JP2877459B2 - Non-sintered cadmium negative electrode plate for alkaline storage batteries - Google Patents
Non-sintered cadmium negative electrode plate for alkaline storage batteriesInfo
- Publication number
- JP2877459B2 JP2877459B2 JP2173399A JP17339990A JP2877459B2 JP 2877459 B2 JP2877459 B2 JP 2877459B2 JP 2173399 A JP2173399 A JP 2173399A JP 17339990 A JP17339990 A JP 17339990A JP 2877459 B2 JP2877459 B2 JP 2877459B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- negative electrode
- cadmium
- active material
- 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
-
- 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
- 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、アルカリ蓄電池に用いられる非焼結式カド
ミウム負極板に関する。The present invention relates to a non-sintered cadmium negative electrode plate used for an alkaline storage battery.
（ロ）従来の技術 カドミウム負極板としては、製造工程が簡易で製造コ
ストの安価な非焼結式カドミウム負極板が工業的に広く
用いられている。この種のカドミウム負極板は、酸化カ
ドミウム粉末等の活物質を糊料液と共に混練して形成し
たペーストを活物質保持体に塗布あるいは充填後、乾燥
を行ない、そのまま負極板として使用する等、更にこの
負極板をアルカリ溶液中に浸漬またはアルカリ溶液中に
て電気化学的処理を行なった後、使用するもの等があ
る。このうち、電気化学的処理をおこなうものについて
は、工程が複雑であり、この処理を省略するために前記
酸化カドミウム等を含むペーストに予備充電物質として
金属カドミウムを混合して用いることが行なわれてい
る。(B) Conventional technology As a cadmium negative electrode plate, a non-sintering type cadmium negative electrode plate having a simple manufacturing process and a low manufacturing cost is widely used industrially. This kind of cadmium negative electrode plate, after applying or filling the active material holding body with a paste formed by kneading an active material such as cadmium oxide powder together with a paste liquid, performing drying, and using it as a negative electrode plate, etc. After the negative electrode plate is immersed in an alkaline solution or subjected to an electrochemical treatment in the alkaline solution, there is one used, for example. Among them, the one which performs an electrochemical treatment has a complicated process, and in order to omit this treatment, a mixture containing metal cadmium as a pre-charging substance is used in a paste containing the cadmium oxide or the like. I have.
ところが一般に、金属カドミウムは、利用率が低く、
この金属カドミウムの反応性を向上させるため、例えば
特開昭62−243254号公報では、インジウムを含有する金
属カドミウムを用いることが提案されている。However, in general, metal cadmium has a low utilization rate,
In order to improve the reactivity of this metal cadmium, for example, Japanese Patent Application Laid-Open No. Sho 62-243254 proposes to use metal cadmium containing indium.
また、非焼結式カドミウム負極板では、酸素ガス吸収
性能を向上させるために、例えば特開昭60−216449号公
報に開示されているように、負極板表面にニッケルある
いは炭素などの耐アルカリ性の導電性物質からなる導電
層を形成し、負極板表面の導電性を高め、極板表面にお
ける金属カドミウムの生成を促進させることが提案され
ている。Further, in the non-sintered cadmium negative electrode plate, in order to improve the oxygen gas absorption performance, for example, as disclosed in Japanese Patent Application Laid-Open No. 60-216449, the surface of the negative electrode plate is resistant to alkali such as nickel or carbon. It has been proposed to form a conductive layer made of a conductive material to increase the conductivity of the surface of the negative electrode plate and promote the production of metal cadmium on the surface of the electrode plate.
しかし、負極板表面にニッケルからなる導電層を形成
した場合には、充電時に水素ガスが発生し易くなり、ま
た更に活物質の利用率を向上させるために金属カドミウ
ム中にインジウムを含有させると、より一層水素ガスが
発生し易くなる。一方負極板表面に炭素粉末からなる導
電層を形成しただけでは、やはり前記せる問題を解決す
るには至らない。However, when a conductive layer made of nickel is formed on the surface of the negative electrode plate, hydrogen gas is easily generated at the time of charging, and when indium is contained in metal cadmium in order to further improve the utilization rate of the active material, Hydrogen gas is more easily generated. On the other hand, simply forming a conductive layer made of carbon powder on the surface of the negative electrode plate still does not solve the above problem.
（ハ）発明が解決しようとする課題 本発明は前記問題点に鑑みてなされたものであって、
充電時における水素ガスの発生が抑制できると共に、活
物質の利用率及び酸素ガス吸収性能が向上した非焼結式
カドミウム負極板を提供するものである。(C) Problems to be solved by the invention The present invention has been made in view of the above problems,
An object of the present invention is to provide a non-sintered cadmium negative electrode plate that can suppress generation of hydrogen gas at the time of charging and improve the utilization rate of an active material and oxygen gas absorption performance.
（ニ）課題を解決するための手段 本発明は、酸化カドミウム粉末とインジウム含有金属
カドミウム粉末とを主成分とする活物質層と、該活物質
の表面に配置された炭素粉末とニッケル粉末との混合導
電層とを備え、アルカリ溶液中にて化学的に予備水和さ
れたアルカリ蓄電池用非焼結式カドミウム負極板であっ
て、活物質1gあたりの前記ニッケルの表面積をｘcm2、
活物質総量に対する前記インジウムの量をｙ重量％とし
た時、 ｘ≧0.001…、ｙ≧0.002… ｙ≦−0.7x＋0.05… 上記、、の関係式を満たすことを特徴とするもの
である。(D) Means for Solving the Problems The present invention provides an active material layer mainly composed of cadmium oxide powder and indium-containing metal cadmium powder, and a carbon powder and a nickel powder arranged on the surface of the active material. A mixed conductive layer, a non-sintered cadmium negative electrode plate for an alkaline storage battery chemically prehydrated in an alkaline solution, wherein the surface area of the nickel per 1 g of the active material is xcm 2 ,
When the amount of the indium with respect to the total amount of the active material is defined as y weight%, x ≧ 0.001..., Y ≧ 0.002... Y ≦ −0.7x + 0.05.
（ホ）作用 負極板表面に炭素粉末とニッケル粉末の混合層を用い
ることにより、ニッケル粉末添加に伴う水素発生を抑制
し、炭素粉末のみを用いる場合よりも、更に酸素ガス吸
収性能を高める条件を見い出すことができる。しかし、
この条件は、金属カドミウム中に含まれるインジウム量
と密接な関係がある。これはインジウム量が増加する
と、負極の充電電位が卑な電位となるからである。ま
た、活物質層の酸化カドミウム粉末をアルカリ溶液中に
て化学的に水和し、水洗、乾燥して負極板とする場合に
おいては、インジウムの添加量や、添加せるニッケル粉
末の表面積により、性能が左右されることを見い出し
た。(E) Action By using a mixed layer of carbon powder and nickel powder on the surface of the negative electrode plate, it is possible to suppress the generation of hydrogen due to the addition of nickel powder, and to improve the oxygen gas absorption performance more than when only carbon powder is used. Can be found. But,
This condition is closely related to the amount of indium contained in the metal cadmium. This is because when the amount of indium increases, the charge potential of the negative electrode becomes lower. In the case where the cadmium oxide powder of the active material layer is chemically hydrated in an alkaline solution, washed with water and dried to form a negative electrode plate, the performance depends on the amount of indium added and the surface area of the nickel powder to be added. Was found to be affected.
そこで種々の実験結果より、活物質1gあたりのニッケ
ルの表面積をｘcm2、活物質総量に対するインジウムの
量をｙ重量％とした時、 ｘ≧0.001…、ｙ≧0.002… ｙ≦−0.7x＋0.05… 上記、、の関係式を満たすように、インジウム及
びニッケルを添加使用することで、充電時における水素
ガスの発生が抑制できると共に、活物質の利用率及び酸
素ガス吸収性能を向上させることができる。Therefore, from various experimental results, when the surface area of nickel per 1 g of the active material is xcm 2 , and the amount of indium with respect to the total amount of the active material is y% by weight, x ≧ 0.001..., Y ≧ 0.002. By adding and using indium and nickel so as to satisfy the above relational expression, generation of hydrogen gas during charging can be suppressed, and the utilization rate of the active material and the oxygen gas absorption performance can be improved. .
（ヘ）実施例 所定量のインジウムを含むカドミウム塩溶液と亜鉛粉
末を反応させて置換法により生成したインジウムを含有
する金属カドミウム粉末20重量％と酸化カドミウム粉末
80重量％からなる活物質粉末と、結着剤としてのメチル
セルロース溶液と補強材としてのナイロン短繊維等とを
混練してペーストした。このペーストをパンチングメタ
ルに塗着、乾燥し、ベース極板を作製した。(F) Example 20% by weight of indium-containing cadmium metal powder containing indium and cadmium oxide powder produced by a substitution method by reacting a cadmium salt solution containing a predetermined amount of indium with zinc powder
An active material powder consisting of 80% by weight, a methylcellulose solution as a binder, and nylon short fibers as a reinforcing material were kneaded and pasted. This paste was applied to a punching metal and dried to produce a base electrode plate.
次に、BET法による比表面積が５m2/gのニッケル粉末
と、アセチレンブラックおよびメチルセルロース溶液を
所定量混合したスラリーを、前記ベース極板に、ローラ
転写法により塗布、乾燥して、表面に導電層を有するカ
ドミウム極板を作製した。Next, a slurry obtained by mixing a predetermined amount of a nickel powder having a specific surface area of 5 m 2 / g by a BET method, acetylene black and a methylcellulose solution was applied to the base electrode plate by a roller transfer method, and dried to form a conductive film on the surface. A cadmium electrode having a layer was prepared.
このカドミウム極板を過剰の25％KOH水溶液（25％）
に１時間浸漬し、水洗、乾燥し、化学的水和処理を行な
い、カドミウム負極板を作製した。そして、このカドミ
ウム負極板と、焼結式ニッケル正極板を用い、密閉型ニ
ッケル−カドミウム蓄電池（SCサイズ、公称容量1.3A
H）を作製した。This cadmium plate is replaced with an excess 25% KOH aqueous solution (25%)
For 1 hour, washed with water, dried, and subjected to a chemical hydration treatment to produce a cadmium negative electrode plate. Using this cadmium negative electrode plate and sintered nickel positive electrode plate, a sealed nickel-cadmium storage battery (SC size, nominal capacity 1.3A)
H) was prepared.
（テスト１） 前記せるカドミウム負極板を使用し、活物質総量（酸
化カドミウム80重量％、金属カドミウム20重量％として
換算）に対する、インジウム量と、負極板利用率との関
係を調べた。ここで利用率の測定は、過剰量の25重量％
のKOH水溶液中にて、金属ニッケル板を対極として、0.3
Aで極板容量の160％を充電した後、0.5Aで−1.0V（VS対
極）になるまで放電して行ったものである。(Test 1) Using the cadmium negative electrode plate described above, the relationship between the amount of indium and the negative electrode plate utilization rate with respect to the total amount of the active material (converted as 80% by weight of cadmium oxide and 20% by weight of metal cadmium) was examined. Here, the measurement of the utilization rate is 25% by weight of the excess amount.
In a KOH aqueous solution of
After charging 160% of the electrode plate capacity at A, the battery was discharged at 0.5 A until it reached -1.0 V (VS counter electrode).
この結果を、第１図に示す。第１図は活物質総量に対
するインジウム量は、負極板利用率との関係を示す図で
ある。第１図より、導電層中のニッケルの表面積が異な
っても、金属カドミウム中のインジウム量（ｙ）が活物
質総量に対し、0.002重量％以上となるとき、負極板利
用率が大きくなることがわかる。The result is shown in FIG. FIG. 1 is a diagram showing the relationship between the amount of indium with respect to the total amount of active materials and the utilization rate of the negative electrode plate. From FIG. 1, it can be seen that even if the surface area of nickel in the conductive layer is different, when the amount of indium (y) in the metal cadmium is 0.002% by weight or more with respect to the total amount of the active material, the utilization rate of the negative electrode plate may increase. Recognize.
