JPS6196663A - Thin battery - Google Patents
Thin batteryInfo
- Publication number
- JPS6196663A JPS6196663A JP21883084A JP21883084A JPS6196663A JP S6196663 A JPS6196663 A JP S6196663A JP 21883084 A JP21883084 A JP 21883084A JP 21883084 A JP21883084 A JP 21883084A JP S6196663 A JPS6196663 A JP S6196663A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- active material
- current collector
- thin battery
- added
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は薄型電池で特に負極合剤の利用高向丘に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a thin battery, and particularly to the use of a negative electrode mixture.
〈従来技術〉
近年1時計、電卓、カメラ、玩具等のエレクトaニクス
化に伴って電池の小型化、薄型化が進められており、ボ
タン型電池や平板状電池が市販されるにいたっている。<Prior art> In recent years, as watches, calculators, cameras, toys, etc. have become more electronic, batteries have become smaller and thinner, and button-shaped batteries and flat batteries have become commercially available. .
中でもプラスチックシートで包装された薄型電池は金属
aSボタン電池とくらべて可撓性があり、さらに大面積
化や任意の形状のものを作りやすい等の種々の利点を有
している、
電池の薄型化は単に小型化へのニーズからだけでなく、
ディスプレー、印刷物、写真フィルム等の薄型製品との
一体化した利用法の点からも大いに期待される。Among them, thin batteries wrapped in plastic sheets are more flexible than metal AS button batteries, and have various advantages such as larger area and ease of manufacturing into arbitrary shapes. This is not only due to the need for miniaturization;
There are also great expectations for its integrated use with thin products such as displays, printed matter, and photographic film.
従来この棟の電池における負極用電極は負極活物質粉末
をエーテル化デンプンやヒドロキシエチルセルロース等
の水浴性多糖類、ポリアクリル改ナトリウム、ポリビニ
ルアルコール等の水、饗性高分子あるいはアクリル酸エ
マルジョン、酢酸エマルジョン等のエマルジョン樹脂を
バインダーに用いスクリーン印刷やスフイージングによ
り負極集電体に塗布乾燥させることにより作成していた
。Conventionally, the negative electrode in batteries in this building has been prepared by combining negative active material powder with water-based polysaccharides such as etherified starch and hydroxyethyl cellulose, water such as polyacrylic modified sodium, polyvinyl alcohol, etc., fertile polymers, acrylic acid emulsions, acetic acid emulsions, etc. These emulsion resins were used as a binder and were applied to a negative electrode current collector by screen printing or sifting and then dried.
しかし水溶性高分子をバインダーに用いた場合は電解液
にバインダーが膨潤、溶解し集電体との密着性が経時的
に悪くなり電池内部抵抗が徐々に増大してしまう。However, when a water-soluble polymer is used as a binder, the binder swells and dissolves in the electrolyte, and its adhesion with the current collector deteriorates over time, resulting in a gradual increase in battery internal resistance.
またエマルジョン樹脂をバインダーに用いた場合、負極
活物質粒子と集電体との密着体との密着性は良好である
が負極活物質問の密着性が悪い。Further, when an emulsion resin is used as a binder, the adhesion between the negative electrode active material particles and the current collector is good, but the adhesion between the negative electrode active material particles is poor.
さらに負極活物質粉末を上述の各種バインダーな用いイ
ンキ化した場合、該インキの溶媒として水を用いている
ため負極活物質を塗布乾燥させる過程で負極活物質が酸
化され電池容量の低下が間頂となっていた。Furthermore, when the negative electrode active material powder is made into an ink using the above-mentioned various binders, since water is used as a solvent for the ink, the negative electrode active material is oxidized during the process of applying and drying the negative electrode active material, resulting in a decrease in battery capacity. It became.
′ さらにスクリーン印刷等の印刷方式により負
極集電体に塗油する場合、該インキが凝集しやすく印刷
適性が極めて悪い欠点を有していた。'Furthermore, when applying oil to the negative electrode current collector by a printing method such as screen printing, the ink tends to aggregate, resulting in extremely poor printability.
そこで本発明者は負極活物質粉末を水に不溶の有機高分
子バインダーと該バインダーを俗解することのできる有
機溶剤によりインキ化して負極集電体に塗布乾燥し負極
用電極を作成した。Therefore, the present inventor created an electrode for a negative electrode by forming an ink from a negative electrode active material powder using a water-insoluble organic polymer binder and an organic solvent in which the binder can be commonly understood, and applying the ink to a negative electrode current collector and drying it.
しかし水に不溶の有機高分子バインダーと該バインダー
を溶解することのできる有機溶剤によりインキ化すると
負極活物質を塗布乾燥させる過程での負極活物質の酸化
は極めて減少し、さらに負極電極を作成するとぎスクリ
ーン印刷を行う場合は印刷適性も良好であるが負極活物
質の利用率が極めて悪(なり実用上問題となっていた。However, if an ink is formed using an organic polymer binder that is insoluble in water and an organic solvent that can dissolve the binder, oxidation of the negative electrode active material during the process of applying and drying the negative electrode active material is extremely reduced, and furthermore, the negative electrode is created. When screen printing is performed, the printability is good, but the utilization rate of the negative electrode active material is extremely poor (which has become a practical problem).
〈発明が解決しようとする問題点〉
本発明は以上の現況に対してなされたものであり、かさ
密度が1.2.!i’/cril以下の該有機浴剤に不
溶の粉末状物質を負極合剤に添加した負極電極を用いる
ことにより、活物質の利用率に極めてすぐれた薄型電池
を提供するものである。<Problems to be Solved by the Invention> The present invention has been made in response to the above-mentioned current situation, and has a bulk density of 1.2. ! By using a negative electrode in which a powdery substance insoluble in the organic bath agent of i'/cril or less is added to the negative electrode mixture, a thin battery with an extremely high utilization rate of the active material is provided.
〈問題点を解決するための手段〉 以下本発明を図面の参照により詳細に説明する。〈Means for solving problems〉 The present invention will be explained in detail below with reference to the drawings.
第1図は本例における薄型電池負極電極の断面を示す説
明図である。本発明により負極合剤(11中に粉末状物
質が添加されている。該粉末状物質の添加量は負極活物
質の裡類や粒径およびバインダーの量により決定される
が、25%以下が好ましく、25%以上添加してもそれ
以上の利用率の向上は認めらねない。FIG. 1 is an explanatory diagram showing a cross section of a thin battery negative electrode in this example. According to the present invention, a powdery substance is added to the negative electrode mixture (11).The amount of the powdery substance added is determined by the type and particle size of the negative electrode active material and the amount of binder, but it is preferably 25% or less. Preferably, even if it is added in an amount of 25% or more, no further improvement in the utilization rate will be observed.
さらに該粉末状添加物質の種類は、がさ密度が1.2M
9/d以下のものであればよく、例えば超微粒子状無水
アルミナ(日本アエロジル(mAERO8f L a
luminarn oxid6 C)超微粒子状無水
酸化チタン(日本アエロジル@AERO8ILtita
nium oxide P−25)等の金属酸化物。Furthermore, the type of powdered additive substance has a bulk density of 1.2M.
9/d or less, for example, ultrafine anhydrous alumina (Nippon Aerosil (mAERO8f La
luminarn oxide6 C) Ultrafine particulate anhydrous titanium oxide (Japan Aerosil @AERO8ILtita
metal oxides such as nium oxide P-25).
ホ11エチレン微粒末、ポリテトラフルオロエチレン微
粒末等の有機高分子微粉末あるいはアセチレンブラック
、グラファイト、ケッチェンブラック等のカーボンブラ
ック等が有効である。Organic polymer fine powders such as E11 ethylene fine particles and polytetrafluoroethylene fine particles, or carbon blacks such as acetylene black, graphite, and Ketjen black are effective.
これは該粉末物質を添加しない場合、有機高分子バイン
ダーが負極活物質粒末な覆い活物質利用率が低い。しか
し粉末物質を添加することにより、負極活物質表面を蔓
っている有慨高分子バインダーが不完全となり活物質利
用率が向上するためである。さらに該粉末物質がミクロ
な貫通孔を有する場合、該貫通孔を介し電池反応が進行
し、活物質利用率が向上する。This is because when the powder material is not added, the utilization rate of the covering active material is low because the organic polymer binder is the negative electrode active material particles. However, this is because the addition of the powder material makes the saturated polymer binder extending over the surface of the negative electrode active material incomplete, thereby improving the utilization rate of the active material. Furthermore, when the powder material has microscopic through-holes, the battery reaction proceeds through the through-holes, improving the active material utilization rate.
特にアセチレンブラック、ケッチェンブラック等のカー
ボンブラックのような導電剤を負極合剤に添加すること
により活物質利用率が向上するとともに負極活物質と集
電体との電子導電性が慣めてよくなり、電池内部抵抗が
極めて低くなる。In particular, by adding a conductive agent such as carbon black such as acetylene black or Ketjen black to the negative electrode mixture, the utilization rate of the active material is improved and the electronic conductivity between the negative electrode active material and the current collector is improved. Therefore, the internal resistance of the battery becomes extremely low.
〈実施例〉 下記に本実施例で用いた負極合剤インキ組成を示す。<Example> The negative electrode mixture ink composition used in this example is shown below.
