JP3092815B2 - Substrate for sintered substrate of sintered electrode, method for producing the same, and sintered substrate using the substrate - Google Patents
Substrate for sintered substrate of sintered electrode, method for producing the same, and sintered substrate using the substrateInfo
- Publication number
- JP3092815B2 JP3092815B2 JP03029646A JP2964691A JP3092815B2 JP 3092815 B2 JP3092815 B2 JP 3092815B2 JP 03029646 A JP03029646 A JP 03029646A JP 2964691 A JP2964691 A JP 2964691A JP 3092815 B2 JP3092815 B2 JP 3092815B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- sintered
- plating
- sintered body
- 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
- Electroplating Methods And Accessories (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Powder Metallurgy (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、アルカリ電池などの電
極として用いられる焼結式電極の焼結基体用の基板、そ
の製造方法および上記基板を用いた焼結基体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate for a sintered substrate of a sintered electrode used as an electrode of an alkaline battery or the like, a method for producing the substrate, and a sintered substrate using the substrate.
【０００２】[0002]
【従来の技術】従来、アルカリ電池などの電極として用
いられる焼結式電極の焼結基体用の基板としては、鉄製
で表面にニッケルメッキを施したパンチングメタルが多
用されていた（例えば、「Ａｌｋａｌｉｎｅ Ｓｔｏｒ
ａｇｅ Ｂａｔｔｅｒｉｓ」（１９６９、Ｔｈｅ Ｅｌ
ｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ Ｉｎ
ｃ，Ｓａｌｋｉｎｄ著、ｐ１６６）。2. Description of the Related Art Conventionally, as a substrate for a sintered substrate of a sintered electrode used as an electrode of an alkaline battery or the like, a punching metal made of iron and nickel-plated on its surface has been frequently used (for example, Alkaline). Stor
age Batteris "(1969, The El
electrochemical Society In
c, by Salkind, p166).
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記基板は、
焼結基体の作製にあたって、その表面にニッケル粉末を
主成分とするスラリーを塗布したときにスラリーの付着
性が悪く、また、得られた焼結基体の基板と焼結体部分
との接着強度が小さいという問題があった。本発明は、
上記問題点を解決し、ニッケル粉末を主成分とするスラ
リーの付着性が良好で、かつ、基板と焼結体部分との接
着強度が大きい焼結基体が得られる基板を提供すること
を目的とする。However, the above substrate is
In producing a sintered substrate, when a slurry containing nickel powder as a main component is applied to the surface of the substrate, the adhesiveness of the slurry is poor, and the bonding strength between the substrate and the sintered body of the obtained sintered substrate is low. There was a problem of being small. The present invention
It is an object of the present invention to provide a substrate that solves the above problems and has a good adhesion of a slurry containing nickel powder as a main component, and a sintered substrate having a large adhesive strength between the substrate and a sintered body portion. I do.
【０００４】[0004]
【課題を解決するための手段】本発明は、パンチングメ
タルなどの多孔性金属板の表面にメッキを施した後、加
熱して酸化することにより、表面を凹凸化させて、表面
の粗度を中心線平均あらさ（Ｒａ）で０．８〜３．０μ
ｍにすることによって、ニッケル粉末を主成分とするス
ラリーの付着性を良好にし、かつ、その上に焼結体を形
成したときに、焼結体部分との接着強度が大きい基板が
得られるようにして、上記目的を達成したものである。According to the present invention, a surface of a porous metal plate such as a punching metal is plated and then heated and oxidized to make the surface uneven, thereby reducing the surface roughness. 0.8-3.0 μm in center line average roughness (Ra)
By setting m , the adhesiveness of the slurry containing nickel powder as a main component is improved, and when a sintered body is formed thereon, a substrate having a large adhesive strength with the sintered body portion can be obtained. Thus, the above object has been achieved.
【０００５】すなわち、多孔性金属板の表面にメッキを
施し、それを加熱して酸化すると、平坦であった面が凹
凸化する。これを表面の粗度で表すと、上記メッキ−加
熱処理前に表面の粗度が中心線平均あらさ（Ｒａ）で
０．１〜０．５μｍ程度であったものが、処理後には中
心線平均あらさ（Ｒａ）で０．８〜３．０μｍ程度に粗
面化する。これは、加熱して酸化することにより密度が
変化し、それに伴って表面の形状が変化するからである
と考えられる。[0005] That is, when the surface of a porous metal plate is plated and heated to be oxidized, the flat surface becomes uneven. When this is expressed in terms of surface roughness, the surface roughness before the plating-heating treatment was about 0.1 to 0.5 μm in center line average roughness (Ra), but after the treatment, the center line was rough. The surface is roughened to an average roughness (Ra) of about 0.8 to 3.0 μm . This is considered to be because the density changes by heating and oxidizing, and the surface shape changes accordingly.
【０００６】上記の中心線平均あらさ（Ｒａ）は、ＪＩ
Ｓ Ｂ ０６０１に規定されるもので、本発明ではその
測定をカットオフ値０．８mmで測定している。The center line average roughness (Ra) is determined by JI
It is specified in SB0601, and in the present invention, the measurement is performed at a cutoff value of 0.8 mm.
【０００７】多孔性金属板としては、例えば、パンチン
グメタル、エキスパンドメタル、金網などが用いられ
る。そして、この多孔性金属板の材質は、特に限定され
るものではなく、各種のものを使用できるが、通常は価
格、強度面などから鉄製のものが用いられる。As the porous metal plate, for example, a punching metal, an expanded metal, a wire mesh, or the like is used. The material of the porous metal plate is not particularly limited, and various materials can be used. Usually, iron is used from the viewpoint of cost and strength.
【０００８】上記多孔性金属板の表面に施すメッキは、
電解メッキ、無電解メッキのいずれでもよく、材質的に
も、各種のものを採用し得るが、例えば、ニッケルメッ
キ、ニッケル−コバルト合金メッキ、ニッケル−クロム
合金メッキ、ニッケル−スズ合金メッキなどのニッケル
合金メッキ、銅メッキ、黄銅メッキなどの銅合金メッ
キ、上記メッキを含む多層メッキなどが好ましい。これ
らは、加熱により酸化されて凹凸化しやすいという特性
がある。The plating applied to the surface of the porous metal plate is as follows:
Either electrolytic plating or electroless plating may be used, and various materials may be used. For example, nickel plating, nickel-cobalt alloy plating, nickel-chromium alloy plating, nickel-tin alloy plating, etc. Preferred are alloy plating, copper plating, copper alloy plating such as brass plating, and multilayer plating including the above plating. These have a characteristic that they are easily oxidized by heating and become uneven.
【０００９】メッキの厚みは、１〜１０μｍ程度でよ
く、通常は１〜５μｍ程度で充分である。メッキに使用
するメッキ浴としては、電解メッキの場合、ワット浴、
スルファミン酸浴、全塩化物浴、酢酸ニッケルメッキ浴
などがあり、無電解メッキの場合、酸性浴、アルカリ性
浴などがある。The thickness of the plating may be about 1 to 10 μm, and usually about 1 to 5 μm is sufficient. As the plating bath used for plating, in the case of electrolytic plating, a watt bath,
There are a sulfamic acid bath, a total chloride bath, a nickel acetate plating bath and the like, and in the case of electroless plating, there are an acidic bath and an alkaline bath.
【００１０】メッキ後は、洗浄、乾燥し、加熱して酸化
する。この酸化により、密度が変化し、表面が凹凸化す
る。上記酸化のための加熱は、８００〜１０００℃で行
うのが適切であり、特に８５０〜９００℃で行うのが好
ましい。８００℃より低温では表面が凹凸化しにくく、
また、１０００℃より高温になると電気炉などの加熱装
置の損傷が早くなる。加熱時間は３〜２０分が適切であ
り、特に５〜１５分が好ましい。After plating, it is washed, dried, heated and oxidized. Due to this oxidation, the density changes and the surface becomes uneven. The heating for the oxidation is suitably performed at 800 to 1000 ° C, particularly preferably at 850 to 900 ° C. If the temperature is lower than 800 ° C., the surface is hardly uneven,
If the temperature is higher than 1000 ° C., damage to a heating device such as an electric furnace is accelerated. The heating time is suitably from 3 to 20 minutes, particularly preferably from 5 to 15 minutes.
【００１１】そして、上記処理による凹凸化によって、
基板へのニッケル粉末を主成分とするスラリーの付着性
が良好になり、かつ、焼結させるポイントが増加して、
その上に焼結体を形成して焼結基板を作製したときに基
板と焼結体部分との接着強度が向上する。[0011] Then, by making the surface uneven by the above processing,
The adhesion of the slurry containing nickel powder as a main component to the substrate is improved, and the sintering point increases,
When a sintered body is formed thereon to produce a sintered substrate, the adhesive strength between the substrate and the sintered body part is improved.
【００１２】[0012]
【実施例】つぎに、実施例を挙げて本発明をより具体的
に説明する。 実施例１ 厚さ７０μｍ、開孔率３５面積％のパンチングメタルを
脱脂、洗浄した後、ニッケルの無電解メッキ液「Ｂｌｕ
ｅ Ｓｕｍｅｒ」（日本カニゼン社製）に浸漬し、９０
℃で５分間無電解メッキを行った。その後、洗浄、乾燥
を行い、空気中８５０℃で１０分間加熱して酸化した。
加熱前のメッキの厚みは平均値で３μｍであった。上記
処理後のパンチングメタルの表面の粗度を触針式表面あ
らさ測定機で測定したところ、中心線平均あらさ（Ｒ
ａ）で１．８μｍであった。なお、上記メッキ−加熱処
理前のパンチングメタルの表面の粗度は中心線平均あら
さ（Ｒａ）で０．４μｍであった。Next, the present invention will be described more specifically with reference to examples. Example 1 A punching metal having a thickness of 70 μm and a porosity of 35 area% was degreased and washed, and then a nickel electroless plating solution “Blu
e Sumer "(Nippon Kanigen Co., Ltd.)
Electroless plating was performed at 5 ° C. for 5 minutes. Thereafter, the substrate was washed and dried, and was oxidized by heating at 850 ° C. for 10 minutes in the air.
The average thickness of the plating before heating was 3 μm. The roughness of the surface of the punched metal after the above treatment was measured with a stylus-type surface roughness measuring instrument, and the center line average roughness (R
It was 1.8 μm in a). The surface roughness of the punched metal before the plating-heating treatment was 0.4 μm in center line average roughness (Ra).
【００１３】つぎに、上記処理後のパンチングメタルを
基板として用い、該基板上に、カルボニルニッケル粉末
（Ｉｎｃｏ社製ｔｙｐｅ２５５）とメチルセルロースを
主成分とするゲルとを重量比で２：３になるように混合
することによって得られたスラリーを塗布し、乾燥した
後、還元雰囲気中８５０℃で１０分間焼結して、焼結体
部分の空孔率が８４体積％の焼結基体を得た。Next, the punched metal after the above treatment is used as a substrate, and carbonyl nickel powder (type 255 manufactured by Inco) and a gel containing methylcellulose as a main component are formed on the substrate in a weight ratio of 2: 3. The obtained slurry was applied, dried, and then sintered in a reducing atmosphere at 850 ° C. for 10 minutes to obtain a sintered substrate having a sintered body portion having a porosity of 84% by volume.
【００１４】実施例２ 実施例１と同様のパンチングメタルの表面に下記組成の
メッキ浴を用い、下記の条件下で電解メッキを行った。組成 硫酸ニッケル ２４０ｇ／リットル 塩化ニッケル ４５ｇ／リットル ホウ酸 ３０ｇ／リットル条件 ｐＨ 4.0 温度 ４０℃ 電流密度 ４Ａ／ｄｍ2 時間 ２分Example 2 Electroplating was performed on the surface of a punching metal similar to that in Example 1 by using a plating bath having the following composition under the following conditions. Composition Nickel sulfate 240 g / l Nickel chloride 45 g / l Boric acid 30 g / l Condition pH 4.0 Temperature 40 ° C Current density 4 A / dm 2 hours 2 minutes
【００１５】上記電解メッキ後、実施例１と同様に洗
浄、乾燥を行い、空気中８５０℃で１０分間加熱して酸
化した。加熱前のメッキの厚みは平均値で３μｍであっ
た。上記処理後のパンチングメタルの表面の粗度を触針
式表面あらさ測定機で測定したところ、中心線平均あら
さ（Ｒａ）で１．４μｍであった。After the above-mentioned electrolytic plating, washing and drying were carried out in the same manner as in Example 1, and oxidized by heating at 850 ° C. for 10 minutes in the air. The average thickness of the plating before heating was 3 μm. The roughness of the surface of the punched metal after the above treatment was measured by a stylus type surface roughness measuring instrument, and was found to be 1.4 μm in center line average roughness (Ra).
【００１６】つぎに、上記処理後のパンチングメタルを
基板として用い、該基板上に実施例１と同様のスラリー
を塗布し、以後、実施例１と同様にして、焼結体部分の
空孔率が８４体積％の焼結基体を得た。Next, using the punched metal after the above treatment as a substrate, the same slurry as in Example 1 was applied to the substrate, and thereafter, the porosity of the sintered body portion was determined in the same manner as in Example 1. Was 84% by volume.
【００１７】実施例３ 実施例１と同様のパンチングメタルの表面に下記組成の
ニッケル−コバルト合金メッキ浴を用い、下記の条件下
で電解メッキを行った。組成 硫酸ニッケル ２４０ｇ／リットル 塩化ニッケル ４５ｇ／リットル ホウ酸 ３０ｇ／リットル ギ酸 ３０ｃｃ／リットル 硫酸コバルト １５ｇ／リットル ホルムアルデヒド 2.5ｇ／リットル条件 ｐＨ 4.0 温度 ６０℃ 電流密度 ５Ａ／ｄｍ2 時間 ２分Example 3 The same punching metal as in Example 1 was electroplated on the surface of a punching metal using a nickel-cobalt alloy plating bath having the following composition under the following conditions. Composition Nickel sulfate 240g / L Nickel chloride 45g / L Boric acid 30g / L Formic acid 30cc / L Cobalt sulfate 15g / L Formaldehyde 2.5g / L Condition pH 4.0 Temperature 60 ° C Current density 5A / dm 2 hours 2 minutes
【００１８】上記電解メッキ後、実施例１と同様に洗
浄、乾燥を行い、空気中８５０℃で１０分間加熱して酸
化した。加熱前のメッキの厚みは平均値で３μｍであっ
た。上記処理後のパンチングメタルの表面の粗度を触針
式表面あらさ測定機で測定したところ、中心線平均あら
さ（Ｒａ）で１．６μｍであった。After the above-mentioned electrolytic plating, washing and drying were performed in the same manner as in Example 1, and oxidation was performed by heating in air at 850 ° C. for 10 minutes. The average thickness of the plating before heating was 3 μm. The roughness of the surface of the punched metal after the above treatment was measured by a stylus type surface roughness measuring instrument and found to be 1.6 μm in center line average roughness (Ra).
【００１９】つぎに、上記処理後のパンチングメタルを
基板として用い、該基板上に実施例１と同様のスラリー
を塗布し、以後、実施例１と同様にして、焼結体部分の
空孔率が８４体積％の焼結基体を得た。Next, using the punched metal after the above treatment as a substrate, the same slurry as in Example 1 was applied to the substrate, and thereafter the porosity of the sintered body portion was determined in the same manner as in Example 1. Was 84% by volume.
【００２０】比較例１ 実施例１と同様のパンチングメタルをメッキや加熱する
ことなく、そのまま基板として用い、この基板上に実施
例１と同様のスラリーを塗布し、以後、実施例１と同様
にして、焼結体部分の空孔率が８４体積％の焼結基体を
得た。なお、基板として用いたパンチングメタルの表面
粗度は、中心線平均あらさ（Ｒａ）で０．４μｍであ
る。Comparative Example 1 The same punching metal as in Example 1 was used as a substrate without plating or heating, and the same slurry as in Example 1 was applied to this substrate. Thus, a sintered substrate having a porosity of 84% by volume in the sintered body was obtained. The surface roughness of the punched metal used as the substrate was 0.4 μm in terms of center line average roughness (Ra).
