JP3232936B2 - Cylindrical air battery - Google Patents
Cylindrical air batteryInfo
- Publication number
- JP3232936B2 JP3232936B2 JP02412895A JP2412895A JP3232936B2 JP 3232936 B2 JP3232936 B2 JP 3232936B2 JP 02412895 A JP02412895 A JP 02412895A JP 2412895 A JP2412895 A JP 2412895A JP 3232936 B2 JP3232936 B2 JP 3232936B2
- Authority
- JP
- Japan
- Prior art keywords
- cylindrical air
- current collector
- battery
- air battery
- catalyst layer
- 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 - Fee Related
Links
Classifications
-
- 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
- Hybrid Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Inert Electrodes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、円筒形空気電池に関
し、特に電解液のクリーピングを防止するようにした円
筒形空気電池に関するものである。The present invention relates to relates to a cylindrical air battery, to a cylindrical air battery in particular so as to prevent Kuripin grayed of the electrolyte.
【０００２】[0002]
【従来の技術】従来の円筒形空気電池では、円筒形空気
電池の空気極の金属集電体には導電性を高めるためにニ
ッケルめっきが施され、この集電体に触媒層とガス拡散
性を有する撥水性の樹脂多孔膜を圧着し、３層構造の空
気極としていた。このため、電池を長期に保存すると電
解液が集電体にまで拡がり、長期保存に対する放電性能
に問題があった。The cylindrical air battery Background of the Invention Conventionally, the metal current collector of the cylindrical air battery cathode nickel is plated to enhance conductivity, a catalyst layer and a gas diffusion in the collector A water-repellent resinous porous membrane having a water-repellent property was pressed to form a three-layer air electrode. For this reason, when the battery is stored for a long period of time, the electrolytic solution spreads to the current collector, and there is a problem in the discharge performance for the long-term storage.
【０００３】[0003]
【発明が解決しようとする課題】上記のような従来の方
法において電池に構成しようとした場合、初期的には放
電性能に優れていても、長期の保存においてはアルカリ
電解液が触媒層内を部分的に浸透し、さらには金属集電
体表面へクリーピングし、これが原因となって撥水性の
樹脂多孔膜と触媒層との界面に液膜が形成され、触媒層
内の反応の場である気−液−固層の３層界面へ活物質で
ある酸素の供給が妨げられて放電性能の低下に至ってし
まうという問題がある。If you try to configure a battery in traditional method as described above that [0005], even if the initially excellent in discharge performance, the long-term storage is alkaline electrolyte catalyst layer Partially penetrates and further creeps to the surface of the metal current collector, which results in the formation of a liquid film at the interface between the water-repellent porous resin membrane and the catalyst layer, and the reaction field in the catalyst layer. However, there is a problem that supply of oxygen as an active material to the three-layer interface of the gas-liquid-solid layer is hindered and the discharge performance is reduced.
【０００４】本発明の目的は、従来法での上記課題を解
決し、クリーピングが防止されて、 長期保存における放
電性能に優れた円筒形空気電池を提供するものである。An object of the present invention is to solve the above problems of the conventional method, is prevented Kuripin grayed, there is provided an excellent cylindrical air battery discharge performance in the long term storage.
【０００５】[0005]
【課題を解決するための手段】上記の目的を達成するた
め、本発明の円筒形空気電池では、ニッケル−ポリテト
ラフルオロエチレンの分散めっきを施した集電体とこの
回りに形成された触媒層とを有し、さらに前記触媒層の
外周側にガス透過能を有する撥水性の樹脂多孔膜を有し
てなる円筒状空気極を正極とすることを特徴とする。To achieve the above object, according to an aspect of, the cylindrical air battery of the present onset bright nickel - catalyst formed current collector subjected to dispersion plating polytetrafluoroethylene and this around And a cylindrical air electrode having a water-repellent resin porous film having gas permeability on the outer peripheral side of the catalyst layer.
【００６】[0086]
【作用】本発明によれば、ニッケル−ポリテトラフルオ
ロエチレンの分散めっきを施した集電体を円筒状の空気
極の集電体として用いているので、長期の保存における
アルカリ電解液の集電体表面へのクリーピングが防止さ
れ、放電特性に優れたものとなっている。ここで、分散
めっきとは、通常のめっき液中に、例えばＳｉＣ、ポリ
テトラフルオロエチレンなどの粒子を懸獨分散させてめ
っきを行い、生成してくるめっき皮膜中に分散させた粒
子を取り込ませためっきのことであり、その結果、めっ
き皮膜自身の機能に粒子の持つ機能を付与させることが
できる。この第一の発明では、ニッケル−ポリテトラフ
ルオロエチレンの分散めっきによりポリテトラフルオロ
エチレンの撥水性をニッケルめっき皮膜に与えること
で、長期保存における放電性能の優れた電池を得ること
ができる。According to the present invention, the current collector coated with nickel-polytetrafluoroethylene dispersion plating is used as the current collector of the cylindrical air electrode. It prevents creeping on the body surface and has excellent discharge characteristics. Here, the dispersion plating means that, for example, particles such as SiC and polytetrafluoroethylene are suspended and dispersed in a normal plating solution to perform plating, and the dispersed particles are taken into a generated plating film. As a result, the function of the particles can be imparted to the function of the plating film itself. In the first invention, a battery having excellent discharge performance in long-term storage can be obtained by imparting water repellency of polytetrafluoroethylene to the nickel plating film by nickel-polytetrafluoroethylene dispersion plating.
【０００７】[0007]
【実施例】以下に本発明の実施例の円筒形空気電池の実
施例を図面に基づいて説明する。 （実施例１） 図１（Ａ）に本発明を適用した単３形空気亜鉛電池の構
造半断面図を示し、図１（Ｂ）に図１（Ａ）の空気電池
の正極として用いた円筒状空気極の部分の拡大断面図を
示す。図中の４は、３層構造の円筒状空気極であり、内
側から触媒層１、ニッケル−ポリテトラフルオロエチレ
ンの分散めっきを施した金属集電体２、撥水性フッ素樹
脂多孔膜層３からなっている。この分散めっきを施した
集電体２は、図２に示すように、ニッケルめっき層５と
ポリテトラフルオロエチレン粒子６とステンレス製集電
体７とからなる。なお、ニッケル−ポリテトラフルオロ
エチレンの分散めっき用のメッキ液としては、工業的に
は、商品名：ニムフロン（登録商標）やカニフロン（登
録商標）が知られている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a cylindrical air battery according to the present invention will be described below with reference to the drawings. (Example 1) FIG. 1A shows a half cross-sectional view of the structure of an AA zinc battery to which the present invention is applied, and FIG. 1B shows a cylinder used as a positive electrode of the air battery of FIG. 1A. FIG. 2 shows an enlarged sectional view of a portion of the air electrode. Numeral 4 in the figure denotes a cylindrical air electrode having a three-layer structure, from the inside, a catalyst layer 1, a metal current collector 2 plated with nickel-polytetrafluoroethylene dispersion, and a water-repellent fluororesin porous film layer 3. Has become. As shown in FIG. 2, the current collector 2 subjected to the dispersion plating includes a nickel plating layer 5, polytetrafluoroethylene particles 6, and a current collector 7 made of stainless steel. Incidentally, nickel - as the plating solution for dispersion plating of polytetrafluoroethylene, the industrial, trade name: NIMUFLON (registered trademark) or Kanifuron (registered trademark) is known.
【０００８】また、上記円筒状空気極では、集電体に触
媒シートをプレスにより圧着してある。この触媒シート
は、活性炭、マンガン酸化物、アセチレンブラック、フ
ッ素樹脂粉末を混合し、この混合合剤にエチルアルコー
ルを加え混練した後、押出成形し偏平形の帯状の合剤と
し、さらにこの帯状合剤を加熱した２本のローラーに通
して圧延し、０．６ｍｍのシート状にしたものである。
２３０℃で乾燥を行ったのち、集電体層側にガス透過能
を有する撥水性のフッ素樹脂多孔膜をプレスにより圧着
することにより、触媒層、集電体層およびフッ素樹脂多
孔膜層からなる３層構造の平板の空気極を作製する。こ
のように作製した平板の空気極を触媒層側が内側になる
ように湾曲させ、触媒層とフッ素樹脂多孔膜の両端部の
一部を重ねて筒形とする。ついで、この重なった部分の
触媒層およびフッ素樹脂多孔膜の一部を取り除いて露出
した集電体層をスポット溶接し、気密状態にない溶接部
に合成ゴム系の接着剤を充填し気密に補修する。以上の
工程により、３層構造の円筒状空気極を作る。この３層
構造の円筒状空気極の上部は鋼板にニッケルめっきを施
した金属製の外カップ１６と内カップ１７とで挟み込ま
れ封口されている。正極上部をこのように封口した後、
外カップ底部の３ヶ所に備えたプロジェクション部と正
極缶底部とをスポット溶接することにより集電、導通さ
せている。また、円筒状空気極の下部に、凹部に合成ゴ
ム系の封止剤１８を塗布した樹脂成形体１９を挿入し、
次にこの樹脂成形体の内周側に金属製リング２２を挿入
する。さらに、底板２０を溶接した集電子２１を挿入し
た樹脂成形封口体１９′を嵌め合わせ、正極缶１１を機
械的に押圧して樹脂成形体の凹部を空気極側に密着させ
封口する。ゲル状亜鉛負極９は、円筒状空気極内に構成
挿入されたセパレータ８を介して内部に充填されてい
る。図中、１５は皿底紙、１０は空気拡散紙、１２は絶
縁チューブ、１３は空気取り入れ孔で電池を使用するま
では密封シール１４でシールされている。In the cylindrical air electrode, a catalyst sheet is pressed on the current collector by pressing. This catalyst sheet is prepared by mixing activated carbon, manganese oxide, acetylene black, and fluororesin powder, adding ethyl alcohol to the mixed mixture, kneading the mixture, and extruding to form a flat band-shaped mixture. The agent was rolled through two heated rollers to form a 0.6 mm sheet.
After drying at 230 ° C., a water-repellent fluororesin porous film having gas permeability is pressed on the current collector layer side by pressing to form a catalyst layer, a current collector layer, and a fluororesin porous film layer. A flat air electrode having a three-layer structure is manufactured. The air electrode of the flat plate produced in this manner is curved so that the catalyst layer side is on the inside, and the catalyst layer and a part of both ends of the fluororesin porous membrane are overlapped to form a cylindrical shape. Next, the catalyst layer in the overlapped portion and a part of the fluororesin porous film were removed, and the exposed current collector layer was spot-welded, and a non-hermetic weld was filled with a synthetic rubber-based adhesive to repair the hermetic seal. I do. Through the above steps, a cylindrical air electrode having a three-layer structure is formed. The upper part of the cylindrical air electrode having the three-layer structure is sandwiched and sealed between an outer cup 16 and an inner cup 17 made of nickel-plated steel. After sealing the upper part of the positive electrode in this way,
Current collection and conduction are performed by spot welding the projection portion provided at three places on the bottom of the outer cup and the bottom of the positive electrode can. Also, a resin molded body 19 having a concave portion coated with a synthetic rubber-based sealant 18 is inserted below the cylindrical air electrode,
Next, a metal ring 22 is inserted into the inner peripheral side of the resin molded body. Further, the resin-molded sealing body 19 ′ into which the current collector 21 to which the bottom plate 20 is welded is inserted is fitted, and the positive electrode can 11 is mechanically pressed to bring the concave portion of the resin molded body into close contact with the air electrode side to seal. The gelled zinc negative electrode 9 is filled inside via a separator 8 inserted and configured in a cylindrical air electrode. In the drawing, reference numeral 15 denotes a dish bottom paper, 10 denotes air diffusion paper, 12 denotes an insulating tube, and 13 denotes an air intake hole which is sealed with a hermetic seal 14 until the battery is used.
【０００９】以上の方法で構成、作製した単３サイズの
円筒形空気電池（実施例１）、ニッケルめっきを施した
金属集電体を用いて上記と同様の方法で構成、作製した
電池（従来例１）を用いて、初期放電試験と保存後放電
試験（６０℃、１ヶ月密封）を実施した。なお、放電試
験の試験個数はそれぞれ１０個とした。その試験結果を
表１に示した。AA size cylindrical air battery constructed and manufactured by the above method (Example 1), and a battery constructed and fabricated by the same method as described above using a nickel-plated metal current collector (conventional example) Using Example 1), an initial discharge test and a discharge test after storage (sealed at 60 ° C. for one month) were performed. The number of discharge tests was set to ten. The test results are shown in Table 1.
【００１０】[0010]
【表１】 [Table 1]
【００１１】表１から明らかなように、実施例１の電池
は、６０℃、１ヶ月の保存後でも、放電性能が初期放電
性能に対して７６〜９８％の維持率（（保存後の放電容
量／初期放電容量）×１００）であり、また性能（σ）
のばらつきも少ない。一方、従来例１の電池では初期の
放電性能は実施例１とほぼ同等であるが、保存後の放電
性能は維持率３４〜６８％であり、また性能（σ）のば
らつきも大きい。このように本発明による構成の電池の
場合、保存後の放電性能が向上、安定していることがわ
かる。As apparent from Table 1, the battery of Example 1 had a discharge performance of 76 to 98% of the initial discharge performance even after storage at 60 ° C. for one month ((discharge after storage). Capacity / initial discharge capacity) × 100) and the performance (σ)
Is small. On the other hand, in the battery of the conventional example 1, the initial discharge performance is almost the same as that of the example 1, but the discharge performance after storage is 34 to 68%, and the performance (σ) varies greatly. Thus, in the case of the battery having the configuration according to the present invention, it can be seen that the discharge performance after storage is improved and stable.
【００１２】[0012]
【発明の効果】以上の説明で明らかなように、本発明に
よれば、ニッケル−ポリテトラフルオロエチレンの分散
めっきを施した集電体に触媒層とフッ素樹脂多孔膜とを
圧着し、３層構造の円筒状空気極としたものを正極とし
て用いることにより、クリーピングが防止され、長期保
存での放電性能に優れた円筒形空気電池を提供すること
ができる。As is apparent from the above description, according to the present invention, the catalyst layer and the fluororesin porous film are pressure-bonded to the nickel-polytetrafluoroethylene-dispersed current collector to form a three-layer structure. By using a cylindrical air electrode having a structure as a positive electrode, creeping is prevented, and a cylindrical air battery having excellent discharge performance in long-term storage can be provided.
【００１３】[0013]
【図１】（Ａ）本発明の実施例１の円筒形空気電池の半
断面図 （Ｂ）図１（Ａ）の空気電池に用いた円筒状空気極の部
分拡大断面図1A is a half sectional view of a cylindrical air battery according to a first embodiment of the present invention; FIG. 1B is a partially enlarged sectional view of a cylindrical air electrode used in the air battery of FIG. 1A;
【図２】本発明の実施例１の円筒形空気電池で用いる円
筒状空気極を構成する集電体の断面図FIG. 2 is a sectional view of a current collector constituting a cylindrical air electrode used in the cylindrical air battery according to the first embodiment of the present invention.
１ 触媒層 ２ 集電体 ３ フッ素樹脂多孔膜 ４ 円筒状空気極 ５ ニッケルめっき層 ６ ポリテトラフルオロエチレン粒子 ７ ステンレス製集電体 ８ セパレータ ９ ゲル状負極亜鉛 １０ 空気拡散紙 １１ 正極缶 １２ 絶縁チューブ １３ 空気取り入れ孔 １４ 密封シール １５ 皿底紙 １６ 金属製外カップ １７ 金属製内カップ １８ 封止剤 １９ 樹脂成形体 １９′樹脂成形封口体 ２０ 底板 ２１ 集電子 ２２ 金属製リング DESCRIPTION OF SYMBOLS 1 Catalyst layer 2 Current collector 3 Fluororesin porous film 4 Cylindrical air electrode 5 Nickel plating layer 6 Polytetrafluoroethylene particles 7 Stainless steel current collector 8 Separator 9 Gelled negative electrode zinc 10 Air diffusion paper 11 Positive electrode can 12 Insulating tube DESCRIPTION OF SYMBOLS 13 Air intake hole 14 Sealing seal 15 Dish bottom paper 16 Metal outer cup 17 Metal inner cup 18 Sealant 19 Resin molded body 19 'Resin molded sealing body 20 Bottom plate 21 Current collector 22 Metal ring
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久保 勲 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 小林 茂雄 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平５−144482（ＪＰ，Ａ) 特開 昭59−180973（ＪＰ，Ａ) 特開 平４−73865（ＪＰ，Ａ) 特開 昭61−200672（ＪＰ，Ａ) 特開 昭59−35362（ＪＰ，Ａ) 特開 平７−278864（ＪＰ，Ａ) 特開 平７−14618（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/86 H01M 4/66 H01M 12/06 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Isao Kubo 1006 Kadoma Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (56) References JP-A-5-144482 (JP, A) JP-A-59-180973 (JP, A) JP-A-4-73865 (JP, A) JP-A-61-200672 (JP, A) JP-A-59-35362 (JP, A) JP-A-7-278864 (JP, A) JP-A-7-14618 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/86 H01M 4/66 H01M 12/06
Claims (1)
の分散めっきを施した集電体とこの回りに形成された触
媒層とを有し、さらに前記触媒層の外周側にガス透過能
を有する撥水性の樹脂多孔膜を有してなる円筒状空気極
を正極とすることを特徴とする円筒形空気電池。1. A water-repellent material having a current collector on which nickel-polytetrafluoroethylene is dispersedly plated and a catalyst layer formed around the current collector, and further having a gas-permeable ability on the outer peripheral side of the catalyst layer. A cylindrical air battery characterized in that a cylindrical air electrode having a resin porous membrane is used as a positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02412895A JP3232936B2 (en) | 1995-02-13 | 1995-02-13 | Cylindrical air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02412895A JP3232936B2 (en) | 1995-02-13 | 1995-02-13 | Cylindrical air battery |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001205871A Division JP3642297B2 (en) | 2001-07-06 | 2001-07-06 | Cylindrical air battery |
| JP2001205872A Division JP3642298B2 (en) | 2001-07-06 | 2001-07-06 | Cylindrical air battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08222231A JPH08222231A (en) | 1996-08-30 |
| JP3232936B2 true JP3232936B2 (en) | 2001-11-26 |
Family
ID=12129679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02412895A Expired - Fee Related JP3232936B2 (en) | 1995-02-13 | 1995-02-13 | Cylindrical air battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3232936B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150111114A1 (en) * | 2012-04-25 | 2015-04-23 | Hitachi Zosen Corporation | Functional porous material, metal-air battery, and method for manufacturing functional porous material |
| JP5873579B1 (en) * | 2015-02-06 | 2016-03-01 | 古河電池株式会社 | Metal air battery |
-
1995
- 1995-02-13 JP JP02412895A patent/JP3232936B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08222231A (en) | 1996-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3475527B2 (en) | Cylindrical air battery | |
| CN1253385A (en) | Air electrode and metal-air battery made of same | |
| JP3039055B2 (en) | Manufacturing method of cylindrical air cell and cylindrical air electrode | |
| JP3232936B2 (en) | Cylindrical air battery | |
| JPS63294672A (en) | Button type air-zinc cell | |
| JPH08264186A (en) | Cylindrical air zinc battery | |
| JP3348236B2 (en) | Air electrode current collecting material for air battery using alkaline electrolyte and air battery using alkaline electrolyte provided with the same | |
| JP3395440B2 (en) | Air electrode current collecting material for air battery and air battery provided with the same | |
| JPH08306398A (en) | Cylindrical air cell | |
| JP3642298B2 (en) | Cylindrical air battery | |
| JP3642297B2 (en) | Cylindrical air battery | |
| JP4395899B2 (en) | Air battery | |
| JPH07211322A (en) | Air electrode, manufacture thereof, and air battery using the electrode | |
| JPH11191440A (en) | Air electrode and air battery using the same | |
| JP2001043864A (en) | Cylindrical air electrode and cylindrical air battery | |
| JP2000082503A (en) | Air cell | |
| JPH1012288A (en) | Cylindrical air battery and manufacture therefor | |
| JPH08287920A (en) | Cylindrical air electrode and battery using it | |
| JPH0557707B2 (en) | ||
| JP4639372B2 (en) | Air battery manufacturing method | |
| JP2877809B2 (en) | Manufacturing method of button type air battery | |
| JPS6261279A (en) | Button type air cell | |
| JPH09306509A (en) | Manufacture of oxygen-reduced electrode, and battery therewith | |
| JPS63138668A (en) | Thin type air cell | |
| JPS607000Y2 (en) | button air-zinc battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |