JPS6174256A - Flat lithium cell - Google Patents
Flat lithium cellInfo
- Publication number
- JPS6174256A JPS6174256A JP59195532A JP19553284A JPS6174256A JP S6174256 A JPS6174256 A JP S6174256A JP 59195532 A JP59195532 A JP 59195532A JP 19553284 A JP19553284 A JP 19553284A JP S6174256 A JPS6174256 A JP S6174256A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- sheet metal
- metal terminal
- ethylene
- copolymer resin
- 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.)
- Granted
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
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は平板型リチウム電池に関し、さらにシール性を
大幅に改善した長期信頼性に優れる平板型リチウム電池
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flat lithium battery, and more particularly to a flat lithium battery with significantly improved sealing properties and excellent long-term reliability.
従来、１対のシート状金属端子板の間に積層状の発電要
素を保有せしめるとともに、前記１対のシート状金属端
子板の周辺端部の間に環状絶縁部材としてエチレン−酢
酸ビニル共重合（Ｋ−ＶＡＣ）、ポリエチレン（Ｐｚ）
、ポリアミドレジン等の熱溶融性の合成樹脂、またはこ
れらにワックス、ピッチ等の瀝青物質を含有させた樹脂
を挾込み、前記発電要素を密封した偏平型電池が知られ
ていた。例えば実開昭５８−１７６５６６号公報にこの
ような従来の電池構造と環状絶縁部材が開示されている
。Conventionally, a laminated power generating element is held between a pair of sheet metal terminal plates, and an annular insulating member made of ethylene-vinyl acetate copolymer (K- VAC), polyethylene (Pz)
2. Description of the Related Art Flat batteries have been known in which a heat-melting synthetic resin such as polyamide resin, or a resin containing a bituminous substance such as wax or pitch is sandwiched between the resin and the power generating element is sealed. For example, such a conventional battery structure and annular insulating member are disclosed in Japanese Utility Model Application Publication No. 58-176566.
しかし、従来の電池はルクランシエ型電池なので、シー
ト状金属端子板が電解液にて腐食を受けないように、こ
のシート状金属端子板の内面に導電性カーボンフィルム
が配設されている。However, since the conventional battery is a Lecrancier type battery, a conductive carbon film is disposed on the inner surface of the sheet metal terminal plate to prevent the sheet metal terminal plate from being corroded by the electrolyte.
従って、この従来電池の正、負極端子を兼ねるシート状
金属端子板は内面に４電性カーボンフイルムが配設され
ている分だけ厚みが厚くなり、シート状金属端子板単独
を用いた電池に比べて電池厚みを薄く出来ない欠点があ
った。Therefore, the sheet metal terminal plate that serves as the positive and negative terminals of conventional batteries is thicker due to the four-electrode carbon film disposed on the inner surface, compared to a battery using only a sheet metal terminal plate. However, there was a drawback that the battery thickness could not be made thinner.
また、１対のシート状金属端子板の間に積層状の発電要
素を保有せしめるとともに、前記１対のシート状金属端
子板の周辺端部の間に環状絶縁部材を挾込み、前記発電
要素を密封した平板型リチウム電池における環状絶縁部
材の具備すべき特性は次の通りである。Further, a laminated power generation element is held between a pair of sheet metal terminal plates, and an annular insulating member is inserted between peripheral ends of the pair of sheet metal terminal plates to seal the power generation element. The characteristics that the annular insulating member in a flat plate lithium battery should have are as follows.
すなわち、
１モルの過塩素酸リチウムを含有したプロピレンカーボ
ネートからなる有機電解液に接触した状四で溶解、膨潤
しないこと。さらに、ニッケル。That is, it should not dissolve or swell when in contact with an organic electrolyte consisting of propylene carbonate containing 1 mole of lithium perchlorate. Plus, nickel.
ステンレスなどのシート状金属端子板との接着性が良好
なこと。また、外部からの水分侵入に対して十分なバリ
ヤー性を有すること。Good adhesion to sheet metal terminal plates such as stainless steel. Also, it must have sufficient barrier properties against moisture intrusion from the outside.
前記の有機電解液に接着した状態で、接着性が低下した
すせず、良好なこと。Good condition with no decrease in adhesion when adhered to the organic electrolyte.