（テスト２） 次に、作製した電池を使用し、カドミウム負極板にお
ける活物質総量あたりの導電層中のニッケルの表面積
と、電池平衡内部圧力との関係を調べた。ここで電池平
衡内部圧力は、25℃にて1.3A充電時のものである。(Test 2) Next, using the fabricated battery, the relationship between the surface area of nickel in the conductive layer per total amount of the active material in the cadmium negative electrode plate and the battery internal pressure was examined. Here, the battery equilibrium internal pressure is the one at the time of charging at 1.3 A at 25 ° C.
この結果を第２図に示す。第２図は活物質総量に対す
るニッケルの表面積と電池平衡内部圧力との関係を示す
図である。第２図より、カドミウム負極板の導電層中の
ニッケルの表面積（ｘ）が、活物質総量に対し0.001m2
以上となると、電池平衡内部圧力が低下し、酸素ガス吸
収性能が向上することがわかる。The result is shown in FIG. FIG. 2 is a diagram showing the relationship between the surface area of nickel and the battery internal pressure with respect to the total amount of active materials. FIG. 2 shows that the surface area (x) of nickel in the conductive layer of the cadmium negative electrode plate was 0.001 m 2 with respect to the total amount of the active material.
From the above, it can be seen that the battery equilibrium internal pressure decreases and the oxygen gas absorption performance improves.
（テスト３） 作製した電池のカドミウム負極板中の活物質総量に対
する導電層中のニッケル表面積と、電池内水素分圧との
関係を調べた。ここで電池内水素分圧は。10℃にて2.6A
で、公称容量の160％充電したときのものである。(Test 3) The relationship between the surface area of nickel in the conductive layer and the hydrogen partial pressure in the battery with respect to the total amount of the active material in the cadmium negative electrode plate of the manufactured battery was examined. Here is the partial pressure of hydrogen in the battery. 2.6A at 10 ° C
At 160% of the nominal capacity.
第３図に、この結果を示す。第３図は活物質総量に対
するニッケルの表面積と電池内水素分圧との関係を示す
図である。ここで、金属カドミウム中のインジウム量
は、０重量％、0.005重量％、0.01重量％、0.02重量
％、0.03重量％、0.05重量％、0.08重量％とした。第３
図より、インジウム量により水素ガス発生を抑制できる
ニッケルの添加量の上限が異なっており、インジウム量
が多くなるほど、ニッケルの表面積の上限が低くなるこ
とがわかる。FIG. 3 shows the results. FIG. 3 is a diagram showing the relationship between the surface area of nickel and the hydrogen partial pressure in the battery with respect to the total amount of the active material. Here, the indium content in the metal cadmium was 0% by weight, 0.005% by weight, 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.05% by weight, and 0.08% by weight. Third
From the figure, it can be seen that the upper limit of the amount of nickel that can suppress the generation of hydrogen gas differs depending on the amount of indium, and the upper limit of the surface area of nickel decreases as the amount of indium increases.
このようにして得たテスト１、２、３の結果を第４図
にまとめ、カドミウム負極板におけるインジウム量
（ｙ）と、ニッケルの表面積（ｘ）の最適値を斜線で示
した。ここで黒丸は、第３図で示した各インジウム量に
おけるニッケルの表面積の上限をプロットしたものであ
る。The results of Tests 1, 2, and 3 obtained in this manner are summarized in FIG. 4, and the optimum values of the amount of indium (y) and the surface area (x) of nickel in the cadmium negative electrode plate are shown by oblique lines. Here, the black circles are plots of the upper limit of the surface area of nickel at each indium content shown in FIG.
第４図より、ｘ≧0.001、ｙ≧0.002、ｙ≦−0.7x＋0.
05を満たす領域に入るように、ニッケルの表面積及びイ
ンジウム量を決定することで、負極板の利用率及び酸素
ガス吸収性能が向上し、水素ガス発生のないカドミウム
負極板を得ることができる。From FIG. 4, x ≧ 0.001, y ≧ 0.002, y ≦ −0.7x + 0.
By determining the surface area and the amount of indium of nickel so as to enter the region satisfying 05, the utilization rate and oxygen gas absorption performance of the negative electrode plate are improved, and a cadmium negative electrode plate free of hydrogen gas generation can be obtained.
（ト）発明の効果 本発明のアルカリ蓄電池用非焼結式カドミウム負極板
によれば、充電時における水素ガスの発生が抑制できる
と共に、活物質の利用率及び酸素ガス吸収性能を向上さ
せることが可能となり、電池特性の向上が計れるもので
あり、その工業的価値は極めて大きい。(G) Effects of the Invention According to the non-sintered cadmium negative electrode plate for an alkaline storage battery of the present invention, generation of hydrogen gas during charging can be suppressed, and the utilization rate of active material and oxygen gas absorption performance can be improved. It is possible to improve the battery characteristics, and its industrial value is extremely large.
第１図は活物質総量に対するインジウム量と負極板利用
率との関係を示す図、第２図は活物質総量に対するニッ
ケル表面積と電池平衡内部圧力との関係を示す図、第３
図は活物質総量に対するニッケル表面積と電池内水素分
圧との関係を示す図、第４図はニッケル表面積とインジ
ウム量との関係を示す図である。FIG. 1 is a diagram showing the relationship between the amount of indium and the utilization rate of the negative electrode plate with respect to the total amount of the active material, FIG. 2 is a diagram showing the relationship between the nickel surface area and the battery internal pressure with respect to the total amount of the active material, and FIG.
The figure shows the relationship between the nickel surface area and the hydrogen partial pressure in the battery with respect to the total amount of active material, and FIG. 4 shows the relationship between the nickel surface area and the amount of indium.
Claims (1)
属カドミウム粉末とを主成分とする活物質層と、該活物
質層の表面に配置された炭素粉末とニッケル粉末との混
合導電層とを備え、アルカリ溶液中にて化学的に予備水
和されたカドミウム負極板であって、 活物質1gあたりの前記ニッケルの表面積をｘm2、活物質
総量に対する前記インジウムの量をｙ重量％とした時 ｘ≧0.001…、ｙ≧0.002… ｙ≦−0.7x＋0.05… 上記、、の関係式を満たすことを特徴とするアル
カリ蓄電池用非焼結式カドミウム負極板。1. An active material layer comprising cadmium oxide powder and indium-containing metal cadmium powder as main components, and a mixed conductive layer of carbon powder and nickel powder disposed on the surface of the active material layer, A cadmium negative electrode plate chemically prehydrated in an alkaline solution, wherein the surface area of the nickel per 1 g of the active material is xm 2 , and the amount of the indium relative to the total amount of the active material is y% by weight. 0.001 ..., y≥0.002 ... y <-0.7x + 0.05 ... A non-sintered cadmium negative electrode plate for an alkaline storage battery, characterized by satisfying the above relational expression.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2173399A JP2877459B2 (en) | 1990-06-29 | 1990-06-29 | Non-sintered cadmium negative electrode plate for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2173399A JP2877459B2 (en) | 1990-06-29 | 1990-06-29 | Non-sintered cadmium negative electrode plate for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0462751A JPH0462751A (en) | 1992-02-27 |
| JP2877459B2 true JP2877459B2 (en) | 1999-03-31 |
Family
ID=15959695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2173399A Expired - Fee Related JP2877459B2 (en) | 1990-06-29 | 1990-06-29 | Non-sintered cadmium negative electrode plate for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2877459B2 (en) |
-
1990
- 1990-06-29 JP JP2173399A patent/JP2877459B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0462751A (en) | 1992-02-27 |
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