JP2009224070A - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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JP2009224070A
JP2009224070A JP2008064778A JP2008064778A JP2009224070A JP 2009224070 A JP2009224070 A JP 2009224070A JP 2008064778 A JP2008064778 A JP 2008064778A JP 2008064778 A JP2008064778 A JP 2008064778A JP 2009224070 A JP2009224070 A JP 2009224070A
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cathode
width
secondary battery
anode
current collecting
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JP5334429B2 (en
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Katsunori Suzuki
克典 鈴木
Takayuki Mitani
貴之 三谷
Hiroshi Morikawa
拓是 森川
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Vehicle Energy Japan Inc
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Hitachi Vehicle 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
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium secondary battery for securing battery performance through restraint of damage of collecting lead. <P>SOLUTION: The lithium-ion secondary battery includes an electrode group wound around an axis core through a separator so that a cathode plate 18 and an anode plate shall not come in contact with each other. Cathode and anode active matter mixtures are nearly uniformly coated on either face of a metal foil of cathode and anode collectors. Non-coated parts of the cathode and the anode active material mixtures are formed at one end part side in a length direction of the metal foil. The non-coated parts are notched like comb teeth, each rest part after notching forming cathode tabs 2 as well as anode tabs. A lead-out tip end of each cathode and anode tab is jointed to each cathode and anode collecting ring. Each cathode and anode tab includes a cathode tab thin part 2a and an anode tab thin part, each at one site between a lead-out base end and a tip end. Each thin part takes on the same gentle arc shape at either side edge. Each cathode and anode tab is bent with the thin part as a base point. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明はリチウム二次電池に係り、特に、正極活物質としてリチウム含有遷移金属酸化物、負極活物質としてリチウムイオンを吸蔵、放出可能な材料をそれぞれ金属箔に塗着した正負極板が捲回された電極群を備え、金属箔から直接導出され所定幅を有する複数の集電リードが集電部材に接合されたリチウム二次電池に関する。   The present invention relates to a lithium secondary battery, and in particular, a positive and negative electrode plate in which a lithium-containing transition metal oxide as a positive electrode active material and a material capable of inserting and extracting lithium ions as a negative electrode active material are coated on a metal foil. The present invention relates to a lithium secondary battery including a plurality of current collecting leads, each of which has a predetermined width and is directly derived from a metal foil and joined to a current collecting member.

非水電解液二次電池は、高エネルギ密度を有するため、様々な用途に用いられている。近年では、大型非水電解液二次電池も開発されており、例えば、動力源にモータを使用する電気自動車用やモータと内燃機関とを併用するハイブリッド電気自動車用の電源としても用いられている。このような用途においては、電池に高入出力特性が求められており、この要求に適応した電池としてリチウム二次電池が注目されている。   Non-aqueous electrolyte secondary batteries have high energy density and are used in various applications. In recent years, large nonaqueous electrolyte secondary batteries have also been developed, and are used, for example, as power sources for electric vehicles that use a motor as a power source or for hybrid electric vehicles that use a motor and an internal combustion engine in combination. . In such applications, high input / output characteristics are required for batteries, and lithium secondary batteries are attracting attention as batteries that meet these requirements.

通常、リチウム二次電池では、以下のような捲回式の内部構造を有している。すなわち、金属箔に活物質をそれぞれ塗着した正負極板が帯状に形成され、正負極板がセパレータを介して直接接触しないように断面渦巻状に捲回された電極群が形成されている。正負極板の捲回時には、捲きズレを防止するため、テンションをかけながら捲回される。この電極群が電池容器に収容され、非水電解液注液後、電池容器が電池蓋で封口されている。   Usually, a lithium secondary battery has the following wound internal structure. That is, a positive and negative electrode plate in which an active material is coated on a metal foil is formed in a strip shape, and an electrode group wound in a spiral cross section is formed so that the positive and negative electrode plates are not in direct contact via the separator. When the positive and negative electrode plates are wound, they are wound while applying tension to prevent twisting. This electrode group is accommodated in the battery container, and after pouring the non-aqueous electrolyte, the battery container is sealed with a battery lid.

電気自動車用電源等の高入出力特性を要求されるリチウム二次電池では、内部抵抗を低減するために、正負極板の金属箔からそれぞれ多数の集電リードが直接導出されている。集電リードとしては、電池の高出力化を図るため、例えば、正負極集電体である金属箔の一部に活物質を塗着せずに残しておき、矩形状に加工することで直接集電リードが導出される。導出された集電リードの端部は、電極群の両側にそれぞれ配置された円盤状の集電部材の周縁に接合されている。このとき、集電リードと集電部材とを確実に接合するために、例えば、円盤状の集電部材の外周面と金属製リングの内周面とで集電リードの端部を挟んで溶接する技術も開示されている（特許文献１参照）。   In a lithium secondary battery requiring high input / output characteristics such as a power source for an electric vehicle, a large number of current collecting leads are directly derived from the metal foil of the positive and negative electrode plates in order to reduce internal resistance. In order to increase the output of the battery, for example, the current collecting lead may be directly collected by processing it into a rectangular shape by leaving an active material uncoated on part of the metal foil that is a positive and negative current collector. Electrical leads are derived. The end portions of the derived current collecting leads are joined to the peripheral edges of the disk-shaped current collecting members disposed on both sides of the electrode group. At this time, in order to reliably join the current collecting lead and the current collecting member, for example, the end of the current collecting lead is welded between the outer peripheral surface of the disk-shaped current collecting member and the inner peripheral surface of the metal ring. The technique to do is also disclosed (refer patent document 1).

特開２００１−１１８５６１号公報JP 2001-118561 A

しかしながら、捲回式のリチウム二次電池では、電池使用中の振動、温度変化や充放電の繰返しに伴う活物質の膨張収縮等が生じるため、捲回時にかけられたテンションにより電極群の外周部で不安定な捲き戻りが起こる。一方、集電リードが接合された集電部材が電極群より小さい直径を有していることが一般的なため、電極群の外周側の集電リードは電極群の内側に引っ張られることとなる。電極群の捲き戻りが起こると集電リードに過大な張力がかかり、集電リードが破損（切断）しやすくなるため、内部抵抗の上昇を引き起こし出力等の電池性能の低下を招きやすくなる。また、破損した集電リードがセパレータを圧迫、貫通して正負極板間の短絡を起こすこともある。   However, in a wound lithium secondary battery, vibration during use of the battery, temperature change, and expansion / contraction of the active material due to repeated charge / discharge, etc., occur. Therefore, the outer periphery of the electrode group is caused by tension applied during winding. An unstable whispering occurs. On the other hand, since the current collecting member to which the current collecting lead is joined generally has a smaller diameter than the electrode group, the current collecting lead on the outer peripheral side of the electrode group is pulled inside the electrode group. . When the electrode group is rolled back, excessive tension is applied to the current collecting lead, and the current collecting lead is likely to be broken (cut), so that the internal resistance is increased and the battery performance such as output is easily lowered. In addition, a damaged current collecting lead may press and penetrate the separator to cause a short circuit between the positive and negative electrode plates.

本発明は上記事案に鑑み、集電リードの破損を抑制し電池性能を確保することができるリチウム二次電池を提供することを課題とする。   In view of the above-described case, an object of the present invention is to provide a lithium secondary battery that can prevent damage to a current collecting lead and ensure battery performance.

上記課題を解決するために、本発明は、正極活物質としてリチウム含有遷移金属酸化物、負極活物質としてリチウムイオンを吸蔵、放出可能な材料をそれぞれ金属箔に塗着した正負極板が捲回された電極群を備え、前記金属箔から直接導出され所定幅を有する複数の集電リードが集電部材に接合されたリチウム二次電池において、前記集電リードは、一部に幅細部を有しており、該幅細部を基点として屈曲していることを特徴とする。   In order to solve the above-described problems, the present invention provides a positive and negative electrode plate in which a lithium-containing transition metal oxide as a positive electrode active material and a material capable of inserting and extracting lithium ions as a negative electrode active material are coated on a metal foil. In a lithium secondary battery comprising a plurality of current collecting leads and a plurality of current collecting leads that are directly derived from the metal foil and have a predetermined width are joined to a current collecting member, the current collecting leads partially have a width detail. It is characterized in that it is bent with the width detail as a base point.

本発明では、集電リードが一部に幅細部を有しているので、その幅細部を基点として屈曲させることで、電極群の捲き戻りが生じても集電リードにかかる張力が緩和されることから、集電リードの破損を抑制し電池性能を確保することができる。   In the present invention, since the current collecting lead has a width detail in a part, the tension applied to the current collecting lead is alleviated even if the electrode group is rolled back by bending the width detail as a base point. For this reason, it is possible to prevent the current collecting lead from being damaged and to secure the battery performance.

この場合において、幅細部を金属箔からの導出基部と集電部材に接合された端部との間に形成することができる。また、幅細部は、側縁が緩やかな弧状を呈しており、集電リードの最大幅に対して０．７倍以上の幅を有することが好ましい。   In this case, a width detail can be formed between the base derived from the metal foil and the end joined to the current collecting member. Further, it is preferable that the width detail has a gentle arc shape at the side edge, and has a width of 0.7 times or more with respect to the maximum width of the current collecting lead.

本発明によれば、集電リードが一部に幅細部を有しており、その幅細部を基点として屈曲しているので、集電リードの破損を抑制し電池性能を確保することができる、という効果を得ることができる。   According to the present invention, the current collecting lead has a width detail in a part, and since it is bent with the width detail as a base point, it is possible to suppress the current collecting lead and ensure the battery performance. The effect that can be obtained.

以下、図面を参照して、本発明を適用した密閉円筒型リチウムイオン二次電池の実施の形態について説明する。   Hereinafter, embodiments of a sealed cylindrical lithium ion secondary battery to which the present invention is applied will be described with reference to the drawings.

（構成）
図１に示すように、本実施形態の密閉円筒型リチウムイオン二次電池２０は、帯状の正負極板が直接接触しないようにポリエチレン製微多孔薄膜のセパレータを介して中空状でガラス含有樹脂製の軸芯１の周りに断面渦巻状に捲回された電極群６を備えている。電極群６は、有底円筒状の電池缶７に収容されている。 (Constitution)
As shown in FIG. 1, the sealed cylindrical lithium ion secondary battery 20 of the present embodiment is hollow and made of a glass-containing resin through a polyethylene microporous thin film separator so that the strip-like positive and negative electrode plates are not in direct contact with each other. The electrode group 6 wound around the shaft core 1 in a spiral shape is provided. The electrode group 6 is housed in a bottomed cylindrical battery can 7.

電極群６の上側には、軸芯１のほぼ延長線上に正極板から電位を集電するための正極集電リング（集電部材）４が配置されている。正極集電リング４は、軸芯１の上端部に固定されている。正極集電リング４の周囲から一体に張り出している鍔部周縁には、正極板から導出された正極タブ（集電リード）２の端部が超音波溶接で接合されている。正極集電リング４の上方には、正極外部端子となる円盤状の上蓋１４が配置されている。   On the upper side of the electrode group 6, a positive electrode current collecting ring (current collecting member) 4 for collecting a potential from the positive electrode plate is disposed on a substantially extension line of the shaft core 1. The positive electrode current collecting ring 4 is fixed to the upper end portion of the shaft core 1. The edge part of the positive electrode tab (current collection lead) 2 led out from the positive electrode plate is joined by ultrasonic welding to the peripheral edge of the collar part integrally protruding from the periphery of the positive electrode current collecting ring 4. A disc-shaped upper lid 14 serving as a positive electrode external terminal is disposed above the positive electrode current collecting ring 4.

上蓋１４は、鉄製でニッケルメッキが施された円盤状の上蓋キャップを有している。上蓋キャップの中央部には上方に向けて突出した円筒状の突起が形成されており、突起の上面には電池内部で発生したガスを排出するための開口部１５が形成されている。上蓋キャップの周縁部はダイヤフラム１２の周縁部でかしめられている。ダイヤフラム１２は、アルミニウム合金製で下方（電極群６側）に突出した反転部を有する皿状に形成されている。ダイヤフラム１２の反転部は正極集電リング４に形成された開口内に収容されている。皿状の底部は平面状でありダイヤフラム１２の中央部を形成している。ダイヤフラム１２の中央部と周縁部との間には、薄肉化されており電池内圧が上昇したときに開裂する開裂溝が形成されている。   The upper lid 14 has a disk-shaped upper lid cap made of iron and nickel-plated. A cylindrical protrusion protruding upward is formed at the center of the upper lid cap, and an opening 15 for discharging gas generated inside the battery is formed on the upper surface of the protrusion. The peripheral edge portion of the upper lid cap is caulked by the peripheral edge portion of the diaphragm 12. The diaphragm 12 is made of an aluminum alloy and is formed in a dish shape having a reversing portion protruding downward (on the electrode group 6 side). The inversion part of the diaphragm 12 is accommodated in an opening formed in the positive electrode current collecting ring 4. The dish-shaped bottom is flat and forms the center of the diaphragm 12. Between the central part and the peripheral part of the diaphragm 12, a thinning groove is formed that is cleaved when the battery internal pressure rises.

正極集電リング４の中央部上面には、接続板９が摩擦攪拌溶接で接合されている。正極集電リング４の鍔部上面には、円環状で絶縁性のポリプロピレン製ブッシュ１７が配置されている。接続板９の上面には、ダイヤフラム１２の中央部底面が摩擦攪拌溶接で接合されている。この接合により、ブッシュ１７は、正極集電リング４とダイヤフラム１２とで挟持される。ダイヤフラム１２と接続板９との接合強度は、リチウムイオン二次電池２０の内圧が上昇したときにダイヤフラム１２が作動（反転部が上蓋キャップ側に反転）するように、摩擦攪拌溶接で調整されている。   A connection plate 9 is joined to the upper surface of the central portion of the positive electrode current collecting ring 4 by friction stir welding. An annular and insulating polypropylene bush 17 is disposed on the upper surface of the collar portion of the positive electrode current collecting ring 4. The bottom surface of the central portion of the diaphragm 12 is joined to the upper surface of the connection plate 9 by friction stir welding. By this joining, the bush 17 is sandwiched between the positive electrode current collecting ring 4 and the diaphragm 12. The bonding strength between the diaphragm 12 and the connection plate 9 is adjusted by friction stir welding so that the diaphragm 12 operates (the reversing part is reversed to the upper lid cap side) when the internal pressure of the lithium ion secondary battery 20 is increased. Yes.

上蓋１４の周縁部は、絶縁性及び耐熱性のＥＰＤＭ樹脂製ガスケット１０を介して電池缶７にかしめられており、リチウムイオン二次電池２０が密閉されている。また、電池缶７内には、図示を省略した非水電解液が注液されている。非水電解液には、エチレンカーボネートとジメチルカーボネートとの体積比１：１の混合溶媒中にリチウム塩として６フッ化リン酸リチウム（ＬｉＰＦ６）を１モル／リットル溶解したものが用いられている。 The peripheral edge of the upper lid 14 is caulked to the battery can 7 via an insulating and heat-resistant EPDM resin gasket 10, and the lithium ion secondary battery 20 is sealed. In addition, a non-aqueous electrolyte solution (not shown) is injected into the battery can 7. As the non-aqueous electrolyte, a solution obtained by dissolving 1 mol / liter of lithium hexafluorophosphate (LiPF 6 ) as a lithium salt in a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 1 is used. .

一方、電極群６の下側には負極板から電位を集電するための負極集電リング（集電部材）５が配置されている。負極集電リング５の内周面には軸芯１の下端部外周面が固定されている。負極集電リング５の外周縁には、負極板から導出された負極タブ（集電リード）３の端部が超音波溶接で接合されている。負極集電リング５の下部には電気的導通のための銅製の負極リード板８が固定されており、負極リード板８は、正極集電リング４と軸芯１との中央部分に電極棒を挿入することで、電池缶７の内底面に抵抗溶接で接合されており、電池缶７と負極板とが電気的に接続されている。   On the other hand, a negative electrode current collecting ring (current collecting member) 5 for collecting a potential from the negative electrode plate is disposed below the electrode group 6. The outer peripheral surface of the lower end portion of the shaft core 1 is fixed to the inner peripheral surface of the negative electrode current collecting ring 5. At the outer peripheral edge of the negative electrode current collecting ring 5, the end of the negative electrode tab (current collecting lead) 3 led out from the negative electrode plate is joined by ultrasonic welding. A copper negative electrode lead plate 8 for electrical continuity is fixed to the lower part of the negative electrode current collecting ring 5, and the negative electrode lead plate 8 has an electrode bar at the central portion between the positive electrode current collecting ring 4 and the shaft core 1. By inserting, the battery can 7 is joined to the inner bottom surface by resistance welding, and the battery can 7 and the negative electrode plate are electrically connected.

図２に示すように、電極群６を構成する正極板１８は、正極集電体となる厚さ２０μｍのアルミニウム箔（金属箔）１９を有している。アルミニウム箔１９の両面には、正極活物質合剤が略均一に塗着されている。正極活物質合剤には、正極活物質としてのマンガン酸リチウム等のリチウムマンガン複合酸化物（ＬｉＭｎＯ２、ＬｉＭｎ２Ｏ４）の粉末、導電材の炭素材料、結着剤のポリフッ化ビニリデン（以下、ＰＶＤＦと略記する。）が配合されている。これらを粘度調整溶媒のｎ−メチルピロリドン（以下、ＮＭＰと略記する。）に混合して、略均一となるようにコーネルデスパで分散、混練されてペーストが作製される。このペーストがアルミニウム箔１９に塗布され、乾燥後に厚さ９０μｍになるようにプレスされて正極板１８が形成される。なお、アルミニウム箔１９の長手方向一側の端部には、幅３０ｍｍの正極活物質合剤の未塗着部が形成されている。 As shown in FIG. 2, the positive electrode plate 18 constituting the electrode group 6 has an aluminum foil (metal foil) 19 having a thickness of 20 μm serving as a positive electrode current collector. The positive electrode active material mixture is applied to both surfaces of the aluminum foil 19 substantially uniformly. The positive electrode active material mixture includes a powder of lithium manganese composite oxide (LiMnO 2 , LiMn 2 O 4 ) such as lithium manganate as a positive electrode active material, a carbon material for a conductive material, and polyvinylidene fluoride as a binder (hereinafter referred to as a positive electrode active material mixture). , Abbreviated as PVDF). These are mixed with a viscosity adjusting solvent, n-methylpyrrolidone (hereinafter abbreviated as NMP), and dispersed and kneaded by Cornell Despa so as to be substantially uniform, thereby producing a paste. This paste is applied to the aluminum foil 19 and pressed to a thickness of 90 μm after drying to form the positive electrode plate 18. In addition, the uncoated part of the positive electrode active material mixture of width 30mm is formed in the edge part of the longitudinal direction one side of the aluminum foil 19. FIG.

正極活物質合剤の未塗着部は櫛状（矩形状）に切り欠かれており、切り欠き残部で正極タブ２が形成されている。換言すれば、正極タブ（切り欠き残部）２は、アルミニウム箔１９の長手方向と交差する方向に導出されている。また、各正極タブ２は、導出基部と端部との間の１箇所に幅細部２ａを有している。幅細部２ａは、両側縁がほぼ同じ緩やかな弧状を呈している。また、幅細部２ａは、正極タブ２の幅Ｗに対する最小幅Ｗａの比Ｗａ／Ｗが０．７以上（最小幅Ｗａが幅Ｗの０．７倍以上）に設定されている。すなわち、幅細部２ａは、幅細部２ａ以外の部分と比べて幅細に形成されている。なお、本例では、正極タブ２の幅Ｗは５ｍｍに設定されており、隣り合う正極タブ２の間隔が５０ｍｍ、正極タブ２の導出基部から端部までの長さは２５ｍｍに設定されている。   The uncoated portion of the positive electrode active material mixture is cut out in a comb shape (rectangular shape), and the positive electrode tab 2 is formed in the remaining portion of the cutout. In other words, the positive electrode tab (notch remaining portion) 2 is led out in a direction intersecting with the longitudinal direction of the aluminum foil 19. Moreover, each positive electrode tab 2 has the width | variety detail 2a in one place between the derivation | leading-out base and an edge part. The width detail 2a has a gentle arc shape with substantially the same side edges. In the width detail 2a, the ratio Wa / W of the minimum width Wa to the width W of the positive electrode tab 2 is set to 0.7 or more (the minimum width Wa is 0.7 times or more of the width W). That is, the width detail 2a is formed narrower than the portion other than the width detail 2a. In this example, the width W of the positive electrode tab 2 is set to 5 mm, the interval between the adjacent positive electrode tabs 2 is set to 50 mm, and the length from the leading base to the end of the positive electrode tab 2 is set to 25 mm. .

一方、負極板は、負極集電体となる厚さ１０μｍの圧延銅箔（金属箔）を有している。圧延銅箔の両面には、負極活物質合剤が略均一に塗着されている。負極活物質合剤には、負極活物質としての黒鉛、結着剤のＰＶＤＦが配合されている。これらを粘度調整溶媒のＮＭＰに混合して、略均一となるようにコーネルデスパで分散、混練されてペーストが作製される。このペーストが圧延銅箔に塗布され、乾燥後に厚さ７０μｍになるようにプレスされて負極板が形成される。圧延銅箔の長手方向端部には、正極板１８と同様に幅細部を有した負極タブ３が形成される。   On the other hand, the negative electrode plate has a rolled copper foil (metal foil) having a thickness of 10 μm serving as a negative electrode current collector. The negative electrode active material mixture is applied substantially uniformly on both surfaces of the rolled copper foil. In the negative electrode active material mixture, graphite as a negative electrode active material and PVDF as a binder are blended. These are mixed with NMP which is a viscosity adjusting solvent, and dispersed and kneaded by Cornell Despa so as to be substantially uniform, thereby producing a paste. This paste is applied to a rolled copper foil and pressed to a thickness of 70 μm after drying to form a negative electrode plate. Similarly to the positive electrode plate 18, the negative electrode tab 3 having a width detail is formed at the end in the longitudinal direction of the rolled copper foil.

（電池組み立て）
リチウムイオン二次電池２０は、以下の手順で組み立てられる。すなわち、正極タブ２および負極タブ３を電極群６の互いに反対側の両端面に位置するように配置して、捲きズレを防止するためにテンションを掛けながら捲回して電極群６を作製する。正極集電リング４、負極集電リング５に正負極タブをそれぞれ幅細部で屈曲させて接合した後、電極群６を電池缶７に収容する。負極リード板８を電池缶７の内底面に抵抗溶接で接合した後、正極集電リング４の中央部上面に接続板９を摩擦攪拌溶接で接合する。電池缶７の電極群６より上側に上蓋１４を載せるための段付け部を形成する段付け加工を施し、非水電解液を注液した後、段付け部に上蓋１４を載せ、電池缶７と上蓋１４とをガスケット１０を介してかしめる。その後、上蓋キャップに形成された開口部１５から溶接用の回転ツール（溶接治具）を差込み、ダイヤフラム１２の上面に回転ツールを圧接しながら回転させることでダイヤフラム１２と接続板９とを摩擦攪拌溶接で接合し、リチウムイオン二次電池２０の組み立てを完成させる。 (Battery assembly)
The lithium ion secondary battery 20 is assembled in the following procedure. That is, the positive electrode tab 2 and the negative electrode tab 3 are disposed so as to be positioned on opposite end surfaces of the electrode group 6 and wound while applying tension to prevent the electrode group 6 from being produced. After the positive and negative electrode tabs are bent and joined to the positive electrode current collecting ring 4 and the negative electrode current collecting ring 5 with width details, the electrode group 6 is accommodated in the battery can 7. After the negative electrode lead plate 8 is joined to the inner bottom surface of the battery can 7 by resistance welding, the connection plate 9 is joined to the upper surface of the central portion of the positive electrode current collecting ring 4 by friction stir welding. A stepping process for forming a stepped portion for placing the upper lid 14 on the upper side of the electrode group 6 of the battery can 7 is performed, and after pouring a non-aqueous electrolyte, the upper lid 14 is placed on the stepped portion, and the battery can 7 And the upper lid 14 are caulked through the gasket 10. Thereafter, a rotating tool (welding jig) for welding is inserted from the opening 15 formed in the upper lid cap, and the diaphragm 12 and the connecting plate 9 are frictionally stirred by rotating while rotating the rotating tool against the upper surface of the diaphragm 12. It joins by welding and the assembly of the lithium ion secondary battery 20 is completed.

（作用等）
次に、本実施形態のリチウムイオン二次電池２０の作用等について、幅細部２ａの作用を中心に説明する。なお、幅細部は、正負極タブ両方に形成されているが、いずれも同様の作用を示すため、以下、正極側の幅細部２ａのみについて説明する。 (Action etc.)
Next, the operation and the like of the lithium ion secondary battery 20 of the present embodiment will be described focusing on the operation of the width detail 2a. Although the width details are formed on both the positive and negative electrode tabs, since both exhibit the same function, only the width detail 2a on the positive electrode side will be described below.

図３に示すように、集電リードに幅細部を持たない従来の捲回式リチウムイオン二次電池では、電池使用中の振動、温度変化や充放電の繰返しに伴う活物質の膨張収縮等が生じると、捲回時にかけられたテンションにより電極群の外周部で不安定な捲き戻りが起こる。この捲き戻りは、電極群の捲回方向に沿って生じるため、電極群の外周側ほど捲き戻り量が大きくなる。このため、電極群の外周側の集電リードに過大な張力がかかり、破損ないし切断することがある。また、集電リードを集電部材に接合するときに、集電リードに張力がかかり、破損ないし切断することもある。集電リードが破損ないし切断した場合、内部抵抗の上昇を引き起こし出力等の電池性能の低下を招きやすくなる。また、破損した集電リードがセパレータを圧迫、貫通して正負極板間の短絡を起こすこともある。本実施形態は、これらの問題を解決することができるリチウムイオン二次電池である。   As shown in FIG. 3, in a conventional wound type lithium ion secondary battery in which the current collecting lead does not have detail, vibration during use of the battery, temperature change, expansion / contraction of the active material due to repeated charge / discharge, etc. When this occurs, an unstable roll-back occurs at the outer periphery of the electrode group due to the tension applied during winding. Since this whirling occurs along the winding direction of the electrode group, the whirling amount increases toward the outer peripheral side of the electrode group. For this reason, excessive tension is applied to the current collecting leads on the outer peripheral side of the electrode group, which may be broken or cut. Further, when the current collecting lead is joined to the current collecting member, tension is applied to the current collecting lead, which may cause breakage or cutting. When the current collecting lead is damaged or cut, the internal resistance is increased, and the battery performance such as output is easily lowered. In addition, a damaged current collecting lead may press and penetrate the separator to cause a short circuit between the positive and negative electrode plates. The present embodiment is a lithium ion secondary battery that can solve these problems.

本実施形態では、正極タブ２が幅細部２ａを有しており、正極タブ２は幅細部２ａを基点として屈曲している。すなわち、正極タブ２に余裕があるので、電極群作製時や電池使用時に正極タブ２にかかる張力が緩和されることから、正極タブ２の破損を抑制することができる。   In the present embodiment, the positive electrode tab 2 has a width detail 2a, and the positive electrode tab 2 is bent with the width detail 2a as a base point. That is, since there is room in the positive electrode tab 2, the tension applied to the positive electrode tab 2 is relaxed when the electrode group is manufactured or the battery is used, so that the damage of the positive electrode tab 2 can be suppressed.

また、幅細部で幅が急激に変化している（三角状や矩形状に形成した）場合や幅細部の幅が細すぎる場合には、幅細部が却って破損しやすくなり、また、正極タブの通電抵抗も高くなる。本実施形態では、幅細部２ａは、両側縁がほぼ同じ緩やかな弧状を呈しており、幅Ｗａが正極タブ２の幅Ｗの０．７倍以上に形成されている。このため、幅細部２ａを破損させることなく正極タブ２の抵抗増大が抑制されるので、電池性能を確保することができる。   Also, if the width changes abruptly in the width details (formed in a triangular or rectangular shape) or if the width of the width details is too thin, the width details tend to break, and the positive tab The energization resistance is also increased. In the present embodiment, the width detail 2 a has a gentle arc shape on both side edges, and the width Wa is 0.7 times or more the width W of the positive electrode tab 2. For this reason, since the increase in resistance of the positive electrode tab 2 is suppressed without damaging the width detail 2a, battery performance can be ensured.

なお、本実施形態では、全ての正極タブ２、負極タブ３が幅細部を有している例を示したが、本発明はこれに制限されるものではない。例えば、電極群６の外周側ほど捲き戻りが大きくなるため、外周側の集電リードのみが幅細部を有していてもよいが、電極群作製時の破損を考慮すれば、全ての集電リードが幅細部を有していることが好ましい。また、本実施形態では、各集電リードが幅細部を１箇所有している例を示したが、本発明はこれに限定されるものではなく、１つの集電リードが複数の幅細部を有していてもよい。   In this embodiment, an example in which all the positive electrode tabs 2 and the negative electrode tabs 3 have width details is shown, but the present invention is not limited to this. For example, as the outer peripheral side of the electrode group 6 becomes larger, only the current collecting lead on the outer peripheral side may have a width detail. However, considering the damage at the time of manufacturing the electrode group, Preferably, the lead has a width detail. In this embodiment, an example in which each current collecting lead has one width detail is shown, but the present invention is not limited to this, and one current collecting lead has a plurality of width details. You may have.

また、幅細部の形成される位置は、金属箔からの導出基部と集電部材に接合された端部との間であれば制限されるものではない。導出基部（電極群６）側の方が端部側と比べて、破損（切断）しやすいことを考慮すれば、集電リードの中央部より基部側の近傍であることが好ましい。   Moreover, the position where the width detail is formed is not limited as long as it is between the lead-out base from the metal foil and the end joined to the current collecting member. Considering that the lead-out base (electrode group 6) side is more likely to be broken (cut) than the end side, it is preferable that the lead-out base (electrode group 6) is closer to the base side than the central portion of the current collecting lead.

更に、本実施形態では、アルミニウム箔１９の正極活物質合剤の未塗着部および圧延銅箔の負極活物質合剤の未塗着部をそれぞれ櫛状に切り欠くことにより正極タブ２および負極タブ３を導出する例を示したが、本発明はこれに制限されるものではなく、例えば、三角状等としてもよい。また、正極タブ２、負極タブ３の幅や間隔等にも制限のないことはもちろんである。更に、正極タブ２，負極タブ３のいずれか一方のみが幅細部を有するようにしてもよいが、電極群６の捲き戻りを考えれば、正極タブ２、負極タブ３の両方に幅細部を有するようにすることが好ましい。   Furthermore, in this embodiment, the positive electrode tab 2 and the negative electrode are formed by cutting out the uncoated portion of the positive electrode active material mixture of the aluminum foil 19 and the uncoated portion of the negative electrode active material mixture of the rolled copper foil, respectively. Although an example of deriving the tab 3 has been shown, the present invention is not limited to this, and may be triangular, for example. Needless to say, there are no restrictions on the width and interval of the positive electrode tab 2 and the negative electrode tab 3. Furthermore, only one of the positive electrode tab 2 and the negative electrode tab 3 may have a width detail, but considering the rebound of the electrode group 6, both the positive electrode tab 2 and the negative electrode tab 3 have a width detail. It is preferable to do so.

また更に、本実施形態では、正極活物質にリチウムマンガン複合酸化物を例示したが、本発明はこれらに限定されるものではなく、リチウム含有遷移金属酸化物であればよい。本実施形態以外で使用することができる正極活物質としては、例えば、化学式ＬｉＭｎ１−ｘＭｘＯ２、ＬｉＭｎ２−ｘＭｘＯ４（Ｍは、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ等から選ばれる１種以上の遷移金属）で表されるリチウムマンガン遷移金属複合酸化物を挙げることができる。また、結晶構造についても特に制限はなく、スピネル型、層状型、オリビン型のいずれの結晶構造を有していてもよい。また、本実施形態では、負極活物質に黒鉛を例示したが、本発明はこれに限定されるものではなく、リチウム二次電池に使われるものであればよい。本実施形態以外で使用することができる負極活物質としては、例えば、非晶質炭素等の炭素材や金属リチウムを使用することができる。また、非水電解液、導電材および結着剤等についても特に制限はなく、通常、リチウム二次電池に使用される材料を用いてもよいことはもちろんである。 Furthermore, in the present embodiment, the lithium manganese composite oxide is exemplified as the positive electrode active material, but the present invention is not limited thereto, and any lithium-containing transition metal oxide may be used. Examples of the positive electrode active material that can be used other than the present embodiment include, for example, chemical formula LiMn 1-x MxO 2 , LiMn 2−x MxO 4 (M is one or more selected from Mn, Fe, Co, Ni, etc.) Lithium transition metal composite oxide represented by (transition metal). The crystal structure is not particularly limited, and may have any crystal structure of spinel type, layered type, and olivine type. In the present embodiment, graphite is exemplified as the negative electrode active material. However, the present invention is not limited to this, and any material may be used as long as it is used for a lithium secondary battery. As a negative electrode active material that can be used in other than the present embodiment, for example, a carbon material such as amorphous carbon or metallic lithium can be used. Moreover, there is no restriction | limiting in particular also about a non-aqueous electrolyte, a electrically conductive material, a binder, etc. Of course, you may use the material normally used for a lithium secondary battery.

更にまた、本実施形態では、円筒型のリチウムイオン二次電池２０を例示したが、本発明は電池形状に制限されるものではなく、正負極板が捲回されたリチウム二次電池に適用することができる。円筒型以外の電池形状として、例えば、角型等の多角形状の電池に適用することもできる。また、電池容量、サイズ等についても特に制限されるものではない。
更に、本発明が適用可能な電池構造としては、本実施形態の有底円筒状容器（缶）に電池上蓋がかしめられた構造以外に、例えば、正負極外部端子がそれぞれ電池蓋を貫通し電池容器内で軸芯を介して押し合っている構造を挙げることができる。 Furthermore, in the present embodiment, the cylindrical lithium ion secondary battery 20 is illustrated, but the present invention is not limited to the battery shape, and is applied to a lithium secondary battery in which the positive and negative electrode plates are wound. be able to. As a battery shape other than the cylindrical shape, for example, it can be applied to a polygonal battery such as a square shape. Also, the battery capacity, size, etc. are not particularly limited.
Furthermore, as a battery structure to which the present invention can be applied, in addition to the structure of the bottomed cylindrical container (can) of the present embodiment in which the battery upper lid is caulked, for example, positive and negative external terminals penetrate the battery lid, respectively. An example of the structure is that they are pressed together through an axis in the container.

次に、本実施形態に従い作製したリチウムイオン二次電池２０の実施例について説明する。なお、比較のために作製した比較例についても併記する。   Next, examples of the lithium ion secondary battery 20 manufactured according to the present embodiment will be described. A comparative example prepared for comparison is also shown.

（実施例１）
実施例１では、集電リードの幅Ｗを５ｍｍ、幅細部２ａの最小幅Ｗａを４ｍｍ、すなわち、比Ｗａ／Ｗを０．８に設定してリチウムイオン二次電池２０を作製した。なお、電池容量は６Ａｈに設定した。 Example 1
In Example 1, the lithium ion secondary battery 20 was manufactured by setting the width W of the current collecting lead to 5 mm, the minimum width Wa of the width detail 2a to 4 mm, that is, the ratio Wa / W to 0.8. The battery capacity was set to 6 Ah.

（実施例２）
実施例２では、幅細部２ａの最小幅Ｗａを３．５ｍｍ、すなわち、比Ｗａ／Ｗを０．７に設定する以外は実施例１と同様にしてリチウムイオン二次電池２０を作製した。 (Example 2)
In Example 2, a lithium ion secondary battery 20 was produced in the same manner as in Example 1 except that the minimum width Wa of the width detail 2a was set to 3.5 mm, that is, the ratio Wa / W was set to 0.7.

（比較例１）
比較例１では、集電リードに幅細部を形成しないこと以外は実施例１と同様にしてリチウムイオン二次電池を作製した。（図３参照） (Comparative Example 1)
In Comparative Example 1, a lithium ion secondary battery was produced in the same manner as in Example 1 except that the width detail was not formed on the current collecting lead. (See Figure 3)

（比較例２）
比較例２では、集電リードの幅Ｗを３ｍｍにする以外は比較例１と同様にしてリチウムイオン二次電池を作製した。 (Comparative Example 2)
In Comparative Example 2, a lithium ion secondary battery was fabricated in the same manner as in Comparative Example 1 except that the current collecting lead width W was 3 mm.

（試験評価）
各実施例及び比較例のリチウムイオン二次電池について、それぞれ４０個作製したときの集電リードの切断本数を測定し、平均値を算出した。その結果を下表１に示す。 (Test evaluation)
About the lithium ion secondary battery of each Example and the comparative example, the cutting number of the current collection lead when 40 each was produced was measured, and the average value was computed. The results are shown in Table 1 below.

また、各実施例及び比較例のリチウムイオン二次電池それぞれの集電リード４０本について、５０Ａ通電時の電圧変化から直流抵抗値を測定した。直流抵抗値の最小、最大および平均値を下表１にあわせて示す。   Further, for 40 current collecting leads of each of the lithium ion secondary batteries of each Example and Comparative Example, the DC resistance value was measured from the voltage change at the time of 50 A energization. The minimum, maximum and average DC resistance values are shown in Table 1 below.

Figure 2009224070
Figure 2009224070

表１に示すように、比較例１、２のリチウムイオン二次電池は、集電リードの切断が多くみられた。また、集電リードに幅細部を形成させずに集電リードの幅全体を狭くした比較例２のリチウムイオン二次電池では、作製時の集電リードの切断を抑制することができないばかりか、幅を狭くした分で却って切断本数が増加した。これに対して、実施例１、２のリチウムイオン二次電池２０では、集電リードの切断がほとんど見られなかった。ここのことから、幅細部を形成したことにより、破損が抑制されていることが判った。更に、実施例１、２のリチウムイオン二次電池２０では、直流抵抗値の平均値も比較例１、２のリチウムイオン二次電池に比べて低いことから、高出力を得られることが判明した。一方、図4に示すように、リード切れの本数が少ない電池ほど、直流抵抗が低く、またその分布も小さいことが判った。そして、実施例１、２のリチウムイオン二次電池２０では、直流抵抗値の分布（表１における最大値と最小値との差）が比較例１、２のリチウムイオン二次電池に比べて小さいことから、電池性能が維持されることが判った。従って、集電リードに幅細部を形成したことにより、集電リードの破損を抑制し電池性能を確保できることが明らかとなった。   As shown in Table 1, in the lithium ion secondary batteries of Comparative Examples 1 and 2, many current collector leads were cut. Further, in the lithium ion secondary battery of Comparative Example 2 in which the entire width of the current collecting lead is reduced without forming the width detail in the current collecting lead, not only the cutting of the current collecting lead at the time of production can be suppressed, The number of cuts increased with the narrower width. On the other hand, in the lithium ion secondary batteries 20 of Examples 1 and 2, the current collector leads were hardly cut. From this, it was found that the damage was suppressed by forming the width details. Furthermore, in the lithium ion secondary battery 20 of Examples 1 and 2, since the average value of the DC resistance value was lower than that of the lithium ion secondary batteries of Comparative Examples 1 and 2, it was found that high output could be obtained. . On the other hand, as shown in FIG. 4, it was found that the battery with fewer lead breaks has lower DC resistance and a smaller distribution. In the lithium ion secondary batteries 20 of Examples 1 and 2, the DC resistance distribution (difference between the maximum value and the minimum value in Table 1) is smaller than that of the lithium ion secondary batteries of Comparative Examples 1 and 2. From this, it was found that the battery performance was maintained. Therefore, it has been clarified that the formation of the width detail in the current collecting lead can prevent the current collecting lead from being damaged and ensure the battery performance.

また、表１に示すように、比Ｗａ／Ｗを０．８に設定した実施例１では、比Ｗａ／Ｗを０．７に設定した実施例２より集電リードの切断本数が少なく、直流抵抗値の平均値も小さくなっていることが判った。従って、比Ｗａ／Ｗは０．７以上でも大きめに設定することが集電リードの破損や電池性能の確保には有効であることが判った。   Further, as shown in Table 1, in Example 1 in which the ratio Wa / W was set to 0.8, the number of cuts of the current collecting leads was smaller than in Example 2 in which the ratio Wa / W was set to 0.7, and the direct current It was found that the average value of the resistance value was also small. Therefore, it has been found that setting the ratio Wa / W to be larger even if 0.7 or more is effective in securing the current collecting lead and ensuring the battery performance.

本発明は集電リードの破損を抑制し電池性能を確保することができるリチウム二次電池を提供するため、リチウム二次電池の製造、販売に寄与するので、産業上の利用可能性を有する。   Since the present invention provides a lithium secondary battery capable of suppressing the damage of the current collecting lead and ensuring the battery performance, it contributes to the manufacture and sale of the lithium secondary battery, and thus has industrial applicability.

本発明を適用した実施形態の密閉円筒型リチウムイオン二次電池の断面図である。It is sectional drawing of the airtight cylindrical lithium ion secondary battery of embodiment to which this invention is applied. 実施形態のリチウムイオン二次電池を構成する正極板を模式的に示す平面図である。It is a top view which shows typically the positive electrode plate which comprises the lithium ion secondary battery of embodiment. 従来のリチウムイオン二次電池を構成する正極板を模式的に示す平面図である。It is a top view which shows typically the positive electrode plate which comprises the conventional lithium ion secondary battery. 実施例および比較例のリチウムイオン二次電池における直流抵抗値の測定結果を示すグラフである。It is a graph which shows the measurement result of the direct current | flow resistance value in the lithium ion secondary battery of an Example and a comparative example.

符号の説明Explanation of symbols

２ 正極タブ（集電リード）
２ａ 幅細部
３ 負極タブ（集電リード）
４ 正極集電リング（集電部材）
５ 負極集電リング（集電部材）
６ 電極群
１８ 正極板
１９ アルミニウム箔（金属箔）
２０ 密閉円筒型リチウムイオン二次電池（リチウム二次電池） 2 Positive electrode tab (current collecting lead)
2a Detail of width 3 Negative electrode tab (current collecting lead)
4 Positive current collector ring (current collector)
5 Negative current collector ring (current collector)
6 Electrode group 18 Positive electrode plate 19 Aluminum foil (metal foil)
20 Sealed cylindrical lithium ion secondary battery (lithium secondary battery)

Claims (3)

正極活物質としてリチウム含有遷移金属酸化物、負極活物質としてリチウムイオンを吸蔵、放出可能な材料をそれぞれ金属箔に塗着した正負極板が捲回された電極群を備え、前記金属箔から直接導出され所定幅を有する複数の集電リードが集電部材に接合されたリチウム二次電池において、前記集電リードは、一部に幅細部を有しており、該幅細部を基点として屈曲していることを特徴とするリチウム二次電池。   It comprises an electrode group in which positive and negative electrode plates each coated on a metal foil with a lithium-containing transition metal oxide as a positive electrode active material and a lithium ion storage and release material as a negative electrode active material are wound on the metal foil. In a lithium secondary battery in which a plurality of current-collecting leads led out and having a predetermined width are joined to a current-collecting member, the current-collecting lead has a width detail in a part thereof, and is bent with the width detail as a base point. A lithium secondary battery characterized by comprising: 前記幅細部は、前記金属箔からの導出基部と前記集電部材に接合された端部との間に形成されていることを特徴とする請求項１に記載のリチウム二次電池。   The lithium secondary battery according to claim 1, wherein the width detail is formed between a base portion derived from the metal foil and an end portion joined to the current collecting member. 前記幅細部は、側縁が緩やかな弧状を呈しており、前記集電リードの最大幅に対して０．７倍以上の幅を有することを特徴とする請求項１または請求項２に記載のリチウム二次電池。   3. The width detail according to claim 1, wherein a side edge of the width detail has a gentle arc shape and has a width of 0.7 times or more with respect to a maximum width of the current collecting lead. Lithium secondary battery.
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