JPH06101327B2 - Alkaline zinc secondary battery - Google Patents
Alkaline zinc secondary batteryInfo
- Publication number
- JPH06101327B2 JPH06101327B2 JP58004356A JP435683A JPH06101327B2 JP H06101327 B2 JPH06101327 B2 JP H06101327B2 JP 58004356 A JP58004356 A JP 58004356A JP 435683 A JP435683 A JP 435683A JP H06101327 B2 JPH06101327 B2 JP H06101327B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- active material
- battery
- electrode
- secondary battery
- 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
- 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
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明はアルカリ亜鉛二次電池に関し、特にその亜鉛極
の改良に関する。TECHNICAL FIELD The present invention relates to an alkaline zinc secondary battery, and particularly to improvement of a zinc electrode thereof.
（ロ）従来技術 この種亜鉛極は種々改良がなされ、近年においては例え
ばアメリカ特許第3,954,501号に開示されているよう
に、亜鉛活物質を未焼結で撥水性のフツ素樹脂の繊維状
結合網にて抱束し、活物質のガス及び電解液との接触を
高度に維持せしめる構造のものが提案されている。(B) Prior art This kind of zinc electrode has undergone various improvements, and in recent years, as disclosed in, for example, U.S. Pat. No. 3,954,501, a zinc active material is a non-sintered, water-repellent fluororesin fibrous bond. A structure having a structure in which it is bound by a net and highly maintained in contact with the gas of the active material and the electrolytic solution has been proposed.
而して亜鉛極をアルカリ電極液中で放電した場合、周知
のようにZn（OH）-- 4を形成して電解液中に溶出し、更
に放電が進行して電解液がZn（OH）-- 4で飽和するとZn
(OH)2として沈殿し電槽下部に堆積することになる。When discharged to Thus to zinc electrode in an alkaline electrode solution, Zn as is well known (OH) - 4 the formed eluted into the electrolytic solution, further liquid discharge progresses electrolytic Zn (OH) - When saturated with 4 Zn
It will be precipitated as (OH) 2 and will be deposited at the bottom of the battery case.
次に充填を行うと電解液中のZn（OH）-- 4は、金属亜鉛
となつて亜鉛極上に復元析出するのであるが、電槽下部
に堆積したZn(OH)2は金属亜鉛に戻ることはできない。Then Zn in electrolytic solution to perform the filling (OH) - 4 is, although to restore precipitated summer and metallic zinc Te zinc superb, Zn (OH) 2 deposited on the lower electrode tank returns to metallic zinc It is not possible.
このように充放電を繰返すと、活物質として再生できな
いZn(OH)2が蓄積することになり、亜鉛極（１）′自身
は第１図（イ）に示す初期の状態からサイクル経過後の
状態図である（ロ）に示す如く表面の亜鉛活物質（２）
が消耗することになる。このため亜鉛極の表面は亜鉛活
物質のみが除かれてフツ素樹脂の繊維状網（３）が高密
度に存在し、フツ素樹脂が撥水性を有することから残存
の亜鉛活物質への電解液の供給が困難となりサイクル特
性の劣下を引起す結果となる。When the charge and discharge are repeated in this way, Zn (OH) 2 which cannot be regenerated as an active material is accumulated, and the zinc electrode (1) 'itself becomes a state after the cycle has elapsed from the initial state shown in Fig. 1 (a). As shown in the state diagram (b), the zinc active material on the surface (2)
Will be consumed. For this reason, only the zinc active material is removed from the surface of the zinc electrode, and the fibrous network (3) of fluororesin is present at a high density, and since the fluororesin has water repellency, electrolysis to the remaining zinc active material is performed. This makes it difficult to supply the liquid, resulting in deterioration of cycle characteristics.
かかる点に鑑み本発明者は、亜鉛活物質を抱束する未焼
結フツ素樹脂の繊維状結合網に、親水性の、あるいは親
水性を付与した繊維体を絡みつけて混在せしめる亜鉛極
について、特願昭55−110858号で先に提案した。この提
案は、充放電の繰返しにより、亜鉛極の表面が未焼結フ
ツ素樹脂の繊維状結合網により覆われても、電解液が親
水性繊維体を介して残存する亜鉛活物質に円滑に供給さ
れ、アルカリ亜鉛二次電池のサイクル特性を向上させる
ことができるものである。In view of such a point, the present inventor has proposed a zinc electrode in which a fibrous bond network of a non-sintered fluororesin that bundles a zinc active material is entangled with a hydrophilic or hydrophilically imparted fibrous body. , Which was previously proposed in Japanese Patent Application No. 55-110858. In this proposal, even if the surface of the zinc electrode is covered with a fibrous bond network of unsintered fluororesin by repeated charging and discharging, the electrolytic solution smoothly flows into the zinc active material remaining through the hydrophilic fibrous body. When supplied, the cycle characteristics of the alkaline zinc secondary battery can be improved.
ところがその後の研究によると、混在する親水性繊維
体、あるいは界面活性剤を付与して親水性とした繊維体
は、充放電を繰返すと、その繊維体は徐々に初期の親水
性が失われていき、親水性能力が低下する。このため電
解液が残存する亜鉛活物質に円滑に供給されなくなり、
サイクル寿命の向上に限界があることがわかつた。However, according to subsequent research, the hydrophilic fibrous materials mixed with each other, or the fibrous material to which the surfactant was added to make it hydrophilic, gradually loses its initial hydrophilicity after repeated charging and discharging. And the hydrophilic ability is reduced. Therefore, the electrolytic solution is not smoothly supplied to the remaining zinc active material,
It was found that there is a limit to the improvement of cycle life.
（ハ）発明の目的 本発明はかかる点に鑑み発明されたものにして、サイク
ル寿命をより一層向上したアルカリ亜鉛二次電池を提供
せんとするものである。(C) Object of the invention The present invention has been made in view of the above points and provides an alkaline zinc secondary battery having a further improved cycle life.
（ニ）発明の構成 本発明によるアルカリ亜鉛二次電池は、未焼結で撥水性
のフツ素樹脂の繊維状結合網により亜鉛活物質を抱束
し、前記繊維状結合網に中空繊維体を絡みつけるように
混在せしめてなる亜鉛極を備えてなるものであり、充放
電の繰返しにより亜鉛極の表面が未焼結のフツ素樹脂の
繊維状結合網で覆われても、電解液が中空繊維体を介し
て残存する亜鉛活物質に円滑に供給され、サイクル特性
をより一層向上せんとするものである。(D) Structure of the Invention In the alkaline zinc secondary battery according to the present invention, a zinc active material is bound by a fibrous bond network of unsintered and water-repellent fluororesin, and a hollow fiber body is attached to the fibrous bond network. It is equipped with a zinc electrode that is mixed so as to be entwined, and even if the surface of the zinc electrode is covered with a fibrous bond network of unsintered fluorine resin due to repeated charging and discharging, the electrolyte solution is hollow. It is smoothly supplied to the remaining zinc active material through the fibrous body to further improve the cycle characteristics.
（ホ）実施例 本発明の一実施例を説明する。(E) Example An example of the present invention will be described.
酸化亜鉛100重量％、酸化水銀２重量％及びポリオレフ
イン中空繊維体２重量％を混合した混合物に、ポリテト
ラフルオロエチレイのデイスパージヨン（濃度60％）５
重量％及び水50重量％を加えせん断力を与えつつ混練す
る。得られた混練物を圧延ローラーにより0.7mmの厚み
に圧延したペーストシートを陰極集電体の両面に当接
し、圧延圧着して厚み1mmの亜鉛極を得る。To a mixture of 100% by weight of zinc oxide, 2% by weight of mercury oxide and 2% by weight of polyolefin hollow fiber body, polytetrafluoroethylene dispersion (concentration 60%) 5
Add wt% and 50 wt% of water and knead while applying shearing force. A paste sheet obtained by rolling the obtained kneaded product with a rolling roller to a thickness of 0.7 mm is brought into contact with both surfaces of the cathode current collector and rolled and pressure-bonded to obtain a zinc electrode having a thickness of 1 mm.
上記亜鉛極５枚と周知の焼結式ニツケル極４枚を用いて
容量2AHのニルケル−亜鉛電池（Ａ）を作成した。A nickel-zinc battery (A) having a capacity of 2 AH was prepared by using the above-mentioned five zinc electrodes and four known sintering type nickel electrodes.
次に、比較のためポリオレフイン中空繊維体に代つて親
水性繊維であるポリオレフイン繊維を混入した亜鉛極を
作成し、他の実施例と同様の比較電池（Ｂ）を作成し
た。Next, for comparison, a zinc electrode containing hydrophilic polyolefin fibers in place of the polyolefin hollow fiber body was prepared, and a comparative battery (B) similar to the other examples was prepared.
第２図及び第３図は、夫々放充電サイクル経過後の実施
例による電池（Ａ）と比較電池（Ｂ）の亜鉛極表面の部
分拡大図である。これらの図面において、（１）は亜鉛
極、（２）は亜鉛活物質、（３）は未焼結フツ素樹脂の
繊維状結合網、（４）はポリオレフイン中空繊維体、
（５）はポリオレフイン繊維である。2 and 3 are partially enlarged views of the zinc electrode surface of the battery (A) according to the example and the comparative battery (B) after the discharge charging cycle has passed. In these drawings, (1) is a zinc electrode, (2) is a zinc active material, (3) is a fibrous bond network of unsintered fluorine resin, (4) is a polyolefin hollow fiber body,
(5) is a polyolefin fiber.
第４図は実施例による電池（Ａ）と比較電池との充放電
サイクル特性を示す。尚、充放電条件は、400mAで５時
間充電した後、500mAで電池電圧が1.0Vに達するまで放
電した。１サイクル目の放電容量を100とし、放電容量
を百分率で示した。この図面より本発明による実施例の
電池（Ａ）は、比較電池（Ｂ）に比しサイクル特性が改
善されていることがわかる。FIG. 4 shows charge / discharge cycle characteristics of the battery (A) according to the example and the comparative battery. The charging / discharging conditions were such that the battery was charged at 400 mA for 5 hours and then discharged at 500 mA until the battery voltage reached 1.0V. The discharge capacity in the first cycle was 100, and the discharge capacity was shown in percentage. From this drawing, it is understood that the battery (A) of the example according to the present invention has improved cycle characteristics as compared with the comparative battery (B).
この理由を考察するに、比較電池（Ｂ）におけるポリオ
レフイン繊維（５）は、充放電サイクルの進行につれ親
水性能力が次第に低下し、電解液が亜鉛活物質（２）に
供給され難くなる。これに対し、本発明による実施例の
電池（Ａ）におけるポリオレフイン中空繊維体（４）
は、充放電サイクルが進行しても、繊維中の中空が維持
され、この中空を通じて電解液が亜鉛活物質（２）に供
給され続ける。また中空繊維体（４）の側壁も多孔性で
あるため、、中空内の電解液は側壁を通り抜けて亜鉛活
物質（２）に供給され続けるため、亜鉛活物質（２）の
広い範囲にわたつて電解液が供給されることになり、サ
イクル特性が向上するものと考えられる。Considering the reason for this, the hydrophilic ability of the polyolefin fibers (5) in the comparative battery (B) gradually decreases as the charging / discharging cycle progresses, and it becomes difficult to supply the electrolytic solution to the zinc active material (2). In contrast, the polyolefin hollow fiber body (4) in the battery (A) of the example according to the present invention
Even if the charge / discharge cycle progresses, the hollow in the fiber is maintained, and the electrolytic solution is continuously supplied to the zinc active material (2) through the hollow. Further, since the side wall of the hollow fiber body (4) is also porous, the electrolytic solution inside the hollow continues to be supplied to the zinc active material (2) through the side wall, so that the zinc active material (2) is spread over a wide range. It is considered that the electrolytic solution is then supplied and the cycle characteristics are improved.
尚、混入する中空繊維体としては、ポリアミド中空繊
維、ポリオレフイン中空繊維、ポリエステル中空繊維及
びポリスチレン中空繊維等を利用できる。As the hollow fiber body to be mixed, polyamide hollow fiber, polyolefin hollow fiber, polyester hollow fiber, polystyrene hollow fiber and the like can be used.
（ヘ）発明の効果 以上の如く本発明は、未焼結で撥水性のフツ素樹脂の繊
維状結合網に亜鉛活物質を抱束するものであつて、前記
繊維状結合網に中空繊維体を絡みつけるように混在させ
るものであるから、充放電の繰返しによる亜鉛活物質の
溶解溶出によつて、亜鉛極表面が前記繊維状結合網によ
り覆われる状態に至つても、前記中空繊維の中空を介し
て電極内部の亜鉛活物質への電解液の供給が円滑になさ
れるため、かかる亜鉛極を用いるアルカリ亜鉛二次電池
のサイクル特性を向上させることができ、その工業的価
値大なるものである。(F) Effect of the Invention As described above, the present invention is a method for binding a zinc active material to a fibrous bond network of unsintered and water-repellent fluororesin, wherein the fibrous bond network is a hollow fiber body. Therefore, even if the zinc electrode surface is covered with the fibrous bond network by the dissolution and elution of the zinc active material due to repeated charging and discharging, the hollow fibers are hollow. Since the electrolytic solution is smoothly supplied to the zinc active material inside the electrode via the electrode, it is possible to improve the cycle characteristics of the alkaline zinc secondary battery using such a zinc electrode, which is of great industrial value. is there.
第１図は従来の二次電池における亜鉛極の部分拡大図で
あり、（イ）は初期状態図、（ロ）はサイクル経過後の
状態図である。第２図及び第３図は夫々サイクル経過後
における本発明による実施例の電池及び比較電池の各亜
鉛極の部分拡大図である。第４図は本発明による実施例
の電池と比較電池のサイクル特性比較図である。 （１）…亜鉛極、（３）…フツ素樹脂の繊維状結合網、
（２）…亜鉛活物質、（４）…中空繊維。FIG. 1 is a partially enlarged view of a zinc electrode in a conventional secondary battery, (a) is an initial state diagram, and (b) is a state diagram after a cycle has elapsed. FIG. 2 and FIG. 3 are partial enlarged views of the zinc electrodes of the battery of the example of the present invention and the comparative battery after the lapse of cycles, respectively. FIG. 4 is a cycle characteristic comparison diagram of the battery of the example according to the present invention and the comparative battery. (1) ... Zinc electrode, (3) ... Fluorine resin fibrous bond network,
(2) ... Zinc active material, (4) ... Hollow fiber.
Claims (1)
網により亜鉛活物質を抱束し、前記繊維状結合網に中空
繊維体を絡みつけるように混在せしめてなる亜鉛極を備
えたアルカリ亜鉛二次電池。1. A zinc electrode in which a zinc active material is bound by a fibrous bond network of a non-sintered and water-repellent fluororesin, and hollow fiber bodies are entwined with the fibrous bond network so as to be mixed. Equipped with alkaline zinc secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58004356A JPH06101327B2 (en) | 1983-01-14 | 1983-01-14 | Alkaline zinc secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58004356A JPH06101327B2 (en) | 1983-01-14 | 1983-01-14 | Alkaline zinc secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59128768A JPS59128768A (en) | 1984-07-24 |
| JPH06101327B2 true JPH06101327B2 (en) | 1994-12-12 |
Family
ID=11582114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58004356A Expired - Lifetime JPH06101327B2 (en) | 1983-01-14 | 1983-01-14 | Alkaline zinc secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06101327B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2229725A1 (en) * | 1997-02-18 | 1998-08-18 | Sumitomo Chemical Company, Limited | Cathode for lithium secondary battery |
| JP7344090B2 (en) * | 2019-11-01 | 2023-09-13 | 株式会社日本触媒 | electrode precursor |
-
1983
- 1983-01-14 JP JP58004356A patent/JPH06101327B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59128768A (en) | 1984-07-24 |
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