JPH0773047B2 - Negative electrode for sealed alkaline storage battery - Google Patents
Negative electrode for sealed alkaline storage batteryInfo
- Publication number
- JPH0773047B2 JPH0773047B2 JP61194431A JP19443186A JPH0773047B2 JP H0773047 B2 JPH0773047 B2 JP H0773047B2 JP 61194431 A JP61194431 A JP 61194431A JP 19443186 A JP19443186 A JP 19443186A JP H0773047 B2 JPH0773047 B2 JP H0773047B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- active material
- porosity
- material layer
- storage 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/246—Cadmium electrodes
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
- H01M10/526—Removing gases inside the secondary cell, e.g. by absorption by gas recombination on the electrode surface or by structuring the electrode surface to improve gas recombination
-
- 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】 産業上の利用分野 本発明は、密閉形アルカリ蓄電池に用いる負極のガス吸
収能の向上に関するものである。TECHNICAL FIELD The present invention relates to improvement of gas absorption capacity of a negative electrode used in a sealed alkaline storage battery.
従来の技術 従来、この種の密閉形アルカリ蓄電池の代表的なものに
ニッケル−カドミウム蓄電池があるが、この電池に用い
るカドミウム負極は、製造コストが安価なペースト式カ
ドミウム負極が多く用いられている。しかし、製造コス
トが安価である利点をもつ反面、電子伝導性に劣るため
負極表面に金属カドミウムが生成し難く、過充電時に正
極から発生する酸素ガスの吸収能力が悪い欠点があっ
た。このため、負極の多孔度を増加させる方法や、負極
板の表面に撥水性を持つ樹脂を塗布して酸素ガスの通過
を良くする方法が提案されている。しかし、前者は負極
の強度を低下させ、後者では極板表面付近の電解液量が
減少し活物質利用率を低下させる。そこで、負極板の表
面に炭素粉末を塗着し導電層を設ける方法が提案されて
いる（特開昭60−63875号公報）。2. Description of the Related Art Conventionally, a nickel-cadmium storage battery is a typical example of this type of sealed alkaline storage battery, and as a cadmium negative electrode used in this battery, a paste-type cadmium negative electrode, which is inexpensive to manufacture, is often used. However, although it has an advantage of low manufacturing cost, it has a drawback that metal cadmium is difficult to be generated on the surface of the negative electrode due to poor electron conductivity and the ability to absorb oxygen gas generated from the positive electrode during overcharge is poor. Therefore, a method of increasing the porosity of the negative electrode and a method of applying a water-repellent resin to the surface of the negative electrode plate to improve the passage of oxygen gas have been proposed. However, the former lowers the strength of the negative electrode, and the latter lowers the amount of the electrolytic solution near the surface of the electrode plate and lowers the active material utilization rate. Therefore, a method has been proposed in which carbon powder is applied to the surface of the negative electrode plate to form a conductive layer (JP-A-60-63875).
発明が解決しようとする問題点 このような従来の構成では、負極の放電容量密度を増加
させるために活物質を高密度に充填した場合、カドミウ
ム負極板の表面に炭素粉末からなる導電層を形成しただ
けでは、急速充電時に電池内圧が上昇するという問題が
あった。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In such a conventional configuration, when the active material is densely packed to increase the discharge capacity density of the negative electrode, a conductive layer made of carbon powder is formed on the surface of the cadmium negative electrode plate. However, there is a problem that the internal pressure of the battery increases at the time of quick charging.
本発明は、このような問題点を解決するもので、安価で
簡単な構成により酸素ガス吸収能の優れた密閉形アルカ
リ蓄電池用負極を提供することを目的とするものであ
る。The present invention solves such a problem, and an object of the present invention is to provide a negative electrode for a sealed alkaline storage battery, which has a low cost and a simple structure and is excellent in oxygen gas absorption capacity.
問題点を解決するための手段 この問題点を解決するために本発明は、芯金付近の活物
質層の多孔度が負極表面の多孔度より小さく、かつ負極
板表面の活物質層には導電性粉末を有する構成とするこ
とにより、酸素ガス吸収能の優れた密閉形アルカリ蓄電
池用負極を提供するものである。Means for Solving the Problems In order to solve this problem, the present invention is directed to that the porosity of the active material layer in the vicinity of the core metal is smaller than the porosity of the negative electrode surface, and the active material layer on the negative electrode plate surface is electrically conductive. The present invention provides a negative electrode for a sealed alkaline storage battery, which has an excellent oxygen gas absorption capacity by having a composition containing a conductive powder.
作用 この構成により本発明は、負極板表面層のみを活物質と
導電性粉末の混合層とし、しかも高多孔度に構成するこ
とにより、高密度に活物質を充填した場合でも酸素ガス
の吸収と酸化カドミウムの還元を効率良く行って負極の
酸素ガス吸収能を向上させることができる。また、芯金
付近の活物質層は低多孔度であるため、高容量密度の負
極板を得ることができる。Action With this configuration, the present invention has only the negative electrode plate surface layer as a mixed layer of the active material and the conductive powder, and by having a high porosity, absorbs oxygen gas even when the active material is densely packed. Cadmium oxide can be efficiently reduced to improve the oxygen gas absorption capacity of the negative electrode. Further, since the active material layer near the core bar has a low porosity, a negative electrode plate having a high capacity density can be obtained.
実 施 例 第１図は、本発明の一実施例による負極板の断面図であ
る。第１図において、１は高多孔度の活物質層、２は低
多孔度の活物質層、３は芯材である。Example 1 FIG. 1 is a sectional view of a negative electrode plate according to an example of the present invention. In FIG. 1, 1 is a high-porosity active material layer, 2 is a low-porosity active material layer, and 3 is a core material.
具体的には酸化カドミウム粉末500gをエチレングリコー
ル150c.c.にポリビニルアルコール4gを溶解した溶液で
ペースト状にする。このペーストをニッケルメッキ鉄製
の厚さ0.1mmの穴あき板に塗着し乾燥して厚さ約0.4mmの
低多孔度の活物質層２を形成する。Specifically, 500 g of cadmium oxide powder is made into a paste by using a solution in which 4 g of polyvinyl alcohol is dissolved in 150 g of ethylene glycol. This paste is applied to a perforated plate made of nickel-plated iron and having a thickness of 0.1 mm and dried to form a low-porosity active material layer 2 having a thickness of about 0.4 mm.
次に、酸化カドミウム粉末250gと導電性粉末であるニッ
ケル粉末250gの混合物を上記と同様の溶液で練合したペ
ーストを、上記極板表面に再び塗着し、乾燥し、高多孔
度の活物質層１を形成する。負極板の厚さは約052mmで
ある。実施例で用いた負極板の多孔度を次表に示す。な
お負極Ａは従来例の電極で活物質層１を設けない構成で
ある。Next, a paste prepared by kneading a mixture of 250 g of cadmium oxide powder and 250 g of nickel powder, which is a conductive powder, with the same solution as above was applied again to the surface of the electrode plate and dried, and the active material having high porosity was used. Form layer 1. The thickness of the negative electrode plate is about 052 mm. The porosity of the negative electrode plate used in the examples is shown in the following table. The negative electrode A is an electrode of a conventional example, and the active material layer 1 is not provided.
表に示した負極Ａ〜Ｄを用い、公知の焼結式ニッケル正
極と組み合わせSCサイズで公称容量1700mAhのニッケル
−カドミウム蓄電池を構成した。第２図に、０℃におけ
る充電率と公称容量に対して200％充電時の電池内圧の
関係を示した。第２図から明らかなように、従来例のニ
ッケル粉末を有する高多孔度の活物質層１を設けない負
極Ａを用いた電池の内圧は、充電率が1cmAで10Kg/cm2以
上になり、酸素ガス吸収能は非常に悪い。したがって、
安全弁が作動し、漏液，サイクル寿命が短い等の問題が
生じる。しかしながら、ニッケル粉末を含む高多孔度の
活物質層１を設けた電極B,C,Dを用いた電池の内圧は、
6.5Kg/cm2以下であり、これらの負極は酸素ガス吸収能
が優れていることがわかる。多孔度35〜50％のニッケル
粉末を含む活物質層１を設けることにより、充電時に負
極板表面付近に多量の活性な金属カドミウムが生成しや
すくなる。その結果、正極から発生する酸素ガスは、負
極の金属カドミウムと反応しやすくなり、急速充電時に
おいても電池内圧が上昇しない。 Using the negative electrodes A to D shown in the table, a nickel-cadmium storage battery having a nominal capacity of 1700 mAh was constructed in SC size in combination with a known sintered nickel positive electrode. FIG. 2 shows the relationship between the charging rate at 0 ° C. and the battery internal pressure at 200% charge with respect to the nominal capacity. As is apparent from FIG. 2, the internal pressure of the battery using the negative electrode A in which the high-porosity active material layer 1 having the nickel powder of the conventional example is not used is 10 Kg / cm 2 or more at the charging rate of 1 cmA, The oxygen gas absorption capacity is very poor. Therefore,
The safety valve operates, causing problems such as liquid leakage and short cycle life. However, the internal pressure of the battery using the electrodes B, C, and D provided with the high-porosity active material layer 1 containing nickel powder is
It is 6.5 Kg / cm 2 or less, which means that these negative electrodes have excellent oxygen gas absorption ability. By providing the active material layer 1 containing nickel powder having a porosity of 35 to 50%, a large amount of active metal cadmium is easily generated near the surface of the negative electrode plate during charging. As a result, the oxygen gas generated from the positive electrode easily reacts with the metal cadmium of the negative electrode, and the battery internal pressure does not rise even during rapid charging.
導電性粉末であるニッケル粉末を有する活物質層１の多
孔度は、35％以下になると電池内圧が10Kg/cm2以上にな
り、酸素ガス吸収能は低下する。また、50％以上では負
極板表面に生成する金属カドミウム量が減少し、ガス吸
収能も低下することになる。したがって、ニッケル粉末
を有する活物質層１の多孔度は35〜50％の範囲が適切で
ある。芯金付近の活物質層２の多孔度は、35％以上にな
ると極板強度や容量密度が低下する問題が生じ、電池構
成上好ましくない。したがって、活物質層２の多孔度は
25〜35％が適切である。When the porosity of the active material layer 1 having the nickel powder which is the conductive powder is 35% or less, the internal pressure of the battery is 10 kg / cm 2 or more, and the oxygen gas absorption capacity is lowered. On the other hand, when it is 50% or more, the amount of metal cadmium generated on the surface of the negative electrode plate decreases, and the gas absorption capacity also decreases. Therefore, the porosity of the active material layer 1 having the nickel powder is appropriately in the range of 35 to 50%. When the porosity of the active material layer 2 in the vicinity of the core metal is 35% or more, there arises a problem that the electrode plate strength and the capacity density are lowered, which is not preferable in the battery structure. Therefore, the porosity of the active material layer 2 is
25-35% is appropriate.
なお、本実施例では導電性粉末にニッケル粉末を用いた
が、カーボン，銅，コバルト粉末等の導電性を有する物
質であれば同様の効果が得られる。Although nickel powder is used as the conductive powder in this embodiment, similar effects can be obtained as long as it is a substance having conductivity such as carbon, copper, and cobalt powder.
発明の効果 以上のように本発明によれば、芯金を中心として、その
両側に負極活物質層を塗着された負極において、芯金付
近の活物質層の多孔度が負極板表面の多孔度より小さ
く、かつ負極板表面の活物質層にのみ導電性粉末を有す
る構造とすることにより、高密度に活物質が充填された
場合でも、酸素ガスの吸収と酸化カドミウムの還元を効
率良く行って急速充電時において電池内圧が上昇しな
い、すなわち、酸素ガス吸収能に優れた負極板を提供で
きると云う効果が得られる。EFFECTS OF THE INVENTION As described above, according to the present invention, in a negative electrode in which a negative electrode active material layer is coated on both sides of a core metal, the porosity of the active material layer near the core metal is the porosity of the surface of the negative electrode plate. And the conductive material is contained only in the active material layer on the surface of the negative electrode plate, the oxygen gas can be absorbed and the cadmium oxide can be reduced efficiently even when the active material is densely packed. The effect is that the internal pressure of the battery does not rise during rapid charging, that is, a negative electrode plate having an excellent oxygen gas absorption capacity can be provided.
第１図は本発明の一実施例による負極板の断面図、第２
図は０℃における充電率と公称容量に対して200％充電
時の電池内圧との関係を示す図である。 １……導電性粉末を有する高多孔度の活物質層、２……
低多孔度の活物質層、３……芯金。FIG. 1 is a sectional view of a negative electrode plate according to an embodiment of the present invention.
The figure shows the relationship between the charging rate at 0 ° C. and the battery internal pressure at the time of 200% charging with respect to the nominal capacity. 1 ... Highly porous active material layer containing conductive powder, 2 ...
Low-porosity active material layer, 3 ... core metal.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松本 功 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 昭57−72264（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isao Matsumoto 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) Reference JP-A-57-72264 (JP, A)
Claims (2)
を配した負極において、芯金付近の活物質層の多孔度が
負極表面の多孔度より小さく、かつ負極表面の活物質層
内にのみ導電性粉末を有することを特徴とする密閉形ア
ルカリ蓄電池用負極。1. A negative electrode in which a negative electrode active material layer is arranged on both sides of a core metal, and the porosity of the active material layer near the core metal is smaller than the porosity of the negative electrode surface and the active material layer on the negative electrode surface. A negative electrode for a sealed alkaline storage battery, which has a conductive powder only inside.
あり、導電性粉末を有する負極表面付近の多孔度が35〜
50％である特許請求の範囲第１項記載の密閉形アルカリ
蓄電池用負極。2. The porosity of the active material layer near the core metal is 25 to 35%, and the porosity near the surface of the negative electrode having the conductive powder is 35 to 35%.
The negative electrode for a sealed alkaline storage battery according to claim 1, which is 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61194431A JPH0773047B2 (en) | 1986-08-20 | 1986-08-20 | Negative electrode for sealed alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61194431A JPH0773047B2 (en) | 1986-08-20 | 1986-08-20 | Negative electrode for sealed alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6351050A JPS6351050A (en) | 1988-03-04 |
| JPH0773047B2 true JPH0773047B2 (en) | 1995-08-02 |
Family
ID=16324484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61194431A Expired - Lifetime JPH0773047B2 (en) | 1986-08-20 | 1986-08-20 | Negative electrode for sealed alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0773047B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5772264A (en) * | 1980-10-20 | 1982-05-06 | Matsushita Electric Ind Co Ltd | Cadmium electrode for alkaline battery and its manufacture |
-
1986
- 1986-08-20 JP JP61194431A patent/JPH0773047B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6351050A (en) | 1988-03-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |