JP4382557B2 - Non-aqueous secondary battery - Google Patents

Non-aqueous secondary battery Download PDF

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JP4382557B2
JP4382557B2 JP2004101208A JP2004101208A JP4382557B2 JP 4382557 B2 JP4382557 B2 JP 4382557B2 JP 2004101208 A JP2004101208 A JP 2004101208A JP 2004101208 A JP2004101208 A JP 2004101208A JP 4382557 B2 JP4382557 B2 JP 4382557B2
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negative electrode
positive electrode
current collector
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coating film
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JP2005285691A (en
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浩児 占部
勇人 樋口
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Hitachi Maxell Energy Ltd
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    • 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

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Description

本発明は、角筒形状や円筒形状のリチウムイオン二次電池などの非水二次電池に関し、正極と負極とがセパレータを介して巻回された電極巻回体を収容した非水二次電池に関する。   The present invention relates to a non-aqueous secondary battery such as a rectangular tube-shaped or cylindrical lithium-ion secondary battery, and a non-aqueous secondary battery containing an electrode winding body in which a positive electrode and a negative electrode are wound via a separator. About.

正極および負極の電極は、製造上の理由などによって巻回方向の端部で金属製の集電体がそれぞれ露出してしまう。リチウムイオン二次電池では、正極の塗膜と、露出状態の負極集電体とが向かい合うと、充放電の繰り返しで正極の塗膜に含有するリチウムが、負極集電体の表面にデンドライト（樹枝状晶）として析出する。このデンドライトが成長するとセパレータを突き破り、正極と負極とが短絡する。   In the positive electrode and the negative electrode, metal current collectors are exposed at the ends in the winding direction due to manufacturing reasons, for example. In a lithium ion secondary battery, when the coating film of the positive electrode and the exposed negative electrode current collector face each other, lithium contained in the positive electrode coating film is repeatedly charged and discharged to the surface of the negative electrode current collector. Precipitate as a crystal). When this dendrite grows, it breaks through the separator, and the positive electrode and the negative electrode are short-circuited.

このため、従来は特許文献１に示すごとく、負極の塗膜を正極の塗膜の先端よりもさらに巻回方向の先端側に延ばして、正極の塗膜と、露出状態の負極集電体とが向かい合わないようにしていた。この場合、正極集電体が負極の塗膜や負極集電体に対面することになる。   For this reason, conventionally, as shown in Patent Document 1, the negative electrode coating film is further extended to the front end side in the winding direction than the front end of the positive electrode coating film, and the positive electrode coating film, the exposed negative electrode current collector, Was not facing each other. In this case, the positive electrode current collector faces the negative electrode coating film or the negative electrode current collector.

特開平１０−２４１７３７号公報（段落番号００１８−００２６、図１）Japanese Patent Laid-Open No. 10-241737 (paragraph numbers 0018-0026, FIG. 1) 特開平１０−３２６６２９号公報（段落番号００１１−００１３、図１）JP-A-10-326629 (paragraph number 0011-0013, FIG. 1) 特開２００１−８５０６６号公報（段落番号００１５−００１６、図２）JP 2001-85066 A (paragraph numbers 0015-0016, FIG. 2) 特開２００１−２６６９４６号公報（段落番号００３５、図１）JP 2001-266946 A (paragraph number 0035, FIG. 1) 特開２００４−６３３４３号公報（段落番号００４２、図２）Japanese Patent Laying-Open No. 2004-63343 (paragraph number 0042, FIG. 2)

正極集電体はアルミニウム製、負極集電体は銅製であってそれぞれ電気抵抗が小さい。さらに負極活物質の主成分は炭素であるために負極の塗膜も電気抵抗が小さい。このため、過充電などで電池が高温になってセパレータが収縮あるいは破れ、正負の集電体どうしが接触し、あるいは正極集電体が負極の塗膜に接触した場合には、過大な短絡電流が流れて電池内部で急激な発熱を生じ、電池が装着された機器などに悪影響を与えるおそれがある。   The positive electrode current collector is made of aluminum and the negative electrode current collector is made of copper, and each has a low electric resistance. Furthermore, since the main component of the negative electrode active material is carbon, the coating film of the negative electrode also has a low electrical resistance. Therefore, if the battery becomes hot due to overcharging, etc., the separator shrinks or tears, the positive and negative current collectors contact each other, or the positive current collector contacts the negative electrode coating, an excessive short circuit current May flow and suddenly generate heat inside the battery, which may adversely affect the device on which the battery is mounted.

この場合、特許文献１〜５に示すごとく、巻回方向の端部において正極あるいは負極の端部に絶縁体を配すれば前記接触を防ぐことはできる。ところが、デンドライトの生成防止のために、負極の塗膜を正極の塗膜の先端よりも巻回方向の先端側に延ばすことには変わりがないため、正極集電体が負極の塗膜や負極集電体に対面する。したがって、何らかの理由でセパレータのみならず絶縁体まで破損した場合に、正負の集電体どうしの接触や、正極集電体と負極の塗膜との接触を防止できないことになる。   In this case, as shown in Patent Documents 1 to 5, the contact can be prevented if an insulator is provided at the end of the positive electrode or the negative electrode at the end in the winding direction. However, in order to prevent the formation of dendrites, there is no change in extending the negative electrode coating film toward the front end side in the winding direction from the front end of the positive electrode coating film. Facing the current collector. Therefore, when not only the separator but also the insulator is broken for some reason, it is impossible to prevent the contact between the positive and negative current collectors and the contact between the positive electrode current collector and the negative electrode coating film.

そこで本発明の目的は、セパレータのみならず絶縁体まで破損しても正負の集電体どうしの接触や、正極集電体と負極の塗膜との接触が生じないうえ、デンドライトの生成を防止できる非水二次電池を提供することにある。   Therefore, the object of the present invention is to prevent contact between the positive and negative current collectors and contact between the positive electrode current collector and the negative electrode coating film even when the insulator as well as the separator is damaged, and to prevent the formation of dendrites. The object is to provide a non-aqueous secondary battery that can be used.

本発明が対象とする非水二次電池は、図１に示すごとく、正極活物質を含有する塗膜１７が正極集電体１９の裏表両面に配された正極９と、負極活物質を含有する塗膜２０が負極集電体２１の裏表両面に配された負極１０と、リチウムイオンが透過可能なセパレータ１１とを有しており、正極９と負極１０とがセパレータ１１を介して巻回された電極巻回体７を収容してある。   As shown in FIG. 1, the nonaqueous secondary battery targeted by the present invention contains a positive electrode 9 in which a coating film 17 containing a positive electrode active material is disposed on both sides of a positive electrode current collector 19, and a negative electrode active material. The coating film 20 to be coated has a negative electrode 10 disposed on both sides of the negative electrode current collector 21 and a separator 11 that is permeable to lithium ions. The positive electrode 9 and the negative electrode 10 are wound around the separator 11. The electrode winding body 7 is accommodated.

その負極１０の巻回方向の先端は、それに対面する正極９の塗膜１７・１７の先端よりも巻回方向に後退して、負極１０が露出状態の正極集電体１９に対面しないようにしてある。負極１０の先端部と、正極９における負極１０の先端部に対面する部分との少なくとも一方に、リチウムイオン非透過性の絶縁体が介在していることを特徴とする。   The tip of the negative electrode 10 in the winding direction is set back from the tip of the coating film 17 or 17 of the positive electrode 9 facing the negative electrode 10 in the winding direction so that the negative electrode 10 does not face the exposed positive electrode current collector 19. It is. A lithium ion impermeable insulator is interposed between at least one of the tip of the negative electrode 10 and the portion of the positive electrode 9 facing the tip of the negative electrode 10.

ここでの負極１０の先端は、電極巻回体７の巻回方向の外周側の先端の場合と、内周側の先端の場合とが該当し、外周側の場合には正極９の塗膜１７・１７の先端よりも巻回方向の内周側に後退しており、内周側の場合には正極９の塗膜１７・１７の先端よりも巻回方向の外周側に後退している。本発明は、製造上の理由で負極集電体２１が露出してもデンドライトの生成を防止できるものであり、負極１０の先端部において負極集電体２１が露出している場合と、負極集電体２１が露出していない場合とが含まれる。   Here, the tip of the negative electrode 10 corresponds to the tip on the outer peripheral side in the winding direction of the electrode winding body 7 and the tip on the inner peripheral side, and in the case of the outer peripheral side, the coating film of the positive electrode 9 It has retracted to the inner peripheral side in the winding direction from the tips of 17 and 17, and in the case of the inner peripheral side, it has retracted to the outer peripheral side in the winding direction from the tips of the coating films 17 and 17 of the positive electrode 9. . The present invention can prevent the formation of dendrite even if the negative electrode current collector 21 is exposed for manufacturing reasons. The negative electrode current collector 21 is exposed at the tip of the negative electrode 10, and The case where the electric body 21 is not exposed is included.

絶縁体は、図１に示すごとく塗料２２で形成されていてもよいし、図３に示すごとくテープ２３であってもよい。絶縁体の材料としては、ポリイミド樹脂、ポリアミド樹脂、ポリウレタン樹脂、フッ素樹脂、シリコン樹脂、エポキシ樹脂あるいはアクリル樹脂などが該当する。   The insulator may be formed of a paint 22 as shown in FIG. 1 or a tape 23 as shown in FIG. Examples of the insulator material include polyimide resin, polyamide resin, polyurethane resin, fluorine resin, silicon resin, epoxy resin, and acrylic resin.

セパレータ１１には、その全体にわたってリチウムイオンが透過可能な微孔を分散状に設けられている。かかるセパレータ１１において、図５に示すごとく、負極１０の先端部に対面する部分１１ａ・１１ａの微孔を塞いで絶縁体とすることで、その部分１１ａ・１１ａではリチウムイオンが透過しないようにすることができる。ここでは前記部分１１ａ・１１ａの微孔を融着する場合も含まれ、さらに前記微孔を融着するとともに負極１０の先端部の外周側および内周側のセパレータ１１・１１どうしを融着する場合も含まれる。   The separator 11 is provided with fine pores that can transmit lithium ions in a dispersed manner throughout the separator 11. In such a separator 11, as shown in FIG. 5, the minute holes of the portions 11 a and 11 a facing the tip of the negative electrode 10 are closed to form an insulator so that lithium ions do not pass through the portions 11 a and 11 a. be able to. Here, the case where the micro holes of the portions 11a and 11a are fused is included, and the micro holes are further fused, and the outer peripheral side and inner peripheral side separators 11 and 11 of the negative electrode 10 are fused. Cases are also included.

本発明によれば、負極１０が露出状態の正極集電体１９に対面しないようにしてあるので、過充電などで電池が高温になってセパレータ１１が収縮あるいは破れても、正負の集電体１９・２１どうしが接触したり、正極集電体１９が負極１０の塗膜２０に接触したりすることがなく、過大な短絡電流が流れて電池内部で急激な発熱を生じることを確実に防止できる。このうえで、負極１０の先端部で負極集電体２１が露出していても、負極１０の先端部と正極９との間に絶縁体が介在するので、デンドライトの生成を確実に防止できる。   According to the present invention, since the negative electrode 10 does not face the exposed positive electrode current collector 19, even if the battery becomes hot due to overcharge or the like and the separator 11 contracts or breaks, the positive and negative current collectors 19 and 21 are not in contact with each other, and the positive electrode current collector 19 is not in contact with the coating film 20 of the negative electrode 10, thereby reliably preventing an excessive short circuit current from flowing and causing sudden heat generation inside the battery. it can. In addition, even if the negative electrode current collector 21 is exposed at the tip of the negative electrode 10, since an insulator is interposed between the tip of the negative electrode 10 and the positive electrode 9, it is possible to reliably prevent the formation of dendrite.

セパレータ１１において、負極１０の先端部に対面する部分１１ａ・１１ａの微孔を塞いでリチウムイオンが透過しないようにすると、前記部分１１ａ・１１ａを加熱して微孔を融着することで塞ぐことができるので、塗料の塗布やテープの貼り付けなどに比べて絶縁体を容易に形成できるうえ、絶縁体が塗料やテープに比べて嵩張らないことになる。   In the separator 11, if the micropores of the portions 11 a and 11 a facing the tip of the negative electrode 10 are blocked so that lithium ions do not permeate, the portions 11 a and 11 a are heated and sealed by fusing the micropores. Therefore, an insulator can be easily formed as compared with application of a paint or application of a tape, and the insulator is not bulky as compared with a paint or a tape.

（実施例１） 図１および図２は、本発明が対象とする非水二次電池の実施例１を示しており、上面が開口する有底筒形状のアルミニウム製の電池ケース１と、電池ケース１の上面開口を塞ぐアルミニウム製の封口板２と、電池ケース１内の上端に配されたプラスチック製のインシュレータ３とを有する。封口板２の中央には、絶縁パッキング５を介して負極端子６が貫通状に取り付けられている。電池ケース１内には、電極巻回体７および非水電解液が収容されている。 (Example 1) FIG. 1 and FIG. 2 show Example 1 of a non-aqueous secondary battery targeted by the present invention, a battery case 1 made of aluminum having a bottomed cylindrical shape with an open top surface, and a battery An aluminum sealing plate 2 that closes the upper surface opening of the case 1 and a plastic insulator 3 disposed at the upper end of the battery case 1 are provided. A negative electrode terminal 6 is attached to the center of the sealing plate 2 through an insulating packing 5 in a penetrating manner. In the battery case 1, an electrode winding body 7 and a non-aqueous electrolyte are accommodated.

電極巻回体７は、帯状の正極９と、帯状の負極１０とを絶縁性を有する帯状のセパレータ１１を挟んで積層し、この積層を巻回してなる。封口板２は、その外周縁が電池ケース１の上端開口周縁にレーザーで密閉状にシール溶接する。負極端子６の下端には、導電タブ１３が溶接されており、この導電タブ１３が負極１０に接続される。電池ケース１の上端内面には、導電タブ１５が溶接されており、この導電タブ１５が正極９に接続される。これにより、電池ケース１が正極端子を兼ねる。セパレータ１１は、厚さ寸法が２０μｍのポリエチレンフィルムからなり、セパレータ１１の全体にわたってリチウムイオンが透過可能な微孔が分散状に設けられている。   The electrode winding body 7 is formed by laminating a strip-shaped positive electrode 9 and a strip-shaped negative electrode 10 with a strip-shaped separator 11 having insulation therebetween, and winding this stack. The outer peripheral edge of the sealing plate 2 is hermetically sealed and welded to the upper end opening peripheral edge of the battery case 1 with a laser. A conductive tab 13 is welded to the lower end of the negative electrode terminal 6, and the conductive tab 13 is connected to the negative electrode 10. A conductive tab 15 is welded to the inner surface of the upper end of the battery case 1, and the conductive tab 15 is connected to the positive electrode 9. Thereby, the battery case 1 serves also as a positive electrode terminal. The separator 11 is made of a polyethylene film having a thickness of 20 μm, and micropores through which lithium ions can be transmitted are provided in a dispersed manner throughout the separator 11.

電極巻回体７の正極９は、図１に示すごとく正極活物質を含有する塗膜１７を帯状の正極集電体１９の裏表両面に配することで形成してある。負極１０は、負極活物質を含有する塗膜２０を帯状の負極集電体２１の裏表両面に配することで形成してある。なお、正極９および負極１０の巻回方向の両端では、製造上の理由などで集電体１９・２１がそれぞれ露出することがあり、ここでは集電体１９・２１の一部がそれぞれ露出している状態で説明する。   As shown in FIG. 1, the positive electrode 9 of the electrode winding body 7 is formed by disposing a coating film 17 containing a positive electrode active material on both the front and back surfaces of a strip-shaped positive electrode current collector 19. The negative electrode 10 is formed by disposing a coating film 20 containing a negative electrode active material on both the front and back surfaces of a strip-shaped negative electrode current collector 21. The current collectors 19 and 21 may be exposed at both ends in the winding direction of the positive electrode 9 and the negative electrode 10 due to manufacturing reasons. Here, a part of the current collectors 19 and 21 is exposed. Explain in the state.

つまり、電極巻回体７において、巻回方向の最外周側となる負極１０の負極集電体２１の先端２１ａは、その外周側の正極９の塗膜１７の先端１７ａ、および内周側の正極９の塗膜１７の先端１７ｂよりも巻回方向の内周側に後退しており、負極１０が露出状態の正極集電体１９に対面しないようにしてある。   That is, in the electrode winding body 7, the tip 21 a of the negative electrode current collector 21 of the negative electrode 10 on the outermost peripheral side in the winding direction is the tip 17 a of the coating film 17 of the positive electrode 9 on the outer peripheral side and the tip 17 a of the inner peripheral side. It is set back from the front end 17b of the coating film 17 of the positive electrode 9 toward the inner peripheral side in the winding direction so that the negative electrode 10 does not face the exposed positive electrode current collector 19.

負極１０の最外周側の先端部には、リチウムイオンが透過しないリチウムイオン非透過性を有するポリイミド塗料２２が、絶縁体としてそれぞれ塗布されている。ポリイミド塗料２２は、固形成分（ポリイミド樹脂）を１５重量％含有するＮＭＰ（Ｎ−メチル２ピロリロン）の溶液からなる。ポリイミド塗料２２は、負極１０の先端に露出している負極集電体２１の全体と、負極１０の裏表の塗膜２０の先端部とを被覆している。ポリイミド塗料２２は、塗布後にホットプレート上で加熱乾燥する。これにより、負極１０の先端部で露出している負極集電体２１と、正極９との間に絶縁体が介在することになる。   A polyimide coating 22 having a lithium ion impermeability that does not allow lithium ions to pass through is applied as an insulator to the tip of the outermost peripheral side of the negative electrode 10. The polyimide coating 22 is made of a solution of NMP (N-methyl 2-pyrrolylone) containing 15% by weight of a solid component (polyimide resin). The polyimide coating 22 covers the entire negative electrode current collector 21 exposed at the tip of the negative electrode 10 and the tip of the coating film 20 on the back and front of the negative electrode 10. The polyimide coating 22 is heated and dried on a hot plate after application. Thereby, an insulator is interposed between the negative electrode current collector 21 exposed at the tip of the negative electrode 10 and the positive electrode 9.

正極９は、以下のようにして作製した。正極活物質としてのＬｉＣｏＯ2 に、導電助剤として鱗片状黒鉛を加えて混合し、この混合物と、ポリフッ化ビニリデンをＮ−メチルピロリドンに溶解させた溶液とを混合して、ペースト状の正極塗料を調整した。このペースト状の正極塗料は、７０メッシュの網を通過させて大きなものを取り除いた後、厚さ１５μｍの帯状のアルミニウム箔からなる正極集電体１９の裏表両面に均一に塗布し、乾燥して塗膜１７を形成した。 The positive electrode 9 was produced as follows. LiCoO 2 as a positive electrode active material is mixed with scaly graphite as a conductive additive, and this mixture is mixed with a solution in which polyvinylidene fluoride is dissolved in N-methylpyrrolidone to obtain a paste-like positive electrode paint Adjusted. This paste-like positive electrode paint is passed through a 70-mesh net to remove a large one, and is then uniformly applied to both the front and back surfaces of a positive electrode current collector 19 made of a strip-shaped aluminum foil having a thickness of 15 μm and dried. A coating film 17 was formed.

前記乾燥後の帯状体は、圧縮成形されて所定の寸法に切断したのち、導電タブ１５を溶接する。なお、最外周の正極９において正極集電体１９の外周面と、導電タブ１５の接続箇所とには、正極塗料が塗布されていない。   The dried band-like body is compression-molded and cut to a predetermined size, and then the conductive tab 15 is welded. In the outermost positive electrode 9, the positive electrode paint is not applied to the outer peripheral surface of the positive electrode current collector 19 and the connection portion of the conductive tab 15.

負極１０は、以下のようにして作製した。負極活物質としての黒鉛系炭素材料を、ポリフッ化ビニリデンをＮ−メチルピロリドンに溶解させた溶液に混合して、ペースト状の負極塗料を調整した。このペースト状の負極塗料は、７０メッシュの網を通過させて大きなものを取り除いた後、厚さ１０μｍの帯状の銅箔からなる負極集電体２１の裏表両面に均一に塗布し、乾燥して塗膜２０を形成した。なお、負極１０は、導電タブ１３の接続箇所には負極塗料が塗布されていない。前記乾燥後の帯状体は、圧縮成形して所定の寸法に切断したのち、これに導電タブ１３を溶接した。   The negative electrode 10 was produced as follows. A graphite-type carbon material as a negative electrode active material was mixed with a solution in which polyvinylidene fluoride was dissolved in N-methylpyrrolidone to prepare a paste-like negative electrode paint. This paste-like negative electrode paint is passed through a 70-mesh net to remove a large one, and then uniformly applied to both the front and back surfaces of the negative electrode current collector 21 made of a strip-like copper foil having a thickness of 10 μm, and dried. A coating film 20 was formed. In the negative electrode 10, the negative electrode paint is not applied to the connection portion of the conductive tab 13. The dried band-like body was compression-molded and cut into a predetermined size, and the conductive tab 13 was welded thereto.

非水電解質は、エチレンカーボネート（ＥＣ）と、ジエチルカーボネート（ＤＥＣ）とを体積比１：２の割合で混合した溶媒に、ＬｉＰＦ6 を１ｍｏｌ／ｄｍ3 の濃度になるように溶解して調製した。 The nonaqueous electrolyte was prepared by dissolving LiPF 6 to a concentration of 1 mol / dm 3 in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 2. .

なお、巻回方向の最内周側となる負極１０の負極集電体２１の先端（基端）は、その外周側の正極９の塗膜１７および内周側の塗膜１７の先端よりも巻回方向の外周側に後退し、最内周側の負極１０が露出状態の正極集電体１９に対面しないようにしてもよい。この場合、負極１０の最内周側の先端部にもポリイミド塗料２２を塗布する。   In addition, the front-end | tip (base end) of the negative electrode collector 21 of the negative electrode 10 used as the innermost circumference side of a winding direction is rather than the front-end | tip of the coating film 17 of the positive electrode 9 of the outer peripheral side, and the coating film 17 of an inner peripheral side. The innermost negative electrode 10 may recede to the outer peripheral side in the winding direction so that it does not face the exposed positive electrode current collector 19. In this case, the polyimide coating 22 is also applied to the innermost peripheral tip of the negative electrode 10.

（実施例２） 実施例２では、図３に示すごとく、負極１０の巻回方向の最外周側の先端部に、リチウムイオン非透過性のポリイミド製の絶縁テープ２３を絶縁体として貼り付けた。絶縁テープ２３は、負極１０の先端で露出している負極集電体２１の全体と、負極１０の裏表の塗膜２０の先端部とを被覆している。絶縁テープ２３の厚さ寸法は４５μｍ、テープ本体の樹脂の厚さ寸法は２５μｍとした。その他の点は、実施例１と同じであるので説明を省略する。 (Example 2) In Example 2, as shown in FIG. 3, the insulating tape 23 made of polyimide that is impermeable to lithium ions was pasted as an insulator to the tip of the negative electrode 10 on the outermost peripheral side in the winding direction. . The insulating tape 23 covers the entire negative electrode current collector 21 exposed at the tip of the negative electrode 10 and the tip of the coating film 20 on the back and front of the negative electrode 10. The thickness dimension of the insulating tape 23 was 45 μm, and the thickness dimension of the resin of the tape body was 25 μm. Since the other points are the same as those of the first embodiment, description thereof is omitted.

（実施例３） 実施例３では、実施例２において、ポリプロピレン製の絶縁テープ２３の厚さ寸法を５５μｍにした。テープ本体の樹脂の厚さ寸法は３０μｍとした。その他の点は、実施例２と同じであるので説明を省略する。 (Example 3) In Example 3, in Example 2, the thickness dimension of the polypropylene insulating tape 23 was set to 55 µm. The thickness of the resin of the tape body was 30 μm. Since the other points are the same as those of the second embodiment, the description thereof is omitted.

（実施例４） 実施例４では、図４に示すごとく、正極９に前記ポリイミド塗料２２を塗布した。ポリイミド塗料２２は、前記負極集電体２１の先端部の外周側となる正極９の塗膜１７の先端１７ａ付近、および内周側となる正極９の塗膜１７の先端１７ｂ付近に塗布した。その他の点は、実施例１と同じであるので説明を省略する。 (Example 4) In Example 4, the polyimide coating 22 was applied to the positive electrode 9 as shown in FIG. The polyimide coating 22 was applied to the vicinity of the tip 17a of the coating film 17 of the positive electrode 9 on the outer peripheral side of the tip of the negative electrode current collector 21, and the vicinity of the tip 17b of the coating film 17 of the positive electrode 9 on the inner peripheral side. Since the other points are the same as those of the first embodiment, description thereof is omitted.

（実施例５） 実施例５では、正極９に前記ポリイミド製の絶縁テープ２３を配した。その絶縁テープ２３は、前記負極集電体２１の先端部の外周側となる正極９の塗膜１７の先端１７ａ付近、および内周側となる正極９の塗膜１７の先端１７ｂ付近に貼り付けた。その他の点は、実施例４と同じであるので説明を省略する。 Example 5 In Example 5, the polyimide insulating tape 23 was disposed on the positive electrode 9. The insulating tape 23 is attached to the vicinity of the tip 17a of the coating film 17 of the positive electrode 9 on the outer peripheral side of the tip portion of the negative electrode current collector 21 and the vicinity of the tip 17b of the coating film 17 of the positive electrode 9 on the inner peripheral side. It was. Since the other points are the same as those of the fourth embodiment, the description thereof is omitted.

（実施例６） 実施例６では、実施例５において、ポリプロピレン製の絶縁テープ２３を配した。その絶縁テープ２３の厚さ寸法は５５μｍ、テープ本体の樹脂の厚さ寸法は３０μｍとした。その他の点は、実施例５と同じであるので説明を省略する。 (Example 6) In Example 6, the insulating tape 23 made of polypropylene was arranged in Example 5. The thickness dimension of the insulating tape 23 was 55 μm, and the thickness dimension of the resin of the tape body was 30 μm. Since the other points are the same as those of the fifth embodiment, description thereof is omitted.

（実施例７） 実施例７では、実施例２と同様に負極１０にポリイミド製の絶縁テープ２３を貼り付けることに加えて、実施例５と同様に正極９にもポリイミド製の絶縁テープ２３を貼り付けた。その他の点は、実施例１と同じであるので説明を省略する。 (Example 7) In Example 7, in addition to sticking the polyimide insulating tape 23 to the negative electrode 10 as in Example 2, the polyimide insulating tape 23 was also applied to the positive electrode 9 as in Example 5. Pasted. Since the other points are the same as those of the first embodiment, description thereof is omitted.

（実施例８） 実施例８では、図５に示すごとく、負極１０の先端部の外周側および内周側のセパレータ１１・１１において、負極１０の先端部に対面する部分１１ａ・１１ａをそれぞれ１５０℃に加熱して、その部分１１ａ・１１ａの微孔を融着させてリチウムイオンを透過不能にした。その他の点は、実施例１と同じであるので説明を省略する。 (Example 8) In Example 8, as shown in FIG. 5, in the separators 11 and 11 on the outer peripheral side and the inner peripheral side of the negative electrode 10, 150 portions 11a and 11a facing the front end of the negative electrode 10 are provided. The micropores of the portions 11a and 11a were fused to make lithium ions impermeable. Since the other points are the same as those of the first embodiment, description thereof is omitted.

（実施例９） 実施例９では、実施例７において、負極１０に配するポリイミド製の絶縁テープ２３の厚さ寸法を４５μｍにした。そのテープ本体の樹脂の厚さ寸法は２５μｍとした。その他の点は、実施例７と同じであるので説明を省略する。 (Example 9) In Example 9, in Example 7, the thickness dimension of the polyimide insulating tape 23 disposed on the negative electrode 10 was set to 45 µm. The thickness dimension of the resin of the tape body was 25 μm. Since the other points are the same as those of the seventh embodiment, the description thereof is omitted.

（実施例１０） 実施例１０では、実施例７において、正極９に配するポリイミド製の絶縁テープ２３の厚さ寸法を４５μｍにした。そのテープ本体の樹脂の厚さ寸法は２５μｍとした。その他の点は、実施例７と同じであるので説明を省略する。 (Example 10) In Example 10, in Example 7, the thickness dimension of the polyimide insulating tape 23 disposed on the positive electrode 9 was set to 45 µm. The thickness dimension of the resin of the tape body was 25 μm. Since the other points are the same as those of the seventh embodiment, the description thereof is omitted.

（実施例１１） 実施例１１では、図６に示すごとく、負極１０の先端部の外周側および内周側のセパレータ１１・１１において、負極１０の先端部に対面する部分をそれぞれ１５０℃に加熱して、その部分１１ａ・１１ａの微孔を融着させるとともに外周側および内周側のセパレータ１１・１１どうしを融着した。その他の点は、実施例１と同じであるので説明を省略する。 Example 11 In Example 11, as shown in FIG. 6, in the outer peripheral side and inner peripheral side separators 11 and 11 of the negative electrode 10, the portions facing the negative electrode 10 are heated to 150 ° C., respectively. Then, the fine holes of the portions 11a and 11a were fused, and the separators 11 and 11 on the outer peripheral side and the inner peripheral side were fused. Since the other points are the same as those of the first embodiment, description thereof is omitted.

（比較例１） 実施例１において、ポリイミド塗料２２の塗布を省略した。その他の点は実施例１と同じである。 (Comparative example 1) In Example 1, application | coating of the polyimide coating material 22 was abbreviate | omitted. The other points are the same as in the first embodiment.

（比較例２） 比較例１において、電極巻回体７は、図７に示すごとく、巻回方向の最外周となる負極１０の負極集電体２１の先端２１ａが、その外周側の正極９の塗膜１７の先端１７ａ、および内周側の正極９の塗膜１７の先端１７ｂよりも巻回方向の外周側に位置して、負極１０が露出状態の正極集電体１９に対面している。ポリイミド塗料２２の塗布は省略した。その他の点は、実施例１と同じである。 (Comparative example 2) In the comparative example 1, as shown in FIG. 7, the electrode winding body 7 has the tip 21a of the negative electrode current collector 21 of the negative electrode 10 which is the outermost periphery in the winding direction, and the positive electrode 9 on the outer peripheral side. The negative electrode 10 faces the positive electrode current collector 19 in an exposed state, located on the outer peripheral side in the winding direction from the front end 17a of the coating film 17 and the front end 17b of the coating film 17 of the inner peripheral side positive electrode 9. Yes. The application of the polyimide paint 22 was omitted. Other points are the same as those in the first embodiment.

実施例１〜１１および比較例１・２の各電池を、２５℃で８００ｍＡの定電流で4.２Ｖまで充電し、4.２Ｖに達したのちは4.２Ｖの定電圧で2.５時間だけ充電した。次いで８００ｍＡの定電流で終止電圧が3.０Ｖになるまで放電したのち、８００ｍＡの定電流で4.２Ｖまで充電することを、2.５時間の条件で５回繰り返し、充電状態でオーブンによって１５０℃で１０分間の加熱を行った。   The batteries of Examples 1 to 11 and Comparative Examples 1 and 2 were charged to 4.2 V at a constant current of 800 mA at 25 ° C. After reaching 4.2 V, the battery was constant at 4.2 V for 2.5 hours. Just charged. Next, after discharging to a final voltage of 3.0 V at a constant current of 800 mA, charging to 4.2 V at a constant current of 800 mA is repeated 5 times under the condition of 2.5 hours, and 150 times by an oven in the charged state. Heating was performed at 0 ° C. for 10 minutes.

前記加熱での各電池の温度を測定した。更に各電池を分解して、負極１０の先端部でのリチウム析出の状態を確認した。表１はその結果を示す。   The temperature of each battery during the heating was measured. Furthermore, each battery was disassembled, and the state of lithium deposition at the tip of the negative electrode 10 was confirmed. Table 1 shows the results.

Figure 0004382557
Figure 0004382557

実施例１〜１１の各電池では、最高電池温度が１７０℃以下であって発火もない。これは、電池内部で短絡が生じてなく、発熱がほぼ無いためと考えられる。比較例１の電池では、最高電池温度が１７６℃もあり、電池内部で僅かに短絡が生じて発熱が生じたためと考えられる。比較例１の電池では発火が生じた。これは、電池内部で多大な短絡が生じたためと考えられる。   In each battery of Examples 1 to 11, the maximum battery temperature is 170 ° C. or less and there is no ignition. This is presumably because no short circuit occurs inside the battery and there is almost no heat generation. The battery of Comparative Example 1 has a maximum battery temperature of 176 ° C., which is considered to be due to heat generation due to a slight short circuit inside the battery. In the battery of Comparative Example 1, ignition occurred. This is probably because a large number of short circuits occurred inside the battery.

このように、実施例１〜１１の各電池では、電池温度が高温になっても発熱の小さい、安全性に優れた電池を得ることができた。   As described above, in each of the batteries of Examples 1 to 11, it was possible to obtain a battery with low heat generation and excellent safety even when the battery temperature became high.

前記実施例において、ポリイミド塗料２２や絶縁テープ２３を正極９に配する場合には、正極９や負極１０の伸縮などを考慮して、ポリイミド塗料２２や絶縁テープ２３を巻回方向に長めに配する。また、前記実施例８・１１において、セパレータ１１・１１の融着部分１１ａ・１１ａも、セパレータ１１の熱収縮などを考慮して巻回方向に長めに形成する。   In the above embodiment, when the polyimide coating 22 and the insulating tape 23 are arranged on the positive electrode 9, the polyimide coating 22 and the insulating tape 23 are arranged longer in the winding direction in consideration of expansion and contraction of the positive electrode 9 and the negative electrode 10. To do. Moreover, in the said Example 8 * 11, the fusion | melting part 11a * 11a of the separators 11 * 11 is also formed long in the winding direction in consideration of the thermal contraction etc. of the separator 11. FIG.

各実施例において、負極１０の先端を正極９の塗膜１７・１７の先端よりも巻回方向に後退させ、かつ負極１０および正極９の少なくとも一方を前記ポリイミド塗料２２や絶縁テープ２３の絶縁体で被覆することを、電極巻回体７の巻回方向の外周側の先端と、内周側の先端との双方、あるいはいずれか一方のみに行なうものであってもよい。扁平角形の電池の場合には、電極巻回体７は巻回したのちに電池ケース１に合わせて扁平状に押し潰し変形される。本発明は、負極１０の先端部において、負極集電体２１の先端まで塗膜２０で覆われて負極集電体２１が露出していない場合でも適用できる。   In each example, the tip of the negative electrode 10 is retracted in the winding direction from the tips of the coating films 17 and 17 of the positive electrode 9, and at least one of the negative electrode 10 and the positive electrode 9 is an insulator of the polyimide paint 22 or the insulating tape 23. The coating may be performed on both or only one of the outer peripheral end and the inner peripheral end in the winding direction of the electrode winding body 7. In the case of a flat rectangular battery, the wound electrode body 7 is crushed and deformed in a flat shape in accordance with the battery case 1 after being wound. The present invention is applicable even when the tip of the negative electrode 10 is covered with the coating film 20 up to the tip of the negative electrode current collector 21 and the negative electrode current collector 21 is not exposed.

実施例１の電極巻回体の要部を示す断面図Sectional drawing which shows the principal part of the electrode winding body of Example 1 電池の縦断面図Battery longitudinal section 実施例２の電極巻回体の要部を示す断面図Sectional drawing which shows the principal part of the electrode winding body of Example 2 実施例４の電極巻回体の要部を示す断面図Sectional drawing which shows the principal part of the electrode winding body of Example 4 実施例８の電極巻回体の要部を示す断面図Sectional drawing which shows the principal part of the electrode winding body of Example 8. 実施例１１の電極巻回体の要部を示す断面図Sectional drawing which shows the principal part of the electrode winding body of Example 11 比較例２の電極巻回体の要部を示す断面図Sectional drawing which shows the principal part of the electrode winding body of the comparative example 2

符号の説明Explanation of symbols

７ 電極巻回体
９ 正極
１０ 負極
１１ セパレータ
１７ 正極塗膜
１９ 正極集電体
２０ 負極塗膜
２１ 負極集電体
２２ ポリイミド塗料
２３ 絶縁テープ 7 Electrode Winding Body 9 Positive Electrode 10 Negative Electrode 11 Separator 17 Positive Electrode Coating 19 Positive Electrode Current Collector 20 Negative Electrode Coating 21 Negative Electrode Current Collector 22 Polyimide Paint 23 Insulating Tape

Claims (4)

正極活物質を含有する塗膜が正極集電体の裏表両面に配された正極と、負極活物質を含有する塗膜が負極集電体の裏表両面に配された負極と、リチウムイオンが透過可能なセパレータとを有しており、
前記正極と前記負極とが前記セパレータを介して巻回された電極巻回体を収容した非水二次電池であって、
前記負極の巻回方向の先端が、それに対面する前記正極の塗膜の先端よりも巻回方向に後退して、前記負極が露出状態の前記正極集電体に対面しないようにしてあり、
前記負極の先端部と、前記正極における前記負極の先端部に対面する部分との少なくとも一方に、リチウムイオン非透過性の絶縁体が介在していることを特徴とする非水二次電池。 A positive electrode in which a coating film containing a positive electrode active material is arranged on both sides of the positive electrode current collector, a negative electrode in which a coating film containing a negative electrode active material is arranged on both sides of the negative electrode current collector, and lithium ions are transmitted. A possible separator,
A non-aqueous secondary battery containing an electrode winding body in which the positive electrode and the negative electrode are wound through the separator,
The tip of the negative electrode in the winding direction is set back from the tip of the coating film of the positive electrode facing it in the winding direction so that the negative electrode does not face the exposed positive electrode current collector,
A non-aqueous secondary battery, wherein a lithium ion impermeable insulator is interposed between at least one of a tip portion of the negative electrode and a portion of the positive electrode facing the tip portion of the negative electrode. 前記絶縁体が、塗料で形成されている請求項１記載の非水二次電池。   The non-aqueous secondary battery according to claim 1, wherein the insulator is made of a paint. 前記絶縁体が、テープである請求項１記載の非水二次電池。   The non-aqueous secondary battery according to claim 1, wherein the insulator is a tape. 正極活物質を含有する塗膜が正極集電体の裏表両面に配された正極と、負極活物質を含有する塗膜が負極集電体の裏表両面に配された負極と、セパレータとを有しており、
前記正極と前記負極とが前記セパレータを介して巻回された電極巻回体を収容した非水二次電池であって、
前記負極の巻回方向の先端が、それに対面する前記正極の塗膜の先端よりも巻回方向に後退して、前記負極が露出状態の前記正極集電体に対面しないようにしてあり、
前記セパレータには、その全体にわたってリチウムイオンが透過可能な微孔を分散状に設けてあり、
前記セパレータにおいて、前記負極の先端部に対面する部分の前記微孔を塞いで絶縁体とすることで、その部分ではリチウムイオンが透過しないようにしたことを特徴とする非水二次電池。 A positive electrode in which a coating film containing a positive electrode active material is disposed on both sides of the positive electrode current collector, a negative electrode in which a coating film containing a negative electrode active material is disposed on both sides of the negative electrode current collector, and a separator. And
A non-aqueous secondary battery containing an electrode winding body in which the positive electrode and the negative electrode are wound through the separator,
The tip of the negative electrode in the winding direction is set back from the tip of the coating film of the positive electrode facing it in the winding direction so that the negative electrode does not face the exposed positive electrode current collector,
The separator is provided with fine pores that are permeable to lithium ions throughout the separator,
The non-aqueous secondary battery according to claim 1, wherein in the separator, the micropores in a portion facing the tip portion of the negative electrode are closed to form an insulator so that lithium ions do not pass therethrough.
JP2004101208A 2004-03-30 2004-03-30 Non-aqueous secondary battery Expired - Fee Related JP4382557B2 (en)

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