JPS6019625B2 - alkaline battery - Google Patents
alkaline batteryInfo
- Publication number
- JPS6019625B2 JPS6019625B2 JP55065510A JP6551080A JPS6019625B2 JP S6019625 B2 JPS6019625 B2 JP S6019625B2 JP 55065510 A JP55065510 A JP 55065510A JP 6551080 A JP6551080 A JP 6551080A JP S6019625 B2 JPS6019625 B2 JP S6019625B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- alkaline battery
- polyethylene
- polyethylene film
- graft
- 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
Links
- 239000004698 Polyethylene Substances 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 30
- 238000010030 laminating Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Description
【発明の詳細な説明】
この発明はセパレータの構成を改良したアルカＩＪ電池
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an alkaline IJ battery with an improved separator structure.
最近、ラジオ、テープレコーダ、４・型計算機等の電池
を電源とする小型電子機器のの普及発達に伴ない、これ
に用いられる電池も小型でかつ高容量化されることが望
まれている。2. Description of the Related Art Recently, with the spread and development of small electronic devices powered by batteries, such as radios, tape recorders, and 4-inch calculators, it has been desired that the batteries used in these devices be smaller and have higher capacity.
このような要望を満たすものとしては、単位体積当りの
容量の大きなアルカリ電池がある。アルカリ電池におい
ては、陰極剤と陽極合剤とがセパレータにより隔絶され
電解液のみがセパレータを介して陰陽両極間を移動して
反応が行われる。An alkaline battery that satisfies this demand has a large capacity per unit volume. In an alkaline battery, a cathode material and an anode mixture are separated by a separator, and only the electrolyte moves between the cathode and anode electrodes via the separator, and a reaction takes place.
ところが、このようなアルカリ電池の長寿命化を阻むも
のとして陽極酸化物等に起因するセパレータの劣化があ
り、これを避けるため耐酸化性、耐アルカリ性を有する
ポリエチレンがセパレータの材料として用いられている
。However, one obstacle to extending the life of such alkaline batteries is the deterioration of the separator caused by anodic oxides, etc. To avoid this, polyethylene, which has oxidation and alkali resistance, is used as the material for the separator. .
さらにそのイオン交換性、保水性を満足させるためにア
クリル酸、メタアクリル酸等を重合することが行われて
いる。このようなアクリル酸やメタアクリル酸をグラフ
ト重合したポリエチレン膜をセパレータとして用いる場
合、グラフト率が小さいと電気抵抗が大きくなって電池
のインピーダンスが増大する欠点がある。Furthermore, in order to satisfy the ion exchange properties and water retention properties, acrylic acid, methacrylic acid, etc. are polymerized. When such a polyethylene film graft-polymerized with acrylic acid or methacrylic acid is used as a separator, there is a drawback that if the grafting ratio is small, the electrical resistance becomes large and the impedance of the battery increases.
一方グラフト率が大きくなると親水性を増して電気抵抗
は減少するが、銀イオンの透過量が増し銀イオンの還元
量も増大するので耐酸化性が悪化し貯蔵特性が低下する
。On the other hand, when the grafting rate increases, hydrophilicity increases and electrical resistance decreases, but the amount of silver ions permeated increases and the amount of silver ions reduced increases, resulting in deterioration of oxidation resistance and storage properties.
したがってグラフト率の大きなポリエチレン膜をセパレ
ータに使用すると電池のインピーダンスが低く大電流放
電および低温特性は良くなるが、貯蔵特性が悪くなり、
特に長期貯蔵あるいは高温貯蔵において内部短絡をおこ
すおそれがある。この発明は上記の事情を解決するため
のもので、セパレータとしてグラフト重合ポリエチレン
膜のグラフト率の異なるものを複数枚ラミネートして一
体に構成したものを用いることにより、インピーダンス
が小さくしかも貯蔵特性を向上することのできるアルカ
リ電池を提供しようとするものである。Therefore, if a polyethylene film with a high graft ratio is used as a separator, the impedance of the battery will be low and the large current discharge and low temperature characteristics will be improved, but the storage characteristics will be deteriorated.
There is a risk of internal short circuits, especially during long-term storage or high-temperature storage. This invention is intended to solve the above-mentioned circumstances. By using a separator made by laminating a plurality of graft polymerized polyethylene membranes with different graft ratios, the impedance is small and the storage characteristics are improved. The aim is to provide an alkaline battery that can
すなわち、このアルカリ電池はアクリル酸またはメタア
クリル酸をグラフト重合する場合のグラフト率が比較的
大きなポリエチレン膜とグラフト率が比較的小さなポリ
エチレン膜とをラミネートしてセパレータを構成し、グ
ラフト率が比較的大きなポリエチレン膜によって表面の
親水性を大きくし濡れ特性を向上してインピーダンスの
低下を図り、一方グラフト率が比較的小さなポリエチレ
ン膜によって銀イオンの透過と還元量を少なくして耐酸
化特性を向上し、したがって貯蔵特性を改善するもので
ある。That is, in this alkaline battery, a separator is constructed by laminating a polyethylene film with a relatively high graft ratio and a polyethylene film with a relatively low graft ratio when graft polymerizing acrylic acid or methacrylic acid, and the graft ratio is relatively low. A large polyethylene film increases the hydrophilicity of the surface, improves wetting properties, and lowers impedance, while a polyethylene film with a relatively small graft ratio reduces silver ion permeation and reduction, improving oxidation resistance. , thus improving storage properties.
このアルカリ電池は両ポリエチレン膜の有する欠点を補
い合って性能の向上を計るものということができる。This alkaline battery can be said to improve performance by compensating for the drawbacks of both polyethylene films.
なお、グラフト率は下記の式によって算出した値である
。Note that the grafting rate is a value calculated using the following formula.
グラフト率（％）＝グラフト共重合後の重量−プラスチ
ックフィルムの重量Ｘ，。Graft rate (%)=weight after graft copolymerization−weight of plastic film X.
〇プラスチックフィルムの重量以下図面を参照してこの
発明の一実施例を説明する。〇Weight of plastic film An embodiment of the present invention will be described with reference to the drawings.
第１図において１はニッケルメッキした鋼板よりなる有
底短円筒状の金属容器で陽極端子を兼ねるものである。In FIG. 1, reference numeral 1 denotes a short cylindrical metal container with a bottom made of nickel-plated steel plate, which also serves as an anode terminal.
この金属容器１の内部には酸化銀活物質に黒鉛を電導剤
として添加し成形した、陽極合剤２を充填し後に詳述す
るイオン透過性のセパレータ３、苛性カリまたは苛性ソ
ーダの水溶液を含有した多孔性繊維物質からなる電解液
保持剤４、アマルガム化した亜鉛粉末を電解液例えばカ
ルボキシメチルセルローズ、ポリビニルアルコール等の
粘結剤にてゲル状にした陰極剤５を順次積層して収納す
る。６は金属容器１の関口部７を封口する陰極端子を兼
ねた金属封□板でニッケルメッキした鋼板を用いている
。The inside of this metal container 1 is filled with an anode mixture 2 made by adding graphite as a conductive agent to a silver oxide active material, an ion-permeable separator 3 to be described in detail later, and a porous hole containing an aqueous solution of caustic potash or caustic soda. An electrolytic solution holding agent 4 made of a fibrous material and a cathode material 5 made of an electrolytic solution made of amalgamated zinc powder gelled with a binder such as carboxymethyl cellulose or polyvinyl alcohol are sequentially laminated and housed. Reference numeral 6 is a metal sealing plate which also serves as a cathode terminal for sealing the entrance 7 of the metal container 1, and is made of a nickel-plated steel plate.
８は金属容器１と金属封□板６との間を絶縁するととも
にその間隙を密封する絶縁パッキングで、金属容器１の
開□部７を内側に轡曲ごせてこれを縦着している。8 is an insulating packing that insulates the gap between the metal container 1 and the metal sealing plate 6 and seals the gap therebetween, and the opening 7 of the metal container 1 is bent inward to attach it vertically. .
なお、図中９は環体である。この発明のアルカリ電池に
おいてセパレータ３としては、アクリル酸またはメタア
クリル酸をグラフト重合した際のグラフト率の異なる複
数個のポリエチレン膜をラミネートして一体に構成した
ものを用いる。Note that 9 in the figure is a ring. In the alkaline battery of the present invention, the separator 3 is constructed by laminating a plurality of polyethylene films having different graft ratios when graft polymerizing acrylic acid or methacrylic acid.