一般に、リチウム電池は負極活物質として金属リチウム
を用いる。リチウムはＬｉ＋Ｈ，Ｏ→Ｌ Ｌ ＯＲ＋
’／２ もの反応により、水と反応して水酸化リチウム
となる。また、水素ガスも発生する。Generally, lithium batteries use metallic lithium as a negative electrode active material. Lithium is Li+H, O→L L OR+
'/2 Reacts with water to form lithium hydroxide. Hydrogen gas is also generated.
この水酸化リチウムは発を要素としては働らかない不要
物質である。さらに、リチウム表面がこの水酸化リチウ
ムで被われてしまうと、電池の内部抵抗が大きくなり、
電池反応が著しく阻害される従って、電池の外部からの
水分侵入は断じて、遮断しなければならない。This lithium hydroxide is an unnecessary substance that does not function as a gaseous element. Furthermore, if the lithium surface is covered with this lithium hydroxide, the internal resistance of the battery will increase.
Since the battery reaction is significantly inhibited, moisture intrusion from outside the battery must be completely prevented.
水分侵入に対するこの環状絶縁部材のバリヤー性の基準
としては、８０℃、ＲＥ［９０〜９５％下で１０日間貯
蔵したのち、外部から内部に侵入する水分−が１５００
ｐｐｍ 以内である。The standard for the barrier property of this annular insulating member against moisture intrusion is that after 10 days of storage at 80°C and RE [90 to 95%], the moisture intrusion from the outside to the inside must be 1500%.
Within ppm.
これに対して、従来％池の環状絶縁部材はエチレン−酢
酸ビニル、ＰＫ、ポリアミドレジン等の熱溶融性の合成
樹脂を使用しているが、エチレン−酢酸ビニル及びポリ
アミドレジンは耐電解液性、シート状金属端子板との接
着性及びバリヤー性が十分でなく、満足の得られるレベ
ルではない。On the other hand, the annular insulating members of conventional % ponds use heat-melting synthetic resins such as ethylene-vinyl acetate, PK, and polyamide resins, but ethylene-vinyl acetate and polyamide resins have electrolyte resistance, The adhesion and barrier properties with the sheet metal terminal plate are not sufficient and are not at a satisfactory level.
ＰＫは耐電解液性、バリヤー性は良好であるが、シート
状金属端子板との接着性が全くないので使用できない欠
点があった。Although PK has good electrolyte resistance and barrier properties, it has the disadvantage that it cannot be used because it has no adhesiveness with sheet metal terminal plates.
そこでこの発明は従来のこのような欠点を解決すること
により、薄くて、シール性が大幅に改善された長期信頼
性に優れる平板型リチウム電池を得ることを目的として
いる。Therefore, the object of the present invention is to solve these conventional drawbacks, thereby providing a flat plate type lithium battery that is thin, has significantly improved sealing properties, and has excellent long-term reliability.
上記問題点を′Ｍ決するためにこの発明は、内面に導電
性カーボンフィルムを配設したシート状金属端子板に替
えて、シート状金属端子板単独を正、負極端子を兼ねる
外装ケースとして用いることにより電池厚みを薄くした
。In order to solve the above problems, the present invention uses a sheet-shaped metal terminal plate alone as an exterior case that also serves as positive and negative electrode terminals, instead of a sheet-shaped metal terminal plate with a conductive carbon film arranged on the inner surface. This made the battery thinner.
さらに、この発明は、所定の輪郭形状に形成された１対
のシート状金属端子板の間に積層状の発電要素を保有せ
しめるとともに、前記１対のシート状金属端子板の周辺
端部の間に環状絶縁部材としてヒートシール性と金属と
の接着性を有したフッ素樹脂を挾込み、前記発電要素を
密封することにより、電池のシール性を大幅に向上せし
め、外部からの水分侵入を遮断したので、長期信頼性の
優れた平板型リチウム電池が実現できた。Further, the present invention has a laminated power generating element held between a pair of sheet metal terminal plates formed in a predetermined contour shape, and an annular shape between the peripheral ends of the pair of sheet metal terminal plates. By inserting a fluororesin with heat-sealability and adhesion to metal as an insulating member and sealing the power generating element, the sealing performance of the battery was greatly improved and moisture infiltration from the outside was blocked. A flat plate lithium battery with excellent long-term reliability has been realized.
本発明者は電池のシール性に対して重要な技術となる環
状絶縁部材の材質選定を鋭意研究した。The inventors of the present invention have conducted extensive research into the selection of materials for the annular insulating member, which is an important technique for improving the sealing properties of batteries.
まず、耐電解液性について詳細に検討した。既に、種々
の高分子材料について、１モルＬ Ｌ Ｃ１ｏ。First, we examined the electrolyte resistance in detail. Already, for various polymeric materials, 1 mol L L C1o.
含有のプロビレ７カーボネート溶液、５０℃で１ｏケ月
間の安定性と膨潤度を評価基準とした耐講演要旨集、Ｐ
５１〜５６（１９７６）に報告されている。A collection of lecture abstracts based on the stability and degree of swelling of the Probire 7 carbonate solution at 50°C for 1 month as evaluation criteria, P
51-56 (1976).
この報告によれば、塩化ビニル、アクリル樹脂、ＡＢＳ
樹脂は完全に浴解し、ポリカーボネート、エポキシ樹力
旨は破壊する。さらに、ポリイミド、６−ナイロン、ポ
リビニルアルコールは安定性、膨潤度に若干問題が残る
。According to this report, vinyl chloride, acrylic resin, ABS
The resin completely dissolves in the bath and the polycarbonate and epoxy resin properties are destroyed. Furthermore, polyimide, 6-nylon, and polyvinyl alcohol have some problems in stability and degree of swelling.
結局、ポリ四フッ化エチレン（以下、ＦＴＦＫト略記す
る。）ｌポリエチレン、ポリプロピレンが、プロピレン
カーボネート中でも膨潤も少なく安定であることが報告
されている。In the end, it has been reported that polytetrafluoroethylene (hereinafter abbreviated as FTFK), polyethylene, and polypropylene are stable with little swelling even in propylene carbonate.
本発明者はさらにエチレン−酢酸ビニル共重合樹脂、ホ
ットメルトタイプポリアミド樹脂、ホットメルトタイプ
ポリエステル樹脂の耐電解液性を調べたが、いずれの樹
脂も安定性及び膨潤度が悪く、電池の環状絶縁部材及び
シール材として使用できない。The present inventor further investigated the electrolytic solution resistance of ethylene-vinyl acetate copolymer resin, hot melt type polyamide resin, and hot melt type polyester resin, but all resins had poor stability and swelling degree, and the annular insulation of the battery Cannot be used as a component or sealant.
試験試料はエチレン−酢酸ビニル共重合樹脂としてＵＥ
６８０．ＵＫ７５０（東洋曹達工業（株）製、商品名ウ
ルトラセン）で、ＵＫ６８０（７）酢％ヒニｋ 含Ｎ
敏は１５％、ＵＺ７５０の酢酸ビニル含有には３２％で
ある。The test sample was UE as an ethylene-vinyl acetate copolymer resin.
680. UK750 (manufactured by Toyo Soda Kogyo Co., Ltd., trade name Ultrasen), UK680 (7) Vinegar% Hini K Contains N
The vinyl acetate content of UZ750 is 32%.
ホットメルトタイプポリアミド樹脂としてＤＰＸｌ ５
５８ 、ＤＰＸｌ １６５ 、マクロメルト６２４０、
（いずれもヘンケル日本（株）製、商品名パーサロン
）である。DPXl 5 as hot melt type polyamide resin
58, DPXl 165, Macromelt 6240,
(Both are manufactured by Henkel Japan Co., Ltd., trade name: Persalon).
ホットメルトタイプポリエステル樹月旨として、ＡＨＭ
５４ Ｑ （旭化成工業（株）製、商品名ハープツク）
、Ｒ−５０（東しく株）ｙ！、商品名ケミット）、Ｂ−
８０３，Ｅ−８０４（ダイアボンド工業（株）、商品名
メルトロン）である。AHM as hot melt type polyester
54 Q (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name Harptsuk)
, R-50 (Toshiku Co., Ltd.) y! , trade name Chemit), B-
803, E-804 (Diabond Industries Co., Ltd., trade name: Meltron).
試験方法は１モルＬ ｉ Ｃ！ ｔｏ、含有プロピレン
カーボネート浴１３０ｃｃに試験試料１１を浸漬したの
ち、６０°Ｃ１４０日間放置し、試験試料の安定性、膨
潤度を調べた。The test method is 1 mol Li C! The test sample 11 was immersed in 130 cc of propylene carbonate bath, and then left at 60°C for 140 days, and the stability and degree of swelling of the test sample were examined.
以上詳述した耐電解液性試験結果から、平板型リチウム
電池の環状絶縁部材及びシール材として優れている高分
子材料はＦＴ７に、ポリエチレン、ポリプロピレンに限
定されることが判った。From the results of the electrolyte resistance test detailed above, it was found that polymer materials that are excellent as annular insulating members and sealing materials for flat plate lithium batteries are limited to FT7, polyethylene, and polypropylene.
次に、このように絞り込まれたＦＴ’ＦＩ！ｉ 、ポリ
エチレン、ポリプロピレンとニッケル、ステンレス、ア
ルミニウムとの接着性を調べた。Next, FT'FI narrowed down like this! i. Adhesion between polyethylene and polypropylene and nickel, stainless steel, and aluminum was investigated.
この扱者試験はＦＴＰＫはホットバー法、ポリエチレン
とポリプロピレンはインパルス法によりヒートシールし
たが、いずれもニッケル、ステンレス、アルミニウムと
は接層しなかった。In this operator test, FTPK was heat-sealed by the hot bar method, and polyethylene and polypropylene were heat-sealed by the impulse method, but none of them came into contact with nickel, stainless steel, or aluminum.
以上の通り、耐電解液性を向上させるためには、官能基
を持たない爾分子材料を使用しなければならない。一方
、官能基を持たない高分子材料。As mentioned above, in order to improve electrolyte resistance, it is necessary to use an amorphous material that does not have functional groups. On the other hand, polymer materials without functional groups.
すなわち、ＰＴＩＰＥ、ポリエチレン、ポリプロピレン
は金属との接層が不可であり、シート状金属端子板の周
縁部の間に用いる環状絶縁部材になり得ない。That is, PTIPE, polyethylene, and polypropylene cannot be in contact with metal, and cannot be used as an annular insulating member between the peripheral edges of a sheet metal terminal plate.
本発明者は環状絶縁部材の具備すべき特性、すなわち、
（１）耐電解液性、（２）金属との接着性、（３）水分
のバリヤー性を同時に満足する材料として、撥水性を有
し、吸水率０％（２４ｈｒ）のＰＴＦＦｉを変性し、金
属との接着性を改善して使用することにＭＦＡしたので
ある。因に、ポリエチレンとポリプロピレンの吸水率は
α０１％以下（２４ｈｒ）である。吸水率はＡ Ｓ Ｔ
Ｍ −Ｄ ５７０によった。種々の検討を加えた結果
、ＦＴＦＥを変性したフッ素樹脂の中で、本発明に係る
ヒートシール性と金属との接着性を有したフッ素樹脂と
Ｌｒ４フッ化エチレン−バー７０口アルコキシエチレン
共重合樹脂（以下、ＰＦＡと略記する。ｍ−ｐ、５２０
℃、吸水率α０６％（２４ｈｒ））１４フク化エチレン
−６フッ化プロピレン共重合樹脂（以下、ＦＥｉＰと略
記する。ｍ−ｐ、 ２７０°Ｃ１吸水率１０１％以下（
２４ｈｒ））、ｚチレンー４フッ化エチレン共重合樹脂
（以下、ＥＴ？Ｅと略記する。ｍ−Ｐ、２６０℃、吸水
率（Ｌｏｉ％以下（２４ｈｒ））、３フッ化塩化エチレ
ン樹脂（以下、ＰＯＴＦＩ！；と略記する。ｍ’ｐ、
２１５°Ｃ１吸水率０％（２４ｈｒ））＋フッ化ビニリ
デン樹脂（以下、ＰＶ（ｌ Ｆと略記する。ｍ−ｐ、
１７０℃、＠水率Ｑ、０４％（２４ｈｒ））、フッ化ビ
ニル樹脂（以下、ｐｖｙと略記する。ｍ−ｐ、２００℃
、吸水率ａ５％以下（２４ｈ ｒ ） ）”？ア’４０
本発明に係る上記フッ素樹脂のうち、Ｅ Ｔ Ｆ Ｋを
１対のシート状ニッケル端子板の周辺端部の間に環状絶
縁部材として挾込み、含有水分量が５ｐｐｍの有機電解
液のみを密封した容器を作り、８０°Ｃ，ＲＨ９０〜９
５％の恒温恒湿槽内に貯蔵して、外部から容器内に侵入
する水分量を求めた。The present inventor has determined the characteristics that the annular insulating member should have, namely:
As a material that simultaneously satisfies (1) electrolyte resistance, (2) adhesion to metals, and (3) moisture barrier properties, we modified PTFFi, which has water repellency and has a water absorption rate of 0% (24 hours), MFA was developed to improve its adhesion to metals. Incidentally, the water absorption rate of polyethylene and polypropylene is α01% or less (24 hr). Water absorption rate is A S T
According to M-D 570. As a result of various studies, among the fluororesins modified with FTFE, the fluororesin and Lr4 fluoroethylene-bar 70-mouth alkoxyethylene copolymer resin having heat sealing properties and adhesion to metal according to the present invention were selected. (Hereinafter abbreviated as PFA. m-p, 520
°C, water absorption rate α06% (24hr)) 14-fluorinated ethylene-6-fluorinated propylene copolymer resin (hereinafter abbreviated as FEiP. m-p, 270°C1 water absorption rate 101% or less (
24hr)), z tyrene-tetrafluoroethylene copolymer resin (hereinafter abbreviated as ET?E), m-P, 260°C, water absorption rate (Loi% or less (24hr)), trifluorochloride ethylene resin (hereinafter abbreviated as ET?E), Abbreviated as POTFI!; m'p,
215°C1 water absorption rate 0% (24hr)) + vinylidene fluoride resin (hereinafter abbreviated as PV (l F) m-p,
170°C, @water ratio Q, 04% (24hr)), vinyl fluoride resin (hereinafter abbreviated as pvy, m-p, 200°C
, water absorption rate a5% or less (24hr))"?A'40
Among the above-mentioned fluororesins according to the present invention, E T F K was inserted between the peripheral edges of a pair of sheet-like nickel terminal plates as an annular insulating member, and only the organic electrolyte with a moisture content of 5 ppm was sealed. Make a container and heat it to 80°C, RH90~9
The container was stored in a 5% constant temperature and humidity chamber, and the amount of moisture that entered the container from the outside was determined.
ＥＴＦＥは旭硝子（株）の商品名であるアフロンＣ！Ｏ
Ｐフィルム（厚み１００μ）を使用した。ETFE is Afron C!, a product name of Asahi Glass Co., Ltd. O
A P film (thickness 100 μm) was used.
シート状ニッケル端子板の厚みは３０μである５ ０
ｍｍ Ｘ ５０ ｒａｒｔに切出したシート状ニアケル
端子板に外寸法５０ ｒａｎ Ｘ ５０關、内寸法４ｏ
訓Ｘ４０ｒａｎであるロ字形ＥＴＰＫフィルム枠をホッ
トスタンプピング装置により熱溶着した。熱溶着の条件
は、温度３２０ ’Ｃ、圧カ４０４／ｃＩｄ、圧着時間
３秒であった。The thickness of the sheet-like nickel terminal plate is 30μ50
Outer dimension: 50 ran x 50 mm, inner dimension: 4o
A square-shaped ETPK film frame of 40 ran was heat-welded using a hot stamping machine. The conditions for thermal welding were a temperature of 320'C, a pressure of 404/cId, and a pressure bonding time of 3 seconds.
このように予めＥｉＴＦＦｉフィルムからなる環状絶縁
部材をシート状ニッケル端子板に熱溶着したもの同志を
インパルス法により、三方ｔ−ヒートシールする。この
袋状容器を１ｏ″″１〜１０″″３ｔｏｒｒで３時間、
乾燥したのち、含有水分量０． ＯＱ ５％以下のグロ
ーブボックス内で電解液２００μｔを注入しグローブボ
ックス内でインパルス法により残り一方をヒートシール
を行い、完全に電解液のみを密封した。The annular insulating member made of the EiTFFi film is heat-sealed to the sheet-like nickel terminal plate in advance in this manner, and then the two are heat-sealed on three sides by the impulse method. This bag-shaped container was heated at 1 o''''1 to 10''''3 torr for 3 hours.
After drying, the moisture content is 0. 200 μt of electrolyte was injected into a glove box with an OQ of 5% or less, and the remaining half was heat-sealed by the impulse method in the glove box to completely seal only the electrolyte.
前記条件でこの容器を貯蔵したのち、グローブボックス
内でこの容器を開封し、容器内の電解液をマイクロシリ
ンジにて１０．０μを採集した。After storing this container under the above conditions, this container was opened in a glove box, and 10.0 μm of the electrolyte in the container was collected with a microsyringe.
