JPH05205718A - Button type alkaline battery - Google Patents
Button type alkaline batteryInfo
- Publication number
- JPH05205718A JPH05205718A JP4032602A JP3260292A JPH05205718A JP H05205718 A JPH05205718 A JP H05205718A JP 4032602 A JP4032602 A JP 4032602A JP 3260292 A JP3260292 A JP 3260292A JP H05205718 A JPH05205718 A JP H05205718A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene film
- electric resistance
- graft
- positive electrode
- film
- 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
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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)
- Sealing Battery Cases Or Jackets (AREA)
- Cell Separators (AREA)
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はボタン型アルカリ電池に
関する。より詳しくは、負極剤と正極剤との間に介在す
るセパレータの積層構造に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a button type alkaline battery. More specifically, it relates to a laminated structure of a separator interposed between a negative electrode agent and a positive electrode agent.
【０００２】[0002]
【従来の技術】近年、酸化銀電池、水銀電池、アルカリ
マンガン電池、ニッケル亜鉛電池等のアルカリ電池が、
様々な種類の卓上機器や携帯機器の電源として用いら
れ、一層の小型化及び高性能化が求められている。アル
カリ電池は、基本的に負極剤と正極剤とがセパレータに
より隔絶された構造を有しており、内部は電解液で満た
されている。両極部における電気化学反応の進行に伴な
って電解液のみがセパレータを介して両極間を移動でき
る様になってる。その為、電池特性はセパレータの性能
に大きく依存している。2. Description of the Related Art In recent years, alkaline batteries such as silver oxide batteries, mercury batteries, alkaline manganese batteries, nickel zinc batteries, etc.
It is used as a power source for various types of desktop devices and portable devices, and is required to be further miniaturized and have higher performance. An alkaline battery basically has a structure in which a negative electrode agent and a positive electrode agent are separated by a separator, and the inside is filled with an electrolytic solution. Only the electrolytic solution can move between both electrodes through the separator as the electrochemical reaction progresses in both electrodes. Therefore, the battery characteristics largely depend on the performance of the separator.
【０００３】従来から、セパレータの性能を改善する為
に、積層構造のものが用いられている。これは、セロフ
ァン膜を基本とし表面及び裏面に種々の機能膜を組み合
せた構成となっている。機能膜としては、ポリエチレン
膜、不織布、紙等が用いられている。これらの材料を用
いたセパレータの積層構造としては以下に列挙するもの
が従来用いられている。即ち、ポリエチレン膜とセロフ
ァン膜とポリエチレン膜の３層ラミネート構成や、ポリ
エチレン膜とセロファン膜と不織布の３枚を組み合せた
構成や、ポリエチレン膜と第１のセロファン膜と第２の
セロファン膜と不織布の４枚を組み合せた構成等であ
る。Hitherto, in order to improve the performance of the separator, a laminated structure has been used. This has a structure in which various functional films are combined on the front surface and the back surface based on the cellophane film. As the functional film, polyethylene film, non-woven fabric, paper or the like is used. As the laminated structure of the separator using these materials, those listed below are conventionally used. That is, a three-layer laminated structure of a polyethylene film, a cellophane film and a polyethylene film, a combination of three films of a polyethylene film, a cellophane film and a non-woven fabric, a polyethylene film, a first cellophane film, a second cellophane film and a non-woven fabric. For example, the structure is a combination of four sheets.
【０００４】中間層に位置するセロファン膜は、親水性
及び保液性に優れ、電気抵抗が小さく且つ銀イオン等の
正極活物質を還元する作用があるので、優れた透過抑制
機能を有するという利点がある。しかしながら、セロフ
ァン膜はセルロース系である為、減極剤等の酸化剤と接
触すると容易に酸化され劣化する。この為、正負極間の
イオンや分子の透過を起し易くなってしまうという欠点
がある。この欠点を補う為、一般に耐酸化性を有するポ
リエチレン膜がセロファン膜と積層され、少なくとも正
極側に対面する様に配置されている。このポリエチレン
膜はイオン交換性及び保水性を付与する為に、表面の改
質された材料を用いている。具体的には、放射線を用い
てアクリル酸又はメタクリル酸の様なカルボキシル基を
有するモノマーをグラフト重合させている。The cellophane film located in the intermediate layer is excellent in hydrophilicity and liquid retention, has a small electric resistance, and has an action of reducing a positive electrode active material such as silver ion, and thus has an excellent permeation suppressing function. There is. However, since the cellophane film is cellulosic, it is easily oxidized and deteriorates when it comes into contact with an oxidizing agent such as a depolarizer. For this reason, there is a disadvantage that ions and molecules are easily transmitted between the positive and negative electrodes. In order to compensate for this drawback, a polyethylene film having oxidation resistance is generally laminated with a cellophane film and arranged so as to face at least the positive electrode side. This polyethylene membrane uses a material whose surface is modified in order to impart ion exchangeability and water retention. Specifically, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is graft-polymerized by using radiation.
【０００５】かかる表面改質ポリエチレン膜の特性はグ
ラフト率に大きく依存している。例えば、グラフト率が
大きくなると親水性が増し電気抵抗が小さくなる一方、
銀イオン等の陽極活物質に対する透過率が増し電池容量
の保存性が低下する。逆に、グラフト率が小さいと容量
保存性は向上するが膜の電気抵抗が大きくなり、閉路電
圧（以下ＣＣＶと表わす。Ｃｌｏｓｅｄ Ｃｉｒｃｕｉ
ｔ Ｖｏｌｔａｇｅの略である。）が低下する。この様
に、ポリエチレン膜のグラフト率、即ち電気抵抗の選定
が電池性能に大きく影響し極めて重要である。The properties of such surface-modified polyethylene membranes are highly dependent on the graft ratio. For example, when the graft ratio increases, the hydrophilicity increases and the electric resistance decreases,
The transmittance of the anode active material such as silver ions is increased, and the storage capacity of the battery capacity is reduced. On the contrary, when the graft ratio is small, the capacity storage property is improved, but the electric resistance of the film is increased, and the closed circuit voltage (hereinafter referred to as CCV. Closed Circuit).
Abbreviation for t Voltage. ) Is reduced. As described above, the graft ratio of the polyethylene film, that is, the selection of the electric resistance has a great influence on the battery performance and is extremely important.
【０００６】[0006]
【発明が解決しようとする課題】セロファン膜の両面に
グラフト重合したポリエチレン膜でラミネートした３層
構造のセパレータを使用する場合、従来正極側に面した
ポリエチレン膜と負極側に面したポリエチレン膜は同一
のグラフト率で表面処理されており同一の電気抵抗を有
していた。従って、グラフト率の比較的小さいポリエチ
レン膜を用いた場合には、電気抵抗が大きくなり容量保
存性が向上する一方、ＣＣＶ特性が悪くなるという課題
あるいは問題点がある。他方、グラフト率の比較的高い
ポリエチレン膜を表裏両面に共通に用いると、電気抵抗
が小さくなる為ＣＣＶ特性が向上する一方、容量保存性
が低下するという課題あるいは問題点がある。この様
に、従来ＣＣＶ特性と容量保存性を両立させともに改善
する事が非常に困難であった。When a separator having a three-layer structure in which a polyethylene film graft-polymerized is laminated on both sides of a cellophane film is used, the polyethylene film facing the positive electrode side and the polyethylene film facing the negative electrode side are conventionally the same. The surface treatment was performed at a grafting ratio of 1 and had the same electric resistance. Therefore, when a polyethylene film having a relatively small graft ratio is used, there is a problem or a problem that CCV characteristics are deteriorated while electric resistance is increased and capacity storability is improved. On the other hand, when a polyethylene film having a relatively high graft ratio is commonly used on both front and back surfaces, there is a problem or problem that CCV characteristics are improved because electric resistance is reduced, but capacity preservation is deteriorated. As described above, it has been very difficult to improve both the CCV characteristics and the capacity storability together.
【０００７】[0007]
【課題を解決するための手段】上述した従来の技術の課
題に鑑み、本発明はＣＣＶ特性と容量保存性とをともに
改善する事のできる３層ラミネート構造を有するボタン
型アルカリ電池用セパレータを提供する事を目的とす
る。かかる目的を達成する為に以下の手段を講じた。即
ち、アルカリ電池の負極剤と正極剤との間に介在させる
セパレータとして、アクリル酸又はメタクリル酸をグラ
フト重合したグラフト率が比較的小さく電気抵抗が大き
い第１のポリエチレン膜と、セロファン膜と、グラフト
率が比較的大きく電気抵抗が小さい第２のポリエレン膜
とをラミネートして一体成形したものを用いた。そし
て、第１の電気抵抗が大きいグラフト重合ポリエチレン
膜を正極剤側に配置するという手段を講じた。具体的に
は、セパレータの第１のポリエチレン膜の電気抵抗は１
５０〜５００ｍΩ・cm2 の範囲に設定し、第２のポリエ
チレン膜の電気抵抗が１００〜２００ｍΩ・cm2 の範囲
に設定する。SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, the present invention provides a button type alkaline battery separator having a three-layer laminate structure capable of improving both CCV characteristics and capacity storability. The purpose is to do. The following measures have been taken in order to achieve this object. That is, as a separator to be interposed between a negative electrode agent and a positive electrode agent of an alkaline battery, a first polyethylene film having a relatively small graft ratio obtained by graft polymerization of acrylic acid or methacrylic acid and a large electric resistance, a cellophane film, and a graft A second polyethylene film having a relatively high rate and a low electric resistance was laminated and integrally molded. Then, the first means for arranging the graft-polymerized polyethylene film having a large electric resistance on the positive electrode agent side was taken. Specifically, the electrical resistance of the first polyethylene film of the separator is 1
Set in the range of 50~500mΩ · cm 2, the electric resistance of the second polyethylene film is set in the range of 100~200mΩ · cm 2.
【０００８】[0008]
【作用】上述した様に、本発明においては正極剤側に面
するポリエチレン膜の電気抵抗を大きくし、且つ負極剤
側に面するポリエチレン膜の電気抵抗を小さく設定し
た。これにより、アルカリ電池のＣＣＶ特性を低下させ
る事なく優れた容量保存性を得る事ができる。換言する
と、正極剤側のポリエチレン膜の電気抵抗を大きくし且
つ負極剤側のポリエチレン膜の電気抵抗を小さくする事
により、容量保存性を低下させる事なくＣＣＶ特性の優
れた電池を得る事ができる。As described above, in the present invention, the electrical resistance of the polyethylene film facing the positive electrode agent side is set high, and the electrical resistance of the polyethylene film facing the negative electrode agent side is set low. As a result, it is possible to obtain excellent storage capacity without deteriorating the CCV characteristics of the alkaline battery. In other words, by increasing the electric resistance of the polyethylene film on the side of the positive electrode agent and decreasing the electric resistance of the polyethylene film on the side of the negative electrode agent, a battery having excellent CCV characteristics can be obtained without deteriorating the storage stability of the capacity. ..
【０００９】[0009]
【実施例】以下図面を参照して本発明の好適な実施例を
詳細に説明する。図１は本発明にかかるボタン型アルカ
リ電池の一実施例を示す模式的な断面図であって、本発
明を酸化銀電池ＳＲ６１６ＳＷ（外径６．８mm、高さ
１．６mm）に適用した例である。図示する様に、酸化銀
電池は負極剤１とこの負極剤１を収納する封口板２とを
備えている。この封口板２は負極端子を兼ねている。封
口板２には封口パッキン３を介して正極ケース４が嵌合
している。この封口パッキン３は例えばナイロン材料か
ら構成されており、封口板２からなる負極端子と正極ケ
ース４からなる正極端子とを電気的に絶縁している。正
極ケース４の内底部には酸化銀を主成分とするペレット
状の正極剤５が配置されている。この様に密封された電
池の内部には電解液が満たされる。本例では電解液とし
て苛性ソーダ水溶液を用いた。しかしながら、本発明は
必ずしもこれに限られるものではなく他のアルカリ水溶
液を用いる事ができる。又、本発明は酸化銀電池に限ら
れるものではなく、様々な種類の負極剤及び正極剤を用
いたアルカリ電池に適用可能である事はいうまでもな
い。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a schematic sectional view showing an embodiment of a button type alkaline battery according to the present invention, in which the present invention is applied to a silver oxide battery SR616SW (outer diameter 6.8 mm, height 1.6 mm). Is. As shown in the figure, the silver oxide battery includes a negative electrode agent 1 and a sealing plate 2 that accommodates the negative electrode agent 1. The sealing plate 2 also serves as a negative electrode terminal. The positive electrode case 4 is fitted to the sealing plate 2 via the sealing packing 3. The sealing packing 3 is made of, for example, a nylon material, and electrically insulates the negative electrode terminal composed of the sealing plate 2 and the positive electrode terminal composed of the positive electrode case 4. On the inner bottom of the positive electrode case 4, a pellet-shaped positive electrode material 5 containing silver oxide as a main component is arranged. The battery thus sealed is filled with the electrolytic solution. In this example, a caustic soda aqueous solution was used as the electrolytic solution. However, the present invention is not necessarily limited to this, and other alkaline aqueous solution can be used. Further, it goes without saying that the present invention is not limited to silver oxide batteries, but can be applied to alkaline batteries using various types of negative electrode agents and positive electrode agents.
【００１０】負極剤１と正極剤５を互いに分離する様に
セパレータ６が介在している。このセパレータ６は、負
極剤１に接する第２ポリエチレン膜８と、正極剤５に接
する第１ポリエチレン膜７と両ポリエチレン膜によって
ラミネートされたセロファン膜９とからなる３層構造を
有している。A separator 6 is interposed so as to separate the negative electrode agent 1 and the positive electrode agent 5 from each other. The separator 6 has a three-layer structure including a second polyethylene film 8 in contact with the negative electrode agent 1, a first polyethylene film 7 in contact with the positive electrode agent 5, and a cellophane film 9 laminated with both polyethylene films.
【００１１】第１ポリエチレン膜７は、アクリル酸又は
メタクリル酸をグラフト重合したものであり、グラフト
率が比較的小さな材料を用いている。この為電気抵抗が
比較的大きく、好ましくは１５０〜５００ｍΩ・cm2 の
範囲に設定されている。又、第２ポリエチレン膜８もア
クリル酸又はメタクリル酸をグラフト重合した材料を用
いている。この場合、グラフト率の比較的大きな材料を
選択しており電気抵抗が比較的小さい。好ましくは、電
気抵抗は１００〜２００ｍΩ・cm2 の範囲に設定されて
いる。これら一対の第１ポリエチレン膜７及び第２ポリ
エチレン膜８をセロファン膜９に両面から重ね合わせ一
体成形する事により積層セパレータ６を得ている。The first polyethylene film 7 is obtained by graft-polymerizing acrylic acid or methacrylic acid and uses a material having a relatively small graft ratio. For this reason, the electric resistance is relatively large and is preferably set in the range of 150 to 500 mΩ · cm 2 . The second polyethylene film 8 is also made of a material obtained by graft-polymerizing acrylic acid or methacrylic acid. In this case, a material having a relatively large graft ratio is selected and the electric resistance is relatively small. Preferably, the electric resistance is set in the range of 100 to 200 mΩ · cm 2 . The pair of the first polyethylene film 7 and the second polyethylene film 8 is superposed on the cellophane film 9 from both sides and integrally molded to obtain the laminated separator 6.
【００１２】本実施例では、第１ポリエチレン膜７の電
気抵抗値の下限を１５０ｍΩ・cm2に設定している。仮
に、第１ポリエチレン膜７の電気抵抗をこの下限値以下
に設定すると、銀イオンの透過量が著しく増してしまい
所望の容量保存性が得られにくい。又、本実施例では第
１ポリエチレン膜の電気抵抗の上限値を５００ｍΩ・cm
2 に設定している。仮に、第１ポリエチレン膜の電気抵
抗をこの上限値を越えて設定すると、内部抵抗の増大に
より所望のＣＣＶ特性が得られない。In this embodiment, the lower limit of the electric resistance of the first polyethylene film 7 is set to 150 mΩ · cm 2 . If the electrical resistance of the first polyethylene film 7 is set below this lower limit value, the amount of silver ions permeated significantly increases, making it difficult to obtain the desired capacity preservation property. In this embodiment, the upper limit of the electric resistance of the first polyethylene film is 500 mΩ · cm.
It is set to 2 . If the electric resistance of the first polyethylene film is set to exceed this upper limit value, the desired CCV characteristics cannot be obtained due to the increase of the internal resistance.
【００１３】一方、本実施例では第２ポリエチレン膜の
電気抵抗を１００〜２００ｍΩ・cm2 の範囲に設定して
いる。第２ポリエチレン膜の電気抵抗が低い程ＣＣＶ特
性が向上する。しかしながら、アクリル酸又はメタクリ
ル酸を用いたグラフト重合により表面改質を行なった場
合、製造技術上電気抵抗を１００ｍΩ・cm2 以下にする
のは困難である。この為、１００ｍΩ・cm2 を第２ポリ
エチレン膜の電気抵抗の下限値とした。一方、上限値２
００ｍΩ・cm2 については一応の目安であり、内部抵抗
をできるだけ下げる事によりＣＣＶ特性が改善される。On the other hand, in this embodiment, the electric resistance of the second polyethylene film is set in the range of 100 to 200 mΩ · cm 2 . The lower the electric resistance of the second polyethylene film is, the more the CCV characteristics are improved. However, when the surface is modified by graft polymerization using acrylic acid or methacrylic acid, it is difficult to reduce the electric resistance to 100 mΩ · cm 2 or less in terms of manufacturing technology. Therefore, 100 mΩ · cm 2 was set as the lower limit of the electric resistance of the second polyethylene film. On the other hand, the upper limit 2
00mΩ · cm 2 is a tentative guideline, and CCV characteristics are improved by reducing the internal resistance as much as possible.
【００１４】なお、グラフト重合されたポリエチレン膜
の電気抵抗は、交流式電圧降下法（１kHz)により測定し
た。測定雰囲気温度は２０±１℃に設定され、グラフト
重合ポリエチレン試料を４０％ＫＯＨ（比重１．４００
±０．００５）水溶液中に１２時間以上浸漬した後取り
出して電気抵抗を測定した。The electrical resistance of the graft-polymerized polyethylene film was measured by the AC voltage drop method (1 kHz). The measurement atmosphere temperature was set to 20 ± 1 ° C., and the graft-polymerized polyethylene sample was treated with 40% KOH (specific gravity 1.400).
(± 0.005) It was immersed in an aqueous solution for 12 hours or more and then taken out to measure the electric resistance.
【００１５】[0015]
【発明の効果】本発明の効果を確認する為サンプルを作
製して容量保存性及びＣＣＶ特性について評価を行なっ
た。なお比較の為、サンプルは発明品１種類と従来品２
種類について作製した。測定結果を説明する前に各サン
プルの内容を以下に説明する。In order to confirm the effects of the present invention, samples were prepared and evaluated for capacity preservation and CCV characteristics. For comparison, the sample is one invention product and two conventional products.
It produced about the kind. Before explaining the measurement results, the contents of each sample will be described below.
【００１６】発明品サンプルについては、電気抵抗２０
０ｍΩ・cm2 で厚み２７μｍのグラフト重合された第１
ポリエチレン膜と、厚み２１μｍのセロファン膜と、電
気抵抗１００ｍΩ・cm2 で厚み２７μｍを有するグラフ
ト重合された第２ポリエチレン膜とをこの順にラミネー
トして一体成形したものをセパレータとして用い、図１
に示すボタン型アルカリ電池を作製した。なお、電気抵
抗が大きい第１のポリエチレン膜を正極側に配置してい
る。For the invention sample, the electric resistance 20
Graft-polymerized first with a thickness of 0 μm · cm 2 and a thickness of 27 μm
A polyethylene film, a cellophane film having a thickness of 21 μm, and a graft-polymerized second polyethylene film having an electric resistance of 100 mΩ · cm 2 and a thickness of 27 μm are laminated in this order and integrally molded, and used as a separator.
A button type alkaline battery shown in was prepared. The first polyethylene film having a large electric resistance is arranged on the positive electrode side.
【００１７】従来品１のサンプルについては、電気抵抗
１５０ｍΩ・cm2 で厚み２７μｍを有するグラフト重合
された第１ポリエチレン膜と、厚み２１μｍのセロファ
ン膜と、電気抵抗１５０ｍΩ・cm2 で厚み２７μｍを有
するグラフト重合された第２ポリエチレン膜とをこの順
にラミネートして一体成形したものをセパレータとして
用い、図１に示すボタン型アルカリ電池を作製した。こ
の従来品１は発明品に比較すると第１ポリエチレン膜が
低い電気抵抗を有しており、第２ポリエチレン膜が高い
電気抵抗を有している。従って、セパレータトータルと
しての電気抵抗は発明品と等しい。The sample of the conventional product 1 has a graft-polymerized first polyethylene film having an electric resistance of 150 mΩ · cm 2 and a thickness of 27 μm, a cellophane film having a thickness of 21 μm, and an electric resistance of 150 mΩ · cm 2 and a thickness of 27 μm. A button-type alkaline battery shown in FIG. 1 was prepared by using as a separator an integrally molded product obtained by laminating a graft-polymerized second polyethylene film in this order. In this conventional product 1, the first polyethylene film has a lower electric resistance and the second polyethylene film has a higher electric resistance as compared with the invention product. Therefore, the electric resistance of the separator as a whole is equal to that of the invention product.
【００１８】従来品２のサンプルについては、電気抵抗
２００ｍΩ・cm2 で厚み２７μｍを有するグラフト重合
された第１ポリエチレン膜と、厚み２１μｍのセロファ
ン膜と、電気抵抗２００ｍΩ・cm2 で厚み２７μｍを有
するグラフト重合された第２ポリエチレン膜とをこの順
にラミネートして一体成形したものをセパレータとして
用い、図１に示すボタン型アルカリ電池を作製した。こ
の従来品２は第２ポリエチレン膜が発明品サンプルより
高い電気抵抗を有しているとともに、第１ポリエチレン
膜の電気抵抗は発明品と等しい。従ってセパレータトー
タルとしては発明品より電気抵抗は高い。The sample of Conventional Product 2 has a graft-polymerized first polyethylene film having an electric resistance of 200 mΩ · cm 2 and a thickness of 27 μm, a cellophane film having a thickness of 21 μm, and an electric resistance of 200 mΩ · cm 2 and a thickness of 27 μm. A button-type alkaline battery shown in FIG. 1 was prepared by using as a separator an integrally molded product obtained by laminating a graft-polymerized second polyethylene film in this order. In this conventional product 2, the second polyethylene film has higher electric resistance than the invention sample, and the electric resistance of the first polyethylene film is equal to that of the invention product. Therefore, the electric resistance of the separator as a whole is higher than that of the invention product.
【００１９】図２は上述した各サンプルについて容量保
存率を測定した結果を示すグラフである。横軸に保存日
数を取り縦軸に容量保存率を取っている。加速をかける
為サンプルを６０℃の温度で保存した。又、終止電圧は
１．４Ｖとした。なお、放電負荷抵抗は６８ｋΩのもの
を用いた。各測定値は１０個のサンプルの平均値であ
る。グラフ中、カーブＡが本発明品の測定結果を表わ
し、カーブＢが従来品１の測定結果を表わし、カーブＣ
が従来品２の測定結果を表わしている。このグラフから
明らかな様に、低い電気抵抗の第１ポリエチレン膜から
なるセパレータを用いた従来品１は４０日経過後容量保
存率が急激に低下している。これに対して、本発明品及
び従来品２は保存日数１００日を越えても９０％以上の
容量保存率を維持している。FIG. 2 is a graph showing the results of measuring the capacity preservation ratios of the above-mentioned samples. The horizontal axis shows the number of storage days and the vertical axis shows the capacity storage rate. The sample was stored at a temperature of 60 ° C. for acceleration. The final voltage was 1.4V. The discharge load resistance used was 68 kΩ. Each measurement is the average of 10 samples. In the graph, a curve A represents the measurement result of the product of the present invention, a curve B represents the measurement result of the conventional product 1, and a curve C.
Represents the measurement result of the conventional product 2. As is apparent from this graph, the conventional product 1 using the separator made of the first polyethylene film having a low electric resistance has a sharp decrease in the capacity retention rate after 40 days. On the other hand, the product of the present invention and the conventional product 2 maintain the capacity preservation ratio of 90% or more even after the preservation days of 100 days.
【００２０】図３はＣＣＶ特性の測定結果を表わすグラ
フである。横軸に放電深度を取り縦軸にＣＣＶを取って
いる。ＣＣＶの測定条件は２３℃で２ｋΩの負荷抵抗を
用い５秒間とした。測定値は１０個のサンプルの平均を
表わしている。図２のグラフと同様に、カーブＡが発明
品を表わし、カーブＢが従来品１を表わしカーブＣが従
来品２を表わしている。このグラフから明らかな様に、
高い電気抵抗を有する第２ポリエチレン膜からなるセパ
レータを用いた従来品２はＣＣＶが１．３Ｖ以下である
のに対して、発明品及び従来品１はＣＣＶが１．３Ｖ以
上であった。FIG. 3 is a graph showing the measurement results of CCV characteristics. The horizontal axis represents the depth of discharge and the vertical axis represents CCV. The CCV measurement conditions were 23 ° C. and a load resistance of 2 kΩ for 5 seconds. The measured value represents the average of 10 samples. Similar to the graph of FIG. 2, the curve A represents the invention product, the curve B represents the conventional product 1, and the curve C represents the conventional product 2. As you can see from this graph,
The conventional product 2 using the separator made of the second polyethylene film having a high electric resistance has a CCV of 1.3 V or less, whereas the invention product and the conventional product 1 have a CCV of 1.3 V or more.
【００２１】以上の測定結果から明らかな様に、従来品
１と比較して、発明品は容量保存性において明らかに優
れ且つＣＣＶ特性は劣らない事が解る。又、従来品２に
比較すると、本発明品はＣＣＶ特性が優れているにもか
かわらず容量保存性が劣らない事が解る。この結果か
ら、ＣＣＶ特性はセパレータの積層膜トータルの電気抵
抗に依存するとともに、容量保存性は正極剤側に配置さ
れた第１ポリエチレン膜の電気抵抗に依存する事が判明
した。この原因は、電気抵抗が大きいポリエチレン膜を
正極剤側に配置する事により銀イオンの透過量を少なく
でき、セロファン膜が銀イオンで破壊され難くなる為で
ある。即ち、正極剤側のポリエチレン膜の電気抵抗を大
きくし且つ負極剤側のポリエチレン膜の電気抵抗を小さ
くする事により、ＣＣＶ特性を低下させる事なく容量保
存性に優れたアルカリ電池を提供する事ができる。又、
負極剤側のポリエチレン膜の電気抵抗を小さくする事に
より、容量保存性を低下させる事なくＣＣＶ特性の優れ
たアルカリ電池を提供する事ができる。As is clear from the above measurement results, the invention product is clearly superior in the capacity preservation property and the CCV characteristic is not inferior to the conventional product 1 as compared with the conventional product 1. Further, as compared with the conventional product 2, it can be seen that the product of the present invention is excellent in CCV characteristics, but is not inferior in capacity preservation. From this result, it was found that the CCV characteristics depend on the total electric resistance of the laminated film of the separator, and the capacity preservation property depends on the electric resistance of the first polyethylene film arranged on the positive electrode agent side. The reason for this is that by arranging a polyethylene film having high electric resistance on the positive electrode side, the amount of silver ions permeated can be reduced, and the cellophane film is less likely to be broken by silver ions. That is, by increasing the electric resistance of the polyethylene film on the side of the positive electrode agent and decreasing the electric resistance of the polyethylene film on the side of the negative electrode agent, it is possible to provide an alkaline battery excellent in capacity preservation without lowering CCV characteristics. it can. or,
By reducing the electric resistance of the polyethylene film on the negative electrode agent side, it is possible to provide an alkaline battery having excellent CCV characteristics without deteriorating the capacity storage property.
【図１】本発明にかかるボタン型アルカリ電池の基本的
な構成を示す断面図である。FIG. 1 is a cross-sectional view showing the basic configuration of a button type alkaline battery according to the present invention.
【図２】ボタン型アルカリ電池の容量保存率を測定した
結果を示すグラフである。FIG. 2 is a graph showing the results of measuring the capacity retention of button-type alkaline batteries.
【図３】ボタン型アルカリ電池のＣＣＶ特性を測定した
結果を表わすグラフである。FIG. 3 is a graph showing a result of measuring CCV characteristics of a button type alkaline battery.
１ 負極剤 ２ 封口板 ３ 封口パッキン ４ 正極ケース ５ 正極剤 ６ セパレータ ７ 第１ポリエチレン膜 ８ 第２ポリエチレン膜 ９ セロファン膜 1 Negative agent 2 Sealing plate 3 Sealing packing 4 Positive electrode case 5 Positive electrode agent 6 Separator 7 First polyethylene film 8 Second polyethylene film 9 Cellophane film
Claims (2)
レータとして、アクリル酸又はメタクリル酸をグラフト
重合したグラフト率が比較的小さく電気抵抗が大きい第
１のポリエチレン膜と、セロファン膜と、グラフト率が
比較的大きく電気抵抗が小さい第２のポリエチレン膜と
をラミネートして一体成形したものを用い、第１の電気
抵抗が大きいグラフト重合ポリエチレン膜を正極剤側に
配置した事を特徴とするアルカリ電池。1. A first polyethylene film obtained by graft polymerization of acrylic acid or methacrylic acid, which has a relatively small graft ratio and a large electric resistance, and a cellophane film, as a separator interposed between the negative electrode agent and the positive electrode agent. Alkali characterized in that it is formed by laminating and integrally molding a second polyethylene film having a relatively large electric resistance and a small electric resistance, and a graft-polymerized polyethylene film having a large first electric resistance is arranged on the positive electrode side. battery.
の電気抵抗が１５０〜５００ｍΩ・cm2 の範囲にあり、
第２のポリエチレン膜の電気抵抗が１００〜２００ｍΩ
・cm2 の範囲とした事を特徴とする請求項１記載のアル
カリ電池。2. The electrical resistance of the first polyethylene film of the separator is in the range of 150 to 500 mΩ · cm 2 ,
The electrical resistance of the second polyethylene film is 100 to 200 mΩ
The alkaline battery according to claim 1, wherein the alkaline battery has a range of cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03260292A JP3235161B2 (en) | 1992-01-22 | 1992-01-22 | Button type alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03260292A JP3235161B2 (en) | 1992-01-22 | 1992-01-22 | Button type alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05205718A true JPH05205718A (en) | 1993-08-13 |
| JP3235161B2 JP3235161B2 (en) | 2001-12-04 |
Family
ID=12363412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03260292A Expired - Lifetime JP3235161B2 (en) | 1992-01-22 | 1992-01-22 | Button type alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3235161B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006120549A (en) * | 2004-10-25 | 2006-05-11 | Hitachi Maxell Ltd | Silver oxide battery |
-
1992
- 1992-01-22 JP JP03260292A patent/JP3235161B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006120549A (en) * | 2004-10-25 | 2006-05-11 | Hitachi Maxell Ltd | Silver oxide battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3235161B2 (en) | 2001-12-04 |
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