap is generated between the sealing plug 25 and the peripheral portion of the injection port 24.
  • the inlet 24 and the sealing plug 25 are not limited to the above-described configuration, and may have any configuration as long as it can be sealed after injecting the nonaqueous electrolytic solution into the battery case 2. .
  • the electrode body 30 is formed in a state in which the positive electrode 31 and the negative electrode 32 formed in a strip shape are overlapped with each other so that the separators 33 are positioned between them and below the positive electrode 31 (see FIG. 3).
  • the wound electrode body is formed by winding the positive electrode 31, the negative electrode 32, and the separator 33 in the direction of the white arrow in FIG.
  • a state in which the electrode body 30 is configured by winding the positive electrode 31, the negative electrode 32, and the separator 33 is schematically shown in FIG.
  • the electrode body 30 is formed in a flat shape after being wound in a state where the positive electrode 31, the negative electrode 32, and the separator 33 are overlapped (see FIG. 5). That is, the electrode body 30 is obtained by crushing a cylindrical wound body extending along the axis L to make it flat. As shown in FIG. 2, the flat electrode body 30 is accommodated in the battery case 2.
  • the electrode body 30 formed flat as described above has a pair of bent portions 30a bent so that the positive electrode 31, the negative electrode 32, and the separator 33 are folded back in the thickness direction.
  • the pair of bent portions 30a are located at the ends in the width direction when the electrode body 30 is viewed from the side.
  • the electrode body 30 shown in FIG. 2 is only shown for several layers on the outer peripheral side. However, in FIG. 2, the illustration of the inner peripheral side portion of the electrode body 30 is omitted, and naturally, the positive electrode 31, the negative electrode 32, and the separator 33 are also present on the inner peripheral side of the electrode body 30. .
  • FIG. 3 the positions of the positive electrode 31, the negative electrode 32, and the separator 33 are moved from the actual arrangement and shown in perspective in order to illustrate a state in which the positive electrode 31, the negative electrode 32, and the separator 33 are overlapped.
  • the positive electrode current collector 41, the positive electrode active material layer 42, and the negative electrode 32 of the positive electrode 31 are hatched, although not in cross section.
  • the axial direction of the electrode body 30 means a direction along the axis L.
  • the radial direction of the electrode body 30 means a direction along the thickness direction of the positive electrode 31, the negative electrode 32, and the separator 33 constituting the electrode body 30.
  • the positive electrode 31 has a positive electrode active material layer 42 containing a positive electrode active material provided on one or both sides of a positive electrode current collector 41 made of a metal foil such as aluminum (see FIG. 6).
  • the positive electrode active material layer 42 is provided on both surfaces of the positive electrode current collector 41).
  • the positive electrode 31 has a positive electrode active material that is a lithium-containing oxide capable of occluding and releasing lithium ions, a positive electrode mixture containing a conductive additive and a binder on a positive electrode current collector 41 made of aluminum foil or the like. It is formed by applying and drying.
  • the positive electrode active material layer 42 is formed on the positive electrode current collector 41 other than one end in the longitudinal direction.
  • lithium-containing oxide that is a positive electrode active material examples include Li 1 + x M 1 O 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1, M 1 : Co, Ni, Mn, Al, Mg, Ti, Zr, and the like.
  • Lithium-containing composite oxide having a layered structure represented by one or more selected elements LiMn 2 O 4 or a lithium manganese composite oxide having a spinel structure in which a part of the element is substituted with another element, Li 4 / 3 Ti 5/3 O 4 and a lithium manganese composite oxide synthesized at a low temperature represented by a composition such as a lithium titanium composite oxide having a spinel structure in which part of the element is substituted with another element, LiMn 3 O 6
  • an olivine type compound represented by LiM 2 PO 4 M 2 : one or more elements selected from Co, Ni, Mn, Fe, etc.
  • lithium-containing composite oxide having a layered structure examples include lithium cobalt oxide such as LiCoO 2 and LiNi 1-a Co ab Al b O 2 (0.1 ⁇ a ⁇ 0.3, 0.01 ⁇ b ⁇ 0.2), an oxide containing at least Co, Ni and Mn (LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiNi 3/5 Examples thereof include lithium-containing nickel composite oxides such as Mn 1/5 Co 1/5 O 2 . Note that only one type of material may be used as the positive electrode active material, or two or more types of materials may be used. Further, the positive electrode active material is not limited to the above-described materials.
  • the battery is assembled using a laminate of the negative electrode current collector and the Al layer as the negative electrode precursor, and the assembled battery is charged to form the negative electrode It is preferable to produce this Li—Al alloy because part or all of the irreversible capacity of the positive electrode can be offset by the negative electrode.
  • binders for the positive electrode mixture examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), and imide binders (polyamideimide, polyimide, etc.), An amide binder (polyamide, aramid, etc.) can be used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • imide binders polyamideimide, polyimide, etc.
  • An amide binder polyamide, aramid, etc.
  • conductive assistants related to the positive electrode mixture include graphite (graphite carbon material) such as natural graphite (flaky graphite), artificial graphite; acetylene black, ketjen black, channel black, furnace black, lamp black, Carbon materials such as carbon black such as thermal black; carbon fiber; and the like can be used.
  • graphite carbon material such as natural graphite (flaky graphite), artificial graphite; acetylene black, ketjen black, channel black, furnace black, lamp black, Carbon materials such as carbon black such as thermal black; carbon fiber; and the like can be used.
  • the positive electrode 31 having the positive electrode active material layer 42 and the positive electrode current collector 41 includes, for example, a positive electrode active material, a conductive additive, a binder, and the like in water or an organic solvent such as N-methyl-2-pyrrolidone (NMP). Disperse to prepare a positive electrode mixture-containing composition (slurry, paste, etc.) (the binder may be dissolved in a solvent), which is applied onto the positive electrode current collector 41 and dried, and if necessary It can manufacture by passing through the process of performing press processes, such as a calendar process.
  • NMP N-methyl-2-pyrrolidone
  • the content of the positive electrode active material in the positive electrode mixture is preferably 80 to 98.8% by mass.
  • the content of the conductive auxiliary in the positive electrode mixture is preferably 1.5 to 10% by mass.
  • the binder content in the positive electrode mixture is preferably 0.3 to 10% by mass.
  • the thickness of the positive electrode active material layer 42 is preferably 30 to 300 ⁇ m.
  • the positive electrode current collector 41 a metal foil such as Al and Al alloy, a punching metal, a net, an expanded metal, or the like can be used, but an Al foil is usually preferably used.
  • the thickness of the positive electrode current collector 41 is preferably 10 to 30 ⁇ m.
  • the positive electrode lead is connected to a portion of the positive electrode current collector 41 where the positive electrode mixture is not applied, that is, a portion where the positive electrode current collector 41 is exposed.
  • the negative electrode 32 has a metal base layer 45 containing a copper alloy, and a metal surface layer 46 located on both surfaces of the metal base layer 45 and containing an aluminum alloy.
  • the negative electrode 32 is made of, for example, a clad material composed of a layer containing a copper alloy and a layer containing an aluminum alloy positioned on both surfaces of the layer.
  • the negative electrode 32 has a longer dimension and a shorter dimension in the plan view than the positive electrode active material layer 42 of the positive electrode 31.
  • the negative electrode 32 contains a Li—Al alloy on at least the surface side of the portion of the metal surface layer 46 that overlaps the positive electrode active material layer 42 of the positive electrode 31 in the thickness direction with the separator 33 interposed therebetween after charging of the wound battery 1. . That is, the negative electrode 32 having the metal base layer 45 and the metal surface layer 46 is used as a precursor to charge the wound battery 1 assembled together with the positive electrode 31 described above, thereby sandwiching the separator 33 in the metal surface layer 46. The portion of the positive electrode 31 that overlaps the positive electrode active material layer 42 in the thickness direction is electrochemically reacted with Li ions in the non-aqueous electrolyte. As a result, a Li—Al alloy is formed on at least the surface side of the metal surface layer 46 of the negative electrode 32 that overlaps the positive electrode active material layer 42 of the positive electrode 31 in the thickness direction with the separator 33 interposed therebetween.
  • the metal base layer 45 may be made of nickel or the like.
  • the metal substrate layer 45 may be laminated with the metal surface layer 46 by pressure bonding or the like.
  • the metal surface layer 46 may be provided only on one side of the metal base layer 45.
  • a metal layer containing an element that can be alloyed with Li (for example, Si or Sn) may be provided on one side or both sides of the metal base layer 45.
  • the thickness of the metal surface layer 46 provided on one surface of the metal base layer 45 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more.
  • the metal surface layer 46 has a thickness of 150 ⁇ m or less, more preferably 70 ⁇ m or less, and more preferably 50 ⁇ m or less, on the one surface of the metal base layer 45. preferable.
  • the negative electrode 32 has an electrical insulating property at the end of the negative electrode 32 in the longitudinal direction and at the outermost periphery of the negative electrode 32 in the electrode body 30, that is, at the end of the winding end, and does not contribute to the battery reaction.
  • a resin protection member 55 is provided.
  • the protective member 55 is provided at the end of the negative electrode 32 at the end of winding, thereby preventing the negative electrode 32 from being pulverized and partially falling off during charging and discharging of the battery.
  • the protective member 55 is provided at an end portion on the winding end side in the longitudinal direction of the negative electrode 32 and a portion within a predetermined range from the end portion in the longitudinal direction. A detailed configuration of the protection member 55 will be described later.
  • the separator 33 preferably has a property (that is, a shutdown function) that closes the pores at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower).
  • the separator 33 can use the separator used for the normal nonaqueous electrolyte secondary battery etc., for example, the microporous film made from polyolefin, such as polyethylene (PE) and polypropylene (PP).
  • the microporous membrane constituting the separator 33 may be, for example, one using only PE or one using only PP, or a laminate of a PE microporous membrane and a PP microporous membrane. It may be.
  • the thickness of the separator 33 is preferably 10 to 30 ⁇ m, for example.
  • a laminated separator in which a heat-resistant porous layer containing an inorganic filler or the like is provided on the surface of a polyolefin microporous film as described above, or tetrafluoroethylene-perfluoro Fluorine resins such as alkoxyethylene copolymers (PFA), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polybutylene terephthalate (PBT), polymethylpentene, cellulose, aramid, polyimide, polyamideimide, and other heat resistant resins
  • PFA alkoxyethylene copolymers
  • PPS polyphenylene sulfide
  • PEEK polyether ether ketone
  • PBT polybutylene terephthalate
  • a non-woven fabric separator or the like can also be used.
  • Nonaqueous electrolyte solvents include, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), and lactone rings.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • MEC methyl ethyl carbonate
  • lactone rings lactone rings
  • aprotic organic solvent such as phosphoric acid triester (trimethyl phosphate, triethyl phosphate, etc.), trimethoxymethane, sulfolane, 3-methyl-2-oxazolidinone, diethyl ether, etc. Rahidorofuran etc.) and the like can be used as alone in a mixed solvent or a mixture of two or more.
  • the lithium salt according to the non-aqueous electrolyte for example, LiClO 4, LiPF 6, LiBF4 , LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3) 2, LiN ( FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO 2 ) 2 [where Rf is a fluoroalkyl group] And at least one selected from the above.
  • LiClO 4 LiPF 6, LiBF4 , LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3) 2, LiN ( FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO
  • the concentration of the non-aqueous electrolyte of these lithium salts is preferably 0.6 to 1.8 mol / l, more preferably 0.9 to 1.6 mol / l.
  • Two or more lithium salts may be used in combination, and in that case, the total concentration of the lithium salts may be adjusted to fall within the above range.
  • vinylene carbonates for the purpose of further improving various characteristics of the battery, vinylene carbonates, cyclic sultone compounds such as 1,3-propane sultone and 1,3-propene sultone, disulfide compounds such as diphenyl disulfide, Benzene compounds such as cyclohexylbenzene, biphenyl, fluorobenzene, t-butylbenzene, fluorine-substituted cyclic carbonates such as 4-fluoro-1,3-dioxolan-2-one (FEC), lithium tetrakis (acetate) borate, Additives such as lithium organic borate such as lithium bis (oxalate) borate (LiBOB) can be added as appropriate.
  • cyclic sultone compounds such as 1,3-propane sultone and 1,3-propene sultone
  • disulfide compounds such as diphenyl disulfide
  • Benzene compounds such as
  • non-aqueous electrolyte the above-mentioned solution (non-aqueous electrolyte) may be used in the form of a gel (gel electrolyte) using a known polymer or other gelling agent.
  • the winding end end portion of the electrode body 30 (the end portion in the longitudinal direction of the negative electrode 32 and the outermost periphery of the negative electrode 32 in the electrode body 30).
  • the protective member 55 is provided on the portion to be protected. In the longitudinal direction of the negative electrode 32, the protective member 55 is provided with a first protective portion 55 a provided from one end portion in the short direction of the negative electrode 32 to the other end portion at the winding end end portion of the electrode body 30.
  • the protection member 55 has second protection portions 55 b provided in a predetermined range from the end portion on the winding end side in the longitudinal direction of the negative electrode 32 at both ends in the short direction of the negative electrode 32. That is, the protection member 55 is provided in a U shape on the winding end side of the negative electrode 32 when viewed from the thickness direction.
  • the protection member 55 may have only the first protection part 55 a provided at the end of the negative electrode 32 on the winding end side in the longitudinal direction of the negative electrode 32, or the second protection part 55 b may be the negative electrode 32. It may be provided only at one end in the short direction.
  • the predetermined range is a range in which pulverization occurs in the negative electrode 32 by charging the wound battery 1.
  • the range in which pulverization occurs in the negative electrode 32 is a range in which a Li—Al alloy is generated in the metal surface layer 46 of the negative electrode 32.
  • the range in which the Li—Al alloy is generated includes the range in which the negative electrode 32 overlaps the positive electrode active material layer 42 when the negative electrode 32 is viewed in the thickness direction, and the repeated charging and discharging of the battery when the Li—Al alloy is generated. And the range in which Li—Al alloying proceeds.
  • the predetermined range may be from one end in the longitudinal direction of the negative electrode 32 to the other end.
  • the first protection part 55 a of the protection member 55 may be provided only at a part of the negative electrode 32 in the short direction at the winding end end of the negative electrode 32 in the electrode body 30.
  • the protective member 55 is preferably provided in a portion of the end portion on the winding end side of the negative electrode 32 that overlaps the positive electrode active material layer 42 in the thickness direction in the electrode body 30.
  • a protective member 55 can be provided. Accordingly, it is possible to more reliably prevent the pulverization of the negative electrode 32 at the end of the negative electrode 32 on the winding end side.
  • the protective member 55 is provided on both surfaces of the end portion of the negative electrode 32 on the winding end side so as to straddle the end surface of the end portion. That is, the protection member 55 is provided in a U-shape when viewed in a cross section perpendicular to the longitudinal direction of the negative electrode 32 (see FIG. 6). In this way, by providing the protective member 55 on the end surface extending in the thickness direction of the negative electrode 32, when the burr or the projection is formed on the end surface, the separator 33 is damaged by the burr or the projection. Can be prevented.
  • the protective member 55 may be provided only on both surfaces of the negative electrode 32 on the winding end side. That is, the protection member 55 may not be provided on the end surface of the end portion on the winding end side of the negative electrode 32.
  • the protective member 55 is formed of tape or resin as will be described later, and is a member different from the negative electrode 32. Thereby, the thickness of the protection member 55 can be adjusted easily.
  • the protective member 55 is made of resin tape (polyethylene terephthalate (PET) tape, polypropylene (PP) tape, polyphenylene sulfide resin (PPS) tape, polyimide tape, etc.), or various resins or ultraviolet curable resins that are cured by ultraviolet rays. It is made of an electrically insulating material that does not contribute to the battery reaction, such as a molded member or an adhesive made of various resins.
  • resin tape polyethylene terephthalate (PET) tape, polypropylene (PP) tape, polyphenylene sulfide resin (PPS) tape, polyimide tape, etc.
  • various resins or ultraviolet curable resins that are cured by ultraviolet rays.
  • It is made of an electrically insulating material that does not contribute to the battery reaction, such as a molded member or an adhesive made of various resins.
  • the wound battery 1 by charging the battery, on the surface side of the metal surface layer 46 of the negative electrode 32 and at least a portion overlapping the positive electrode active material layer 42 when viewed from the thickness direction of the negative electrode 32, A layer containing a Li—Al alloy can be formed. Thereby, the winding type battery 1 with high heat resistance is obtained.
  • the end of winding of the negative electrode 32 in the electrode body 30 is covered with a protective member 55.
  • a protective member 55 it can prevent that pulverization arises in the winding end part of the negative electrode 32 by charging / discharging of the winding type battery 1.
  • FIG. Therefore, it is possible to prevent a part of the negative electrode 32 from falling off due to pulverization at the winding end end of the negative electrode 32. Therefore, it is possible to prevent the battery characteristics of the wound battery 1 from being deteriorated.
  • the protective member 55 is provided at the winding end of the negative electrode 32 so as to cover from one end of the negative electrode 32 in the short direction to the other end, so that the negative electrode 32 is provided at the winding end. Can be more reliably prevented from being pulverized and partly falling off.
  • the protective member 55 so as to cover the end of winding of the negative electrode 32 and the end of the negative electrode 32 in a short direction, the end of winding of the negative electrode 32 is covered. It can prevent more reliably that pulverization and partial drop-off occur at the portion located on the side.
  • the protective member 55 is provided in a portion of the winding end end of the negative electrode 32 that overlaps the positive electrode active material layer 42 across the separator 33 in the radial direction of the electrode body 30. It can prevent more reliably that pulverization arises by charging / discharging of the winding type battery 1.
  • the electrode body 30 is accommodated in the rectangular battery case 2.
  • the electrode body 30 may be accommodated in an exterior body having another configuration.
  • the electrode body 30 may be accommodated in the laminate film exterior body, or may be accommodated in a battery case having another can structure.
  • FIG. 7 shows an example of a wound battery 101 in which the electrode body 30 is accommodated in a laminate film exterior body 110 (exterior body).
  • the wound battery 101 is a secondary battery having a rectangular shape in a plan view in which the electrode body 30 is covered with the laminate film exterior body 110.
  • the wound battery 101 includes an electrode body 30 and a laminate film exterior body 110 that covers the electrode body 30.
  • the wound battery 101 includes a positive electrode connection terminal 121 and a negative electrode connection terminal 122 that are electrically connected to the positive electrode 31 and the negative electrode 32 of the electrode body 30, respectively.
  • a non-aqueous electrolyte similar to that in the above-described embodiment is also enclosed in the wound battery 1.
  • the laminate film exterior body 110 is made of a material in which one side of an aluminum metal foil is covered with nylon and the other side is covered with polypropylene. That is, the laminate film exterior body 110 is made of a material obtained by laminating aluminum with nylon and polypropylene. Thereby, the laminate film exterior body 110 is welded by applying pressure while heating in a state where the laminate film exterior bodies 110 are overlapped.
  • the metal foil is not limited to aluminum but may be formed of other metal materials such as stainless steel.
  • the laminate film outer package 110 is formed in a substantially rectangular shape.
  • the outer peripheral sides of the laminate film exterior body 110 are welded together to form a bulging portion 101a and a seal portion 101b as shown in FIG.
  • the bulging portion 101a is formed by covering the electrode body 30 with the laminate film exterior body 110, and the bulging portion 101a is surrounded by welding the laminate film exterior body 110 to each other around the bulging portion 101a.
  • the seal portion 101b is formed.
  • the positive electrode connection terminal 121 and the negative electrode connection terminal 122 are laminated with the pair of laminate film exterior bodies 110 sandwiched therebetween.
  • the film exterior bodies 110 are fixed by welding.
  • the positive electrode connection terminal 121 and the negative electrode connection terminal 122 are respectively connected to a positive electrode lead and a negative electrode lead 35 attached to the electrode body 30.
  • the electrode body 30 covered with the laminate film exterior body 110 can be electrically connected to the outside.
  • the present invention is not limited to this, and one laminate film exterior body is folded back so as to sandwich the electrode body 30 therebetween. It may be welded.
  • the direction in which the laminate film exterior body is folded back may be the extending direction of the positive electrode connection terminal 121 and the negative electrode connection terminal 122 with respect to the electrode body 30 or the width direction.
  • the electrode body 30 has a flat cross section.
  • the electrode body may have a cylindrical shape having a circular cross section.
  • the negative electrode 32 is constituted by a clad material composed of the metal base layer 45 and the metal surface layer 46.
  • the negative electrode 32 may have a configuration other than the clad material as long as it has a metal base layer and a metal surface layer.
  • the negative electrode 32 is formed by combining a powder containing an element that can be alloyed with Li with a binder or the like, and applying the mixture onto the surface of a metal foil (metal substrate layer) that serves as a current collector. Also good.
  • a powder containing an element that can be alloyed with Li may be used in combination with a negative electrode active material (for example, a carbon material such as graphite) capable of inserting and extracting Li ions.
  • a negative electrode active material for example, a carbon material such as graphite
  • the negative electrode 32 has the metal surface layer 46 on both surfaces of the metal base layer 45.
  • the metal surface layer 46 may be provided only on one surface of the metal base layer 45.
  • the positive electrode may be disposed so that the positive electrode active material layer is positioned at a position facing the metal surface layer 46 with the separator 33 interposed therebetween.
  • the positive electrode 31 and the negative electrode 32 each formed in a strip shape are overlapped with the separator 33 such that the separator 33 is positioned between the two and the lower side of the positive electrode 31, for example.
  • the order in which the positive electrode 31, the negative electrode 32, and the separator 33 are stacked may be any order as long as the secondary battery can be configured.
  • the positive electrode 31 of the electrode body 30 is electrically connected to the outer can 10, but this is not restrictive, and the negative electrode 32 may be electrically connected to the outer can 10.
  • the present invention is applicable to a wound battery having an electrode body formed by winding a positive electrode, a negative electrode, and a separator.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une batterie de type à enroulement présentant un corps d'électrode obtenu par enroulement, d'une manière chevauchante, d'une électrode positive, d'une électrode négative et d'un séparateur qui sont chacun formés sous la forme d'une bande, l'électrode négative contenant un métal allié avec du lithium. L'extrémité arrière de l'électrode négative enroulée est prévue pour ne pas se désintégrer et tomber suite à la charge et à la décharge. Cette batterie de type à enroulement est pourvue d'un corps d'électrode 30 en colonne qui s'étend dans la direction axiale et dans lequel une électrode positive 31, une électrode négative 32, et un séparateur 33 qui sont formés chacun sous la forme d'une bande sont enroulés de telle sorte que le séparateur 33 est positionné entre l'électrode positive 31 et l'électrode négative 32. L'électrode négative 32 contient un élément qui peut former un alliage avec le lithium. L'extrémité arrière de l'électrode négative enroulée 32 dans le corps d'électrode 30 est recouverte par un élément de protection 55.
PCT/JP2017/010543 2017-01-20 2017-03-15 Batterie de type à enroulement Ceased WO2018135011A1 (fr)

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JP2017-008837 2017-01-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110010842A (zh) * 2019-04-10 2019-07-12 河南超力新能源有限公司 卷绕式电芯用极片及圆柱形电池、锌负极片的制备方法
WO2021106763A1 (fr) * 2019-11-28 2021-06-03 株式会社村田製作所 Batterie secondaire, dispositif électronique et outil électrique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63224150A (ja) * 1987-03-11 1988-09-19 Sanyo Electric Co Ltd 非水系二次電池
JPH06231764A (ja) * 1985-03-12 1994-08-19 Hitachi Maxell Ltd ボタン形リチウム有機二次電池およびその製造方法
JP2001085066A (ja) * 1999-07-09 2001-03-30 Matsushita Electric Ind Co Ltd 非水電解液電池
JP2006252879A (ja) * 2005-03-09 2006-09-21 Sanyo Electric Co Ltd 円筒形電池
JP2010165549A (ja) * 2009-01-15 2010-07-29 Sony Corp 二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06231764A (ja) * 1985-03-12 1994-08-19 Hitachi Maxell Ltd ボタン形リチウム有機二次電池およびその製造方法
JPS63224150A (ja) * 1987-03-11 1988-09-19 Sanyo Electric Co Ltd 非水系二次電池
JP2001085066A (ja) * 1999-07-09 2001-03-30 Matsushita Electric Ind Co Ltd 非水電解液電池
JP2006252879A (ja) * 2005-03-09 2006-09-21 Sanyo Electric Co Ltd 円筒形電池
JP2010165549A (ja) * 2009-01-15 2010-07-29 Sony Corp 二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110010842A (zh) * 2019-04-10 2019-07-12 河南超力新能源有限公司 卷绕式电芯用极片及圆柱形电池、锌负极片的制备方法
WO2021106763A1 (fr) * 2019-11-28 2021-06-03 株式会社村田製作所 Batterie secondaire, dispositif électronique et outil électrique

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