JPH0673305B2 - Method for manufacturing spiral electrode for lithium secondary battery - Google Patents
Method for manufacturing spiral electrode for lithium secondary batteryInfo
- Publication number
- JPH0673305B2 JPH0673305B2 JP58150867A JP15086783A JPH0673305B2 JP H0673305 B2 JPH0673305 B2 JP H0673305B2 JP 58150867 A JP58150867 A JP 58150867A JP 15086783 A JP15086783 A JP 15086783A JP H0673305 B2 JPH0673305 B2 JP H0673305B2
- Authority
- JP
- Japan
- Prior art keywords
- micropores
- separator
- secondary battery
- spiral electrode
- lithium secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Description
【発明の詳細な説明】 本発明は方向性のある微細孔を多数有する樹脂フイルム
をセパレータに用いるリチウム二次電池用渦巻電極の製
造方法の改良に係り、電池組立時の内部短絡の発生防止
および充電時の樹枝状電析リチウムによる内部短絡の発
生防止をはかることを目的とする。The present invention relates to an improved method for producing a spiral electrode for a lithium secondary battery, which uses a resin film having a large number of directional micropores as a separator, and prevents the occurrence of internal short circuit during battery assembly and The purpose is to prevent the occurrence of internal short circuit due to dendritic lithium during charging.
渦巻電極は、一般にセパレータを正極板と負極板との間
に介在させた状態で正極板と負極板とを重ね合わせ渦巻
状に巻回することによって作られる。そして通常は正極
板からの正極合剤粉末の剥離による内部短絡の防止をは
かるため、セパレータを袋状にし、その中に正極板を入
れ、正極板をセパレータで包被した状態で正極板と負極
板とが重ね合わされる。The spiral electrode is generally produced by stacking a positive electrode plate and a negative electrode plate in a state where a separator is interposed between the positive electrode plate and the negative electrode plate and winding them in a spiral shape. Usually, in order to prevent an internal short circuit due to the separation of the positive electrode mixture powder from the positive electrode plate, the separator is formed into a bag shape, the positive electrode plate is put therein, and the positive electrode plate and the negative electrode are covered with the separator. The boards are overlaid.
ところで、有機電解質系の電解液を用いる電池では、上
記セパレータの構成材料として微孔性樹脂フイルムと称
される方向性のある微細孔を多数有する樹脂フイルムが
反応に伴なう正極側の体積増加が生じても良好な保液性
を有し電池特性の低下を招くことが少ないことから好用
され、この方向性のある微細孔を多数有する樹脂フイル
ム（以下、微孔性樹脂フイルムという）とポリプロピレ
ン不織布やポリエチレン不織布などの不織布とを重ね合
わせるか、あるいは微孔性樹脂フイルム同士を重ね合わ
せてセパレータとして用いられている。特に微孔性ポリ
プロピレンフイルムとポリプロピレン不織布とを重ね合
わせたものが好用され、通常その微孔性ポリプロピレン
フイルムが負極に対向するように配置される。By the way, in a battery using an organic electrolyte-based electrolytic solution, a resin film having a large number of directional fine pores called a microporous resin film as a constituent material of the separator increases the volume on the positive electrode side accompanying the reaction. The resin film having a large number of directional fine pores (hereinafter referred to as a microporous resin film) is preferably used because it has a good liquid-retaining property and does not cause deterioration of battery characteristics even if It is used as a separator by laminating non-woven fabric such as polypropylene non-woven fabric or polyethylene non-woven fabric, or by laminating microporous resin films. In particular, a laminate of a microporous polypropylene film and a polypropylene nonwoven fabric is preferably used, and the microporous polypropylene film is usually arranged so as to face the negative electrode.
ところが、このような微孔性樹脂フイルムを使用したセ
パレータを用いて渦巻電極を作製し、電池組立を行なう
と、内部短絡の発生がしばしば認められる。特に二次電
池に用いた場合、充電時の内部短絡の発生が著しい。However, when a spiral electrode is produced by using a separator using such a microporous resin film and a battery is assembled, an internal short circuit is often observed. Particularly when used in a secondary battery, the occurrence of internal short circuit during charging is remarkable.
本発明者らはそのような内部短絡の発生原因の究明とそ
の防止対策を見出すべく種々研究を重ねた結果、そのよ
うな内部短絡は、微孔性樹脂フイルムの微細孔の長軸方
向が渦巻状に巻くときの巻き方向に垂直な方向に配置さ
れると、渦巻状に巻回したとき微細孔の幅が広がること
によって引き起されること、特に二次電池では充電時に
電析するリチウムが樹枝状であるため微細孔の幅が広が
るとリチウムがセパレータを貫通しやすくなるために内
部短絡の発生が多くなること、そして、微孔性樹脂フイ
ルムをその微細孔の長軸方向が渦巻状に巻くときの巻き
方向と同じ方向になるように配置して渦巻電極を作製す
るときは、微細孔は長さ方向に伸びるが幅がより狭くな
るため内部短絡の防止はもとよりセパレータ効果が一段
と向上することを見出し、本発明を完成するにいたっ
た。As a result of various studies to find out the cause of occurrence of such an internal short circuit and to find a preventive measure for such an internal short circuit, the present inventors have found that such an internal short circuit is swirled in the long axis direction of the micropores of the microporous resin film. When arranged in a direction perpendicular to the winding direction when wound in a spiral shape, it is caused by the widening of the micropores when wound in a spiral shape. Since it is dendritic and the width of the micropores widens, it becomes easier for lithium to penetrate through the separator and internal short-circuiting will occur more frequently, and the microporous resin film will have a spiral shape in the longitudinal direction of the micropores. When the spiral electrode is manufactured by arranging so that the spiral direction is the same as the winding direction when winding, the micropores extend in the length direction, but the width becomes narrower, so the internal short circuit is prevented and the separator effect is further improved. That Out, it has led to the completion of the present invention.
本発明においてセパレータを用いる微孔性樹脂フイルム
は、たとえばポリエチレン、ポリプロピレン、ナイロン
などの合成樹脂を押出成形によって微細孔を多数有する
ように成形されたフイルムで、その微細孔の径はたとえ
ば長軸方向が0.02〜0.2μｍ、短縮方向が0.01〜0.05μ
ｍである。このような微孔性樹脂フイルムの代表的な市
販例としては「ジュラガード」の商品名でポリプラスチ
ックス（株）より市販されているポリプロピレン製のも
のがあげられ、本発明において特に好用される。The microporous resin film using the separator in the present invention is a film formed by extrusion molding a synthetic resin such as polyethylene, polypropylene or nylon so as to have a large number of micropores, and the diameter of the micropores is, for example, the major axis direction. Is 0.02-0.2μm, shortening direction is 0.01-0.05μ
m. A typical commercially available example of such a microporous resin film is a polypropylene product marketed by Polyplastics Co., Ltd. under the trade name of "Duraguard", which is particularly preferably used in the present invention. It
次に本発明の実施例を図面とともに説明する。Next, an embodiment of the present invention will be described with reference to the drawings.
実施例１ 第１図は本実施例で用いる微孔性ポリプロピレンフイル
ムを模式的に示す平面図であり、この微孔性ポリプロピ
レンフイルム１においては微細孔1aは方向性を有して形
成されている。Example 1 FIG. 1 is a plan view schematically showing a microporous polypropylene film used in this example. In the microporous polypropylene film 1, the micropores 1a are formed to have directionality. .
上記のような微孔性ポリプロピレンフイルム１とポリプ
ロピレン不織布とを重ね合わせてセパレータ２にし、こ
れを長方形の袋状に形成した。その際、微孔性ポリプロ
ピレンフイルム１を外側にし、かつその微細孔1aの長軸
方向が袋状セパレータ２の長さ方向と同一方向になるよ
うに配置して袋状にした。The microporous polypropylene film 1 and the polypropylene non-woven fabric as described above were laminated to form a separator 2, which was formed into a rectangular bag shape. At this time, the microporous polypropylene film 1 was placed outside and the micropores 1a were arranged so that the long axis direction thereof was the same as the length direction of the bag-shaped separator 2 to form a bag shape.
第２図に示すように、この袋状セパレータ内２に、二硫
化チタンを正極活物質とし、ステンレス鋼製の集電網４
に保持させた正極板３を入れ、一方、リチウムをステン
レス鋼製の集電網に圧着して負極板５を形成し、これを
前記セパレータ２で包被した正極板３と重ね合わせ、蓋
７付きの集電パイプ６を芯にして渦巻状に巻いて渦巻電
極を形成した。As shown in FIG. 2, in the bag-shaped separator 2, titanium disulfide is used as a positive electrode active material, and a stainless steel collector network 4 is used.
The positive electrode plate 3 held by the separator is put into the positive electrode plate 3, and the negative electrode plate 5 is formed by pressure-bonding lithium to a stainless steel collector net. The current collecting pipe 6 was used as a core and wound in a spiral shape to form a spiral electrode.
この渦巻電極において、微孔性ポリプロピレンフイルム
１はその微細孔1aの長軸方向が袋状セパレータ２の長さ
方向と同一方向になるように配置されているため、渦巻
状に巻回する方向と微細孔の長軸方向とが同一方向にな
っている。In this spiral electrode, since the microporous polypropylene film 1 is arranged such that the long axis direction of the micropores 1a is the same as the length direction of the bag-shaped separator 2, the microporous polypropylene film 1 has a spiral winding direction. The long axis direction of the fine holes is the same direction.
上記のようにして製造された渦巻電極を筒形の電池ケー
スに入れ、電解液として1,3−ジオキソランと1,2−ジメ
トキシエタンとの容量比が70:30の混合溶媒にLiB(C6H5)
4を0.6モル/l溶解されたものを用い、ハーメチックシー
ルして電池を製造した。The spiral electrode manufactured as described above was placed in a cylindrical battery case, and LiB (C 6 was added to a mixed solvent having a capacity ratio of 1,3-dioxolane and 1,2-dimethoxyethane of 70:30 as an electrolytic solution. H 5 )
A battery was manufactured by hermetically sealing 4 using 0.6 mol / l dissolved therein.
比較例１ 微孔性ポリプロピレンフイルムをその微細孔の長軸方向
が渦巻状に巻く際の巻き方向に直交するように配置した
ほかは実施例１と同様にして渦巻電極を形成し、以後実
施例１と同様にして電池を製造した。Comparative Example 1 A spiral electrode was formed in the same manner as in Example 1 except that the microporous polypropylene film was arranged so that the long axis direction of the micropores was orthogonal to the winding direction when spirally wound. A battery was manufactured in the same manner as in 1.
上記のようにして製造した実施例１の電池と比較例１の
電池を1.0mAの定電流で放電1.5V〜充電2.7Vの間で充放
電させ、サイクル数と充放電比との関係を調べ、その結
果を第３図に示した。なお、充放電比とは次式に示すよ
うに 各サイクルでの放電電気量と充放電電気量との比であ
り、充放電比が１に近いほど充放電特性が良好なことを
示す。The battery of Example 1 and the battery of Comparative Example 1 manufactured as described above were charged / discharged at a constant current of 1.0 mA between 1.5 V and 2.7 V, and the relationship between the number of cycles and the charge / discharge ratio was examined. The results are shown in FIG. The charge / discharge ratio is as shown in the following equation. It is the ratio of the amount of discharged electricity and the amount of charged and discharged electricity in each cycle. The closer the charge / discharge ratio is to 1, the better the charge / discharge characteristics.
第３図に示すように、実施例１の電池は比較例１の電池
に比べて充放電比が１に近く、充放電特性がすぐれてい
た。比較例１の電池において充放電比が高いのは、渦巻
状に巻回転する際に微孔性ピリプロピレンフイルムの微
細孔がひらいて、そこから樹枝状の電析リチウムが正極
側に貫通して内部短絡を生じることによるものと思われ
る。また実施例１の電池の充放電特性がすぐれているの
は、微孔性ポリプロプイレンフイルムの微細孔がひらか
ず、樹枝状の電析リチウムによる内部短絡の発生が抑制
できたためであると思われる。As shown in FIG. 3, the battery of Example 1 had a charge / discharge ratio close to 1 as compared with the battery of Comparative Example 1, and the charge / discharge characteristics were excellent. The battery of Comparative Example 1 has a high charge / discharge ratio because the micropores of the microporous pyripropylene film are opened during the spiral rotation, and the dendritic electrodeposited lithium penetrates from there to the positive electrode side. This is probably due to an internal short circuit. The reason why the battery of Example 1 has excellent charge / discharge characteristics is probably because the micropores of the microporous polypropylene film were not opened and the occurrence of internal short circuit due to the dendritic lithium was deposited. Be done.
第１図は微孔性ポリプロピレンフイルムを模式的に示す
平面図、第２図は渦巻電極製造時の状態を模式的に示す
一部断面斜視図、第３図は本発明の実施例により製造さ
れた渦巻電極を用いた電池と従来法により製造された渦
巻電極を用いた電池のサイクル数と充放電比との関係を
示す図である。 １……微孔性ポリプロピレンフイルム、 1a……微細孔、２……セパレータFIG. 1 is a plan view schematically showing a microporous polypropylene film, FIG. 2 is a partial sectional perspective view schematically showing a state at the time of manufacturing a spiral electrode, and FIG. 3 is manufactured by an embodiment of the present invention. FIG. 7 is a diagram showing the relationship between the number of cycles and the charge / discharge ratio of a battery using a spiral electrode and a battery using a spiral electrode manufactured by a conventional method. 1 ... Microporous polypropylene film, 1a ... Micropores, 2 ... Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 真辺 俊勝 大阪府茨木市丑寅１丁目１番88号 日立マ クセル株式会社内 (56)参考文献 特開 昭56−59478（ＪＰ，Ａ) 特公 昭57−5026（ＪＰ，Ｂ２) 実公 昭57−51479（ＪＰ，Ｙ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshikatsu Manabe 1-88 No. 1-Tora, Ibaraki-shi, Osaka Prefecture Hitachi Maxell Co., Ltd. (56) Reference JP-A-56-59478 (JP, A) 57-5026 (JP, B2) S.K. 57-51479 (JP, Y2)
Claims (2)
ルムをセパレータに用いるリチウム二次電池用渦巻電極
の製造にあたり、上記樹脂フィルムをその微細孔の長軸
方向が渦巻状に巻くときの巻き方向と同一方向になるよ
うに配置して、渦巻状に巻くことを特徴とするリチウム
二次電池用渦巻電極の製造方法。1. A method for producing a spiral electrode for a lithium secondary battery, which uses a resin film having a large number of directional micropores as a separator, wherein the resin film is wound when the longitudinal direction of the micropores is spirally wound. A method for manufacturing a spiral electrode for a lithium secondary battery, which is arranged in the same direction as the direction and wound in a spiral shape.
するポリプロピレンフィルムとポリプロピレン不織布と
を重ね合わせたものである特許請求の範囲第１項記載の
リチウム二次電池用渦巻電極の製造方法。2. The method for producing a spiral electrode for a lithium secondary battery according to claim 1, wherein the separator is a laminate of a polypropylene film having a large number of directional micropores and a polypropylene nonwoven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58150867A JPH0673305B2 (en) | 1983-08-17 | 1983-08-17 | Method for manufacturing spiral electrode for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58150867A JPH0673305B2 (en) | 1983-08-17 | 1983-08-17 | Method for manufacturing spiral electrode for lithium secondary battery |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7207479A Division JP2732371B2 (en) | 1995-07-20 | 1995-07-20 | Method for manufacturing spiral electrode for lithium secondary battery |
| JP7207478A Division JP2732370B2 (en) | 1995-07-20 | 1995-07-20 | Method for manufacturing spiral electrode for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6041772A JPS6041772A (en) | 1985-03-05 |
| JPH0673305B2 true JPH0673305B2 (en) | 1994-09-14 |
Family
ID=15506109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58150867A Expired - Lifetime JPH0673305B2 (en) | 1983-08-17 | 1983-08-17 | Method for manufacturing spiral electrode for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0673305B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63119171A (en) * | 1986-11-07 | 1988-05-23 | Sanyo Electric Co Ltd | Nonaqueous type secondary battery |
| JP5695928B2 (en) | 2010-04-14 | 2015-04-08 | 東京応化工業株式会社 | Comb-shaped electrode manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5659478A (en) * | 1979-10-17 | 1981-05-22 | Matsushita Electric Ind Co Ltd | Apparatus for manufacture of assembled spiral electrode plates |
| JPS575026A (en) * | 1980-06-13 | 1982-01-11 | Ricoh Co Ltd | Light beam scanner |
| JPS5818868Y2 (en) * | 1980-09-10 | 1983-04-16 | 末男 宮原 | Laundry waste collector |
-
1983
- 1983-08-17 JP JP58150867A patent/JPH0673305B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6041772A (en) | 1985-03-05 |
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