JPH04188562A - Manufacture of cd negative electrode plate - Google Patents
Manufacture of cd negative electrode plateInfo
- Publication number
- JPH04188562A JPH04188562A JP2319979A JP31997990A JPH04188562A JP H04188562 A JPH04188562 A JP H04188562A JP 2319979 A JP2319979 A JP 2319979A JP 31997990 A JP31997990 A JP 31997990A JP H04188562 A JPH04188562 A JP H04188562A
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- negative electrode
- hydroxide
- active substance
- cadmium
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 12
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 5
- 230000000996 additive effect Effects 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 3
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 lidanine Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、密閉型ニッケルーカドミウム蓄電池の如きア
ルカリ蓄電池に用いられるカドミウム負極板の製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for manufacturing a cadmium negative electrode plate used in an alkaline storage battery such as a sealed nickel-cadmium storage battery.
（ロ）従来の技術
密閉型ニッケルーカドミウム蓄電池などのカドミウム酸
化物を主活物質とする負極板を備えたアルカリ蓄電池は
、従来から放電性能の向上が種々検討されている。最近
では民生用の密閉型ニッケルーカドミウム蓄電池の用途
が広がり、電動工具の電源として用いる場合には、特に
、高率放電時の特性向上が求められる。しかし、この高
率放電特性の向上については、多くの検討が行われてい
るが、まだ充分な性能を得るに至ってはいない。(b) Conventional Technology Various studies have been made to improve the discharge performance of alkaline storage batteries, such as sealed nickel-cadmium storage batteries, which are equipped with negative electrode plates containing cadmium oxide as the main active material. Recently, the use of sealed nickel-cadmium storage batteries for consumer use has expanded, and when used as a power source for power tools, improved characteristics are required, especially during high rate discharge. However, although many studies have been made to improve this high rate discharge characteristic, sufficient performance has not yet been achieved.
上記性能向上が充分に行えない原因としては、高率放電
を行った際に、カドミウム負極板の放電可能な容量が減
少し、電池の放電容量が前記負極板の放電可能な容量に
よって規制されることが考えられる。従って、カドミウ
ム負極板の性能を向上することが、高率放電特性の向上
にとって重要な課題となっている。The reason why the above performance improvement cannot be achieved sufficiently is that when performing high rate discharge, the dischargeable capacity of the cadmium negative electrode plate decreases, and the discharge capacity of the battery is regulated by the dischargeable capacity of the negative electrode plate. It is possible that Therefore, improving the performance of the cadmium negative electrode plate is an important issue for improving high rate discharge characteristics.
負極板の性能向上に関しては、カドミウムの充放電反応
（溶解−析出反応）をコントロールする添加剤の検討が
行われている。この添加剤としては、例えば、リダニン
、カルボキシメチルセルロース、メチルセルロース等の
有機物の添加に関するものが数多くあるが、有機系添加
物は電池内で分解して炭酸根を生成し、電解液の濃度を
低下させる。また、通常電池を構成する際には、正極が
完全放電した時に、負極に放電可能な充電部分が残るよ
う、予め負極板に予備充電量を確保りでいるが、前記炭
酸根が生成すると、この負極板の予備充電量が減少する
といった問題がある。In order to improve the performance of negative electrode plates, studies are being conducted on additives that control the charge/discharge reaction (dissolution-precipitation reaction) of cadmium. There are many additives related to the addition of organic substances such as lidanine, carboxymethylcellulose, and methylcellulose, but organic additives decompose within the battery and produce carbonate radicals, reducing the concentration of the electrolyte. . In addition, when constructing a normal battery, a preliminary charge amount is secured in advance on the negative electrode plate so that a dischargeable charged portion remains on the negative electrode when the positive electrode is completely discharged, but when the carbonate radicals are generated, There is a problem that the amount of preliminary charge of this negative electrode plate decreases.
一方、無機系の添加剤では、対極物質である水酸化ニッ
ケルの添加が有効であるが、その反面、電池の自己放電
が増大するという問題があった。On the other hand, when it comes to inorganic additives, the addition of nickel hydroxide as a counter electrode substance is effective, but on the other hand, there is a problem in that the self-discharge of the battery increases.
（ハ）発明が解決しようとする課題
本発明は、上述の如き問題点を解決し、カドミウム負極
板への水酸化ニッケルの添加による放電性能の向上効果
を維持したまま、自己放電を抑制したカドミウム負極板
の製造方法を提供しようとするものである。(c) Problems to be Solved by the Invention The present invention solves the above-mentioned problems, and provides cadmium that suppresses self-discharge while maintaining the effect of improving discharge performance by adding nickel hydroxide to a cadmium negative electrode plate. The present invention aims to provide a method for manufacturing a negative electrode plate.
（ニ）課題・を解決するための手段
本発明のカドミウム負極板の製造方法は、カドミウム酸
化物を主活物質とし、水酸化ニッケルを添加した負極板
に、化成を行った後、前記負極板を高温のアルカリ水溶
液中に放置し、その後、水洗、乾燥するものである。(d) Means for Solving the Problems The method for manufacturing a cadmium negative electrode plate of the present invention includes chemically forming a negative electrode plate containing cadmium oxide as a main active material and adding nickel hydroxide, and then is left in a high-temperature alkaline aqueous solution, then washed with water and dried.
（ホ）１￥＝ 用
アルカリ蓄電池などの自己放電特性を決定する因子とし
ては、不純物と活物質の反応性が考えられる。(e) Reactivity of impurities and active materials can be considered as a factor that determines the self-discharge characteristics of alkaline storage batteries and the like.
不純物としては、水酸化工ンケル、残留硝酸根などがあ
るが、極板を充放電する化成処理］二程によって、極板
中に残存する硝酸根などを除去することができ、自己放
電特性には影響しないほど硝酸根のレベルは低下してい
ると考えられる。Impurities include hydroxide particles, residual nitrate radicals, etc., but the chemical conversion treatment of charging and discharging the electrode plate can remove the nitrate radicals remaining in the electrode plate, improving self-discharge characteristics. It is thought that the level of nitrate radicals is so low that it has no effect.
したがって、自己放電特性を決めるのは、他の要因もあ
るが水酸化ニッケルと活物質との反応性が主たる要因で
はないかと考えられる。その作用については明確ではな
いが、本発明のように化成を行った後、極板を高温のア
ルカリ水）８液に浸漬することによって、水酸化ニッケ
ルと活物質が相互作用して活物質の表面積が小さくなり
、その結果、水酸化ニッケルと活物質との反応性が抑え
られ、自己放電が抑制されると考えられる。Therefore, although there are other factors, it is thought that the reactivity between nickel hydroxide and the active material is the main factor that determines the self-discharge characteristics. Although its effect is not clear, by immersing the electrode plate in high-temperature alkaline water after chemical conversion as in the present invention, the nickel hydroxide and the active material interact and the active material becomes It is thought that the surface area becomes smaller, and as a result, the reactivity between nickel hydroxide and the active material is suppressed, and self-discharge is suppressed.
尚、水酸化ニッケルの添加は放電性能を向上させるため
のものであり、活物質自身の反応性が低下するほどには
表面積が小さくなっていないと考えられる。Note that the addition of nickel hydroxide is for the purpose of improving discharge performance, and it is considered that the surface area is not so small that the reactivity of the active material itself is reduced.
（へ〕 実施例
多孔度８４％のニンケル焼結基板を、硝酸カドミウム水
溶液に浸漬し、乾燥、アルカリ処理を行い、前記焼結基
板中に活物質としての水酸化カドミウムを充填して、カ
ドミウム負極板を作製した。(F) Example A Ninkel sintered substrate with a porosity of 84% is immersed in a cadmium nitrate aqueous solution, dried, and treated with alkali.The sintered substrate is filled with cadmium hydroxide as an active material to form a cadmium negative electrode. A board was made.
このカドミウム負極板への水酸化ニッケルの添加は、前
記硝酸カドミウム水溶液中に硝酸ニッケルを添加し、そ
の添加量を規制することにより行った。Nickel hydroxide was added to the cadmium negative electrode plate by adding nickel nitrate to the cadmium nitrate aqueous solution and regulating the amount added.
また、予備実験の結果により、前記カドミウム負極板の
活物質中のＮｉとＣｄの重量比Ｎｉ／Ｃｄ Ｘ １００
が３付近で、水酸化カドミウムの利用率が最も高い値を
示したので、上記の値が３のカドミウム負極板を作製し
た。In addition, according to the results of preliminary experiments, the weight ratio of Ni to Cd in the active material of the cadmium negative electrode plate is Ni/Cd
Since the utilization rate of cadmium hydroxide showed the highest value when the value was around 3, a cadmium negative electrode plate with the above value of 3 was produced.
このカドミウム負極板を、常温の水酸化カリウム（２５
％）水溶液中で、０．２Ｃ（Ｖ、 Ｓ、公称容ｉｋ）の
電流で２００％充電し、常温の水酸化カリウム（２５％
）水溶液中で、０．２０の電流で放電することによって
化成を行った後、前記水酸化カリウム（２５％）水溶液
と同一濃度の水酸化カリウム（２５％）水溶液を８０℃
に設定し、前記負極板を１６時間浸漬した後、水洗、乾
燥を行い、本発明負極板ａを作製した。This cadmium negative electrode plate was heated to room temperature with potassium hydroxide (25
%) in an aqueous solution with a current of 0.2 C (V, S, nominal capacity ik), and charged to 200% with a current of 0.2 C (V, S, nominal capacity i.
) In an aqueous solution, after performing chemical formation by discharging at a current of 0.20, a potassium hydroxide (25%) aqueous solution having the same concentration as the above potassium hydroxide (25%) aqueous solution was heated at 80°C.
The negative electrode plate was immersed for 16 hours, washed with water, and dried to produce a negative electrode plate a of the present invention.
比較として、本発明負極板ａと同一条件で化成を行った
後、直ちに水洗、乾燥を行い、比較負極板すを作製した
。As a comparison, a comparative negative electrode plate was prepared by performing chemical conversion under the same conditions as the negative electrode plate a of the present invention, and then immediately washing with water and drying.
また、前記硝酸カドミウム水溶液中に硝酸ニッケルを添
加せず、その他は、比較負極板すと同一条件で、比較負
極板Ｃを作製した。Further, a comparative negative electrode plate C was produced under the same conditions as the comparative negative electrode plate except that nickel nitrate was not added to the cadmium nitrate aqueous solution.
上記３種類の負極板と焼結式正極板及びセパレータとを
それぞれ組み合わせて、公称容量１．２ＡＨの本発明電
池Ａ及び比較電池Ｂ、Ｃを作！！！Ｌな。Invention battery A and comparison batteries B and C with a nominal capacity of 1.2AH were made by combining the above three types of negative electrode plates, sintered positive electrode plates, and separators, respectively! ! ! L.
第１表に上記電池のハイレート放電のサイクル特性及び
自己放電特性の結果を示す。Table 1 shows the results of the high-rate discharge cycle characteristics and self-discharge characteristics of the above battery.
ここで、サイクル特性における電池容量は、０゜１、
Ｃ（１２０ｍ Ａ ）の電流で１６時間充電し、８Ｃ（
９，６Ａ ）の電流で放電し、電池電圧が１．ＯＶに達
するまでの放電時間で示した。自己放電特性における保
存前の電池容量は、０． ＩＣ（１２０ｍ Ａ’）の電
流で１６時間充電し、ＩＣ（１，２Ａ ）の電流で放電
し、電池電圧が１．Ｏｖに達するまでの放電時間で示し
た。保存後の電池容量は、保存前の電池容量測定後再び
、（Ｉ。Here, the battery capacity in cycle characteristics is 0°1,
Charged for 16 hours with a current of 8C (120mA),
Discharged with a current of 9.6 A), and the battery voltage reached 1.6 A. It is expressed as the discharge time until reaching OV. The battery capacity before storage in terms of self-discharge characteristics is 0. Charged with an IC (120mA') current for 16 hours, discharged with an IC (1.2A) current, and the battery voltage reached 1. It is expressed as the discharge time until reaching Ov. The battery capacity after storage is determined by measuring the battery capacity before storage (I).
ＩＣ（１２０ｍ Ａ ）の電流で１６時間充電し、４５
℃の恒温槽中に％ケガ間放置した後、ＩＣ（１，２Ａ
”）の電流で放ｔｂ、電池電圧が１．ＯＶに達するまて
゛の放電時間で示した。Charged with IC (120 mA) current for 16 hours, 45
After leaving the IC (1,2A
The battery voltage was discharged at a current of 1.0V, and the discharge time was indicated as 1.OV.
第 １ 表
第１表より、水酸化ニッケルを添加した負極板を備えた
本発明電池Ａ及び比較電池Ｂは比較電池Ｃに比べて、８
Ｃという高率放電によるサイクル特性が向上しているこ
とがわかる。また、比較電池Ｂは自己放電特性が大きく
低下しているのに対して、本発明電池Ａは自己放電特性
が比較電池Ｃ並みに向上しており、サイクル特性及び自
己放電特性の何れの特性も良好であることが２つかる。Table 1 From Table 1, it can be seen that the battery A of the present invention and the comparative battery B equipped with the negative electrode plate to which nickel hydroxide were added had a lower battery charge of 8.
It can be seen that the cycle characteristics due to high rate discharge C are improved. In addition, while Comparative Battery B has significantly deteriorated self-discharge characteristics, Inventive Battery A has self-discharge characteristics improved to the same level as Comparative Battery C, and both cycle characteristics and self-discharge characteristics are improved. There are two things that are good.
（ト）発明の効果
本発明の製造方法によれば、カドミウム酸化物を主活物
質とする負極板に、水酸化工／ケルを添加し、化成工程
終了後、前記負極板を高温のアルカリ水溶液中に放置す
ることによって、アルカリ蓄電池の高率放電時のサイク
ル特性を向上できると共に、自己放電を抑制できるもの
であり、その工業的価値は極めて大である。(G) Effects of the Invention According to the manufacturing method of the present invention, hydroxide/kel is added to a negative electrode plate containing cadmium oxide as the main active material, and after the completion of the chemical conversion process, the negative electrode plate is dissolved in a high-temperature alkaline aqueous solution. By leaving it in the battery, the cycle characteristics of the alkaline storage battery during high rate discharge can be improved and self-discharge can be suppressed, and its industrial value is extremely large.
Claims (1)
ルを添加した負極板に、化成を行った後、前記負極板を
高温のアルカリ水溶液中に放置し、その後、水洗、乾燥
することを特徴とするカドミウム負極板の製造方法。(1) A negative electrode plate containing cadmium oxide as the main active material and nickel hydroxide added thereto is chemically formed, and then the negative electrode plate is left in a high-temperature alkaline aqueous solution, and then washed with water and dried. A method for manufacturing a cadmium negative electrode plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2319979A JP2975673B2 (en) | 1990-11-21 | 1990-11-21 | Method for producing cadmium negative electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2319979A JP2975673B2 (en) | 1990-11-21 | 1990-11-21 | Method for producing cadmium negative electrode plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04188562A true JPH04188562A (en) | 1992-07-07 |
| JP2975673B2 JP2975673B2 (en) | 1999-11-10 |
Family
ID=18116390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2319979A Expired - Fee Related JP2975673B2 (en) | 1990-11-21 | 1990-11-21 | Method for producing cadmium negative electrode plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2975673B2 (en) |
-
1990
- 1990-11-21 JP JP2319979A patent/JP2975673B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2975673B2 (en) | 1999-11-10 |
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