ａｔ水分計にてこの電解液中の水分量を測定した。The amount of water in this electrolyte was measured using an AT moisture meter.
この電解液のみを密封した容器の外部から内部へ侵入し
た水分量測定結果を機械的にガスケットをカシメて封止
したコイン型リチウム電池（ａａ２０１６）容器と比較
して次に示す。The results of measuring the amount of water that entered from the outside into the container in which only the electrolyte was sealed are shown below in comparison with a coin-type lithium battery (AA2016) container sealed by mechanically caulking a gasket.
データはル＝２の平均値を示す。Data represent mean values of 2 = 2.
この第１表よつ現在、広く時計、を草等に多用されてい
る従来のコイン型リチウム電池のシール性より優れたシ
ール性が本発明により得られたことが分る。Table 1 shows that the present invention provides a sealing performance superior to that of conventional coin-type lithium batteries, which are currently widely used in watches, batteries, etc.
以上詳述したように、撥水性を有するフッ素樹脂に着目
して、環状絶縁部材としてヒートシール性と金属との接
着性を有したフッ素樹脂を採用することにより、平板型
リチウム［池のシール性を大幅に向上せしめることがで
きた。As detailed above, by focusing on fluororesin that has water repellency and adopting fluororesin that has heat sealability and adhesion to metal as the annular insulating member, flat lithium was able to significantly improve.
以下に本発明の実施例を図面にもとづいて説明する。 Embodiments of the present invention will be described below based on the drawings.
図は本発明を適用した平板型リチウム電池の一実施例で
、サイズは４０Ｘ４０ＸＱ、５悶である。The figure shows an example of a flat plate lithium battery to which the present invention is applied, and the size is 40X40XQ, 5mm.
図中、１は負極端子を兼ねるシート状金属端子板で厚み
が２０〜１００μである。この１はニッケル、ステンレ
ス等の金属である。このシート状ニッケル端子板１の内
面に金属ネット２が溶接式れている。３は負極活物買で
あるリチウムで金属ネット２に互層されたのち、ローラ
ーにより、金属ネット２に完全に充填されている。４は
セパレータである。In the figure, numeral 1 denotes a sheet metal terminal plate which also serves as a negative electrode terminal and has a thickness of 20 to 100 μm. This 1 is a metal such as nickel or stainless steel. A metal net 2 is welded to the inner surface of this sheet-like nickel terminal plate 1. 3 is a negative electrode active material, lithium, which is alternately layered on the metal net 2, and then completely filled into the metal net 2 by a roller. 4 is a separator.
５は二酸化マンガンを主体とする正極合剤である。６は
金属ネットであり、正極合剤５に対して一部もしくは全
部が埋設され、・正極合剤５と・よく密着している。5 is a positive electrode mixture mainly composed of manganese dioxide. A metal net 6 is partially or completely buried in the positive electrode mixture 5 and is in close contact with the positive electrode mixture 5.
７は正極端子を兼ねるシート状金属端子板で厚みが２０
〜１００μである。この７はニッケル。7 is a sheet metal terminal plate that also serves as a positive terminal and has a thickness of 20 mm.
~100μ. This 7 is nickel.
ステンレス、アルミニウム等の金属である。Metals such as stainless steel and aluminum.
８は本発明に係る環状絶縁部材で、ヒートシール性と金
属との接着性を有したフッ素樹脂のうちＥＴＰＫを使用
した。Ｋ’Ｉ’ＰＫとして旭硝子（株）の商品名である
７７０ンｃｏＰフイルムヲ使用し、厚みは１００μであ
る。8 is an annular insulating member according to the present invention, in which ETPK, which is a fluororesin having heat-sealability and adhesiveness to metal, is used. As K'I'PK, a 770-inch coP film, which is a trade name of Asahi Glass Co., Ltd., is used, and its thickness is 100 μm.
８はシート状金属端子板１．７のそれぞれに予め熱溶着
されることが望ましい。8 is desirably heat-welded to each of the sheet metal terminal plates 1.7 in advance.
組立方法としては、シート状金属端子板１を下にして、
順次、リチウム３．セパレータ４１図には示されていな
いが電解液、正極合剤５等の各発電要素を積層し、最後
にシート状金属端子板７を載置、被せて一対のシート状
金属端子板の周辺端部でヒートシールを行い、電池を完
全密封する。The assembly method is as follows: with the sheet metal terminal plate 1 facing down,
Sequentially, lithium 3. Although not shown in the separator 41 diagram, each power generation element such as an electrolytic solution and a positive electrode mixture 5 is laminated, and finally a sheet metal terminal plate 7 is placed and covered to form a peripheral edge of a pair of sheet metal terminal plates. heat seal the battery to completely seal it.
９は環状絶縁部材８とシート状金属端子板１゜７とが熱
溶着されたヒートシール部である。Reference numeral 9 denotes a heat-sealed portion in which the annular insulating member 8 and the sheet-shaped metal terminal plate 1.7 are thermally welded.
１０は環状絶縁部材８同志が熱溶着されたヒートシール
部である。Reference numeral 10 denotes a heat-sealed portion where the annular insulating members 8 are thermally welded together.
ヒートシール幅は５ｍｙｎである。The heat seal width is 5 myn.
このようにして組立てた電池を室温で、負荷抵抗３０に
Ω定抵抗放電したところ、終止電圧２゜４の場合、７５
７７ＬＡんの放電容瀘が得られた。When the battery assembled in this way was discharged at a constant resistance of 30Ω into a load resistor at room temperature, the final voltage was 75° when the final voltage was 2°4.
A discharge capacity of 77 LA was obtained.
次に、長期間使用したり、保存したりする上での信頼性
を確認するために、を池を８０°Ｃ，ＲＨ９０〜９５％
の恒温恒湿槽に貯蔵し、開路電圧（Ｖｏｃ）、内部抵抗
（Ｒｘ）、厚み（Ｈ）の変化を調べた。この結果を第２
表に示す。データは外＝１０である。Next, in order to confirm reliability in long-term use and storage, the pond was heated at 80°C and RH90-95%.
The samples were stored in a constant temperature and humidity chamber, and changes in open circuit voltage (Voc), internal resistance (Rx), and thickness (H) were examined. This result is the second
Shown in the table. The data is outside = 10.
表中、Ｘはデータ外＝１０の平均値、Ｒはデータの最大
値と最小値の差を示す。In the table, X indicates the average value outside the data = 10, and R indicates the difference between the maximum and minimum values of the data.
第２表より明らかなように、１５日間貯蔵後でもＶＯＯ
は極めて安定している。As is clear from Table 2, even after 15 days of storage, VOO
is extremely stable.
また、Ｒ１，Ｈについてもｒ、Ｈのいずれも若干づつア
ップしているが、数値として実用上問題のないレベルで
ある。Also, regarding R1 and H, both r and H have increased slightly, but the numerical values are at levels that pose no problem in practical terms.
このように本発明電池の貯蔵性能が優れている理由は、
環状絶縁部材として撥水性に富み、かつヒートシール性
と金属との接着性を有したフッ素樹脂を用いて、電池外
部からの水分侵入量を極めて少く抑えているためである
。The reason why the battery of the present invention has such excellent storage performance is as follows.
This is because the annular insulating member is made of a fluororesin that is highly water-repellent, has heat-sealing properties, and has adhesion to metals, thereby minimizing the amount of moisture entering from outside the battery.
さらに１本発明者が見出した加速評価試験法と室温保存
との対応関係（８０”Ｃ，Ｒｕ２Ｏ〜９５％、５日保存
＝室温、常盤、１年保存）から推定すれば、本発明電池
は室温下、６年の貯蔵もしくは使用に十分供されるもの
と考えられる。Furthermore, it is estimated from the correspondence relationship between the accelerated evaluation test method and room temperature storage found by the inventors (80"C, Ru2O ~ 95%, 5 days storage = room temperature, Tokiwa, 1 year storage) that the battery of the present invention It is considered that it can be stored or used for 6 years at room temperature.
以上詳述したように、本発明は１対のシート状金属端子
板の周辺部の間に環状絶縁部材としてヒートシール性と
金属との接着性を有したフッ素樹脂を挾込み、電池を密
封することにより、シール性を大幅に向上する効果があ
る。As described in detail above, the present invention seals a battery by inserting a fluororesin having heat-sealability and adhesiveness to metal as an annular insulating member between the peripheral portions of a pair of sheet-shaped metal terminal plates. This has the effect of significantly improving sealing performance.
本発明は極薄で長期信頼性に優れる平板型リチウム電池
を提供することができ、工Ｃカード、薄型電車９時計、
グリーテイングカード等に応用でき、その工業的価値大
なるものである。The present invention can provide a flat plate lithium battery that is extremely thin and has excellent long-term reliability, and can be used for industrial C cards, thin train 9 watches, etc.
It can be applied to greeting cards, etc., and has great industrial value.
図は本発明を適用した平板型リチクム″ｒＪＬ池の一実
施例を示す断面図である。
１・・・・・・正極のシート状金属端子板２．６・・・
・・・金属ネット
３・・・・・・リチウム
４・・・・・・セパレータ
５・・・・・・正極合剤
７・・・・・・負極のシート状金属端子板８・・・・・
・環状絶縁部材
９．１０・・・・・・ヒートシール部
以 上The figure is a cross-sectional view showing an embodiment of a flat plate-type LYTICUM"rJL pond to which the present invention is applied. 1... Positive electrode sheet metal terminal plate 2.6...
... Metal net 3 ... Lithium 4 ... Separator 5 ... Positive electrode mixture 7 ... Negative electrode sheet metal terminal plate 8 ...・
・Annular insulating member 9.10...Heat seal part or more
Claims (2)
端子板の間に積層状の発電要素を保有せしめるとともに
、前記１対のシート状金属端子板の周辺端部の間に環状
絶縁部材としてヒートシール性と金属との接着性を有し
たフッ素樹脂を挾込み、前記発電要素を密封したことを
特徴とする平板型リチウム電池。(1) A laminated power generation element is held between a pair of sheet metal terminal plates formed in a predetermined contour shape, and a ring-shaped insulating member is provided between the peripheral ends of the pair of sheet metal terminal plates. A flat plate lithium battery characterized in that the power generation element is sealed by sandwiching a fluororesin having heat sealability and adhesiveness to metal.
コキシエチレン共重合樹脂、４フッ化エチレン−６フッ
化プロピレン共重合樹脂、エチレン−４フッ化エチレン
共重合樹脂、３フッ化塩化エチレン樹脂、フッ化ビニリ
デン樹脂、ポリフッ化ビニル樹脂であることを特徴とす
る特許請求の範囲第１項記載の平板型リチウム電池。(2) Fluororesins include tetrafluoroethylene-perfluoroalkoxyethylene copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, ethylene-tetrafluoroethylene copolymer resin, trifluorochloride ethylene resin, The flat lithium battery according to claim 1, characterized in that the battery is made of vinylidene chloride resin or polyvinyl fluoride resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59195532A JPS6174256A (en) | 1984-09-18 | 1984-09-18 | Flat lithium cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59195532A JPS6174256A (en) | 1984-09-18 | 1984-09-18 | Flat lithium cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6174256A true JPS6174256A (en) | 1986-04-16 |
| JPH0522341B2 JPH0522341B2 (en) | 1993-03-29 |
Family
ID=16342653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59195532A Granted JPS6174256A (en) | 1984-09-18 | 1984-09-18 | Flat lithium cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6174256A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739046A1 (en) * | 1995-03-20 | 1996-10-23 | Matsushita Electric Industrial Co., Ltd. | Organic electrolyte batteries |
| JP2005196979A (en) * | 2003-12-26 | 2005-07-21 | Toshiba Corp | Thin nonaqueous electrolyte secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59858A (en) * | 1982-06-09 | 1984-01-06 | Toshiba Battery Co Ltd | Manufacturing method for organic solvent battery |
-
1984
- 1984-09-18 JP JP59195532A patent/JPS6174256A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59858A (en) * | 1982-06-09 | 1984-01-06 | Toshiba Battery Co Ltd | Manufacturing method for organic solvent battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739046A1 (en) * | 1995-03-20 | 1996-10-23 | Matsushita Electric Industrial Co., Ltd. | Organic electrolyte batteries |
| US5656392A (en) * | 1995-03-20 | 1997-08-12 | Matsushita Electric Industrial Co., Ltd. | Organic electrolyte batteries |
| US5851693A (en) * | 1995-03-20 | 1998-12-22 | Matsushita Electric Industrial Co., Ltd. | Organic electrolyte batteries |
| JP2005196979A (en) * | 2003-12-26 | 2005-07-21 | Toshiba Corp | Thin nonaqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0522341B2 (en) | 1993-03-29 |
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