JPH073794B2 - Alkaline zinc storage battery - Google Patents
Alkaline zinc storage batteryInfo
- Publication number
- JPH073794B2 JPH073794B2 JP61272633A JP27263386A JPH073794B2 JP H073794 B2 JPH073794 B2 JP H073794B2 JP 61272633 A JP61272633 A JP 61272633A JP 27263386 A JP27263386 A JP 27263386A JP H073794 B2 JPH073794 B2 JP H073794B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- negative electrode
- area
- battery
- zinc negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明はニッケル−亜鉛蓄電池、銀−亜鉛蓄電池などの
ように負極活物質として亜鉛を用いるアルカリ亜鉛蓄電
池に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to an alkaline zinc storage battery using zinc as a negative electrode active material such as a nickel-zinc storage battery and a silver-zinc storage battery.
（ロ）従来の技術 負極活物質に亜鉛を用いたアルカリ蓄電池はエネルギー
密度が高く、高い作動電圧を有し、経済性に優れている
などの利点を有するが、サイクル寿命が短いという欠点
がある。この原因は放電時に亜鉛がアルカリ電解液中に
亜鉛酸イオンとして溶出し、充電時にこの亜鉛酸イオン
が亜鉛負極表面に樹枝状に金属亜鉛として電析するた
め、充放電を繰り返すとこの樹枝状亜鉛が生長しセパレ
ータを貫通して、正極と接し内部短絡を引き起すことに
起因する。(B) Conventional technology Alkaline storage batteries using zinc as a negative electrode active material have advantages such as high energy density, high operating voltage, and excellent economical efficiency, but have a short cycle life. .. This is because zinc elutes as zincate ions in the alkaline electrolyte during discharge and these zincate ions are deposited as metal zinc on the surface of the zinc negative electrode during charging. Grows, penetrates the separator, contacts the positive electrode, and causes an internal short circuit.
この樹枝状亜鉛の生長を抑制するため種々のセパレータ
材が検討されているが、セパレータが１枚よりなるもの
においては抑制効果が十分でないので、セパレータを数
枚、数種類よりなるものより構成することが種々提案さ
れている。しかし、このようなセパレータの構成を用い
たとしても、亜鉛負極周辺部に余剰の電解液が存在した
り、亜鉛負極周辺部に電流が集中するというエッヂ効果
によって、充放電サイクルの進行と共に亜鉛負極周辺部
の活物質が他の部分に電析して極板変形を生じたり、亜
鉛負極周辺部に樹枝状亜鉛が生長しやすいという問題が
ある。Various separator materials have been studied in order to suppress the growth of this dendritic zinc. However, since the effect of suppressing the separator having only one separator is not sufficient, the separator should be composed of several separators or several separators. Have been proposed. However, even if such a separator structure is used, due to the edge effect that excess electrolyte is present around the zinc negative electrode or current is concentrated around the zinc negative electrode, the zinc negative electrode is advanced as the charge and discharge cycle progresses. There are problems that the active material in the peripheral portion is electrodeposited on other portions to cause electrode plate deformation, and that dendritic zinc easily grows in the peripheral portion of the zinc negative electrode.
そこで実開昭49−34317号公報では亜鉛負極周辺部に耐
アルカリ性樹脂層を設けることが提案されており、亜鉛
負極周辺部の電流集中を抑制する試みがなされている
が、耐アルカリ性樹脂と亜鉛負極が化学結合しているわ
けではなく単に物理的に接触しているものであるため、
電解液が亜鉛負極周辺部に浸透して行き、長期に亘って
その効果を維持できなくなるという問題がある。Therefore, Japanese Utility Model Application Laid-Open No. 49-34317 proposes to provide an alkali resistant resin layer around the zinc negative electrode, and attempts have been made to suppress current concentration around the zinc negative electrode. Since the negative electrode is not chemically bound, it is simply in physical contact,
There is a problem that the electrolytic solution permeates into the peripheral portion of the zinc negative electrode and the effect cannot be maintained for a long period of time.
（ハ）発明が解決しようとする問題点 本発明は充放電サイクルの進行に伴って生じる亜鉛負極
周辺部の変形を抑制し、且樹枝状亜鉛の生長を因とする
電池特性のサイクル劣化を抑制しようとするものであ
る。(C) Problems to be Solved by the Invention The present invention suppresses the deformation of the periphery of the zinc negative electrode caused by the progress of charge / discharge cycles, and suppresses the cycle deterioration of the battery characteristics due to the growth of dendritic zinc. Is what you are trying to do.
（ニ）問題点を解決するための手段 本発明のアルカリ亜鉛蓄電池は亜鉛負極と正極間に、微
孔性フィルムと電解液保持体としての不織布とを含む複
数枚のセパレータを配設してなる電極体を備えたもので
あって、亜鉛負極の最も近くに配設した不織布の面積を
前記正負両極よりも小とし、他のセパレータ部材の面積
を前記正負両極よりも大とした構成とするものである。
尚、亜鉛負極の最も近くに配設した不織布の面積を、前
記亜鉛負極の面積に対して80〜95％とすれば一層の効果
を奏するものである。(D) Means for Solving the Problems The alkaline zinc storage battery of the present invention comprises a plurality of separators including a microporous film and a non-woven fabric as an electrolyte holder between the zinc negative electrode and the positive electrode. An electrode body, wherein the area of the non-woven fabric disposed closest to the zinc negative electrode is smaller than the positive and negative electrodes, and the area of the other separator member is larger than the positive and negative electrodes. Is.
Further, if the area of the non-woven fabric arranged closest to the zinc negative electrode is 80 to 95% of the area of the zinc negative electrode, a further effect can be obtained.
（ホ）作用 亜鉛負極の最も近くに配設した電解液保持体である不織
布の面積を正負両極よりも小さくすることで、亜鉛負極
周辺部における電解液量を制限し反応が集中するのを抑
え、エッヂ効果による電流集中を緩和し、更に、周辺部
の電解液量が規制されているので、亜鉛負極周辺部の変
形及び樹枝状亜鉛の生長を抑制することが可能となる。
また亜鉛負極周辺部に不織布が存在しないことから、過
充電時に正極より発生する酸素ガスが、亜鉛負極と接し
やすくなり、酸素ガスの吸収が速やかに行なわれるので
過充電時の電池内圧上昇を抑制しうる。(E) Action By limiting the area of the non-woven fabric, which is the electrolyte solution holder placed closest to the zinc negative electrode, to be smaller than that of the positive and negative electrodes, the amount of electrolyte solution in the peripheral area of the zinc negative electrode is limited and the reaction is suppressed from concentrating. Since the current concentration due to the edge effect is alleviated and the amount of the electrolyte solution in the peripheral portion is regulated, the deformation of the peripheral portion of the zinc negative electrode and the growth of dendritic zinc can be suppressed.
In addition, since there is no non-woven fabric around the zinc negative electrode, oxygen gas generated from the positive electrode during overcharging is likely to come into contact with the zinc negative electrode, and oxygen gas is absorbed quickly, suppressing an increase in battery internal pressure during overcharging. You can.
（ヘ）実施例 以下に本発明の一実施例を示し詳述する。(F) Example One example of the present invention will be described in detail below.
第１図は本発明のニッケル−亜鉛蓄電池の縦断面図であ
り、１は活物質としての酸化亜鉛及び添加剤としての酸
化インジウムの混合物にポリテトラフルオロエチレンの
ディスパーションを加えて混練、圧延した活物質シート
をパンチングメタル集電体に圧着した亜鉛負極、２はポ
リプロピレン製の微孔性フィルム、3a、3bはナイロン不
織布、４は焼結式ニッケル正極である。ここで亜鉛負極
の最も近くに配設したナイロン不織布3aの面積は亜鉛負
極の面積の90％であり、亜鉛負極とニッケル正極の面積
は略同等である。また他のナイロン不織布36及び微孔正
フィルム２は正負両極よりも大となっており、これを本
発明電池Ａとした。FIG. 1 is a vertical cross-sectional view of a nickel-zinc storage battery of the present invention, in which 1 is a mixture of zinc oxide as an active material and indium oxide as an additive to which a dispersion of polytetrafluoroethylene is added, and the mixture is kneaded and rolled. A zinc negative electrode obtained by pressing an active material sheet onto a punching metal current collector, 2 is a microporous film made of polypropylene, 3a and 3b are nylon nonwoven fabrics, and 4 is a sintered nickel positive electrode. Here, the area of the nylon nonwoven fabric 3a arranged closest to the zinc negative electrode is 90% of the area of the zinc negative electrode, and the areas of the zinc negative electrode and the nickel positive electrode are substantially the same. Further, the other nylon non-woven fabric 36 and the positive micropore film 2 are larger than the positive and negative electrodes, which is referred to as Battery A of the present invention.
比較例として、前記実施例のナイロン不織布3aが他のナ
イロン不織布と同一の大きさのものを用いた他の同一構
成の比較電池Ｂを作製した。As a comparative example, a comparative battery B having the same structure was prepared in which the nylon non-woven fabric 3a of the above-mentioned example had the same size as other nylon non-woven fabrics.
これらの電池を用い充電電流250mAで４時間30分充電
し、直ちに250mAで放電終止電圧1.0Vまで放電を行うと
いう一連の充放電サイクル試験を行い、初期容量の50％
を維持できなくなったところを電池寿命とした。Using these batteries, a series of charge and discharge cycle tests were conducted in which the batteries were charged at a charging current of 250 mA for 4 hours and 30 minutes, and immediately discharged at 250 mA to a discharge end voltage of 1.0 V.
The battery life was defined as the point where the battery could not be maintained.
第２図はこれら電池のサイクル特性比較図である。第２
図より本発明電池Ａのサイクル特性が優れているのがわ
かり、これは亜鉛負極の最も近くに配設した電解液保持
体である不織布の面積を亜鉛負極よりも小さくしている
ため、亜鉛負極周辺部の変形、樹枝状亜鉛の生長が抑制
されたことに基づくものである。FIG. 2 is a comparison diagram of cycle characteristics of these batteries. Second
From the figure, it can be seen that the battery A of the present invention has excellent cycle characteristics. This is because the area of the non-woven fabric, which is the electrolytic solution holder, arranged closest to the zinc negative electrode is smaller than that of the zinc negative electrode. This is because the deformation of the peripheral part and the growth of dendritic zinc were suppressed.
次に本発明電池Ａ、比較電池Ｂを250mAの充電電流で20
時間充電した時の電池内圧を比較した結果を、第３図に
示す。Next, the present battery A and the comparative battery B were charged at a charging current of 250 mA for 20
FIG. 3 shows the results of comparing the internal pressures of the batteries when they were charged for a certain period of time.
第３図より本発明電池Ａに過充電により発生した酸素ガ
スの吸収が速く、電池内圧が5kg/cm2で一定となってい
る。しかし比較電池Ｂは酸素ガスの吸収が遅いため電池
内圧が10kg/cm2以上となり、安全弁が作動し、電解液量
が減少するという現象が発生する。As shown in FIG. 3, the battery A of the present invention absorbs oxygen gas generated by overcharging quickly, and the battery internal pressure is constant at 5 kg / cm 2 . However, since the comparative battery B absorbs oxygen gas slowly, the internal pressure of the battery becomes 10 kg / cm 2 or more, the safety valve operates, and the amount of electrolyte decreases.
次に亜鉛負極の最も近くに配設したナイロン不織布の大
きさについて種々検討した。亜鉛負極の面積を100とし
ナイロン不織布の大きさを130、100、95、90、80、70の
６種類を用いて前述のニッケル−亜鉛蓄電池を組み立
て、前述と同様のサイクル試験を行った。Next, various studies were conducted on the size of the nylon nonwoven fabric arranged closest to the zinc negative electrode. The above-mentioned nickel-zinc storage battery was assembled using six types of nylon nonwoven fabric sizes of 130, 100, 95, 90, 80, and 70 with the area of the zinc negative electrode being 100, and the same cycle test as described above was performed.
この結果を第４図に示す。これより亜鉛負極に対し95〜
80％の面積を有する不織布を用いるとサイクル寿命の向
上が計れる。ナイロン不織布の面積を80％以下とすると
亜鉛負極の利用面積が小さくなるので急にサイクル寿命
が短くなる。また100％以上になると亜鉛負極周辺部の
変形、樹枝状亜鉛の生長が抑制されず、サイクル寿命が
低下する。The results are shown in FIG. From this, 95-
If a non-woven fabric having an area of 80% is used, the cycle life can be improved. If the area of nylon non-woven fabric is 80% or less, the usable area of the zinc negative electrode becomes small and the cycle life suddenly becomes shorter. On the other hand, when it is 100% or more, the deformation of the periphery of the zinc negative electrode and the growth of dendritic zinc are not suppressed, and the cycle life is reduced.
尚、実施例では不織布としてナイロン不織布を用いた
が、ポリプロピレン、レーヨン、ビニロン、コットンな
どの不織布を用いても同様の効果が得られる。また微孔
性フィルムとしては実施例で用いたポリプロピレン製の
もの以外に、セルロース製のセロハン、ポリエチレン製
のものなどを用いることができる。Although nylon non-woven fabric was used as the non-woven fabric in the examples, similar effects can be obtained by using non-woven fabrics such as polypropylene, rayon, vinylon and cotton. As the microporous film, other than the polypropylene film used in the examples, cellulose cellophane, polyethylene film and the like can be used.
（ト）発明の効果 本発明の構成とすることで、亜鉛負極周辺部の変形及び
樹枝状亜鉛の生長が抑制でき、更には過充電時の酸素ガ
ス吸収性能を向上させることができるので、サイクル特
性に優れたアルカリ亜鉛蓄電池が提供でき、その工業的
価値はきわめて大きい。(G) Effect of the Invention With the configuration of the present invention, it is possible to suppress the deformation of the peripheral portion of the zinc negative electrode and the growth of dendritic zinc, and further to improve the oxygen gas absorption performance during overcharge. An alkaline zinc storage battery with excellent characteristics can be provided, and its industrial value is extremely large.
【図面の簡単な説明】 第１図は本発明電池の縦断面図、第２図は電池のサイク
ル特性比較図、第３図は電池内圧比較図、第４図は不織
布の大きさを変えたときの電池のサイクル寿命比較図で
ある。 １…亜鉛負極、２…微孔性フィルム、3a、3b…ナイロン
不織布、４…ニッケル正極、Ａ…本発明電池、Ｂ…比較
電池。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a longitudinal sectional view of a battery of the present invention, FIG. 2 is a battery cycle characteristic comparison diagram, FIG. 3 is a battery internal pressure comparison diagram, and FIG. 4 is different in size of a nonwoven fabric. It is a cycle life comparison figure of the battery at this time. 1 ... Zinc negative electrode, 2 ... Microporous film, 3a, 3b ... Nylon nonwoven fabric, 4 ... Nickel positive electrode, A ... Inventive battery, B ... Comparative battery.
Claims (2)
解液保持体としての不織布とを含む複数枚のセパレータ
を配設してなる電極体を備えたものであって、亜鉛負極
の最も近くに配設した不織布の面積を前記正負両極より
も小とし、他のセパレータ部材の面積を前記正負両極よ
りも大とすることを特徴とするアルカリ亜鉛蓄電池。1. An electrode body comprising a plurality of separators containing a microporous film and a non-woven fabric as an electrolyte holder between a zinc negative electrode and a positive electrode. An area of the non-woven fabric disposed closest to the positive and negative electrodes is smaller than that of the other separator member, and an area of the other separator member is larger than that of the positive and negative electrodes.
の面積を、前記亜鉛負極の面積に対して80〜95％とする
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
亜鉛蓄電池。2. The alkali zinc according to claim 1, wherein the area of the non-woven fabric arranged closest to the zinc negative electrode is 80 to 95% of the area of the zinc negative electrode. Storage battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61272633A JPH073794B2 (en) | 1986-11-14 | 1986-11-14 | Alkaline zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61272633A JPH073794B2 (en) | 1986-11-14 | 1986-11-14 | Alkaline zinc storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63126176A JPS63126176A (en) | 1988-05-30 |
| JPH073794B2 true JPH073794B2 (en) | 1995-01-18 |
Family
ID=17516645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61272633A Expired - Lifetime JPH073794B2 (en) | 1986-11-14 | 1986-11-14 | Alkaline zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH073794B2 (en) |
-
1986
- 1986-11-14 JP JP61272633A patent/JPH073794B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63126176A (en) | 1988-05-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |