WO2013038676A1 - Non-aqueous electrolyte secondary cell - Google Patents

Non-aqueous electrolyte secondary cell Download PDF

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Publication number
WO2013038676A1
WO2013038676A1 PCT/JP2012/005845 JP2012005845W WO2013038676A1 WO 2013038676 A1 WO2013038676 A1 WO 2013038676A1 JP 2012005845 W JP2012005845 W JP 2012005845W WO 2013038676 A1 WO2013038676 A1 WO 2013038676A1
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Prior art keywords
electrode plate
battery
current collector
negative electrode
positive electrode
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PCT/JP2012/005845
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French (fr)
Japanese (ja)
Inventor
一樹 遠藤
杉田　康成
藤川　万郷
西野　肇
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パナソニック株式会社
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Publication of WO2013038676A1 publication Critical patent/WO2013038676A1/en

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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
    • 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
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
    • 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 an electrode plate structure of a nonaqueous electrolyte secondary battery.
  • a separator having a shutdown function that shuts off a short-circuit current by blocking pores due to heat generated by the short-circuit current when the battery is short-circuited is used.
  • the separator melts before the shutdown function, and a large hole is opened in the separator, resulting in meltdown. If the positive electrode and the negative electrode are short-circuited due to this meltdown, further heat generation may occur, and the battery may be abnormally overheated.
  • Patent Documents 1 to 3 disclose that a non-aqueous electrolyte secondary battery in which a wound electrode group is accommodated in a battery can, and a current collector exposed portion of the positive electrode, and a portion facing it. It is described that the current collector exposed portion of the negative electrode arranged in the above manner is formed over a length of one or more rounds in the winding direction.
  • the current collector exposed portion of the positive electrode and the negative electrode provided on the outermost peripheral side Since the short circuit between the two has a smaller resistance than the short circuit between the active materials on the inner peripheral side, a short circuit current flows intensively at the short circuit portion between the current collector exposed portions. As a result, a rapid temperature rise of the battery can be suppressed. Moreover, the rapid temperature rise of a battery can be suppressed more by generating such a short-circuit location between the current collector exposed portions dispersed in the electrode group.
  • the present invention has been made in view of such problems, and its main purpose is to suppress an excessive temperature rise of the battery even when an internal short circuit occurs due to a foreign object such as a nail without impairing the energy density of the battery.
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery excellent in safety.
  • the present invention provides a nonaqueous electrolyte secondary battery including a wound electrode group, and a polar plate having a polarity different from that of the battery can, and at least one round on the outermost side of the electrode group.
  • the current collector exposed portion is provided, and an electrode plate having the same polarity as that of the battery can is provided with a lead connected to the battery can on the inner peripheral side from the central portion in the longitudinal direction.
  • the non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte in which an electrode group in which a positive electrode plate and a negative electrode plate are wound through a separator is housed in a metal battery can together with a non-aqueous electrolyte.
  • An electrolyte secondary battery wherein a positive electrode plate includes a positive electrode current collector and a positive electrode active material layer formed on a surface of the positive electrode current collector, and the negative electrode plate includes a negative electrode current collector and a negative electrode current collector
  • a negative electrode active material layer formed on the surface, and of the positive electrode plate or the negative electrode plate, the electrode plate having a polarity different from that of the battery can is collected on the outermost peripheral side of the electrode group over a length of one turn or more in the winding direction.
  • a positive electrode plate or a negative electrode plate of the same polarity as the battery can is a lead connected to the electrode plate on the inner peripheral side from the central portion in the longitudinal direction of the electrode plate. And the lead is connected to the battery can.
  • a secondary battery can be provided.
  • the short-circuit resistance at the short-circuit portion between the current collector exposed portions generated on the outer peripheral side is the short-circuit resistance at the short-circuit portion between the active material layers generated on the inner peripheral side.
  • the short-circuited portion on the outer peripheral side has a larger contribution to the electronic resistance of the current collector. It was revealed that the short-circuit current is distributed also to the short-circuit portion between the adjacent active material layers.
  • the lead of the electrode plate having the same polarity as that of the battery can is connected to the outer peripheral side of the electrode group.
  • the bypass path cannot be made.
  • the current concentration at the short-circuit portion on the outer peripheral side becomes insufficient due to the contribution of the electronic resistance of the current collector, and the active material layer is relatively The current is easily distributed to the short-circuited points between them.
  • the configuration of the present invention it is possible to concentrate current from the central part and inner peripheral side of the electrode plate to the short-circuited part on the outer peripheral side using a bypass path having a resistance lower than the electronic resistance of the current collector. Therefore, the current to the short-circuit portion between the active material layers can be substantially suppressed. As a result, it is possible to obtain a battery having a high energy density while ensuring sufficient safety against an internal short circuit caused by a foreign object such as a nail.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of a nonaqueous electrolyte secondary battery in one embodiment of the present invention.
  • a cylindrical lithium ion secondary battery will be described as an example.
  • the nonaqueous electrolyte secondary battery in the present invention is not limited to this.
  • a cylindrical lithium ion battery includes a positive electrode current collector made of aluminum foil, a positive electrode plate 5 coated with a positive electrode active material layer, and a negative electrode current collector made of copper foil.
  • a negative electrode plate 6 coated with a material layer, and an electrode group 9 in which the positive electrode plate 5 and the negative electrode plate 6 are wound through a separator 7 are provided.
  • a positive electrode lead 5 a is welded to the positive electrode plate 5, and a negative electrode lead 6 a is welded to the negative electrode plate 6.
  • the electrode group 9 is housed in the battery can 1 together with the electrolytic solution.
  • An upper insulating plate 8a and a lower insulating plate 8b are disposed above and below the electrode group 9, respectively.
  • One end of the negative electrode lead 6 is welded to the bottom of the battery can 1.
  • One end of the positive electrode lead 5 is welded to the metal filter 4.
  • the open end of the battery can 1 is sealed with a sealing plate 2 via a gasket 3.
  • FIG. 2 is a plan view of the negative electrode plate 6 in one embodiment of the present invention developed in the longitudinal direction.
  • FIG. 3 is a plan view of the positive electrode plate 5 in one embodiment of the present invention developed in the longitudinal direction.
  • the negative electrode plate 6 is an electrode plate having the same polarity as that of the battery can 1
  • the present invention can be applied to the case where the positive electrode plate 5 is an electrode plate having the same polarity as that of the battery can 1. Has the same effect.
  • the negative electrode plate 6 in this embodiment has a negative electrode active material layer 14 formed on the surface of the negative electrode current collector, and one turn in the winding direction on the outermost peripheral side of the electrode group 9.
  • the current collector exposed portion 16 has the negative electrode current collector exposed over the above length.
  • a negative electrode lead 6 a connected to the negative electrode plate 6 is provided on the inner peripheral side of the central portion in the longitudinal direction of the negative electrode plate 6.
  • the negative electrode lead 6a is connected to the bottom of the battery can 1 as shown in FIG.
  • the positive electrode plate 5 in this embodiment has a positive electrode active material layer 13 formed on the surface of the positive electrode current collector, and in the winding direction on the outermost peripheral side of the electrode group 9. It has a current collector exposed portion 15 where the positive electrode current collector is exposed over a length of one or more rounds. Furthermore, a positive electrode lead 5 a connected to the positive electrode plate 5 is provided at the center in the longitudinal direction of the positive electrode plate 5. The positive electrode lead 5a is connected to the metal filter 4 as shown in FIG.
  • a large current can be concentrated at the short-circuited portion on the outer peripheral side.
  • the portion of the negative electrode lead 6a connected to the negative electrode plate 6 is not particularly limited as long as the negative electrode lead 6a is on the inner peripheral side of the central portion in the longitudinal direction of the negative electrode plate 6. Further, the negative electrode lead 6 a may be connected to a plurality of portions of the negative electrode plate 6. Increasing the number of the negative electrode leads 6a can further enhance the current concentration effect on the short-circuited portion on the outer peripheral side. However, excessively increasing the number of the negative electrode leads 6a is not preferable because the energy density is lowered.
  • FIGS. 4 to 7 are plan views of the negative electrode plate 6 according to another embodiment of the present invention developed in the longitudinal direction.
  • the negative electrode lead 6 a is connected to the substantially central portion in the longitudinal direction of the negative electrode plate 6.
  • the negative electrode lead 6 a is connected to the innermost peripheral side of the negative electrode plate 6.
  • the negative electrode lead 6 a is also connected to the current collector exposed portion 16 formed on the outermost peripheral side of the negative electrode plate 6. If the negative electrode lead 6a is also connected to the outermost peripheral side, a bypass path to the central part and the inner peripheral side is established before a foreign object such as a nail is pierced. Current concentration effect can be obtained. Further, as shown in FIG.
  • the current collector exposed portion 16 is not formed on the outermost peripheral side of the negative electrode plate 6 at a portion facing the current collector exposed portion 15 of the positive electrode plate 5 shown in FIG. 3. May be. Even in this case, when a foreign object such as a nail is pierced, a short circuit passes through “the current collector on the inner peripheral side of the negative electrode plate 6—the negative electrode lead 6a—the battery can 1—the current collector exposed portion 15 on the outer peripheral side of the positive electrode plate 5”. A current bypass path can be generated.
  • the position of the positive electrode lead 5a is not particularly limited as long as the positive electrode current collector is exposed on both sides. Further, in the positive electrode plate 5 shown in FIG. 3, the positive electrode lead 5a is also provided on the current collector exposed portion 15 on the outer peripheral side of the positive electrode plate 5, thereby “the central portion of the positive electrode plate 5 ⁇ the positive electrode lead 5a ⁇ the positive electrode plate”. Since the bypass path of the current collector exposed portion 15 on the outer peripheral side 5 is also formed, a current concentration effect on the short-circuited portion on the outer peripheral side can be obtained more effectively when a foreign object such as a nail is stuck.
  • the “central portion” means an inner peripheral end portion and an outer peripheral end portion, where L is the distance between the inner peripheral end portion to which the positive electrode active material layer of the positive electrode plate 5 is applied and the outer peripheral end portion.
  • L is the distance between the inner peripheral end portion to which the positive electrode active material layer of the positive electrode plate 5 is applied and the outer peripheral end portion.
  • the range where the distance from each is 2 / 3L or less.
  • the negative electrode active material layer 14 may contain a binder, a thickener, a conductive material, and the like in addition to the negative electrode active material.
  • a carbon material such as natural graphite, a simple substance such as silicon (Si) or tin (Sn), an alloy, or the like can be used.
  • the negative electrode current collector copper foil, copper alloy foil, nickel foil or the like can be used.
  • the thickness of the negative electrode current collector is preferably 5 to 30 ⁇ m and more preferably 5 to 15 ⁇ m from the viewpoint of productivity and energy density.
  • the positive electrode active material layer 13 only needs to contain a binder and a conductive material in addition to the positive electrode active material.
  • a lithium composite metal oxide can be used as the positive electrode active material.
  • LixCoO 2 , LixNiO 2 , LixMnO 2 , or the like can be used as the lithium composite metal oxide.
  • the positive electrode current collector aluminum foil, nickel foil, stainless steel foil, or the like can be used.
  • the thickness of the positive electrode current collector is preferably 5 to 30 ⁇ m and more preferably 10 to 20 ⁇ m from the viewpoint of productivity and energy density.
  • the electrolyte layer having lithium ion conductivity includes a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • the electrolyte layer may include a polyolefin microporous film as a separator.
  • a nonaqueous solvent in which a lithium salt is dissolved is impregnated in the pores of the microporous film.
  • the non-aqueous solvent for example, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and the like can be used. .
  • Example 1 (1) Preparation of negative electrode plate 3 kg of artificial graphite (average particle size 10 ⁇ m, BET specific surface area 3 m 2 / g) and BM-400B (solid content 40% by mass modified styrene-butadiene rubber) manufactured by Nippon Zeon Co., Ltd. ) 75 g and carboxymethyl cellulose (CMC) 30 g were stirred together with an appropriate amount of water in a kneader to prepare a negative electrode mixture slurry. The negative electrode mixture slurry was applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 8 ⁇ m, dried, and rolled to a total thickness of 172 ⁇ m to form the negative electrode active material layer 14. The density of the negative electrode active material layer 14 was 1.7 g / cm 3 .
  • the obtained electrode plate was cut into a width of 58.5 mm and a length of 705 mm, and as shown in FIG. 2, a double-sided current collector exposed portion 16 having a length of 70 mm was provided on the outer peripheral side, and the central portion and the innermost portion were provided. A 6 mm long double-sided current collector exposed portion for lead welding was provided in the middle of the circumferential side. And the negative electrode lead 6a which consists of nickel / copper / nickel clad material was welded to this collector exposed part, and the negative electrode plate 6 was obtained.
  • the obtained electrode plate was cut into a width of 57.5 mm and a length of 640 mm, and as shown in FIG. 3, a double-sided current collector exposed portion having a length of 57 mm was provided on the outer peripheral side, and the length was provided at the center portion. A 6 mm double-sided current collector exposed portion for lead welding was provided. And the lead which consists of aluminum was welded to this collector exposed part, and the positive electrode plate 5 was obtained.
  • the positive electrode plate 5 and the negative electrode plate 6 were wound through a separator 7 (single layer of polyethylene resin having a thickness of 16 ⁇ m) to produce an electrode group 9.
  • the upper insulating plate 8a and the lower insulating plate 8b were disposed above and below the electrode group 9, and then accommodated in a bottomed cylindrical battery can 1 (diameter 18 mm, height 65 mm, inner diameter 17.85 mm).
  • the other end of the positive electrode lead 5 a was connected to the metal filter 4, and the other end of the negative electrode lead 6 a was connected to the bottom surface of the battery can 1.
  • 5.0 g of the nonaqueous electrolyte was injected into the battery can 1.
  • the opening of the battery can 1 was sealed with a sealing plate 2 via a gasket 3. In this way, a battery having a design capacity of 2880 mAh was produced.
  • Example 2 As shown in FIG. 4, a battery was fabricated in the same manner as in Example 1 except that the negative electrode lead 6 a was welded to the central portion of the negative electrode plate 6 and slightly closer to the inner peripheral side to prepare the negative electrode plate 6.
  • Example 3 As shown in FIG. 5, a battery was fabricated in the same manner as in Example 1 except that the negative electrode lead 6 a was welded to the innermost peripheral side of the negative electrode plate 6 to prepare the negative electrode plate 6.
  • Example 4 As shown in FIG. 6, a battery was fabricated in the same manner as in Example 1, except that the negative electrode lead 6a was welded to each of the innermost peripheral side and the outermost peripheral side of the negative electrode plate 6 to prepare the negative electrode plate 6. .
  • Example 5 As shown in FIG. 7, a battery was fabricated in the same manner as in Example 1 except that the length of the negative electrode plate 6 was 635 mm and the current collector exposed portion 16 was not provided on the outermost peripheral side of the negative electrode plate. .
  • Example 6 A battery was fabricated in the same manner as in Example 5, except that the positive electrode lead 5a was welded not only to the central portion of the positive electrode plate 5 but also to the outermost periphery.
  • Example 1 A battery was fabricated in the same manner as in Example 1 except that the negative electrode lead 6a was connected to the outermost peripheral side of the negative electrode plate 6.
  • Comparative Example 2 A battery was fabricated in the same manner as in Comparative Example 1, except that the current collector exposed portions were provided on the innermost peripheral side and the central portion of the negative electrode plate 6 and the positive electrode plate 5 so as to face each other in the winding direction. did.
  • the batteries of Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to the following nail penetration test and charge / discharge test to evaluate the safety of each battery and the discharge battery capacity of each battery.
  • Constant current charging Current value 0.5C, end-of-charge voltage 4.2V Constant voltage charging: Voltage value 4.2V, charging end current 100mA Constant current discharge: current value 0.5C, final discharge voltage 1.0V
  • Example 5 batteries with high battery capacity were obtained without abnormal overheating during nail penetration.
  • Example 5 one abnormal overheating at the time of nail penetration occurred in five batteries.
  • Example 5 since the current collector exposed portion 16 was not provided on the outer peripheral side of the negative electrode plate 6, the contact between the nail and the current collector exposed portion 15 of the positive electrode plate might not be successful, and safety was slightly lowered. it is conceivable that. *
  • Example 6 in which the positive electrode lead 5a was added to the outer peripheral side of the positive electrode plate 5 in Example 5, no abnormal overheating occurred during nail penetration. This is because the current concentration effect to the short-circuited portion on the outer peripheral side is more effectively obtained as a result of the formation of the bypass path of “the center portion of the positive electrode plate 5—the positive electrode lead 5a—the outer peripheral portion of the positive electrode plate”. it is conceivable that.
  • Comparative Examples 1 and 2 a lot of abnormal overheating occurred.
  • Comparative Example 1 although the short-circuit portion between the current collector exposed portions on the outer peripheral side occurs, there is no bypass path to the short-circuit portion on the outer peripheral side, so the current concentration effect is insufficient and the safety is low. .
  • Comparative Example 2 since the current collector exposed portions exist not only on the outer peripheral side but also on the central portion and the inner peripheral side, the safety is slightly improved as compared with Comparative Example 1, but the nail reaches the inner peripheral side. There were many cases where it overheated before.
  • Comparative Example 2 as a result of increasing the current collector exposed portion, a battery having a low battery capacity and a low energy density was obtained.
  • the non-aqueous electrolyte secondary battery according to the present invention is useful as a power source for portable electronic devices, a power source for driving electric tools, electric vehicles, and the like.

Abstract

A nonaqueous electrolyte secondary cell comprising an electrode group (9), the electrode group being obtained by winding a positive electrode plate (5) and a negative electrode plate (6) via a separator (7), and being accommodated together with a nonaqueous electrolyte in a cell canister (1), wherein the positive electrode plate (5) or the negative electrode plate (6) heteropolar with the cell canister (1) has a current collector exposed part (15) in which the current collector is exposed along one or more full circumferences in the winding direction on the outermost periphery of the electrode group (9), the electrode plate that is homopolar with the cell canister (1) has a lead (6a) connected to the electrode plate on the internal peripheral side relative to the longitudinal center of the electrode plate, and the lead (6a) is connected to the cell canister (1).

Description

非水電解質二次電池Nonaqueous electrolyte secondary battery
　本発明は、非水電解質二次電池の極板構造に関する。 The present invention relates to an electrode plate structure of a nonaqueous electrolyte secondary battery.
　近年、携帯電話、ノートパソコンなどの電子機器や車載等の電源に用いる二次電池に対して、高エネルギー密度化が要求されている。この観点から、高エネルギー密度化が可能な非水電解質二次電池が広く普及している。 In recent years, there has been a demand for higher energy density for secondary batteries used in power supplies for electronic devices such as mobile phones and notebook computers and in-vehicle devices. From this point of view, non-aqueous electrolyte secondary batteries capable of increasing the energy density are widely used.
　電池の内部で、内部短絡が発生すると、短絡点に電流が集中して流れるため、電池が発熱する畏れがある。特に、エネルギー密度の高いリチウムイオン電池等の非水電解質二次電池では、大きな短絡電流が流れるため、電池の発熱も大きくなり、その安全対策が重要になっている。 When an internal short circuit occurs inside the battery, the current flows in a concentrated manner at the short circuit point, and the battery may generate heat. In particular, in a non-aqueous electrolyte secondary battery such as a lithium ion battery having a high energy density, since a large short-circuit current flows, the heat generation of the battery also increases, and its safety measures are important.
　一般に、非水電解質二次電池では、電池が内部短絡を起こしたとき、短絡電流による発熱で細孔が閉塞することによって短絡電流を遮断する、シャットダウン機能が付与されたセパレータが用いられている。しかしながら、短絡部の発熱が大きいと、シャットダウンが機能する前に、セパレータが溶融して、セパレータに大きな穴が開く、メルトダウンが生じる。このメルトダウンにより、正極と負極とが短絡すると、さらなる発熱を引き起こし、電池が異常過熱される畏れがある。 Generally, in a non-aqueous electrolyte secondary battery, a separator having a shutdown function that shuts off a short-circuit current by blocking pores due to heat generated by the short-circuit current when the battery is short-circuited is used. However, if the heat generation in the short-circuited part is large, the separator melts before the shutdown function, and a large hole is opened in the separator, resulting in meltdown. If the positive electrode and the negative electrode are short-circuited due to this meltdown, further heat generation may occur, and the battery may be abnormally overheated.
　このような内部短絡に対して、特許文献１～３には、捲回された電極群が電池缶に収容された非水電解質二次電池において、正極の集電体露出部、及びそれに対向して配置された負極の集電体露出部を、捲回方向に１周以上の長さにわたって形成することが記載されている。特に、当該集電体露出部を、電極群の最外周側に形成することによって、釘刺し等による内部短絡が発生しても、最外周側に設けられた正極及び負極の集電体露出部同士の短絡の方が、内周側の活物質同士の短絡よりも抵抗が小さいため、集電体露出部同士の短絡箇所に、集中的に短絡電流が流れる。その結果、電池の急激な温度上昇を抑制することができる。また、このような集電体露出部同士の短絡箇所を、電極群内で分散させて発生させることによって、電池の急激な温度上昇を、より抑制することができる。 With respect to such an internal short circuit, Patent Documents 1 to 3 disclose that a non-aqueous electrolyte secondary battery in which a wound electrode group is accommodated in a battery can, and a current collector exposed portion of the positive electrode, and a portion facing it. It is described that the current collector exposed portion of the negative electrode arranged in the above manner is formed over a length of one or more rounds in the winding direction. In particular, by forming the current collector exposed portion on the outermost peripheral side of the electrode group, even if an internal short circuit occurs due to nail penetration or the like, the current collector exposed portion of the positive electrode and the negative electrode provided on the outermost peripheral side Since the short circuit between the two has a smaller resistance than the short circuit between the active materials on the inner peripheral side, a short circuit current flows intensively at the short circuit portion between the current collector exposed portions. As a result, a rapid temperature rise of the battery can be suppressed. Moreover, the rapid temperature rise of a battery can be suppressed more by generating such a short-circuit location between the current collector exposed portions dispersed in the electrode group.
特開平０８－１５３５４２号公報Japanese Patent Laid-Open No. 08-153542 特開２００７－１０９６１２号公報JP 2007-109612 A
　特許文献１、２に記載されているように、釘刺し等による内部短絡が発生しても、集電体露出部同士の抵抗の小さい短絡箇所を、電極群の最外周側に、さらには、電極群の内周側に分散させて発生させることによって、電池の温度上昇を抑制することができる。 As described in Patent Documents 1 and 2, even if an internal short-circuit occurs due to nail penetration or the like, a short-circuited portion having a small resistance between the current collector exposed portions is arranged on the outermost peripheral side of the electrode group, It is possible to suppress an increase in the temperature of the battery by dispersing and generating it on the inner peripheral side of the electrode group.
　しなしながら、高出力化を図った非水電解質二次電池では、短絡電流も増大するため、従来の対策のみでは、十分な電池の安全性を確保することが難しい。また、集電体露出部同士の短絡箇所を、電極群の内周側に発生させても、当該短絡箇所に釘が到達する前に、内周側の活物質層同士の短絡箇所に電流が流れてしまい、内周側でも局所的な発熱が生じる。このような内周側での局所的な発熱を防ぐには、集電体露出部同士の短絡箇所を多数発生させればよいが、逆に、電池のエネルギー密度の低下を招き、電池の高容量化、高出力化の要請に反する。 However, in non-aqueous electrolyte secondary batteries with high output, the short-circuit current also increases, so it is difficult to ensure sufficient battery safety with conventional measures alone. Further, even if the short-circuited portion between the current collector exposed portions is generated on the inner peripheral side of the electrode group, before the nail arrives at the short-circuited portion, current flows in the short-circuited portion between the active material layers on the inner peripheral side. Flow, and local heat generation occurs on the inner peripheral side. In order to prevent such local heat generation on the inner peripheral side, it is only necessary to generate many short-circuited portions between the current collector exposed portions, but conversely, the energy density of the battery is reduced, and the battery Contrary to the demand for higher capacity and higher output.
　本発明は、かかる課題に鑑みなされたもので、その主な目的は、電池のエネルギー密度を損なうことなく、釘などの異物による内部短絡が生じた場合でも、電池の過度な温度上昇を抑制することのできる、安全性に優れた非水電解質二次電池を提供することにある。 The present invention has been made in view of such problems, and its main purpose is to suppress an excessive temperature rise of the battery even when an internal short circuit occurs due to a foreign object such as a nail without impairing the energy density of the battery. An object of the present invention is to provide a non-aqueous electrolyte secondary battery excellent in safety.
　上記の課題を解決するために、本発明は、捲回された電極群を備えた非水電解質二次電池において、電池缶と異極性の極板に、電極群の最外周側に１周以上の集電体露出部を設けるとともに、電池缶と同極性の極板に、長手方向中央部より内周側に、電池缶と接続されたリードを設けた構成を採用する。 In order to solve the above-described problems, the present invention provides a nonaqueous electrolyte secondary battery including a wound electrode group, and a polar plate having a polarity different from that of the battery can, and at least one round on the outermost side of the electrode group. The current collector exposed portion is provided, and an electrode plate having the same polarity as that of the battery can is provided with a lead connected to the battery can on the inner peripheral side from the central portion in the longitudinal direction.
　すなわち、本発明に係る非水電解質二次電池は、正極板と、負極板とが、セパレータを介して捲回してなる電極群が、非水電解質とともに金属製の電池缶に収容された非水電解質二次電池であって、正極板は、正極集電体と、正極集電体の表面に形成された正極活物質層を含み、負極板は、負極集電体と、負極集電体の表面に形成された負極活物質層を含み、正極板または負極板のうち電池缶と異極性の極板は、電極群の最外周側に、捲回方向に１周以上の長さにわたって集電体が露出した集電体露出部を有し、正極板または負極板のうち電池缶と同極性の極板は、極板の長手方向中央部より内周側に、極板に接続されたリードを有し、かつ、リードは、電池缶に接続されていることを特徴とする。 That is, the non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte in which an electrode group in which a positive electrode plate and a negative electrode plate are wound through a separator is housed in a metal battery can together with a non-aqueous electrolyte. An electrolyte secondary battery, wherein a positive electrode plate includes a positive electrode current collector and a positive electrode active material layer formed on a surface of the positive electrode current collector, and the negative electrode plate includes a negative electrode current collector and a negative electrode current collector A negative electrode active material layer formed on the surface, and of the positive electrode plate or the negative electrode plate, the electrode plate having a polarity different from that of the battery can is collected on the outermost peripheral side of the electrode group over a length of one turn or more in the winding direction. A positive electrode plate or a negative electrode plate of the same polarity as the battery can is a lead connected to the electrode plate on the inner peripheral side from the central portion in the longitudinal direction of the electrode plate. And the lead is connected to the battery can.
　本発明によれば、電池のエネルギー密度を損なうことなく、釘などの異物による内部短絡が生じた場合でも、電池の過度な温度上昇を抑制することのできる、安全性に優れた非水電解質二次電池を提供することができる。 According to the present invention, even when an internal short circuit occurs due to a foreign matter such as a nail without impairing the energy density of the battery, it is possible to suppress an excessive temperature rise of the battery, and to improve the safety of the non-aqueous electrolyte. A secondary battery can be provided.
本発明の一実施形態における非水電解質二次電池の構成を模式的に示した断面図である。It is sectional drawing which showed typically the structure of the nonaqueous electrolyte secondary battery in one Embodiment of this invention. 本発明の一実施形態における負極板を、長手方向に展開した平面図である。It is the top view which expand | deployed the negative electrode plate in one Embodiment of this invention in the longitudinal direction. 本発明の一実施形態における正極板を、長手方向に展開した平面図である。It is the top view which expand | deployed the positive electrode plate in one Embodiment of this invention to the longitudinal direction. 本発明の他の実施形態における負極板を、長手方向に展開した平面図である。It is the top view which expand | deployed the negative electrode plate in other embodiment of this invention in the longitudinal direction. 本発明の他の実施形態における負極板を、長手方向に展開した平面図である。It is the top view which expand | deployed the negative electrode plate in other embodiment of this invention in the longitudinal direction. 本発明の他の実施形態における負極板を、長手方向に展開した平面図である。It is the top view which expand | deployed the negative electrode plate in other embodiment of this invention in the longitudinal direction. 本発明の他の実施形態における負極板を、長手方向に展開した平面図である。It is the top view which expand | deployed the negative electrode plate in other embodiment of this invention in the longitudinal direction.
　本発明者等は、鋭意研究を行った結果、外周側で発生した集電体露出部同士の短絡箇所での短絡抵抗は、内周側で発生した活物質層同士の短絡箇所での短絡抵抗に比べて、充分に低いものの、内部短絡による大電流が発生したとき、極板の中央部に比べて、外周側の短絡箇所は、集電体の電子抵抗の寄与が大きいため、より中央に近い活物質層同士の短絡箇所にも、短絡電流が分配されてしまうことが明らかとなった。 As a result of intensive studies, the present inventors have found that the short-circuit resistance at the short-circuit portion between the current collector exposed portions generated on the outer peripheral side is the short-circuit resistance at the short-circuit portion between the active material layers generated on the inner peripheral side. Compared to the center of the plate, when the large current is generated due to an internal short circuit, the short-circuited portion on the outer peripheral side has a larger contribution to the electronic resistance of the current collector. It was revealed that the short-circuit current is distributed also to the short-circuit portion between the adjacent active material layers.
　この問題を解決するにあたり、電池缶と同極性の極板の中央部より内周側にリードを接続することによって、釘などの異物が刺さった際に、「電池缶と同極性の極板の内周側の活物質層－リード－電池缶－電池缶と異極性の極板の外周側の集電体露出部」を通る短絡電流のバイパス経路を発生させて、外周側の短絡箇所に、大電流を集中させるという着想を得た。 In resolving this problem, when a foreign object such as a nail is stabbed by connecting the lead from the center of the electrode plate with the same polarity as the battery can, By generating a short-circuit current bypass path that passes through the active material layer on the inner peripheral side-lead-battery can-current collector exposed part on the outer peripheral side of the electrode plate of a different polarity from the battery can, I got the idea of concentrating a large current.
　通常、電池缶と同極性の極板のリードは、電極群の外周側に接続されており、このような構成だと、上記バイパス経路はできない。その結果、外周側に集電体露出部同士の短絡箇所を設けても、集電体の電子抵抗の寄与により、外周側の短絡箇所への電流集中が不十分となり、相対的に活物質層同士の短絡箇所へも電流が分配されやすい。 Usually, the lead of the electrode plate having the same polarity as that of the battery can is connected to the outer peripheral side of the electrode group. With such a configuration, the bypass path cannot be made. As a result, even if a short-circuit portion between the current collector exposed portions is provided on the outer peripheral side, the current concentration at the short-circuit portion on the outer peripheral side becomes insufficient due to the contribution of the electronic resistance of the current collector, and the active material layer is relatively The current is easily distributed to the short-circuited points between them.
　一方、本発明の構成を用いると、集電体の電子抵抗より低い抵抗のバイパス経路を用いて、極板の中央部及び内周側から、外周側の短絡箇所に電流を集中させることが可能となるため、活物質層同士の短絡箇所への電流を、実質的に抑制することができる。その結果、釘などの異物による内部短絡に対して、充分な安全性を確保しつつ、かつエネルギー密度の高い電池を得ることが可能となる。 On the other hand, with the configuration of the present invention, it is possible to concentrate current from the central part and inner peripheral side of the electrode plate to the short-circuited part on the outer peripheral side using a bypass path having a resistance lower than the electronic resistance of the current collector. Therefore, the current to the short-circuit portion between the active material layers can be substantially suppressed. As a result, it is possible to obtain a battery having a high energy density while ensuring sufficient safety against an internal short circuit caused by a foreign object such as a nail.
　以下、本発明の実施形態を図面に基づいて詳細に説明する。なお、本発明は、以下の実施形態に限定されるものではない。また、本発明の効果を奏する範囲を逸脱しない範囲で、適宜変更は可能である。さらに、他の実施形態との組み合わせも可能である。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment. Moreover, it can change suitably in the range which does not deviate from the range which has the effect of this invention. Furthermore, combinations with other embodiments are possible.
　図１は、本発明の一実施形態における非水電解質二次電池の構成を模式的に示した断面図である。なお、本実施形態では、円筒型リチウムイオン二次電池を例に説明するが、本発明における非水電解質二次電池は、勿論、これに限定されない。 FIG. 1 is a cross-sectional view schematically showing a configuration of a nonaqueous electrolyte secondary battery in one embodiment of the present invention. In the present embodiment, a cylindrical lithium ion secondary battery will be described as an example. However, the nonaqueous electrolyte secondary battery in the present invention is not limited to this.
　図１に示すように、円筒型リチウムイオン電池は、アルミニウム箔からなる正極集電体に、正極活物質層が塗着された正極板５と、銅箔からなる負極集電体に、負極活物質層が塗着された負極板６と、正極板５及び負極板６がセパレータ７を介して捲回された電極群９を備えている。正極板５には、正極リード５ａが溶接され、負極板６には、負極リード６ａが溶接されている。電極群９は、電解液とともに、電池缶１に収納されている。電極群９の上部及び下部には、上部絶縁板８ａ及び下部絶縁板８ｂが配置されている。負極リード６の一端は、電池缶１の底部に溶接されている。正極リード５の一端は、金属製フィルター４に溶接されている。電池缶１の開口端は、ガスケット３を介して、封口板２で封口されている。 As shown in FIG. 1, a cylindrical lithium ion battery includes a positive electrode current collector made of aluminum foil, a positive electrode plate 5 coated with a positive electrode active material layer, and a negative electrode current collector made of copper foil. A negative electrode plate 6 coated with a material layer, and an electrode group 9 in which the positive electrode plate 5 and the negative electrode plate 6 are wound through a separator 7 are provided. A positive electrode lead 5 a is welded to the positive electrode plate 5, and a negative electrode lead 6 a is welded to the negative electrode plate 6. The electrode group 9 is housed in the battery can 1 together with the electrolytic solution. An upper insulating plate 8a and a lower insulating plate 8b are disposed above and below the electrode group 9, respectively. One end of the negative electrode lead 6 is welded to the bottom of the battery can 1. One end of the positive electrode lead 5 is welded to the metal filter 4. The open end of the battery can 1 is sealed with a sealing plate 2 via a gasket 3.
　図２は、本発明の一実施形態における負極板６を、長手方向に展開した平面図である。また、図３は、本発明の一実施形態における正極板５を、長手方向に展開した平面図である。なお、本実施形態では、負極板６が、電池缶１と同極性の極板である場合を説明するが、正極板５が、電池缶１と同極性の極板である場合も、本発明は同様の効果を奏する。 FIG. 2 is a plan view of the negative electrode plate 6 in one embodiment of the present invention developed in the longitudinal direction. FIG. 3 is a plan view of the positive electrode plate 5 in one embodiment of the present invention developed in the longitudinal direction. In the present embodiment, the case where the negative electrode plate 6 is an electrode plate having the same polarity as that of the battery can 1 will be described. However, the present invention can be applied to the case where the positive electrode plate 5 is an electrode plate having the same polarity as that of the battery can 1. Has the same effect.
　図２に示すように、本実施形態における負極板６は、負極集電体の表面に負極活物質層１４が形成されており、電極群９の最外周側には、捲回方向に１周以上の長さにわたって負極集電体が露出した集電体露出部１６を有している。さらに、負極板６の長手方向中央部より内周側には、負極板６に接続された負極リード６ａを有している。そして、負極リード６ａは、図１に示したように、電池缶１の底部に接続されている。 As shown in FIG. 2, the negative electrode plate 6 in this embodiment has a negative electrode active material layer 14 formed on the surface of the negative electrode current collector, and one turn in the winding direction on the outermost peripheral side of the electrode group 9. The current collector exposed portion 16 has the negative electrode current collector exposed over the above length. Further, a negative electrode lead 6 a connected to the negative electrode plate 6 is provided on the inner peripheral side of the central portion in the longitudinal direction of the negative electrode plate 6. The negative electrode lead 6a is connected to the bottom of the battery can 1 as shown in FIG.
　また、図３に示すように、本実施形態における正極板５は、正極集電体の表面に正極活物質層１３が形成されており、電極群９の最外周側には、捲回方向に１周以上の長さにわたって正極集電体が露出した集電体露出部１５を有している。さらに、正極板５の長手方向中央部には、正極板５に接続された正極リード５ａを有している。そして、正極リード５ａは、図１に示したように、金属製フィルター４に接続されている。 In addition, as shown in FIG. 3, the positive electrode plate 5 in this embodiment has a positive electrode active material layer 13 formed on the surface of the positive electrode current collector, and in the winding direction on the outermost peripheral side of the electrode group 9. It has a current collector exposed portion 15 where the positive electrode current collector is exposed over a length of one or more rounds. Furthermore, a positive electrode lead 5 a connected to the positive electrode plate 5 is provided at the center in the longitudinal direction of the positive electrode plate 5. The positive electrode lead 5a is connected to the metal filter 4 as shown in FIG.
　本実施形態によれば、釘などの異物が刺さった際、「負極板６の内周側の集電体－負極リード６ａ－電池缶１－正極板５の外周側の集電体露出部１５」を通る短絡電流のバイパス経路を発生させることによって、外周側の短絡箇所に、大電流を集中させることができる。これにより、内周側の活物質層同士の短絡箇所への電流を抑制することができ、釘等の異物による内部短絡に対して、充分な安全性を確保しつつ、かつエネルギー密度の高い電池を得ることができる。 According to the present embodiment, when a foreign object such as a nail is pierced, “the current collector on the inner peripheral side of the negative electrode plate 6—the negative electrode lead 6a—the battery can 1—the current collector exposed portion 15 on the outer peripheral side of the positive electrode plate 5”. , A large current can be concentrated at the short-circuited portion on the outer peripheral side. Thereby, it is possible to suppress a current to a short-circuited portion between the active material layers on the inner peripheral side, and to ensure sufficient safety against an internal short-circuit due to a foreign matter such as a nail and a battery having a high energy density. Can be obtained.
　本発明において、負極リード６ａは、負極板６の長手方向中央部より内周側であれば、負極板６に接続される部位は、特に限定されない。また、負極板６の複数の部位に、それぞれ負極リード６ａを接続してもよい。負極リード６ａの本数を増やすことで、外周側の短絡箇所への電流集中効果をより高めることができるが、負極リード６ａの本数を増やしすぎると、エネルギー密度の低下を招くので好ましくない。 In the present invention, the portion of the negative electrode lead 6a connected to the negative electrode plate 6 is not particularly limited as long as the negative electrode lead 6a is on the inner peripheral side of the central portion in the longitudinal direction of the negative electrode plate 6. Further, the negative electrode lead 6 a may be connected to a plurality of portions of the negative electrode plate 6. Increasing the number of the negative electrode leads 6a can further enhance the current concentration effect on the short-circuited portion on the outer peripheral side. However, excessively increasing the number of the negative electrode leads 6a is not preferable because the energy density is lowered.
　図４～図７は、本発明の他の実施形態における負極板６を、長手方向に展開した平面図である。 4 to 7 are plan views of the negative electrode plate 6 according to another embodiment of the present invention developed in the longitudinal direction.
　図４に示した負極板６は、負極リード６ａが、負極板６の長手方向のほぼ中央部に接続されている。また、図５に示した負極板６は、負極リード６ａが、負極板６の最内周側に接続されている。さらに、図６に示した負極板６は、負極板６の最外周側に形成した集電体露出部１６にも、負極リード６ａが接続されている。最外周側にも負極リード６ａが接続されていると、釘などの異物が刺さる前から、中央部や内周側とのバイパス経路が成立しているため、より確実に、外周側の短絡箇所への電流集中効果を得ることができる。また、図７に示すように、負極板６の最外周側には、図３に示した正極板５の集電体露出部１５に対向する部位に、集電体露出部１６を形成しなくてもよい。この場合でも、釘などの異物が刺さると、「負極板６の内周側の集電体－負極リード６ａ－電池缶１－正極板５の外周側の集電体露出部１５」を通る短絡電流のバイパス経路を発生させることができる。 In the negative electrode plate 6 shown in FIG. 4, the negative electrode lead 6 a is connected to the substantially central portion in the longitudinal direction of the negative electrode plate 6. In the negative electrode plate 6 shown in FIG. 5, the negative electrode lead 6 a is connected to the innermost peripheral side of the negative electrode plate 6. Further, in the negative electrode plate 6 shown in FIG. 6, the negative electrode lead 6 a is also connected to the current collector exposed portion 16 formed on the outermost peripheral side of the negative electrode plate 6. If the negative electrode lead 6a is also connected to the outermost peripheral side, a bypass path to the central part and the inner peripheral side is established before a foreign object such as a nail is pierced. Current concentration effect can be obtained. Further, as shown in FIG. 7, the current collector exposed portion 16 is not formed on the outermost peripheral side of the negative electrode plate 6 at a portion facing the current collector exposed portion 15 of the positive electrode plate 5 shown in FIG. 3. May be. Even in this case, when a foreign object such as a nail is pierced, a short circuit passes through “the current collector on the inner peripheral side of the negative electrode plate 6—the negative electrode lead 6a—the battery can 1—the current collector exposed portion 15 on the outer peripheral side of the positive electrode plate 5”. A current bypass path can be generated.
　また、本発明において、正極リード５ａの位置は、両面とも正極集電体が露出している箇所であれば、特に制限されない。また、図３に示した正極板５において、正極リード５ａを、正極板５の外周側の集電体露出部１５にも設けることによって、「正極板５の中央部－正極リード５ａ－正極板５の外周側の集電体露出部１５」のバイパス経路も形成されるため、釘などの異物が刺さった際に、さらに効果的に、外周側の短絡箇所への電流集中効果が得られる。ここで、「中央部」は、正極板５の正極活物質層が塗着された内周側端部と外周側端部の距離をＬとしたとき、内周側端部及び外周側端部からの距離がそれぞれ２／３Ｌ以下である範囲をいう。 In the present invention, the position of the positive electrode lead 5a is not particularly limited as long as the positive electrode current collector is exposed on both sides. Further, in the positive electrode plate 5 shown in FIG. 3, the positive electrode lead 5a is also provided on the current collector exposed portion 15 on the outer peripheral side of the positive electrode plate 5, thereby “the central portion of the positive electrode plate 5−the positive electrode lead 5a−the positive electrode plate”. Since the bypass path of the current collector exposed portion 15 on the outer peripheral side 5 is also formed, a current concentration effect on the short-circuited portion on the outer peripheral side can be obtained more effectively when a foreign object such as a nail is stuck. Here, the “central portion” means an inner peripheral end portion and an outer peripheral end portion, where L is the distance between the inner peripheral end portion to which the positive electrode active material layer of the positive electrode plate 5 is applied and the outer peripheral end portion. The range where the distance from each is 2 / 3L or less.
　次に、本発明の非水電解質二次電池の各構成要素について、具体的に説明する。 Next, each component of the nonaqueous electrolyte secondary battery of the present invention will be specifically described.
　負極活物質層１４は、負極活物質の他に、結着剤、増粘剤及び導電材などを含んでいてもよい。負極活物質としては、例えば、天然黒鉛等の炭素材料や、珪素（Ｓｉ）、錫（Ｓｎ）などの単体又は合金等を用いることができる。 The negative electrode active material layer 14 may contain a binder, a thickener, a conductive material, and the like in addition to the negative electrode active material. As the negative electrode active material, for example, a carbon material such as natural graphite, a simple substance such as silicon (Si) or tin (Sn), an alloy, or the like can be used.
　負極集電体には、銅箔、銅合金箔またはニッケル箔等を用いることができる。負極集電体の厚さは、生産性とエネルギー密度の観点から、５～３０μｍであることが好ましく、５～１５μｍであることがより好ましい。 As the negative electrode current collector, copper foil, copper alloy foil, nickel foil or the like can be used. The thickness of the negative electrode current collector is preferably 5 to 30 μm and more preferably 5 to 15 μm from the viewpoint of productivity and energy density.
　正極活物質層１３は、正極活物質の他に、結着剤及び導電材などを含んでいればよい。正極活物質としては、リチウム複合金属酸化物を用いることができる。リチウム複合金属酸化物は、例えば、ＬｉｘＣｏＯ２、ＬｉｘＮｉＯ２、ＬｉｘＭｎＯ２、等を用いることができる。 The positive electrode active material layer 13 only needs to contain a binder and a conductive material in addition to the positive electrode active material. A lithium composite metal oxide can be used as the positive electrode active material. For example, LixCoO 2 , LixNiO 2 , LixMnO 2 , or the like can be used as the lithium composite metal oxide.
　正極集電体には、アルミニウム箔、ニッケル箔またはステンレス箔等を用いることができる。正極集電体の厚さは、生産性とエネルギー密度の観点から、５～３０μｍであることが好ましく、１０～２０μｍであることがより好ましい。 As the positive electrode current collector, aluminum foil, nickel foil, stainless steel foil, or the like can be used. The thickness of the positive electrode current collector is preferably 5 to 30 μm and more preferably 10 to 20 μm from the viewpoint of productivity and energy density.
　リチウムイオン伝導性を有する電解質層は、非水溶媒及び非水溶媒に溶解するリチウム塩を含む。電解質層は、ポリオレフィン製の微多孔質フィルムをセパレータとして含んでもよく、この場合、微多孔質フィルムの細孔内に、リチウム塩が溶解した非水溶媒が含浸される。非水溶媒としては、例えば、エチレンカーボネ－ト（ＥＣ）、プロピレンカーボネ－ト（ＰＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）及びエチルメチルカーボネート（ＥＭＣ）等を用いることができる。 The electrolyte layer having lithium ion conductivity includes a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent. The electrolyte layer may include a polyolefin microporous film as a separator. In this case, a nonaqueous solvent in which a lithium salt is dissolved is impregnated in the pores of the microporous film. As the non-aqueous solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and the like can be used. .
　以下、本発明を実施例に基づいて詳細に説明するが、実施例は本発明の範囲を限定するものではない。 Hereinafter, the present invention will be described in detail based on examples, but the examples do not limit the scope of the present invention.
　（実施例１）
　（１）負極板の作製
　人造黒鉛（平均粒径１０μｍ、ＢＥＴ比表面積３ｍ２／ｇ）３ｋｇと、日本ゼオン（株）製のＢＭ－４００Ｂ（固形分４０質量％の変性スチレン－ブタジエンゴムの分散液）７５ｇと、カルボキシメチルセルロース（ＣＭＣ）３０ｇとを、適量の水とともに、練合機にて攪拌し、負極合剤スラリーを調製した。負極合剤スラリーを、厚さ８μｍの銅箔からなる負極集電体の両面に塗布し、乾燥し、総厚が１７２μｍとなるように圧延して、負極活物質層１４を形成した。負極活物質層１４の密度は１．７ｇ／ｃｍ３とした。 Example 1
(1) Preparation of negative electrode plate 3 kg of artificial graphite (average particle size 10 μm, BET specific surface area 3 m 2 / g) and BM-400B (solid content 40% by mass modified styrene-butadiene rubber) manufactured by Nippon Zeon Co., Ltd. ) 75 g and carboxymethyl cellulose (CMC) 30 g were stirred together with an appropriate amount of water in a kneader to prepare a negative electrode mixture slurry. The negative electrode mixture slurry was applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 8 μm, dried, and rolled to a total thickness of 172 μm to form the negative electrode active material layer 14. The density of the negative electrode active material layer 14 was 1.7 g / cm 3 .
　得られた極板を、幅５８．５ｍｍ、長さ７０５ｍｍに裁断し、図２に示したように、外周側に、長さ７０ｍｍの両面集電体露出部１６を設け、中央部と最内周側の中間に、長さ６ｍｍのリード溶接用の両面集電体露出部を設けた。そして、この集電体露出部に、ニッケル／銅／ニッケルクラッド材からなる負極リード６ａを溶接し、負極板６を得た。 The obtained electrode plate was cut into a width of 58.5 mm and a length of 705 mm, and as shown in FIG. 2, a double-sided current collector exposed portion 16 having a length of 70 mm was provided on the outer peripheral side, and the central portion and the innermost portion were provided. A 6 mm long double-sided current collector exposed portion for lead welding was provided in the middle of the circumferential side. And the negative electrode lead 6a which consists of nickel / copper / nickel clad material was welded to this collector exposed part, and the negative electrode plate 6 was obtained.
　（２）正極板の作製
　コバルト酸リチウム（ＬｉＣｏＯ２、平均粒径１０μｍ）３ｋｇ、ＰＶＤＦを１２質量％含むＮ－メチル－ピロリドン（ＮＭＰ（Ｎ－ｍｅｔｈｙｌｐｙｒｒｏｌｉｄｏｎｅ））溶液５００ｇ、アセチレンブラック６０ｇ、及び適量のＮＭＰを練合機で攪拌し、正極合剤スラリーを調製した。正極合剤スラリーを、厚さ１５μｍのアルミニウム箔からなる正極集電体の両面に塗布し、乾燥し、総厚が１７０μｍとなるように圧延して、正極活物質層を形成した。 (2) Preparation of positive electrode plate 3 g of lithium cobaltate (LiCoO 2 , average particle size 10 μm), 500 g of N-methyl-pyrrolidone (NMP (N-methylpyrrolidone)) solution containing 12% by mass of PVDF, 60 g of acetylene black, and an appropriate amount NMP was stirred with a kneader to prepare a positive electrode mixture slurry. The positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 15 μm, dried, and rolled to a total thickness of 170 μm to form a positive electrode active material layer.
　得られた極板を、幅５７．５ｍｍ、長さ６４０ｍｍに裁断し、図３に示したように、外周側に、長さ５７ｍｍの両面集電体露出部を設け、中央部に、長さ６ｍｍのリード溶接用の両面集電体露出部を設けた。そして、この集電体露出部に、アルミニウムからなるリードを溶接し、正極板５を得た。 The obtained electrode plate was cut into a width of 57.5 mm and a length of 640 mm, and as shown in FIG. 3, a double-sided current collector exposed portion having a length of 57 mm was provided on the outer peripheral side, and the length was provided at the center portion. A 6 mm double-sided current collector exposed portion for lead welding was provided. And the lead which consists of aluminum was welded to this collector exposed part, and the positive electrode plate 5 was obtained.
　（３）非水電解質の調整
　エチレンカーボネート（ＥＣ）と、ジメチルカーボネート（ＤＭＣ）と、エチルメチルカーボネート（ＥＭＣ）との体積比１：１：１の混合溶媒に、１モル／リットルの濃度でＬｉＰＦ６を溶解させ、さらに全体の３質量％相当のビニレンカーボネートを添加して、非水電解質を得た。 (3) Preparation of non-aqueous electrolyte LiPF at a concentration of 1 mol / liter in a mixed solvent of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in a volume ratio of 1: 1: 1. 6 was dissolved, and further vinylene carbonate corresponding to 3% by mass of the whole was added to obtain a non-aqueous electrolyte.
　（４）密閉型二次電池の作製
　図１に示した構成の円筒型リチウムイオン二次電池を作製した。 (4) Preparation of sealed secondary battery A cylindrical lithium ion secondary battery having the configuration shown in FIG. 1 was prepared.
　正極板５及び負極板６を、セパレータ７（厚み１６μｍのポリエチレン樹脂の単層）を介して捲回し、電極群９を作製した。この電極群９の上部及び下部に、上部絶縁板８ａ及び下部絶縁板８ｂを配置した後、有底円筒型の電池缶１（直径１８ｍｍ、高さ６５ｍｍ、内径１７．８５ｍｍ）に収容した。正極リード５ａの他端を金属製フィルター４に接続し、負極リード６ａの他端を電池缶１の底面に接続した。その後、非水電解質５．０ｇを電池缶１内に注液した。電池缶１の開口部を、ガスケット３を介して、封口板２で封口した。このようにして、設計容量が２８８０ｍＡｈである電池を作製した。 The positive electrode plate 5 and the negative electrode plate 6 were wound through a separator 7 (single layer of polyethylene resin having a thickness of 16 μm) to produce an electrode group 9. The upper insulating plate 8a and the lower insulating plate 8b were disposed above and below the electrode group 9, and then accommodated in a bottomed cylindrical battery can 1 (diameter 18 mm, height 65 mm, inner diameter 17.85 mm). The other end of the positive electrode lead 5 a was connected to the metal filter 4, and the other end of the negative electrode lead 6 a was connected to the bottom surface of the battery can 1. Thereafter, 5.0 g of the nonaqueous electrolyte was injected into the battery can 1. The opening of the battery can 1 was sealed with a sealing plate 2 via a gasket 3. In this way, a battery having a design capacity of 2880 mAh was produced.
　（実施例２）
　図４に示したように、負極板６の中央部やや内周側寄りに、負極リード６ａを溶接して負極板６を作製した以外、実施例１と同様にして、電池を作製した。 (Example 2)
As shown in FIG. 4, a battery was fabricated in the same manner as in Example 1 except that the negative electrode lead 6 a was welded to the central portion of the negative electrode plate 6 and slightly closer to the inner peripheral side to prepare the negative electrode plate 6.
　（実施例３）
　図５に示したように、負極板６の最内周側に負極リード６ａを溶接して負極板６を作製した以外、実施例１と同様にして、電池を作製した。 (Example 3)
As shown in FIG. 5, a battery was fabricated in the same manner as in Example 1 except that the negative electrode lead 6 a was welded to the innermost peripheral side of the negative electrode plate 6 to prepare the negative electrode plate 6.
　（実施例４）
　図６に示したように、負極板６の最内周側と最外周側に、それぞれ負極リード６ａを溶接して負極板６を作製した以外、実施例１と同様にして、電池を作製した。 (Example 4)
As shown in FIG. 6, a battery was fabricated in the same manner as in Example 1, except that the negative electrode lead 6a was welded to each of the innermost peripheral side and the outermost peripheral side of the negative electrode plate 6 to prepare the negative electrode plate 6. .
　（実施例５）
　図７に示したように、負極板６の長さを６３５ｍｍとし、負極板の最外周側に集電体露出部１６を設けなかったこと以外、実施例１と同様にして、電池を作製した。 (Example 5)
As shown in FIG. 7, a battery was fabricated in the same manner as in Example 1 except that the length of the negative electrode plate 6 was 635 mm and the current collector exposed portion 16 was not provided on the outermost peripheral side of the negative electrode plate. .
　（実施例６）
　正極板５の中央部だけでなく最外周側にも正極リード５ａを溶接したこと以外、実施例５と同様にして、電池を作製した。 (Example 6)
A battery was fabricated in the same manner as in Example 5, except that the positive electrode lead 5a was welded not only to the central portion of the positive electrode plate 5 but also to the outermost periphery.
　（比較例１）
　負極板６の最外周側に負極リード６ａを接続したこと以外、実施例１と同様にして、電池を作製した。 (Comparative Example 1)
A battery was fabricated in the same manner as in Example 1 except that the negative electrode lead 6a was connected to the outermost peripheral side of the negative electrode plate 6.
　（比較例２）
　負極板６と正極板５の最内周側及び中央部に、捲回方向に１周にわたり対向するように集電体露出部を設けたこと以外、比較例１と同様にして、電池を作製した。 (Comparative Example 2)
A battery was fabricated in the same manner as in Comparative Example 1, except that the current collector exposed portions were provided on the innermost peripheral side and the central portion of the negative electrode plate 6 and the positive electrode plate 5 so as to face each other in the winding direction. did.
　（電池の評価方法）
　実施例１～６及び比較例１～２の各電池に対して、次に示す釘刺し試験及び充放電試験を行って、各電池の安全性及び各電池の放電電池容量を評価した。 (Battery evaluation method)
The batteries of Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to the following nail penetration test and charge / discharge test to evaluate the safety of each battery and the discharge battery capacity of each battery.
　（１）釘刺し試験
　実施例１～６及び比較例１～２の各電池に対して、以下の条件で充電した。そして、７０℃環境下で、充電状態の電池の側面から、直径２．７ｍｍの鉄釘を１０ｍｍ／秒の速度で貫通させた。同じ試験を各５セルずつ行い、異常過熱に至るかどうか確認した。表１に、その結果を示す。 (1) Nail penetration test The batteries of Examples 1 to 6 and Comparative Examples 1 and 2 were charged under the following conditions. Then, in a 70 ° C. environment, an iron nail having a diameter of 2.7 mm was penetrated from the side surface of the charged battery at a speed of 10 mm / second. The same test was performed 5 cells each, and it was confirmed whether or not abnormal overheating occurred. Table 1 shows the results.
　（充電条件）
　定電流充電：電流値０．５Ｃ，充電終止電圧４．３Ｖ
　定電圧充電：電圧値４．３Ｖ，充電終止電流１００ｍＡ
　（２）充放電試験
　実施例１～６及び比較例１～２の各電池に対して、２５℃環境下で以下の条件で充放電を行い放電電池容量を求めた。表１に、その結果を示す。 (Charging conditions)
Constant current charging: Current value 0.5C, end-of-charge voltage 4.3V
Constant voltage charge: Voltage value 4.3V, charge end current 100mA
(2) Charge / Discharge Test The batteries of Examples 1 to 6 and Comparative Examples 1 and 2 were charged and discharged under the following conditions in a 25 ° C. environment to determine the discharge battery capacity. Table 1 shows the results.
　（充放電条件）
　定電流充電：電流値０．５Ｃ，充電終止電圧４．２Ｖ
　定電圧充電：電圧値４．２Ｖ，充電終止電流１００ｍＡ
　定電流放電：電流値０．５Ｃ，放電終止電圧１．０Ｖ (Charge / discharge conditions)
Constant current charging: Current value 0.5C, end-of-charge voltage 4.2V
Constant voltage charging: Voltage value 4.2V, charging end current 100mA
Constant current discharge: current value 0.5C, final discharge voltage 1.0V
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～４は、釘刺し時の異常過熱もなく、電池容量も高い電池が得られた。実施例５は、釘刺し時の異常過熱が５個の電池中、１個発生した。実施例５は、負極板６の外周側に集電体露出部１６を設けなかったため、釘－正極板の集電体露出部１５間の接触がうまくいかない場合があり、安全性がやや低下したものと考えられる。　　　 As shown in Table 1, in Examples 1 to 4, batteries with high battery capacity were obtained without abnormal overheating during nail penetration. In Example 5, one abnormal overheating at the time of nail penetration occurred in five batteries. In Example 5, since the current collector exposed portion 16 was not provided on the outer peripheral side of the negative electrode plate 6, the contact between the nail and the current collector exposed portion 15 of the positive electrode plate might not be successful, and safety was slightly lowered. it is conceivable that. *
　一方、実施例５に、正極板５の外周側に正極リード５ａを加えた実施例６では、釘刺し時に異常過熱が１個も発生しなかった。これは、「正極板５の中央部－正極リード５ａ－正極板の外周部」のバイパス経路が形成された結果、より効果的に外周側の短絡箇所への電流集中効果が得られたためであると考えられる。 On the other hand, in Example 6 in which the positive electrode lead 5a was added to the outer peripheral side of the positive electrode plate 5 in Example 5, no abnormal overheating occurred during nail penetration. This is because the current concentration effect to the short-circuited portion on the outer peripheral side is more effectively obtained as a result of the formation of the bypass path of “the center portion of the positive electrode plate 5—the positive electrode lead 5a—the outer peripheral portion of the positive electrode plate”. it is conceivable that.
　比較例１及び２は、異常過熱が多く発生した。比較例１は、外周側での集電体露出部同士の短絡箇所は発生するものの、外周側の短絡箇所へのバイパス経路がないため、電流集中効果が不十分であり、安全性が低かった。比較例２は、外周側だけでなく中央部及び内周側にも集電体露出部が存在するため、比較例１に比べるとやや安全性が向上したが、釘が内周側に到達する以前に過熱にいたる場合が多かった。また、比較例２は、集電体露出部を増やした結果、電池容量が低く、エネルギー密度の低い電池になった。 In Comparative Examples 1 and 2, a lot of abnormal overheating occurred. In Comparative Example 1, although the short-circuit portion between the current collector exposed portions on the outer peripheral side occurs, there is no bypass path to the short-circuit portion on the outer peripheral side, so the current concentration effect is insufficient and the safety is low. . In Comparative Example 2, since the current collector exposed portions exist not only on the outer peripheral side but also on the central portion and the inner peripheral side, the safety is slightly improved as compared with Comparative Example 1, but the nail reaches the inner peripheral side. There were many cases where it overheated before. In Comparative Example 2, as a result of increasing the current collector exposed portion, a battery having a low battery capacity and a low energy density was obtained.
　以上の結果より、本発明を用いることで、安全性とエネルギー密度が高い電池が得られることがわかった。 From the above results, it was found that a battery having high safety and high energy density can be obtained by using the present invention.
　本発明に係る非水電解質二次電池は、携帯用電子機器の電源や、電動工具、電気自動車などの駆動用電源等に有用である。 The non-aqueous electrolyte secondary battery according to the present invention is useful as a power source for portable electronic devices, a power source for driving electric tools, electric vehicles, and the like.
　　１　　　電池缶 
　　２　　　封口板 
　　３　　　ガスケット 
　　４　　　金属製フィルター 
　　５　　　正極板 
　　５ａ　　正極リード 
　　６　　　負極板 
　　６ａ　　負極リード 
　　７　　　セパレータ 
　　８ａ　　上部絶縁板 
　　８ｂ　　下部絶縁板 
　　９　　　電極群 
　　１３　　正極活物質層 
　　１４　　負極活物質層 
　　１５　　正極板の集電体露出部 
　　１６　　負極板の集電体露出部  1 Battery can
2 Sealing plate
3 Gasket
4 Metal filter
5 Positive electrode plate
5a Positive lead
6 Negative electrode plate
6a Negative lead
7 Separator
8a Upper insulating plate
8b Lower insulation plate
9 Electrode group
13 Positive electrode active material layer
14 Negative electrode active material layer
15 Current collector exposed portion of positive electrode plate
16 Current collector exposed portion of negative electrode plate

Claims (5)

  1. 　正極板と、負極板とが、セパレータを介して捲回してなる電極群が、非水電解質とともに金属製の電池缶に収容された非水電解質二次電池であって、
    　前記正極板は、正極集電体と、該正極集電体の表面に形成された正極活物質層を含み、
    　前記負極板は、負極集電体と、該負極集電体の表面に形成された負極活物質層を含み、
    　前記正極板または前記負極板のうち前記電池缶と異極性の極板は、前記電極群の最外周側に、捲回方向に１周以上の長さにわたって集電体が露出した集電体露出部を有し、
    　前記正極板または前記負極板のうち電池缶と同極性の極板は、該極板の長手方向中央部より内周側に、該極板に接続されたリードを有し、かつ、該リードは、前記電池缶に接続されている、非水電解質二次電池。     An electrode group in which a positive electrode plate and a negative electrode plate are wound through a separator is a non-aqueous electrolyte secondary battery housed in a metal battery can together with a non-aqueous electrolyte,
    The positive electrode plate includes a positive electrode current collector and a positive electrode active material layer formed on a surface of the positive electrode current collector,
    The negative electrode plate includes a negative electrode current collector and a negative electrode active material layer formed on a surface of the negative electrode current collector,
    Of the positive electrode plate or the negative electrode plate, the electrode plate having a polarity different from that of the battery can is a current collector exposure in which the current collector is exposed over a length of one or more rounds in the winding direction on the outermost peripheral side of the electrode group. Part
    Of the positive electrode plate or the negative electrode plate, the electrode plate having the same polarity as the battery can has a lead connected to the electrode plate on the inner peripheral side from the longitudinal center of the electrode plate, and the lead is A non-aqueous electrolyte secondary battery connected to the battery can.
  2. 　前記電池缶と同極性の極板は、前記電池缶と異極性の極板の前記集電体露出部と対向する部位に、捲回方向に１周以上の長さにわたって集電体が露出した集電体露出部を有している、請求項１に記載の非水電解質二次電池。 In the electrode plate having the same polarity as the battery can, the current collector is exposed over a length of one or more rounds in the winding direction at a portion facing the current collector exposed portion of the electrode plate having a different polarity from the battery can. The nonaqueous electrolyte secondary battery according to claim 1, comprising a current collector exposed portion.
  3. 　前記電池缶と同極性の極板は、前記電極群の最外周側に、リードをさらに有している、請求項１または２に記載の非水電解質二次電池。 The non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the electrode plate having the same polarity as the battery can further has a lead on the outermost peripheral side of the electrode group.
  4. 　前記電池缶と異極性の極板は、前記集電体露出部に、該極板に接続されたリードを有している、請求項１～３の何れか１項に記載の非水電解質二次電池。 The nonaqueous electrolyte battery according to any one of claims 1 to 3, wherein the electrode plate having a polarity different from that of the battery can has a lead connected to the electrode plate in the exposed portion of the current collector. Next battery.
  5. 　前記電池缶と異極性の極板は、該極板の長手方向中央部に、該極板に接続されたリードをさらに有している、請求項４に記載の非水電解質二次電池。 The non-aqueous electrolyte secondary battery according to claim 4, wherein the electrode plate having a polarity different from that of the battery can further includes a lead connected to the electrode plate at a central portion in a longitudinal direction of the electrode plate.
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