負極活物質粉末 亜鉛粉末 100 (
重量部)有機高分子バインダーエチルセルロース
1 (η )粉末状添加物 TiO2+C^03
.却1〜10(tt )有機溶剤 ブチル
セロソルブ 20(//)上記組成を混練し、負極合
剤インキを作成し。Negative electrode active material powder Zinc powder 100 (
Part by weight) Organic polymer binder ethyl cellulose
1 (η) Powdered additive TiO2+C^03
.. 1 to 10 (tt) Organic solvent: butyl cellosolve 20 (//) The above composition was kneaded to prepare a negative electrode mixture ink.
スクリーン印刷で負極集電体(4)に20μの厚さで印
刷を行ない、第1図に示す如くの負極用電極l・1)を
得た。The negative electrode current collector (4) was printed with a thickness of 20 μm by screen printing to obtain a negative electrode 1.1) as shown in FIG.
該負極用集電体(4)としては、黄銅箔やプラスチツク
樹脂:(導電剤を混練して作成した導電性プラスチック
フィルム(2)より成るが、本例では低密度ポリエチレ
ン樹脂に炭素フィラーを20〜40wt%混線した導電
性フィルム(2)とAA箔(3)をラミネートした集電
体を用いた。The negative electrode current collector (4) is made of a conductive plastic film (2) made by kneading a conductive agent with brass foil or plastic resin. A current collector was used in which a conductive film (2) and an AA foil (3) were laminated with ~40 wt% crosstalk.
上記組成中負極活物質粉末に200 meshパス亜鉛
粉末を用いた。また有機溶剤としては負極活物質である
亜鉛に電気化学的に安定であり、該集電体にも化学的に
安定であり、さらにスクリーン印刷用(客側に適するブ
チルセロソルブを用いである。さらに有機高分子バイン
ダーとしては、負極活物質の種類および有機溶剤の種類
により1種々のものb′−使用可能であるが、本例では
負極活物質である亜鉛粉末との分散性が良好で、かつ有
機溶剤であるブチルセロソルブに溶解することカーでき
かつスクリーン印刷に適する粘度を有するエチルi
セルロース?用いた。In the above composition, 200 mesh pass zinc powder was used as the negative electrode active material powder. In addition, as an organic solvent, it is electrochemically stable to zinc, which is the negative electrode active material, and chemically stable to the current collector. Various polymer binders can be used depending on the type of negative electrode active material and the type of organic solvent. Ethyl i that can be dissolved in the solvent butyl cellosolve and has a viscosity suitable for screen printing.
cellulose? Using.
粉末状添加物質としては、かさ密度が1.297−以下
のものであればよいが、微粉末酸化チタン(日本アエロ
ジル@k E ROS I L Tituniumo二
<ide P −25)かさ密度o、 08 g/ c
r!、亜鉛粉末に対する添加量10wt %グラファイ
ト(LON2A LTD、KS−1s)かさ密度0.
1g/cn亜鉛粉末に対する添加量5wt%アセチレン
プラ(電気化学1.掬、デンカブラック)かさ密度0、
os2i/crd亜鉛粉末に対する添加量1.0 w
t%の6種を用いるようにした。The powdered additive substance may be one having a bulk density of 1.297 or less, but fine powder titanium oxide (Japan Aerosil @ KEROSIL Tituniumo2<ide P-25) with a bulk density of 0.08 g /c
r! , Addition amount to zinc powder: 10wt% Graphite (LON2A LTD, KS-1s) Bulk density: 0.
Amount added to 1g/cn zinc powder: 5wt% Acetylene plastic (Electrochemical 1.Kiku, Denka Black) Bulk density: 0,
Addition amount to os2i/crd zinc powder: 1.0 w
Six kinds of t% were used.
このようにして構成した負極電極3種と添加剤を加えな
い以外は同一組成の負極電極を田いた薄型電池の利用惠
を次の第1表に示す。Table 1 below shows the utilization of the three types of negative electrodes constructed in this manner and the thin batteries having the same composition except that no additives were added.
第 1 表
第1表から明らかなように粉末状奈加剤をカロえた本発
明の電池は、添加剤を加えな(・従来品に比較し、電池
利用率が著しく向上して(・ることh′−わかる。特に
アセチレンブラックを負極活物質に僅かi wt%添加
しただけで利用率はioo%近くに達する。Table 1 As is clear from Table 1, the battery of the present invention containing powdered additives has a significantly improved battery utilization rate compared to conventional products (without the addition of additives). '-I see. In particular, when only i wt% of acetylene black is added to the negative electrode active material, the utilization rate reaches nearly ioo%.
次に本発明の負極電極を用いた薄型電池の構成の一例を
第2図により説明する。一方にアルミ箔(3)をラミネ
ートした導電性プラスチックフィルム(2)で構成さね
、る負極集電体(4)上に、負極合剤(1)が塗布され
である。二酸化マンガン、アセチレンブラックおよびエ
マルジョンバインダーよりなる正極合剤(5)が該負極
用集電体と同一構成の正極集電体(8)上に塗布さiし
てあり、また2M過塩素酸岨鉛水溶、夜を含浸させたポ
リエステル不織布よりなるセパレーター(3)を介して
該負極集電体側と密閉されである。また電池肩縁部はシ
ール枠(7)が設けられ正陣集電体(8)及び負極集電
体(4)と熱融着によりシールされているものである。Next, an example of the structure of a thin battery using the negative electrode of the present invention will be explained with reference to FIG. A negative electrode mixture (1) is applied onto a negative electrode current collector (4) consisting of a conductive plastic film (2) laminated with aluminum foil (3) on one side. A positive electrode mixture (5) consisting of manganese dioxide, acetylene black and an emulsion binder is coated on a positive electrode current collector (8) having the same structure as the negative electrode current collector, and 2M lead perchlorate It is sealed to the negative electrode current collector side via a separator (3) made of a polyester nonwoven fabric impregnated with a water-soluble resin. Further, a sealing frame (7) is provided at the shoulder edge of the battery and is sealed with the positive electrode current collector (8) and the negative electrode current collector (4) by thermal fusion.
〈発明の効果〉
以上のように粉末状負極活物質および有機高分子バイン
ダーよりなる負極合剤を有機溶剤によりインキ化し負極
集電体に塗布後乾沫してなる負極電極を有する薄型′電
池において、負極合剤にがさ密度が1.2g/(ffl
以下の該何機溶剤に不溶の粉末物質を添加することによ
り、電池利用率が飛躍的に向上する薄型電池を作成でき
、工業的両値の極めて犬ぎいものである。<Effects of the Invention> As described above, in a thin battery having a negative electrode formed by forming a negative electrode mixture consisting of a powdered negative electrode active material and an organic polymer binder into an ink with an organic solvent, applying it to a negative electrode current collector, and then drying it. , the density of the negative electrode mixture is 1.2 g/(ffl
By adding an insoluble powder substance to the following several solvents, a thin battery with a dramatically improved battery utilization rate can be produced, which is extremely valuable in terms of industrial value.
第1図は本発明の実施例により得た負極電極の断面図、
第2図は薄型電池の断面を示す説明図”、(1)・・・
負極合剤 (2)・・・導電性プラスチックフィルム
f3J・・・アルミニウム箔(4)・・・
負極集電体 (5)・・・正極合剤(61・・・セパレ
ータ−(力・・・シール枠(8)・・・正極集電体FIG. 1 is a cross-sectional view of a negative electrode obtained according to an example of the present invention;
Figure 2 is an explanatory diagram showing the cross section of a thin battery, (1)...
Negative electrode mixture (2)...Conductive plastic film f3J...Aluminum foil (4)...
Negative electrode current collector (5)... Positive electrode mixture (61... Separator (force)... Seal frame (8)... Positive electrode current collector
Claims (1)
なる負極合剤が有機溶剤によりインキ化され、該インキ
化された負極合剤が負極集電体上に塗布後乾燥してなる
負極電極を有する薄型電池において、 該負極合剤に、かさ密度1.2g/cm^3以下の該有
機溶剤に不溶の粉末添加物質を添加してなることを特徴
とする薄型電池。 2)前記粉末添加物質が該負極合剤に対して25重量%
以下に添加されていることを特徴とする特許請求の範囲
第一項記載の薄型電池。 3)前記粉末添加物質がカーボンブラックよりなること
を特徴とする特許請求の範囲第1項及び第2項記載の薄
型電池。[Scope of Claims] 1) A negative electrode mixture consisting of a powdered negative electrode active material and an organic polymer binder is made into an ink using an organic solvent, and the inked negative electrode mixture is applied onto a negative electrode current collector and then dried. 1. A thin battery having a negative electrode comprising: a powder additive material insoluble in the organic solvent having a bulk density of 1.2 g/cm^3 or less is added to the negative electrode mixture. 2) The amount of the powder additive material is 25% by weight based on the negative electrode mixture.
The thin battery according to claim 1, characterized in that the following is added: 3) The thin battery according to claims 1 and 2, wherein the powder additive material is carbon black.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21883084A JPS6196663A (en) | 1984-10-18 | 1984-10-18 | Thin battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21883084A JPS6196663A (en) | 1984-10-18 | 1984-10-18 | Thin battery |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6196663A true JPS6196663A (en) | 1986-05-15 |
Family
ID=16726008
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21883084A Pending JPS6196663A (en) | 1984-10-18 | 1984-10-18 | Thin battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6196663A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005231025A (en) * | 2004-02-21 | 2005-09-02 | Flugel Css Gmbh & Co Kg | Knife sharpener |
-
1984
- 1984-10-18 JP JP21883084A patent/JPS6196663A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005231025A (en) * | 2004-02-21 | 2005-09-02 | Flugel Css Gmbh & Co Kg | Knife sharpener |
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