例えば第２図ａに示すようにグラフト率の比較的大きな
ポリエチレン膜１ １とグラフト率の比較的小さなポリ
エチレン膜１２をラミネートしてセパレータ３を構成し
、グラフト率の比較的小さなポリエチレン膜１２を陽極
合剤２の側となるように酉己設する。また別の実施態様
としては、第２図ｂに示すようにグラフト率の比較的大
きなポリエチレン膜１１を中央にしてその両側にグラフ
ト率の比較的小さなポリエチレン膜１２をラミネートし
てセパレータ３を構成したものを用いる。For example, as shown in FIG. 2a, the separator 3 is constructed by laminating a polyethylene film 11 with a relatively high graft ratio and a polyethylene film 12 with a relatively low graft ratio, and the polyethylene film 12 with a relatively low graft ratio is used as an anode. Place the container so that it is on the side of Mixture 2. In another embodiment, as shown in FIG. 2b, the separator 3 is constructed by laminating a polyethylene film 11 with a relatively high graft ratio in the center with polyethylene films 12 with a relatively low graft ratio on both sides. use something
さらに具体的数値で示すと、いずれの場合にもグラフト
率の大きなポリエチレン膜を４５〜９０％とし、グラフ
ト率の小さなポリエチレン膜のグラフト率を２０〜４０
％とするのが適当である。More specifically, in each case, the polyethylene membrane with a large grafting rate is 45 to 90%, and the grafting rate of a polyethylene membrane with a small grafting rate is 20 to 40%.
% is appropriate.
次に第１表はこの発明をＳＲＩ１２０（外径１１．６側
、高さ２．０５側）に適用した場合と、従来品の場合と
を対比し、それぞれＩＯＮ固のアルカリ電池について６
０午０で長期間貯蔵中の開路電圧の不良発生個数を記録
したものである。Ａ〜Ｄはこの発明によるアルカリ電池
の場合であり、ＡおよびＢは２枚のポリエチレン膜を用
いた場合、ＣおよびＤは３枚のポリエチレン膜を用いた
場合を示している。また、Ｅ〜Ｇは従来品の場合で陽極
側、陰極側とも同一のグラフト率のものを用いた場合を
示すものである。Next, Table 1 compares the case where this invention is applied to SRI120 (outside diameter 11.6 side, height 2.05 side) and the case of conventional products, and compares the cases where this invention is applied to SRI120 (outside diameter 11.6 side, height 2.05 side) and the case of conventional products.
The number of open circuit voltage failures during long-term storage at 0:00 is recorded. A to D are cases of alkaline batteries according to the present invention, A and B are cases where two polyethylene membranes are used, and C and D are cases where three polyethylene membranes are used. Further, E to G show conventional products in which the same grafting ratio was used on both the anode side and the cathode side.
この表によると、この発明のアルカリ電池Ａ〜Ｄの場合
には６０日までは不良の発生がなく、８０日に至って僅
かな個数の不良が発生するが、従来品＊Ｆ、Ｇの場合に
は不良の発生が短い貯蔵期間において開始されることを
知ることができる。According to this table, in the case of the alkaline batteries A to D of this invention, no defects occur until the 60th day, and a small number of defects occur up to the 80th day, but in the case of the conventional products *F and G. It can be seen that the occurrence of defects starts in a short storage period.
第１表
次に第２表は、それぞれ１川固のアルカリ電池について
１歌○の負荷抵抗を接続して連続放電し電圧が１．２Ｖ
に達するまでの時間による放電特性を示したものである
。Table 1 and Table 2 show that each Kawabata alkaline battery is connected to a load resistance of 1 ○ and continuously discharged, resulting in a voltage of 1.2V.
This figure shows the discharge characteristics depending on the time it takes to reach .
第２表
なお、第２表においてＸは１の固の平均値を、Ｒはバラ
ッキ幅を示している。Table 2 In Table 2, X indicates the average value of 1, and R indicates the variation width.
この表によると、この発明によるものの場合にはいずれ
も安定した値を示すのに対し、従来品Ｅの場合には低温
特性が悪くしかもバラッキが大さし、。According to this table, the products according to the present invention all show stable values, while the conventional product E has poor low temperature characteristics and large variations.
さらに従来品Ｆ，Ｇの場合には高温貯蔵後の劣化が大で
あり、バラッキもまた大きくなることを知ることができ
る。以上述べたようにこの発明によれば、セパレータと
してグラフト重合ポリエチレン膜のグラフト率の異なる
ものを複数枚ラミネートして構成したものを用いること
により、インピーダンスが小さくしかも貯蔵特性を向上
することのできるアルカリ電池を提供することができる
。Furthermore, in the case of conventional products F and G, it can be seen that the deterioration after high temperature storage is large, and the variation is also large. As described above, according to the present invention, by using a separator constructed by laminating a plurality of graft-polymerized polyethylene films with different grafting ratios, an alkali which has low impedance and improves storage characteristics can be used. Batteries can be provided.
なお、この発明は上記実施例にのみ限定されるものでは
なく要旨を変更しない範囲において異なる構成をとるこ
とができる。It should be noted that the present invention is not limited to the above-mentioned embodiments, and may have different configurations without changing the gist.
第１図はこの説明の一実施例の概略的な構成を示す縦断
面図、第２図ａｂはこの発明において用いるセパレータ
のそれぞれ異なる例を示す説明図である。
１・・・金属容器、２…陽極合剤、３…セパレータ、４
・・・電解液保持剤、５陰極剤、６・・・金属封口板、
７…開口部、８・・・パッキング、９・・・環体、１１
・・・グラフト率の比較的大きなポリエチレン膜、１２
…グラフト率の比較的小さなポリエチレン膜。
第２図
第１図FIG. 1 is a longitudinal cross-sectional view showing a schematic configuration of an embodiment of the present invention, and FIG. 2 a and b are explanatory views showing different examples of separators used in the present invention. 1... Metal container, 2... Anode mixture, 3... Separator, 4
... Electrolyte holding agent, 5 cathode agent, 6... metal sealing plate,
7... Opening, 8... Packing, 9... Annular body, 11
...Polyethylene membrane with a relatively large graft ratio, 12
...Polyethylene membrane with relatively low grafting rate. Figure 2 Figure 1
Claims (1)
して、アクリル酸またはメタアクリル酸をグラフト重合
したグラフト率が異なる複数枚のポリエチレン膜をラミ
ネートし一体に構成したものを用いたことを特徴とする
アルカリ電池。 ２ グラフト率の比較的大きな第１のポリエチレン膜と
グラフト率の比較的小さな第２のポリエチレン膜とをラ
ミネートしてセパレータを構成し、このセパレータを前
記第２のポリエチレン膜が陽極合剤側となるように配設
したことを特徴とする特許請求の範囲第１項記載のアル
カリ電池。 ３ グラフト率の比較的大きなポリエチレン膜の両側に
グラフト率の比較的小さなポリエチレン膜をラミネート
してセパレータを構成したことを特徴とする特許請求の
範囲第１項記載のアルカリ電池。 ４ グラフト率の比較的大きなポリエチレン膜のグラフ
ト率を４５〜９０％とし、グラフト率の比較的小さなポ
リエチレン膜のグラフト率を２０〜４０％としたことを
特徴とする特許請求の範囲第２項または第３項記載のア
ルカリ電池。[Scope of Claims] 1. A separator interposed between the cathode agent and the anode mixture is a separator that is integrally constructed by laminating a plurality of polyethylene films with different graft ratios obtained by graft polymerizing acrylic acid or methacrylic acid. An alkaline battery characterized in that it is used. 2. A separator is constructed by laminating a first polyethylene film with a relatively large graft ratio and a second polyethylene film with a relatively low graft ratio, and the second polyethylene film is on the anode mixture side of the separator. The alkaline battery according to claim 1, characterized in that the alkaline battery is arranged as follows. 3. The alkaline battery according to claim 1, wherein the separator is constructed by laminating a polyethylene film with a relatively low graft ratio on both sides of a polyethylene film with a relatively high graft ratio. 4. Claim 2, characterized in that the grafting rate of the polyethylene membrane with a relatively large grafting rate is 45 to 90%, and the grafting rate of the polyethylene membrane with a relatively small grafting rate is 20 to 40%, or The alkaline battery according to item 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55065510A JPS6019625B2 (en) | 1980-05-16 | 1980-05-16 | alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55065510A JPS6019625B2 (en) | 1980-05-16 | 1980-05-16 | alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56160759A JPS56160759A (en) | 1981-12-10 |
| JPS6019625B2 true JPS6019625B2 (en) | 1985-05-17 |
Family
ID=13289116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55065510A Expired JPS6019625B2 (en) | 1980-05-16 | 1980-05-16 | alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6019625B2 (en) |
-
1980
- 1980-05-16 JP JP55065510A patent/JPS6019625B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56160759A (en) | 1981-12-10 |
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