JPH08264186A - Cylindrical air zinc battery - Google Patents
Cylindrical air zinc batteryInfo
- Publication number
- JPH08264186A JPH08264186A JP7069084A JP6908495A JPH08264186A JP H08264186 A JPH08264186 A JP H08264186A JP 7069084 A JP7069084 A JP 7069084A JP 6908495 A JP6908495 A JP 6908495A JP H08264186 A JPH08264186 A JP H08264186A
- Authority
- JP
- Japan
- Prior art keywords
- cylindrical
- cylindrical air
- current collector
- ptfe
- dispersed
- 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.)
- Pending
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、円筒形空気亜鉛電池に
関するもので、特に、円筒形空気極の改良に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cylindrical zinc-air battery, and more particularly to improvement of a cylindrical cathode.
【０００２】[0002]
【従来の技術】従来の円筒形空気亜鉛電池の空気極は、
金属集電体、触媒層および触媒層の空気取入側に圧着さ
れたガス透過性を有する撥水性の樹脂多孔膜層の３層か
らなり、金属集電体は、その表面に触媒層との導電性を
高めるために導電性カーボンが塗布されている。2. Description of the Related Art The air electrode of a conventional cylindrical zinc-air battery is
The metal current collector comprises three layers of a metal current collector, a catalyst layer, and a gas-permeable water-repellent resin porous membrane layer press-bonded to the air intake side of the catalyst layer. Conductive carbon is applied to enhance conductivity.
【０００３】[0003]
【発明が解決しようとする課題】前記の空気極を用いた
電池は、初期的には金属集電体と触媒層とが十分に圧着
されているため放電性能は優れているが、長期の保存に
おいては、放電性能が低下するという欠点があった。こ
れは、金属集電体に導電性カーボンを単独で塗布するた
めに、保存中にアルカリ電解液が触媒層内に浸透し、さ
らには金属集電体表面まで伝わることにより、集電体表
面と触媒層との界面に電解液膜が形成され、この液膜の
存在により、触媒層内の反応の場である気ー液ー固相の
３相界面への活物質である酸素の供給が妨げられること
による。本発明は、前記の課題を解決し、長期保存後に
おいても放電性能に優れた円筒形空気亜鉛電池を提供す
るものである。The battery using the air electrode described above is excellent in discharge performance because the metal current collector and the catalyst layer are sufficiently pressure-bonded to each other initially, but the battery is stored for a long time. However, there is a drawback that the discharge performance is deteriorated. This is because the conductive carbon alone is applied to the metal current collector, so that the alkaline electrolyte permeates into the catalyst layer during storage and further reaches the metal current collector surface, so that An electrolytic solution film is formed at the interface with the catalyst layer, and the presence of this liquid film hinders the supply of oxygen, which is an active material, to the three-phase interface of gas-liquid-solid phase, which is a reaction site in the catalyst layer. It depends on what is done. The present invention solves the above-mentioned problems and provides a cylindrical zinc-air battery that has excellent discharge performance even after long-term storage.
【０００４】[0004]
【課題を解決するための手段】本発明は、金属集電体、
この金属集電体を支持体としてその回りに形成された触
媒層、およびこの触媒層の外側に配されたガス透過性の
撥水性多孔膜によって構成される円筒形空気極を具備す
る円筒形空気亜鉛電池において、前記金属集電体の表面
にポリテトラフルオロエチレンを分散した導電性カーボ
ン被膜を形成することを特徴とする。The present invention provides a metal current collector,
Cylindrical air having a cylindrical air electrode composed of a catalyst layer formed around the metal current collector as a support, and a gas-permeable water-repellent porous membrane disposed outside the catalyst layer. In the zinc battery, a conductive carbon film in which polytetrafluoroethylene is dispersed is formed on the surface of the metal current collector.
【０００５】[0005]
【作用】円筒形空気極の金属集電体は、その表面にポリ
テトラフルオロエチレンを分散した導電性カーボン被膜
を有することによって、集電体表面の撥水性が向上す
る。このため、電池を長期保存してもアルカリ電解液の
集電体表面への浸透が抑えられ、触媒層と金属集電体と
の間における電解液膜の形成を防ぐことができるため、
電池の長期保存後の放電性能が向上する。The metal current collector of the cylindrical air electrode has a conductive carbon coating in which polytetrafluoroethylene is dispersed on the surface thereof, whereby the water repellency of the current collector surface is improved. Therefore, even if the battery is stored for a long period of time, the permeation of the alkaline electrolyte into the surface of the current collector is suppressed, and it is possible to prevent the formation of the electrolyte film between the catalyst layer and the metal current collector.
The discharge performance after long-term storage of the battery is improved.
【０００６】[0006]
【実施例】以下、本発明の実施例の円筒形空気亜鉛電池
について、その製法とともに説明する。ニッケルめっき
を施したステンレス綱製の細線を縦糸と横糸として螺旋
状に織り込んだ、いわゆるシームレスの円筒状金網２０
の表面に、ポリテトラフルオロエチレン（ＰＴＦＥ）粉
末を分散させたエポキシ系の導電性カーボン塗料を塗布
したのち、１８０℃で１時間乾燥させることにより、Ｐ
ＴＦＥ粉末を分散させた導電性カーボン被膜１９を形成
した集電体１を作製した。一方、活性炭３ｋｇ、アセチ
レンブラック１．５ｋｇ、マンガン酸化物４ｋｇ及びＰ
ＴＦＥ粉末０．７ｋｇを混合し、エチルアルコールを加
えて混練したものを、押し出し成形によって成形し、偏
平形の帯状の合剤を得た。さらにこの合剤を６０℃に加
熱した２本のローラーに通して圧延することによって、
厚さ７００μｍの触媒シートを作製した。前記触媒シー
トを一定の大きさに切り取り、前記集電体１の内側に這
わせるように配置したのち、前記触媒シートの内側に配
された支えとなるローラーと、前記集電体１の外側に配
されたローラーとによって圧着成形することにより、継
ぎ目のない円筒形の成型体を得た。次に、前記成型体の
外側にＰＴＦＥ粉末の分散液を塗布し、２８０℃で乾燥
を行った。最後にＰＴＦＥ粉末を塗布した側に、ガス透
過能を有する撥水性のＰＴＦＥ多孔フィルムを圧着する
ことにより、円筒形空気極４を得た。図１に円筒形空気
極４の拡大した断面図を示す。集電体１は、円筒状金網
２０をなす、ニッケルめっき処理されたステンレス鋼製
の細線、および前記ステンレス鋼細線の表面に形成され
た、ＰＴＦＥ粉末が分散した導電性カーボン被膜１９に
より構成される。また、円筒形空気極４そのものは、集
電体１、触媒層３および触媒層３の空気取入側の片面に
設けたフッ素樹脂多孔膜２の３層により構成される。EXAMPLES The cylindrical zinc-air batteries of the examples of the present invention will be described below together with their manufacturing methods. A so-called seamless cylindrical wire net 20 in which fine wires made of stainless steel with nickel plating are spirally woven as warp and weft
After applying an epoxy-based conductive carbon coating material in which polytetrafluoroethylene (PTFE) powder is dispersed on the surface of P, it is dried at 180 ° C. for 1 hour.
A current collector 1 having a conductive carbon film 19 in which TFE powder was dispersed was prepared. On the other hand, activated carbon 3 kg, acetylene black 1.5 kg, manganese oxide 4 kg and P
0.7 kg of TFE powder was mixed, ethyl alcohol was added and kneaded, and the mixture was molded by extrusion molding to obtain a flat strip-shaped mixture. Further, by rolling this mixture through two rollers heated to 60 ° C.,
A catalyst sheet having a thickness of 700 μm was produced. After cutting the catalyst sheet into a certain size and arranging the catalyst sheet so as to crawl inside the current collector 1, a supporting roller disposed inside the catalyst sheet and an outside of the current collector 1 are provided. A seamless cylindrical molded body was obtained by press-molding with the arranged rollers. Next, a dispersion liquid of PTFE powder was applied to the outside of the molded body and dried at 280 ° C. Finally, a water-repellent PTFE porous film having gas permeability was pressure-bonded to the side coated with the PTFE powder to obtain a cylindrical air electrode 4. FIG. 1 shows an enlarged sectional view of the cylindrical air electrode 4. The current collector 1 is composed of a nickel-plated stainless steel thin wire forming a cylindrical wire net 20, and a conductive carbon coating 19 in which PTFE powder is dispersed, which is formed on the surface of the stainless steel thin wire. . The cylindrical air electrode 4 itself is composed of three layers of the current collector 1, the catalyst layer 3, and the fluororesin porous membrane 2 provided on one surface of the catalyst layer 3 on the air intake side.
【０００７】図２に、前記円筒形空気極４を用いて作製
した、本発明の実施例の単３形空気亜鉛電池の構造断面
図を示す。この円筒形空気極４の上部は、鋼板にニッケ
ルめっきを施した外カップ１３と内カップ１４とで挟み
込み込まれ、封口されている。外カップ１３と正極外装
缶８の底部とをスポット溶接することによって、円筒形
空気極４の集電体１と正極外装缶８は電気的に導通して
いる。また、円筒形空気極４の下部は、表面に有機封止
材を塗布した樹脂封口体１６と正極外装缶８とで封口さ
れている。ゲル状亜鉛負極６は、円筒形空気極４の内側
にセパレータ５を介して、充填されている。１７は負極
端子をなす底板、１８は負極集電子である。７は正極外
装缶８と空気極４との間に介在させた空気拡散紙、９は
絶縁チューブ、１０は正極外装缶８と絶縁チューブ９に
連通して設けた空気取り入れ孔、１１は空気取り入れ孔
１０を閉塞し、電池を使用する前にはがす密封シール、
１２は皿紙である。FIG. 2 is a structural cross-sectional view of an AA zinc air battery of the embodiment of the present invention, which is manufactured by using the cylindrical air electrode 4. The upper portion of the cylindrical air electrode 4 is sandwiched between an outer cup 13 and an inner cup 14 each having a steel plate plated with nickel and sealed. By spot welding the outer cup 13 and the bottom of the positive electrode outer can 8, the current collector 1 of the cylindrical air electrode 4 and the positive electrode outer can 8 are electrically connected. The lower portion of the cylindrical air electrode 4 is sealed with a resin sealing body 16 having a surface coated with an organic sealing material and a positive electrode outer can 8. The gelled zinc negative electrode 6 is filled inside the cylindrical air electrode 4 with a separator 5 interposed therebetween. Reference numeral 17 is a bottom plate that forms a negative electrode terminal, and 18 is a negative electrode current collector. Reference numeral 7 is an air diffusion paper interposed between the positive electrode outer can 8 and the air electrode 4, 9 is an insulating tube, 10 is an air intake hole provided in communication with the positive electrode outer can 8 and the insulating tube 9, and 11 is air intake. A sealing seal that closes the hole 10 and peels off before using the battery,
12 is a plate.
【０００８】上記のように作製した実施例の単３形空気
亜鉛電池、および比較例である集電体に表面処理を施さ
ない以外は実施例と同様の単３形空気亜鉛電池につい
て、初期および６０℃で１カ月保存後に各種の電流で放
電試験を実施した。なお、サンプル数はそれぞれ１０個
ずつとした。その結果を表１に示す。The AA-zinc air battery of the example produced as described above, and the AA-zinc air battery of the same example as the comparative example except that the current collector was not surface-treated, the initial and After storing at 60 ° C. for 1 month, a discharge test was carried out at various currents. The number of samples was 10 each. Table 1 shows the results.
【０００９】[0009]
【表１】 [Table 1]
【００１０】比較例の電池は、６０℃で１カ月保存後の
放電容量が初期放電容量に対して３５〜６８％であっ
た。それに対して、実施例の電池は、初期の放電容量は
比較例の電池とほぼ同等であるが、保存後の放電容量
は、初期放電容量に対して７６〜９８％となり、大きく
改善されるとともにバラツキも小さくなった。このよう
に、本発明の電池は、保存後の放電性能が向上し、信頼
性も高いことがわかる。The battery of the comparative example had a discharge capacity of 35 to 68% of the initial discharge capacity after storage at 60 ° C. for 1 month. On the other hand, although the initial discharge capacity of the battery of Example was almost the same as that of the battery of Comparative Example, the discharge capacity after storage was 76 to 98% of the initial discharge capacity, which was greatly improved. The variation is also smaller. Thus, it can be seen that the battery of the present invention has improved discharge performance after storage and high reliability.
【００１１】[0011]
【発明の効果】以上のように、本発明によれば、長期保
存後においても放電性能に優れた円筒形空気亜鉛電池が
得られる。As described above, according to the present invention, a cylindrical zinc-air battery having excellent discharge performance even after long-term storage can be obtained.
【図１】本発明の実施例の円筒形空気亜鉛電池に用いた
円筒形空気極の要部の拡大縦断面図である。FIG. 1 is an enlarged vertical sectional view of a main part of a cylindrical air electrode used in a cylindrical zinc-air battery of an embodiment of the present invention.
【図２】同円筒形空気亜鉛電池の半断面図である。FIG. 2 is a half sectional view of the same cylindrical zinc-air battery.
１ 集電体 ２ フッ素樹脂多孔膜 ３ 触媒層 ４ 円筒形空気極 ５ セパレータ ６ ゲル状亜鉛負極 ７ 空気拡散紙 ８ 正極外装缶 ９ 絶縁チューブ １０ 空気取り入れ孔 １１ 密封シール １２ 皿紙 １３ 外カップ １４ 内カップ １６ 樹脂封口体 １７ 底板 １８ 負極集電子 １９ ＰＴＦＥ粉末が分散した導電性カーボン被膜 ２０ ステンレス鋼金網 1 Current Collector 2 Fluororesin Porous Membrane 3 Catalyst Layer 4 Cylindrical Air Electrode 5 Separator 6 Gel Zinc Negative Electrode 7 Air Diffusing Paper 8 Positive Electrode Can 9 Insulation Tube 10 Air Intake Hole 11 Seal Seal 12 Dish Paper 13 Outer Cup 14 Inside Cup 16 Resin sealing body 17 Bottom plate 18 Negative electrode current collector 19 Conductive carbon film in which PTFE powder is dispersed 20 Stainless steel wire mesh
Claims (1)
してその回りに形成された触媒層、およびこの触媒層の
外側に配されたガス透過性の撥水性多孔膜によって構成
される円筒形空気極を具備し、前記金属集電体が、その
表面にポリテトラフルオロエチレンを分散した導電性カ
ーボン被膜を有する円筒形空気亜鉛電池。1. A metal current collector, a catalyst layer formed around the metal current collector as a support, and a gas-permeable water-repellent porous membrane disposed outside the catalyst layer. A cylindrical air zinc battery comprising a cylindrical air electrode, wherein the metal current collector has a conductive carbon coating film in which polytetrafluoroethylene is dispersed on the surface thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7069084A JPH08264186A (en) | 1995-03-28 | 1995-03-28 | Cylindrical air zinc battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7069084A JPH08264186A (en) | 1995-03-28 | 1995-03-28 | Cylindrical air zinc battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08264186A true JPH08264186A (en) | 1996-10-11 |
Family
ID=13392378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7069084A Pending JPH08264186A (en) | 1995-03-28 | 1995-03-28 | Cylindrical air zinc battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08264186A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000036677A1 (en) * | 1998-12-15 | 2000-06-22 | Electric Fuel Limited | An air electrode providing high current density for metal-air batteries |
| JP2003511830A (en) * | 1999-10-13 | 2003-03-25 | ザ ジレット カンパニー | Cathode tube |
| JP2003528435A (en) * | 2000-03-23 | 2003-09-24 | ザ ジレット カンパニー | Battery |
| WO2010138643A1 (en) * | 2009-05-29 | 2010-12-02 | Eveready Battery Company, Inc. | Current collector for catalytic electrode |
| JP2016533006A (en) * | 2013-07-31 | 2016-10-20 | アクアハイドレックス プロプライエタリー リミテッドＡｑｕａｈｙｄｒｅｘ Ｐｔｙ Ｌｔｄ | Three-dimensional composite electrode and manufacturing method |
| US10577700B2 (en) | 2012-06-12 | 2020-03-03 | Aquahydrex Pty Ltd | Breathable electrode structure and method for use in water splitting |
| US11005117B2 (en) | 2019-02-01 | 2021-05-11 | Aquahydrex, Inc. | Electrochemical system with confined electrolyte |
-
1995
- 1995-03-28 JP JP7069084A patent/JPH08264186A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000036677A1 (en) * | 1998-12-15 | 2000-06-22 | Electric Fuel Limited | An air electrode providing high current density for metal-air batteries |
| JP2003511830A (en) * | 1999-10-13 | 2003-03-25 | ザ ジレット カンパニー | Cathode tube |
| JP2003528435A (en) * | 2000-03-23 | 2003-09-24 | ザ ジレット カンパニー | Battery |
| WO2010138643A1 (en) * | 2009-05-29 | 2010-12-02 | Eveready Battery Company, Inc. | Current collector for catalytic electrode |
| US8541135B2 (en) | 2009-05-29 | 2013-09-24 | Eveready Battery Co, Inc. | Current collector for catalytic electrode |
| US10577700B2 (en) | 2012-06-12 | 2020-03-03 | Aquahydrex Pty Ltd | Breathable electrode structure and method for use in water splitting |
| JP2016533006A (en) * | 2013-07-31 | 2016-10-20 | アクアハイドレックス プロプライエタリー リミテッドＡｑｕａｈｙｄｒｅｘ Ｐｔｙ Ｌｔｄ | Three-dimensional composite electrode and manufacturing method |
| US10637068B2 (en) | 2013-07-31 | 2020-04-28 | Aquahydrex, Inc. | Modular electrochemical cells |
| US11018345B2 (en) | 2013-07-31 | 2021-05-25 | Aquahydrex, Inc. | Method and electrochemical cell for managing electrochemical reactions |
| US11005117B2 (en) | 2019-02-01 | 2021-05-11 | Aquahydrex, Inc. | Electrochemical system with confined electrolyte |
| US11682783B2 (en) | 2019-02-01 | 2023-06-20 | Aquahydrex, Inc. | Electrochemical system with confined electrolyte |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |