JP2743416B2 - Zinc plate for rechargeable batteries - Google Patents
Zinc plate for rechargeable batteriesInfo
- Publication number
- JP2743416B2 JP2743416B2 JP63305330A JP30533088A JP2743416B2 JP 2743416 B2 JP2743416 B2 JP 2743416B2 JP 63305330 A JP63305330 A JP 63305330A JP 30533088 A JP30533088 A JP 30533088A JP 2743416 B2 JP2743416 B2 JP 2743416B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- copper
- tin
- current collector
- nickel
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、銀亜鉛電池、ニッケル亜鉛電池等の、電解
液として主にアルカリ水溶液を用いるアルカリ亜鉛二次
電池の負極に用いられる亜鉛極板の集電体の改良に関す
るものである。Description: TECHNICAL FIELD The present invention relates to a collection of zinc electrode plates used for a negative electrode of an alkaline zinc secondary battery such as a silver zinc battery or a nickel zinc battery, which mainly uses an aqueous alkaline solution as an electrolyte. The present invention relates to improvement of an electric body.
従来の技術 アルカリ亜鉛二次電池の負極に用いられる亜鉛極板の
集電体には、従来より、銀あるいは銅、銅−スズ合金の
ネット、エキスパンドメタルおよびパンチドメタルや銅
あるいは鉄に亜鉛、スズ、カドミウム、鉛、タリウム、
インジウム、水銀等の水素過電圧の高い金属をメッキ
し、これをネット、エキスパンドメタルおよびパンチド
メタルに加工したものがある。2. Description of the Related Art Conventionally, a current collector of a zinc electrode plate used for a negative electrode of an alkaline zinc secondary battery has a silver or copper, a net of a copper-tin alloy, an expanded metal and a punched metal, and a copper or an iron with zinc, Tin, cadmium, lead, thallium,
In some cases, a metal having a high hydrogen overvoltage such as indium or mercury is plated and processed into a net, expanded metal, or punched metal.
発明が解決しようとする課題 銀を集電体とする場合は、価格が活物質である亜鉛に
比して高価てあるため、コスト面での問題があった。Problems to be Solved by the Invention When silver is used as the current collector, there is a problem in cost because the price is higher than that of zinc as an active material.
一方、銅を集電体とする場合は、価格が比較的安価で
あり、電気伝導性がすぐれているが、極板を製造する際
に集電体の表面に銅の酸化物が生成し、それが充電時に
電解液に溶解して銅イオンを溶出させ、負極上に表面積
の大きい銅を再析出させて亜鉛の自己放電の招来した
り、それによって発生する水素ガスのために内圧上昇や
漏液が生じるという問題や、深放電を反復させたり、負
荷を接続したままで放置すると電気化学的な腐食によっ
て銅の酸化物が生成し、それによって電気伝導性が低下
するという問題があった。On the other hand, when copper is used as the current collector, the price is relatively inexpensive and the electrical conductivity is excellent, but copper oxide is generated on the surface of the current collector when manufacturing the electrode plate, It dissolves in the electrolytic solution during charging to elute copper ions and reprecipitates copper with a large surface area on the negative electrode, causing self-discharge of zinc, and the internal pressure rise and leakage due to hydrogen gas generated by this. There has been a problem that a liquid is generated, and if deep discharge is repeated or a load is left connected, electrochemical corrosion produces copper oxides, thereby lowering the electrical conductivity.
また、銅−スズ合金、すなわち青銅を集電体とする場
合は、価格が安価であり、電気化学的な耐蝕性や水素過
電圧が銅より良好であるが、圧延等によって、シート状
に加工できるのはスズの含有量が8wt％までの市販の青
銅であるため、電気化学的な耐蝕性の点では不十分であ
るという問題があった。In addition, when the current collector is a copper-tin alloy, that is, bronze, the price is low, and the electrochemical corrosion resistance and the hydrogen overvoltage are better than copper, but can be processed into a sheet by rolling or the like. Is a commercially available bronze having a tin content of up to 8% by weight, which is insufficient in terms of electrochemical corrosion resistance.
これらの欠点を解消するため、前述した銅あるいは鉄
に水素過電圧の高い金属をメッキする方法がある。In order to solve these drawbacks, there is a method of plating copper or iron with a metal having a high hydrogen overvoltage.
ところが、この水素過電圧の高い金属のメッキによる
表面被覆は、被覆の厚みにムラが生じたり、被覆に傷が
生じると、素地金属である銅や鉄が露出して亜鉛の自己
放電の原因になるため、被覆する金属の選択が重要であ
る。However, in the surface coating by plating of a metal with a high hydrogen overvoltage, if the thickness of the coating becomes uneven or if the coating is damaged, the base metal copper or iron is exposed and causes a self-discharge of zinc. Therefore, selection of the metal to be coated is important.
被覆する金属のうち、カドミウム、水銀、タリウム等
は毒性が強く、公害の点で好ましくない。一方、スズは
初期にはかなり良好な特性を示すが、深放電を反復する
使用や負荷を接続したままで放置する使用を継続すると
素地金属が露出しやすいという欠点がある。Among the metals to be coated, cadmium, mercury, thallium and the like are highly toxic and are not preferred in terms of pollution. On the other hand, tin shows fairly good characteristics at the beginning, but has the drawback that the base metal is likely to be exposed if repeated use of deep discharge or continued use with a load connected is continued.
課題を解決するための手段 本発明は、上記した電気化学的な耐蝕性にすぐれた亜
鉛極板の集電体を得るためになされたもので、まず、ス
ズの含有量を種々変化させた銅−スズ合金を試作し、そ
の耐蝕性を電位走査法により評価したところ、第１図の
ような結果が得られた。Means for Solving the Problems The present invention was made in order to obtain a current collector of a zinc electrode plate having excellent electrochemical corrosion resistance as described above. First, copper having variously changed tin contents was used. -A trial production of a tin alloy was performed and its corrosion resistance was evaluated by a potential scanning method. The results shown in FIG. 1 were obtained.
第１図から、スズ含有量が10wt％以上の銅−スズ合金
であれば良好な耐蝕性を示し、特にスズの含有量が38wt
％の銅−スズ合金が最も良好な耐蝕性を示すことがかっ
た。From FIG. 1, it can be seen that a copper-tin alloy having a tin content of 10% by weight or more shows good corrosion resistance, and particularly a tin content of 38% by weight.
% Copper-tin alloy showed the best corrosion resistance.
このことから、本発明の請求項１に係る発明は、スズ
含有量が10wt％以上の銅、スズ合金を素地金属の表面に
被覆した集電体を用い、これに亜鉛活物質を保持したこ
とを特徴とする二次電池用亜鉛極板である。Accordingly, the invention according to claim 1 of the present invention uses a current collector in which the surface of a base metal is coated with a copper or tin alloy having a tin content of 10% by weight or more, and holds a zinc active material in the current collector. It is a zinc electrode plate for secondary batteries characterized by the following.
また、本発明の請求項２に係る発明は、素地金属が銅
である請求項１記載の二次電池用亜鉛極板である。The invention according to claim 2 of the present invention is the zinc electrode for a secondary battery according to claim 1, wherein the base metal is copper.
実施例 以下、本発明の詳細を一実施例により説明する。Examples Hereinafter, details of the present invention will be described with reference to an example.
素地金属として、厚みが0.1mmで、開孔率が約50％の
銅板を用い、この銅板の表面に、スズの含有量が38wt％
の銅−スズ合金メッキを施すために、メッキ浴として、
KCu（CN）2,Na2SO3・H2O,KCN,NaOHの各成分からなるも
のを準備し、アルカリ性電解メッキ法による銅、スズ共
析メッキによって銅−スズ合金メッキ層を形成した。こ
うして得られた銅−スズ合金メッキ層の厚みは２〜10μ
ｍであった。このように作製した集電体の両側にカレン
ダーロール法により作製したシート状の亜鉛活物質を加
圧成形し、L:50mm×W:30mm×t:1.0mmの亜鉛極板を得
た。As a base metal, a copper plate with a thickness of 0.1 mm and a porosity of about 50% is used. The tin content is 38 wt% on the surface of this copper plate.
To apply copper-tin alloy plating, as a plating bath,
KCu (CN) 2, Na 2 SO 3 · H 2 O, KCN, prepares made of each component of NaOH, copper with an alkaline electroless plating method, copper by tin eutectoid plating - forming a tin alloy plating layer. The thickness of the copper-tin alloy plating layer thus obtained is 2 to 10 μm.
m. A sheet-like zinc active material produced by a calender roll method was pressure-formed on both sides of the current collector produced in this manner to obtain a zinc electrode plate of L: 50 mm × W: 30 mm × t: 1.0 mm.
この亜鉛極板４枚と同寸法のニッケル極板３枚を、微
孔性フィルム、セロファン膜及びナイロン不織布からな
るセパレータを介して交互に積み重ねて容量が3AHのニ
ッケル亜鉛電池（Ａ）を製作した。また、比較のため、
銀を亜鉛極板の集電体としたニッケル亜鉛電池（Ｂ）、
銅を亜鉛極板の集電体としたニッケル亜鉛電池（Ｃ）、
素地金属に銅を用い、これにスズメッキを施したものを
亜鉛極板の集電体としたニッケル亜鉛電池（Ｄ）、素地
金属に鉄を用い、これにスズメッキを施したものを亜鉛
極板の集電体としたニッケル亜鉛電池（Ｅ）、素地金属
にニッケルを用い、これにスズメッキを施したものを亜
鉛極板の集電体としたニッケル亜鉛電池（Ｆ）を製作し
た。Three nickel plates having the same dimensions as the four zinc plates were alternately stacked via a separator made of a microporous film, a cellophane film and a non-woven nylon fabric to produce a nickel zinc battery (A) having a capacity of 3 AH. . Also, for comparison,
Nickel-zinc battery (B) using silver as a current collector for zinc plates,
Nickel-zinc battery (C) using copper as a current collector for zinc plates,
Nickel-zinc battery (D) using copper as the base metal and tin-plated current collector for zinc electrode plate, and tin-plated using iron as the base metal and tin-plated A nickel-zinc battery (E) as a current collector and a nickel-zinc battery (F) using nickel as a base metal and tin-plated thereon as a current collector for a zinc electrode plate were produced.
これらのニッケル亜鉛電池（Ａ）〜（Ｆ）を用いて、
電気化学的腐蝕の起こりやすい使用条件である長時間連
続負荷接続法による放電深度の深い充放電サイクル試験
を行った。試験条件は、充電電流0.1CAで12時間充電し
た後、放電電流0.1CA相当で20時間放電するサイクルを
繰り返し、充放電サイクル数と容量との関係を第２図に
示した。Using these nickel zinc batteries (A) to (F),
A charge-discharge cycle test with a deep discharge depth was performed by a long-time continuous load connection method, which is a use condition that easily causes electrochemical corrosion. The test conditions were such that a cycle of charging for 12 hours at a charging current of 0.1 CA and then discharging for 20 hours at a discharging current of 0.1 CA was repeated, and the relationship between the number of charge / discharge cycles and the capacity was shown in FIG.
第２図から、ニッケル亜鉛電池（Ｂ）〜（Ｆ）の中で
は、ニッケル亜鉛電池（Ｂ）が最もすぐれた特性であ
り、本発明の亜鉛極板を用いたニッケル亜鉛電池（Ａ）
とほぼ同等の性能であることがわかる。これに対し、ニ
ッケル亜鉛電池（Ｄ）〜（Ｆ）はいずれも最初の数十サ
イクルはかなり良好な特性を示したが、その後急速に特
性が低下していることがわかる。これは、メッキにより
表面を被覆したスズが、電気化学的腐蝕により酸化され
て剥離するためであり、スズの剥離後の素地金属の中で
は、酸素過電圧が低いニッケルを用いたものが最も悪
く、以下電気化学的腐蝕に対する耐蝕性の低い鉄、銅の
順であることがわかる。2, the nickel zinc battery (B) has the most excellent characteristics among the nickel zinc batteries (B) to (F), and the nickel zinc battery (A) using the zinc electrode plate of the present invention.
It can be seen that the performance is almost the same as. On the other hand, it can be seen that the nickel zinc batteries (D) to (F) all showed fairly good characteristics in the first several tens of cycles, but then rapidly deteriorated in characteristics. This is because tin coated on the surface by plating is oxidized and peeled off by electrochemical corrosion, and among the base metals after peeling off tin, the one using nickel with a low oxygen overvoltage is the worst, In the following, it can be seen that iron and copper are in the order of low corrosion resistance to electrochemical corrosion.
発明の効果 上述した如く、本発明は耐蝕性を向上し、寿命性能の
すぐれた、自己放電量を減少した安価な二次電池用亜鉛
極板を提供することができるので、その工業的価値はき
わめて大である。Effect of the Invention As described above, the present invention can provide an inexpensive zinc electrode for a secondary battery with improved corrosion resistance, excellent life performance, and a reduced amount of self-discharge. Extremely large.
すなわち、本発明の二次電池用亜鉛極板に用いる集電
体は、特に放電深度の深い使用における性能向上を目的
とするものであり、自己放電を防止するために水素過電
圧が高く、かつ電気化学的腐蝕に対する耐蝕性にすぐれ
ていることが求められるのに対し、シート状に加工でき
ない、スズの含有量が10wt％以上である銅−スズ合金
を、アルカリ性電解メッキ法による銅、スズ共析メッキ
によって素地金属の表面に被覆したことにより、シート
状の集電体にしたものである。That is, the current collector used for the zinc electrode for a secondary battery of the present invention is intended to improve the performance particularly when used at a deep discharge depth, and has a high hydrogen overvoltage to prevent self-discharge, and an electric current. It is required to have excellent corrosion resistance against chemical corrosion, but copper-tin alloys, which cannot be processed into a sheet and have a tin content of 10 wt% or more, are co-deposited with copper and tin by alkaline electrolytic plating. The sheet-like current collector is obtained by coating the surface of the base metal by plating.
なお、銅−スズ合金の中に、他の水素過電圧の高い金
属、たとえば、カドミウム、インジウム、鉛、タリウ
ム、ビスマス、亜鉛、水銀、銀などが微量混入していて
も前述した性能に影響するものではない。It should be noted that even if a small amount of other metal having a high hydrogen overvoltage, for example, cadmium, indium, lead, thallium, bismuth, zinc, mercury, silver, etc. is mixed into the copper-tin alloy, the above-described performance is affected. is not.
第１図は銅−スズ合成組成と腐蝕量との関係を示した
図、第２図は本発明の亜鉛極板を用いた電池と従来の集
電体による亜鉛極板を用いた電池の充放電サイクルを比
較した図である。FIG. 1 shows the relationship between the composition of copper-tin and the amount of corrosion, and FIG. 2 shows the charging of a battery using the zinc plate of the present invention and a battery using the conventional zinc plate with a current collector. It is the figure which compared the discharge cycle.
Claims (2)
素地金属の表面に被覆した集電体を用い、これに亜鉛活
物質を保持したことを特徴とする二次電池用亜鉛極板。1. A zinc electrode for a secondary battery, comprising a current collector having a base metal coated with a copper or tin alloy having a tin content of 10% by weight or more and holding a zinc active material. Board.
池用亜鉛極板。2. The zinc electrode for a secondary battery according to claim 1, wherein the base metal is copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63305330A JP2743416B2 (en) | 1988-12-01 | 1988-12-01 | Zinc plate for rechargeable batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63305330A JP2743416B2 (en) | 1988-12-01 | 1988-12-01 | Zinc plate for rechargeable batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0315156A JPH0315156A (en) | 1991-01-23 |
| JP2743416B2 true JP2743416B2 (en) | 1998-04-22 |
Family
ID=17943816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63305330A Expired - Fee Related JP2743416B2 (en) | 1988-12-01 | 1988-12-01 | Zinc plate for rechargeable batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2743416B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5445908A (en) * | 1991-10-17 | 1995-08-29 | Matsushita Electric Industrial Co., Ltd. | Alkaline dry cell |
| JPH05135776A (en) * | 1991-11-13 | 1993-06-01 | Hitachi Maxell Ltd | Cylindrical alkaline battery |
| FR2788887B1 (en) * | 1999-01-27 | 2001-04-20 | Conseil Et De Prospective Scie | ZINC ANODE ALKALINE SECONDARY ELECTROCHEMICAL GENERATORS |
| JP2011142041A (en) * | 2010-01-08 | 2011-07-21 | Sakae:Kk | Hot water heater and hot water heater unit using the same |
| JP5923272B2 (en) * | 2011-10-14 | 2016-05-24 | セイコーインスツル株式会社 | Electrochemical cell, lid and method for producing electrochemical cell |
| JP6347321B2 (en) * | 2014-04-28 | 2018-06-27 | 日産自動車株式会社 | Negative electrode structure, air battery using the same, and method of manufacturing negative electrode structure |
| CN114665067B (en) * | 2022-03-18 | 2023-06-02 | 江西安驰新能源科技有限公司 | Thick pole piece treatment method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6459769A (en) * | 1987-08-31 | 1989-03-07 | Alkali Dry Battery Eng Lab | Negative current collector for zinc-alkaline battery |
-
1988
- 1988-12-01 JP JP63305330A patent/JP2743416B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0315156A (en) | 1991-01-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |