【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解質電池、
特に負極集電性の改良に関する。The present invention relates to a non-aqueous electrolyte battery,
In particular, it relates to the improvement of the negative electrode current collecting property.
【０００２】[0002]
【従来の技術】今日、負極活物質にリチウム等のアルカ
リ金属を用い、プロピレンカーボネート，γ−ブチロラ
クトン，ジメトキシエタン，テトラヒドロフラン，ジオ
キソラン等の有機溶媒に、ＬｉＣｌＯ4，ＬｉＢＦ4，Ｌ
ｉＡｓＦ6，ＬｉＰＦ6，ＬｉＣＦ3ＳＯ3等の溶質を溶解
させた電解液と組み合わせた非水電解質電池は、高エネ
ルギー密度を有することから、電子時計，カメラをはじ
めとする小型電子機器に広く用いられている。2. Description of the Related Art At present, an alkali metal such as lithium is used as a negative electrode active material, and LiClO4 , LiBF4 , L
Non-aqueous electrolyte batteries combined with electrolytes in which solutes such as iAsF6 , LiPF6 , and LiCF3 SO3 are dissolved have a high energy density and are widely used in electronic devices such as electronic watches and cameras. Have been.
【０００３】この種の電池を充電すると、負極表面上に
樹枝状，フィブリル状，針状形態のアルカリ金属、いわ
ゆるデンドライトが析出する。これは、アルカリ金属負
極上に不動態皮膜が存在し、この皮膜の化学的組成や構
造が局所的に異なり、結果として電極全体で不均一な反
応が進行するためである。When a battery of this type is charged, dendrites, dendrites, fibrils, and needles of alkali metal, so-called dendrites, precipitate on the surface of the negative electrode. This is because a passivation film exists on the alkali metal negative electrode, and the chemical composition and structure of the film are locally different, and as a result, a non-uniform reaction proceeds throughout the electrode.
【０００４】このようなデンドライトが生成し、さらに
は成長することにより、負極と正極の間の内部短絡とい
う問題がが生じる。また、次の放電過程では、デンドラ
イトが局所的に溶解して寸断され、充電中に析出させた
すべてのアルカリ金属を溶解させることができなくな
り、結果として充放電効率が著しく低下するといった問
題もある。[0004] The generation and further growth of such dendrite causes a problem of an internal short circuit between the negative electrode and the positive electrode. Further, in the next discharging process, there is a problem that the dendrite is locally melted and cut, so that all the alkali metals deposited during charging cannot be dissolved, and as a result, the charging and discharging efficiency is significantly reduced. .
【０００５】アルカリ金属を活物質とする負極上でのデ
ンドライトを抑制するためには、負極表面上での不動態
皮膜の均一性を向上させればよい。例えば、アルカリ金
属に圧着する集電体として金属箔を用いれば、アルカリ
金属表面の凹凸性は減少し、均一な厚みの皮膜ができる
ことになる。しかし、通常の金属箔を用いると、金属箔
自体に存在する酸化皮膜によって、リチウム等のアルカ
リ金属との接着強度が低下し、析出溶解過程での不均一
な電流分布が起き、デンドライトが形成しやすくなる。In order to suppress dendrite on a negative electrode using an alkali metal as an active material, it is necessary to improve the uniformity of a passive film on the surface of the negative electrode. For example, when a metal foil is used as a current collector to be pressed against an alkali metal, the unevenness of the surface of the alkali metal is reduced, and a film having a uniform thickness can be formed. However, when a normal metal foil is used, the oxide film present on the metal foil itself reduces the adhesive strength with an alkali metal such as lithium, causing a non-uniform current distribution during the deposition and dissolution process, and the formation of dendrites. It will be easier.
【０００６】このような金属箔とアルカリ金属活物質と
の接着性を高める手段として、貫通孔を有する金属箔を
集電体として用い、その両面にアルカリ金属活物質を圧
延し、さらに、250 ℃で２時間真空下で加熱（融解）処
理することによって、貫通孔を通してアルカリ金属を互
いに一体化させる構造の電極が提案されている（特開平
５−２９０８５３）。As means for improving the adhesion between such a metal foil and an alkali metal active material, a metal foil having a through hole is used as a current collector, and the alkali metal active material is rolled on both surfaces thereof. There has been proposed an electrode having a structure in which alkali metals are integrated with each other through a through-hole by heating (melting) treatment under vacuum for 2 hours (Japanese Patent Laid-Open No. 5-290853).
【０００７】[0007]
【発明が解決しようとする課題】しかし、上記のような
方法で、貫通孔を有する金属箔とアルカリ金属を一体化
させても、大きい電流密度での充電過程では、負極上で
のデンドライト形成を抑制することは困難であった。こ
れは、以下の理由による。すなわち、アルカリ金属を加
熱すると、たとえ真空下ではあっても、アルカリ金属の
激しい反応活性のために、アルカリ金属表面での不動態
皮膜は雰囲気中の不純物ガスによって、ますますその厚
みを増す。集電体に用いる金属箔自体にも酸化皮膜が存
在するので、見かけ上、アルカリ金属と貫通孔を有する
金属箔が一体化されても、電気的な接触が十分ではな
い。However, even when a metal foil having a through hole and an alkali metal are integrated by the above-described method, the formation of dendrites on the negative electrode during charging at a large current density is not possible. It was difficult to control. This is for the following reason. That is, when the alkali metal is heated, the passivation film on the alkali metal surface becomes more and more thick due to the impurity gas in the atmosphere due to the intense reaction activity of the alkali metal, even under vacuum. Since the metal foil used for the current collector itself also has an oxide film, even if the alkali metal and the metal foil having the through-hole are integrated, electrical contact is not sufficient.
【０００８】本発明は、このような従来の課題を解決す
るものであり、充放電サイクルを繰り返しても電極反応
の均一性が保たれることによりデンドライトの成長が抑
制される負極を提供し、この負極を用いることによっ
て、充放電サイクル寿命の長い、信頼性の大きい非水電
解質二次電池を提供することを目的とする。The present invention is to solve such a conventional problem, and provides a negative electrode in which the growth of dendrite is suppressed by maintaining the uniformity of the electrode reaction even after repeated charge / discharge cycles. By using this negative electrode, an object is to provide a highly reliable nonaqueous electrolyte secondary battery having a long charge / discharge cycle life.
【０００９】[0009]
【課題を解決するための手段】本発明では、貫通孔を有
する金属箔を、機械的に、アルカリ金属活物質に食い込
ませるとともに、負極活物質を金属箔の開孔部に圧入す
る。さらに、貫通孔を有する金属箔のアルカリ金属が配
置されている側とは反対側に、金属箔や金属板を設置す
る。In the present invention, a metal foil having a through hole is mechanically bitten into an alkali metal active material, and a negative electrode active material is press-fitted into an opening of the metal foil. Further, a metal foil or a metal plate is provided on the side of the metal foil having the through holes opposite to the side on which the alkali metal is disposed.
【００１０】即ち、本発明は、正極と、アルカリイオン
伝導性電解質と、アルカリ金属を活物質とする負極と、
複数個の貫通孔を有する金属箔よりなる前記負極用集電
体とを構成要素とし、前記金属箔を前記アルカリ金属に
食い込ませ、かつ前記アルカリ金属を前記金属箔の貫通
孔開孔部に圧入したことを特徴とする非水電解質電池で
ある。That is, the present invention provides a positive electrode, an alkali ion conductive electrolyte, and a negative electrode using an alkali metal as an active material.
The negative electrode current collector made of a metal foil having a plurality of through-holes as constituent elements, the metal foil being cut into the alkali metal, and the alkali metal being pressed into a through-hole opening of the metal foil. A non-aqueous electrolyte battery characterized by the following.
【００１１】この時、金属箔の貫通孔の直径が、０．０
５ｍｍ以上でかつ１ｍｍ以下であることが有効である。At this time, the diameter of the through hole of the metal foil is 0.0
It is effective that it is 5 mm or more and 1 mm or less.
【００１２】また、貫通孔を有する金属箔の開孔率が、
１０％以上でかつ９０％以下であることが有効である。Further, the opening ratio of the metal foil having a through hole is as follows:
It is effective that it is 10% or more and 90% or less.
【００１３】また、貫通孔を有する金属箔の厚みが、２
μm 以上で５０μm 以下であることが有効である。Further, the thickness of the metal foil having the through hole is 2
It is effective that it is not less than μm and not more than 50 μm.
【００１４】更に、金属箔上の貫通孔の配列は、千鳥格
子状であることが有効である。また、貫通孔を有する金
属箔が、パンチング箔であることが有効である。Further, it is effective that the arrangement of the through holes on the metal foil is a staggered lattice. Further, it is effective that the metal foil having the through holes is a punching foil.
【００１５】また、貫通孔を有する金属箔の一方の面に
アルカリ金属活物質を正極が対向するように配置し、他
の面に、アルカリ金属箔または板，アルカリ金属以外の
金属箔または板のいずれかを配置することが効果的であ
る。Further, an alkali metal active material is disposed on one side of a metal foil having a through hole so that the positive electrode faces the other side, and an alkali metal foil or plate, or a metal foil or plate other than the alkali metal is disposed on the other surface. Arranging any of them is effective.
【００１６】また、本発明の製造方法は、アルカリ金属
活物質に貫通孔を有する金属箔を配置する工程が、平板
型加圧治具または回転ローラーを用いて前記アルカリ金
属活物質と貫通孔を有する金属箔を加圧する工程と、前
記加圧工程により圧着した一体化物を平板型加圧治具ま
たは回転ローラーに対して回転する工程と、前記回転工
程を経た前記一体化物を再度加圧治具により加圧する工
程とを有することを特徴とする。In the production method of the present invention, the step of arranging a metal foil having a through hole in the alkali metal active material includes the step of connecting the through hole with the alkali metal active material by using a flat pressing jig or a rotating roller. Pressurizing the metal foil having the pressing process, rotating the integrated product pressed by the pressing process with respect to a flat-plate-type pressing jig or a rotating roller, and pressing the integrated product after the rotating process again into a pressing jig. And pressurizing by a pressure.
【００１７】[0017]
【発明の実施の形態】アルカリ金属表面には不動態皮膜
があり、この皮膜を物理的に破って金属集電体をアルカ
リ金属内にめり込ませることで、初めて、良好な集電性
が確保される。特に、金属箔表面での孔の外周の切り立
ったエッジ部分をアルカリ金属内にめり込ませること
で、不動態皮膜を破壊することができる。BEST MODE FOR CARRYING OUT THE INVENTION A passivation film is provided on the surface of an alkali metal, and good current collecting properties can be obtained only by physically breaking the film and dipping the metal current collector into the alkali metal. Secured. In particular, the passivation film can be broken by indenting the steep edge portion of the outer periphery of the hole on the surface of the metal foil into the alkali metal.
【００１８】金属箔中の孔の径としては、0.05mm以上が
好ましく、これ以下では、アルカリ金属の孔内への圧入
が困難になるためである。The diameter of the hole in the metal foil is preferably 0.05 mm or more. If the diameter is less than 0.05 mm, it becomes difficult to press the alkali metal into the hole.
【００１９】また、貫通孔を有する金属箔の開孔率とし
ては、10％以上、90％以下であることが望ましく、開孔
率を増加させることによって、孔のエッジの総延長の長
さを大きくすることができる。The opening ratio of the metal foil having the through holes is preferably 10% or more and 90% or less. By increasing the opening ratio, the total length of the edge of the hole can be reduced. Can be bigger.
【００２０】さらに、貫通孔を有する金属箔の厚みで
は、２μm 以上、50μm 以下であることが望ましく、極
端に薄い場合にはアルカリ金属の表面皮膜を破壊するこ
とができず、また、厚い場合には、孔内に深く圧入され
たアルカリ金属の利用率が低下する。Further, the thickness of the metal foil having a through hole is desirably not less than 2 μm and not more than 50 μm. If it is extremely thin, the surface film of the alkali metal cannot be destroyed. In the method, the utilization rate of the alkali metal deeply pressed into the hole is reduced.
【００２１】金属箔上での孔の配列を千鳥格子（即ち、
隣り合う行と列では、孔を互い違いの位置に配置する）
にすると、集電性がさらに良好になる。これは、金属箔
上で孔の数を最密に増加することによって、孔のエッジ
の総延長の長さを大きくすることができるからである。The arrangement of the holes on the metal foil is a staggered grid (ie,
In adjacent rows and columns, stagger holes
In this case, the current collecting property is further improved. This is because the closest extension of the number of holes on the metal foil can increase the total length of the edges of the holes.
【００２２】また、貫通孔を有する金属箔としては、パ
ンチング箔が望ましい。電解メッキ法によって貫通孔を
作製する場合、メッキ浴によって、孔のエッジ部分が酸
化され、集電性が低下するためである。Further, as the metal foil having a through hole, a punching foil is desirable. This is because, when the through-hole is formed by the electrolytic plating method, the edge portion of the hole is oxidized by the plating bath, and the current collecting property is reduced.
【００２３】貫通孔を有する金属箔では、集電は孔のエ
ッジ部分および箔部分で起きるので、孔内に圧入された
アルカリ金属活物質の利用率が低くなることを避けるた
め、貫通孔部分にも金属箔または板を設置することで、
貫通孔部分の集電性が向上し、より均一な電極反応が促
進される。In a metal foil having a through hole, current collection occurs at the edge portion and the foil portion of the hole. Therefore, in order to avoid a reduction in the utilization rate of the alkali metal active material pressed into the hole, the current is collected at the through hole portion. By installing metal foil or plate,
The current collecting property of the through-hole portion is improved, and a more uniform electrode reaction is promoted.
【００２４】以上のような集電性の向上により、アルカ
リ金属を活物質とする電極上でのデンドライトの形成が
抑制される。By the improvement of the current collecting property as described above, the formation of dendrites on the electrode using an alkali metal as an active material is suppressed.
【００２５】以下、本発明の実施の形態を具体的実施例
により説明する。実施例では、電池の組み立てをすべて
アルゴンガス雰囲気下において行った。また、アルカリ
金属としてリチウムを用いたが、他のアルカリ金属やア
ルカリ金属を主成分とする合金、例えば、リチウム−ア
ルミニウム合金を使用しても同様の効果を得ることがで
きた。Hereinafter, embodiments of the present invention will be described with reference to specific examples. In the examples, all the batteries were assembled in an argon gas atmosphere. In addition, although lithium was used as the alkali metal, similar effects could be obtained by using another alkali metal or an alloy mainly containing an alkali metal, for example, a lithium-aluminum alloy.
【００２６】[0026]
【実施例】（実施例１）貫通孔を有する金属箔として、
図１に示した銅パンチング箔を用いた。この銅パンチン
グ箔を直径１９ｍｍの円形に切り取り、その上に、厚さ
１００μｍ，直径１６．８ｍｍのリチウム金属箔を、平
滑性のあるクランプ治具で１回圧着した。このリチウム
金属箔を圧着した銅パンチング箔を負極として、図２に
示した扁平型電池を組み立てた。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を１：１の体積比
で混合した溶媒に、ＬｉＣｌＯ4を１モル／リットルの
割合で溶解したものを用いた。(Example 1) As a metal foil having a through hole,
The copper punched foil shown in FIG. 1 was used. This copper punched foil was cut into a circular shape having a diameter of 19 mm, and a lithium metal foil having a thickness of 100 μm and a diameter of 16.8 mm was pressed once thereon with a smooth jig. The flat battery shown in FIG. 2 was assembled using the copper punched foil obtained by pressing the lithium metal foil as a negative electrode. As the electrolytic solution, a solution obtained by dissolving LiClO4 at a ratio of 1 mol / liter in a solvent in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 1: 1 was used.
【００２７】正極１は、ＬｉＭｎ2Ｏ4粉末、カーボンブ
ラック，および、四弗化ポリエチレン樹脂粉末を混合
し、チタンのエキスパンドメタルからなる集電体２をス
ポット溶接した正極缶３に加圧成型した。セパレータ４
には、ポリプロピレン製多孔質膜を用いた。次に、上記
で作製した負極をリチウム金属箔５が正極側に対向する
ように封口板６に置き、銅パンチング箔７の部分を封口
板にスポット溶接した。そして、貫通孔上にあるリチウ
ム金属箔が直接封口板に接着するように、負極を平面性
のある治具で押さえた。電池の組み立ては、セパレータ
と負極を配置した封口板を転地した後、上記の電解液を
１５０μｌ注入し、次に、ガスケット８を介して正極缶
をかぶせ、正極缶の周縁部を封口板にかしめる手順で行
った。The positive electrode 1 was prepared by mixing LiMn2 O4 powder, carbon black, and polyethylene tetrafluoride resin powder, and press-forming into a positive electrode can 3 in which a current collector 2 made of expanded metal of titanium was spot-welded. . Separator 4
, A polypropylene porous membrane was used. Next, the negative electrode produced above was placed on the sealing plate 6 so that the lithium metal foil 5 was opposed to the positive electrode side, and the portion of the copper punched foil 7 was spot-welded to the sealing plate. Then, the negative electrode was pressed with a flat jig so that the lithium metal foil on the through hole was directly bonded to the sealing plate. To assemble the battery, after the sealing plate on which the separator and the negative electrode are arranged is transferred, 150 μl of the above-described electrolyte is injected, and then the positive electrode can is covered with the gasket 8, and the periphery of the positive electrode can is covered with the sealing plate. The procedure was as follows.
【００２８】（比較例１）厚さ５０μｍ，直径１６.８
ｍｍ のリチウム金属箔を２枚用意し、実施例１と同じ
直径１９ｍｍの円形に切り取った銅パンチング箔の両側
に、リチウム金属箔を圧着した。次に、この一体化物を
250 ℃で２時間、真空下で熱処理した。このように作製
したものを比較例の負極として、図３に示した扁平型電
池を実施例１と同様に組み立てた。(Comparative Example 1) thickness 50 μm, diameter 16.8
2 mm of lithium metal foil was prepared, and a lithium metal foil was pressure-bonded to both sides of a copper punched foil cut into a circle having a diameter of 19 mm as in Example 1. Next, this one
Heat treated under vacuum at 250 ° C. for 2 hours. The flat battery shown in FIG. 3 was assembled in the same manner as in Example 1 using the thus manufactured device as the negative electrode of the comparative example.
【００２９】以上のように作製した実施例１と比較例１
の電池を用いて、３mA/cm2の電流密度で１時間放電し
た。そして、各電池を分解し、負極を取り出し、負極表
面での溶解反応の進行の様子を光学顕微鏡で観察した。Example 1 and Comparative Example 1 produced as described above
Was discharged at a current density of 3 mA / cm2 for 1 hour. Each battery was disassembled, the negative electrode was taken out, and the progress of the dissolution reaction on the negative electrode surface was observed with an optical microscope.
【００３０】図４は、実施例１の負極表面を観察したも
の、図５は比較例１の負極表面を観察したものである。
これらを比較すると、実施例１および比較例１の負極と
も、表面には数多くの孔食が起きているが、実施例１の
負極では、各孔の直径が小さくまた数が多いのに対し、
比較例１の負極では、各孔の直径が大きくまた数もまば
らに存在していることを見出した。FIG. 4 is a view of the negative electrode surface of Example 1, and FIG. 5 is a view of the negative electrode surface of Comparative Example 1.
When these are compared, many pits occur on the surface of both the negative electrodes of Example 1 and Comparative Example 1. On the other hand, in the negative electrode of Example 1, the diameter of each hole is small and the number is large.
In the negative electrode of Comparative Example 1, it was found that the diameter of each hole was large and the number was sparse.
【００３１】すなわち、実施例１の負極では、より均一
な電極反応が進行していることがわかる。これは、実施
例１の電池では銅パンチング箔の貫通孔のエッジ部分が
鋭くリチウム金属箔に食い込むことにより、集電性が良
好になっていると考えられ、また、封口板自体も銅箔の
貫通孔を通じて集電体の役割を果たしているからと考え
られる。That is, it can be seen that a more uniform electrode reaction proceeds in the negative electrode of Example 1. This is considered to be due to the fact that the edge portion of the through hole of the copper punched foil sharply penetrates the lithium metal foil in the battery of Example 1, thereby improving the current collecting property. It is considered that it plays a role of a current collector through the through hole.
【００３２】次に、実施例１と比較例１の電池を用い
て、種々の電流密度で２.０Ｖ まで放電を行った。図６
は、このときの各電池の放電容量をプロットしたもので
ある。図６より、本発明の電池では、高電流密度での放
電特性に優れることがわかる。これは、図４および５か
らも明らかなように、本発明の負極を用いると、電極全
体にわたってリチウム金属の溶解が可能となり、反応抵
抗が著しく減少するからである。Next, the batteries of Example 1 and Comparative Example 1 were discharged to 2.0 V at various current densities. FIG.
Is a plot of the discharge capacity of each battery at this time. FIG. 6 shows that the battery of the present invention has excellent discharge characteristics at a high current density. This is because, as is clear from FIGS. 4 and 5, when the negative electrode of the present invention is used, lithium metal can be dissolved over the entire electrode, and the reaction resistance is significantly reduced.
【００３３】（実施例２）幅３０ｍｍ，長さ６０ｍｍの
銅パンチング箔を用意し、貫通孔ができる限り見えなく
なるように、二つ折りにした。この二つ折りの状態で銅
パンチング箔を直径１９ｍｍの円形に打ち抜いた。そし
て比較例１と同様に、厚さ５０μｍ，直径１６.８ｍｍ
のリチウム金属箔を２枚用意し、２枚重なった銅パンチ
ング箔の両側に、リチウム金属箔を圧着した。このよう
に作製した負極を用いて、比較例１と同様にして扁平型
電池を組み立てた。(Example 2) A copper punched foil having a width of 30 mm and a length of 60 mm was prepared and folded in two so that the through-holes were as invisible as possible. In this folded state, the copper punched foil was punched into a circle having a diameter of 19 mm. Then, as in Comparative Example 1, the thickness was 50 μm and the diameter was 16.8 mm.
Were prepared, and the lithium metal foil was pressure-bonded to both sides of the copper punching foil which was overlapped with the two pieces. Using the negative electrode thus manufactured, a flat battery was assembled in the same manner as in Comparative Example 1.
【００３４】以上のように作製した実施例２の電池に対
し、３mA/cm2の電流密度で１時間放電後、電池を分解
し、負極を取り出して、負極表面での溶解反応の進行の
様子を観察した。その結果、反応の進行の様子は、実施
例１と同様に均一な溶解が起きていることが認められ
た。After discharging for 1 hour at a current density of 3 mA / cm2 with respect to the battery of Example 2 fabricated as described above, the battery was disassembled, the negative electrode was taken out, and the progress of the dissolution reaction on the negative electrode surface was observed. Was observed. As a result, the progress of the reaction was confirmed to be uniform, as in Example 1.
【００３５】（実施例３）図１で示した、銅パンチング
箔を直径１９ｍｍの円形に切り取り、その上に、厚さ１
００μｍ，直径１６.８ｍｍ のリチウム金属箔を置き、
平滑性のあるクランプ治具で圧着した。次に、リチウム
金属箔が圧着した銅パンチング箔を１８０度回転させ、
再び同じ治具（回転はしていない）を用いて、リチウム
金属箔が銅パンチング箔に密着するよう圧着した。この
ときのリチウム金属箔の表面状態は、下地の銅パンチン
グ箔の貫通孔の位置を反映して、全面に均一な模様（お
そらく、わずかな表面皮膜の違いによる干渉が原因）が
浮かび上がった。そして、このようにして作製した負極
を用いて、実施例１と同様な扁平型の非水電解質電池を
組み立てた。Example 3 The copper punched foil shown in FIG. 1 was cut into a circular shape having a diameter of 19 mm, and a thickness of 1 mm was formed thereon.
Place a lithium metal foil of 00 μm and diameter of 16.8 mm,
It was crimped with a smooth clamping jig. Next, rotate the copper punching foil on which the lithium metal foil was pressed by 180 degrees,
Again, using the same jig (not rotated), the lithium metal foil was pressure-bonded to the copper punching foil. At this time, the surface state of the lithium metal foil reflected a position of the through hole of the underlying copper punching foil, and a uniform pattern (probably due to interference due to a slight difference in the surface film) appeared on the entire surface. Then, a flat nonaqueous electrolyte battery similar to that of Example 1 was assembled using the negative electrode thus manufactured.
【００３６】以上のように作製した実施例３の電池を用
いて、１mA/cm2の電流密度で、２．０〜３.５Ｖの電圧
範囲で充放電を繰り返した。また、実施例１で組み立て
た電池を用いて、充放電を行った。なお、実施例１での
負極の表面状態は、１回だけの圧着であるので、下地の
銅パンチング箔の模様を均一に反映しておらず、一部分
は強く圧着されたために金属光沢，他の部分はやや白み
がかった光沢であった。図７は、以上のようにして作製
した電池での、各サイクルの放電容量をプロットしたも
のである。図７より、リチウム金属箔を均一に銅パンチ
ング箔に圧着することで、よりサイクル寿命の長い電池
が得られることがわかる。Using the battery of Example 3 fabricated as described above, charging and discharging were repeated at a current density of 1 mA / cm2 and a voltage range of 2.0 to 3.5 V. Charge and discharge were performed using the battery assembled in Example 1. Since the surface condition of the negative electrode in Example 1 is a single pressure bonding, the pattern of the underlying copper punching foil is not uniformly reflected. The part had a slightly whitish luster. FIG. 7 is a plot of the discharge capacity of each cycle in the battery manufactured as described above. From FIG. 7, it can be seen that a battery having a longer cycle life can be obtained by uniformly pressing the lithium metal foil on the copper punching foil.
【００３７】（実施例４）本実施例では、リチウム金属
箔を銅パンチング箔に圧着する際に、実施例３で用いた
クランプ治具の代わりに、小型の双ローラー（ナイロン
樹脂製）を用いた。直径１９ｍｍの円形に切り取りとっ
た銅パンチング箔の上に、厚さ１００μｍ，直径１６.
８ｍｍのリチウム金属箔を置き、リチウム金属箔が著し
く楕円にならないように双ローラーを通した。続いて、
リチウム金属が圧着した銅パンチング箔の方向を変え
て、再び双ローラーに通し、リチウム金属箔と銅パンチ
ング箔の密着が均一になるように、この操作を繰り返
し、リチウム金属の表面に下地の模様が浮かび上がるよ
うにした。(Embodiment 4) In this embodiment, a small twin roller (made of nylon resin) is used in place of the clamp jig used in Embodiment 3 when pressing a lithium metal foil onto a copper punching foil. Was. On a copper punched foil cut into a circle having a diameter of 19 mm, a thickness of 100 μm and a diameter of 16.
An 8 mm lithium metal foil was placed and passed through a twin roller so that the lithium metal foil did not become significantly elliptical. continue,
Change the direction of the copper punching foil on which the lithium metal is pressed, pass it through the twin rollers again, and repeat this operation so that the adhesion between the lithium metal foil and the copper punching foil is uniform, and the pattern of the base on the surface of the lithium metal is I made it stand out.
【００３８】このようにして作製した負極を用いて、実
施例１および３と同様の扁平型電池を組み立て、１mA/c
m2の電流密度で、２．０〜３.５Ｖ の電圧範囲で充放電
を繰り返した。図８は、リチウム金属箔と銅パンチング
箔を双ローラーに通した回数に対して、電池のサイクル
寿命（容量が初期の半分になったサイクル数）をプロッ
トしたものである。図８より、双ローラーに通す回数が
多くなるほど、サイクル寿命は向上し、３回目でサイク
ル寿命の向上は、ほぼ最高に達することを見出した。Using the thus prepared negative electrode, a flat battery similar to that of Examples 1 and 3 was assembled.
Charge and discharge were repeated at a current density of m2 and a voltage range of 2.0 to 3.5 V. FIG. 8 is a plot of the cycle life of the battery (the number of cycles in which the capacity has been reduced to half of the initial capacity) versus the number of times the lithium metal foil and the copper punching foil have been passed through the twin rollers. From FIG. 8, it was found that the cycle life was improved as the number of times of passing through the twin rollers was increased, and that the improvement of the cycle life reached almost the maximum at the third time.
【００３９】（実施例５）銅パンチング箔での孔径を変
化させた以外は、実施例１と同様の金属箔を用い、扁平
型の電池を組み立てた。ここで、孔の配列は、図１に示
すような千鳥格子であり、開孔率は50％に固定した。表
１に、本実施例で用いたパンチング箔の詳細を示した。Example 5 A flat battery was assembled using the same metal foil as in Example 1 except that the hole diameter in the copper punched foil was changed. Here, the arrangement of the holes was a staggered lattice as shown in FIG. 1, and the opening ratio was fixed at 50%. Table 1 shows details of the punching foil used in this example.
【００４０】[0040]
【表１】[Table 1]
【００４１】（比較例２）貫通孔のない銅箔を用いた他
は、実施例５と同様に扁平型電池を組み立てた。このよ
うに作製した実施例５および比較例２の電池を用いて、
１mA/cm2の電流密度で、２．０〜３.５Ｖ の電圧範囲で
充放電を繰り返した。そして、放電容量が１サイクル目
の半分になったサイクル数をサイクル寿命とした。Comparative Example 2 A flat battery was assembled in the same manner as in Example 5 except that a copper foil having no through-hole was used. Using the batteries of Example 5 and Comparative Example 2 thus manufactured,
Charge / discharge was repeated at a current density of 1 mA / cm2 and a voltage range of 2.0 to 3.5 V. The number of cycles at which the discharge capacity became half of the first cycle was defined as the cycle life.
【００４２】表１に、各電池のサイクル寿命をまとめ
た。表１より、本発明の実施例である銅パンチング箔を
負極集電体に使用した場合には、いずれも、比較例２の
電池よりサイクル寿命に優れることがわかる。しかし、
孔径が1.0mm よりも大きい場合には、貫通孔のない箔の
場合と同等のサイクル寿命となり、また、孔径が0.05mm
よりも小さい場合にも、サイクル寿命の大きな伸びは見
られない。これは、孔径が大きすぎると、孔のエッジ部
分が少なくなり集電性が低下するためであり、また、孔
径が小さすぎると、リチウム金属が孔内へめりこまなく
なるためである。Table 1 summarizes the cycle life of each battery. Table 1 shows that when the copper punched foils of the examples of the present invention were used for the negative electrode current collector, all of them had better cycle life than the battery of Comparative Example 2. But,
When the hole diameter is larger than 1.0 mm, the cycle life is equivalent to that of a foil without through holes, and the hole diameter is 0.05 mm.
Even if it is smaller, no significant increase in cycle life is observed. This is because if the hole diameter is too large, the edge portion of the hole is reduced and the current collecting property is reduced, and if the hole diameter is too small, the lithium metal does not sink into the hole.
【００４３】（実施例６）銅パンチング箔での開孔率を
変化させた以外は、実施例１と同様の金属箔を用い、扁
平型の電池を組み立てた。ここで、孔の配列は、図１に
示すような千鳥格子であり、孔径は0.3mm に固定した。
表２に、本実施例で用いたパンチング箔の詳細を示し
た。(Example 6) A flat battery was assembled using the same metal foil as in Example 1 except that the porosity of the copper punched foil was changed. Here, the arrangement of the holes was a staggered lattice as shown in FIG. 1, and the hole diameter was fixed at 0.3 mm.
Table 2 shows details of the punching foil used in this example.
【００４４】[0044]
【表２】[Table 2]
【００４５】以上のように作製した実施例６の電池を用
いて、１mA/cm2の電流密度，２〜３.５Ｖの電圧範囲で
充放電を繰り返した。そして、放電容量が１サイクル目
の半分になったサイクル数をサイクル寿命とした。Using the battery of Example 6 fabricated as described above, charging and discharging were repeated at a current density of 1 mA / cm2 and a voltage range of2 to 3.5 V. The number of cycles at which the discharge capacity became half of the first cycle was defined as the cycle life.
【００４６】表２に、各電池のサイクル寿命をまとめ
た。表２より、本発明の実施例である銅パンチング箔を
負極集電体に使用した場合には、いずれも、比較例２の
電池よりサイクル寿命に優れることがわかる。ここで、
開孔率が90％になるとサイクル寿命が減少しているの
は、パンチング箔の強度が著しく低下し、リチウム金属
箔内にめりこませることが困難になったためと考えられ
る。また、開孔率が小さくなりすぎると寿命が短くなる
のは、貫通孔のエッジ部分の総延長の長さが短くなるた
めに集電性が低下するためと考えられる。Table 2 summarizes the cycle life of each battery. Table 2 shows that when the copper punched foils of the examples of the present invention were used for the negative electrode current collector, all of them had better cycle life than the battery of Comparative Example 2. here,
It is considered that the reason why the cycle life is reduced when the porosity is 90% is that the strength of the punching foil has been remarkably reduced and it has become difficult to dig into the lithium metal foil. Further, the reason why the life is shortened when the opening ratio becomes too small is considered to be that the current collecting property is reduced because the total length of the edge portion of the through hole is shortened.
【００４７】（実施例７）銅パンチング箔での厚みを変
化させた以外は、実施例１と同様の金属箔を用い、扁平
型の電池を組み立てた。ここで、孔の配列は、図１に示
すような千鳥格子であり、孔径は0.3mm ，開孔率は50％
に固定した。表３に、本実施例で用いたパンチング箔の
詳細を示した。Example 7 A flat battery was assembled using the same metal foil as in Example 1 except that the thickness of the copper punched foil was changed. Here, the arrangement of the holes is a staggered lattice as shown in FIG. 1, the hole diameter is 0.3 mm, and the opening ratio is 50%.
Fixed to. Table 3 shows details of the punching foil used in this example.
【００４８】[0048]
【表３】[Table 3]
【００４９】以上のように作製した実施例７の電池を用
いて、１mA/cm2の電流密度，２〜３.５Ｖの電圧範囲で
充放電を繰り返した。そして、放電容量が１サイクル目
の半分になったサイクル数をサイクル寿命とした。Using the battery of Example 7 manufactured as described above, charging and discharging were repeated at a current density of 1 mA / cm2 and a voltage range of2 to 3.5 V. The number of cycles at which the discharge capacity became half of the first cycle was defined as the cycle life.
【００５０】表３に、各電池のサイクル寿命をまとめ
た。表３より、銅パンチング箔を負極集電体に使用した
場合、サイクル寿命を伸ばすためには、箔の厚みに最適
な範囲があることがわかる。すなわち、箔の厚みが50μ
m より厚くなると、孔内へ深く圧入されたリチウム金属
箔が充放電反応に寄与しなくなり、逆に、厚みが２μm
より薄くなると、箔がリチウム金属箔へめりこまないた
めにリチウム金属の表面を破壊できなくなることが原因
と考えられる。Table 3 summarizes the cycle life of each battery. From Table 3, it can be seen that when using a copper punched foil for the negative electrode current collector, there is an optimum range for the foil thickness in order to extend the cycle life. That is, the thickness of the foil is 50μ
m, the lithium metal foil deeply pressed into the hole does not contribute to the charge / discharge reaction, and conversely, the thickness is 2 μm.
It is considered that when the thickness is smaller, the surface of the lithium metal cannot be destroyed because the foil does not sink into the lithium metal foil.
【００５１】（実施例８）銅パンチング箔での孔の配列
を変化させた以外は、実施例１と同様の金属箔を用い、
扁平型の電池を組み立てた。ここで、パンチング箔の孔
径は0.3mm ，孔間の平均距離は0.404mm に固定した。孔
の配列は、表４に示したような、パターンとした。Example 8 The same metal foil as in Example 1 was used except that the arrangement of holes in the copper punching foil was changed.
A flat battery was assembled. Here, the hole diameter of the punched foil was fixed at 0.3 mm, and the average distance between the holes was fixed at 0.404 mm. The arrangement of the holes was a pattern as shown in Table 4.
【００５２】以上のように作製した実施例８の電池を用
いて、１mA/cm2の電流密度，２〜３.５Ｖの電圧範囲で
充放電を繰り返した。そして、放電容量が１サイクル目
の半分になったサイクル数をサイクル寿命とした。Using the battery of Example 8 manufactured as described above, charging and discharging were repeated at a current density of 1 mA / cm2 and a voltage range of2 to 3.5 V. The number of cycles at which the discharge capacity became half of the first cycle was defined as the cycle life.
【００５３】[0053]
【表４】[Table 4]
【００５４】表４に、各電池のサイクル寿命をまとめ
た。表４より、銅パンチング箔中での貫通孔の配列が、
千鳥（正三角形）や変形千鳥（二等辺三角形）であるも
のを負極集電体に使用した場合、サイクル寿命が向上し
ていることがわかる。これは、配列を千鳥格子状にする
ことによって、孔の存在が最密になり、結果として箔の
開孔率や孔のエッジ部分の総延長の長さが大きくなった
ためである。Table 4 summarizes the cycle life of each battery. From Table 4, the arrangement of through holes in the copper punching foil is
It can be seen that the cycle life is improved when a staggered (regular triangle) or modified staggered (isosceles triangle) is used for the negative electrode current collector. This is because, by forming the arrangement in a staggered lattice pattern, the existence of the holes becomes densest, and as a result, the opening ratio of the foil and the total length of the edge portion of the holes are increased.
【００５５】[0055]
【発明の効果】以上のように、本発明によると、貫通孔
を有する金属箔とアルカリ金属活物質を互いに密着させ
ることによって、電極全体にわたって均一な電池反応が
起きる負極を得ることができる。したがって、充放電サ
イクルを繰り返してもデンドライトの生成が抑制され、
アルカリ金属活物質の電気化学的な失活が緩やかになる
ので、充放電サイクル寿命の長い、信頼性の大きい非水
電解質電池を得ることができる。As described above, according to the present invention, by bringing a metal foil having a through hole and an alkali metal active material into close contact with each other, it is possible to obtain a negative electrode in which a uniform battery reaction occurs over the entire electrode. Therefore, even if the charge and discharge cycle is repeated, generation of dendrite is suppressed,
Since the electrochemical deactivation of the alkali metal active material is moderated, a highly reliable nonaqueous electrolyte battery having a long charge / discharge cycle life can be obtained.
【図１】本発明の第１の実施例と第１の比較例で用いた
金属パンチング箔の拡大模式図FIG. 1 is an enlarged schematic view of a metal punching foil used in a first embodiment of the present invention and a first comparative example.
【図２】本発明の第１の実施例である偏平型電池の縦横
断面を示した図FIG. 2 is a diagram showing a vertical and horizontal cross section of a flat battery according to a first embodiment of the present invention.
【図３】本発明の第１の比較例である偏平型電池の縦横
断面を示した図FIG. 3 is a view showing a vertical and horizontal cross section of a flat battery according to a first comparative example of the present invention.
【図４】本発明の第１の実施例である負極の溶解後の表
面形態を示した図FIG. 4 is a view showing the surface morphology after dissolution of the negative electrode according to the first embodiment of the present invention.
【図５】本発明の第１の比較例である負極の溶解後の表
面形態を示した図FIG. 5 is a view showing a surface morphology after dissolution of a negative electrode according to a first comparative example of the present invention.
【図６】本発明の第１の実施例と第１の比較例である電
池の放電電流密度に対する放電容量をプロットした図FIG. 6 is a diagram plotting the discharge capacity versus the discharge current density of the batteries according to the first embodiment of the present invention and the first comparative example.
【図７】本発明の第３の実施例である電池の放電容量の
サイクル特性を示した図FIG. 7 is a diagram showing cycle characteristics of a discharge capacity of a battery according to a third embodiment of the present invention.
【図８】本発明の第４の実施例である電池の負極を作製
する際に双ローラーに通した回数とそれを用いた電池で
の放電容量をプロットした図FIG. 8 is a diagram plotting the number of passes through a twin roller and the discharge capacity of a battery using the same when producing a negative electrode of a battery according to a fourth embodiment of the present invention.
１，１′ 正極 ２，２′ 正極集電体 ３，３′ 正極缶 ４，４′ セパレータ ５，５′ リチウム金属箔 ６，６′ 封口板 ７，７′ 負極集電体 ８，８′ ガスケット 1,1 'positive electrode 2,2' positive electrode current collector 3,3 'positive electrode can 4,4' separator 5,5 'lithium metal foil 6,6' sealing plate 7,7 'negative electrode current collector 8,8' gasket
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 4/74 Ｈ０１Ｍ 4/74 Ｃ 6/16 6/16 Ｚ 10/40 10/40 ＺContinued on the front page (51) Int.Cl.6 Identification code FI H01M 4/74 H01M 4/74 C 6/16 6/16 Z 10/40 10/40 Z
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10127124AJPH11195415A (en) | 1997-11-05 | 1998-05-11 | Nonaqueous electrolyte battery and its manufacture |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-302443 | 1997-11-05 | ||
| JP30244397 | 1997-11-05 | ||
| JP10127124AJPH11195415A (en) | 1997-11-05 | 1998-05-11 | Nonaqueous electrolyte battery and its manufacture |
| Publication Number | Publication Date |
|---|---|
| JPH11195415Atrue JPH11195415A (en) | 1999-07-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10127124APendingJPH11195415A (en) | 1997-11-05 | 1998-05-11 | Nonaqueous electrolyte battery and its manufacture |
| Country | Link |
|---|---|
| JP (1) | JPH11195415A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008047458A (en)* | 2006-08-18 | 2008-02-28 | Kri Inc | Electrode for power storage device, and power storage device using it |
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