【００２１】上記実施例１〜３で得た焼結基体および比
較例１で得た焼結基体の基板と焼結体部分との接着強度
を調べるため、Ｓｅｂａｓｔｉｏｎ Ｔｅｓｔｅｒ〔オ
ートグラフ Ｑｕａｄ Ｇｒｏｕｐ（Ｓｐｏｋａｎｅ．
ＷＡ）社製〕で引張強度を測定した。その結果を表１に
示す。In order to examine the adhesive strength between the substrate of the sintered substrate obtained in Examples 1 to 3 and the substrate of the sintered substrate obtained in Comparative Example 1 and the sintered body portion, a Sebastion Tester [Autograph Quad Group (Spokane.
WA), the tensile strength was measured. Table 1 shows the results.
【００２２】表１に示す引張強度は６．３５mm2 あたり
の強度であり、測定はそれぞれ５個の試料について行
い、結果を平均値で示している。また、表１に示す基板
と焼結体部分との界面における剥がれは、上記引張強度
の測定時に剥離が生じた時点での剥離面を観察し、５個
の試料の基板と焼結体部分との界面における剥がれの程
度がどの領域に属するかで示している。剥離がすべて基
板と焼結体部分との界面で生じている場合は剥がれの程
度が１００％であり、基板と焼結体部分との界面で剥離
が生じず、焼結体内部で剥離している場合は剥がれの程
度が０％である。The tensile strength shown in Table 1 is the strength per 6.35 mm 2 , and the measurement is performed for each of five samples, and the results are shown as average values. The peeling at the interface between the substrate and the sintered body portion shown in Table 1 was observed at the time when the peeling occurred at the time of measuring the tensile strength. Indicates to which region the degree of peeling at the interface belongs. When all of the peeling occurs at the interface between the substrate and the sintered body, the degree of peeling is 100%, no peeling occurs at the interface between the substrate and the sintered body, and the peeling occurs inside the sintered body. If it is, the degree of peeling is 0%.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１に示すように、実施例１〜３の基板を
用いた場合には、得られた焼結基体の基板と焼結体部分
との引張強度が大きく、また、基板と焼結体部分との界
面における剥がれが少なく、基板と焼結体部分との接着
強度が大きいことを示していた。As shown in Table 1, when the substrates of Examples 1 to 3 were used, the tensile strength between the substrate and the sintered body of the obtained sintered base was large, The peeling at the interface with the body portion was small, indicating that the adhesive strength between the substrate and the sintered body portion was large.
【００２５】[0025]
【発明の効果】以上説明したように、本発明では、多孔
性金属板の表面にメッキを施し、加熱して酸化すること
により、表面の粗度を中心線平均あらさ（Ｒａ）で０．
８〜３．０μｍに高めて、ニッケル粉末を主成分とする
スラリーの付着性が良好で、かつ、その上に焼結体を形
成したときに焼結体部分との接着強度が大きい焼結基体
用の基板を提供することができた。As described above, according to the present invention, the surface of a porous metal plate is plated, heated and oxidized, so that the surface roughness is reduced to a center line average roughness (Ra) of 0.1.
By increasing the thickness to 8 to 3.0 μm , the slurry containing nickel powder as a main component has good adhesion, and when a sintered body is formed thereon, the adhesive strength with the sintered body portion is large. A substrate for a substrate could be provided.
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Claims (4)
で０．８〜３．０μｍであることを特徴とする焼結式電
極の焼結基体用の基板。The surface roughness is determined by the center line average roughness (Ra).
A substrate for a sintered substrate of a sintered electrode, characterized by having a thickness of 0.8 to 3.0 μm .
後、加熱して酸化し、表面を凹凸化することを特徴とす
る請求項１記載の焼結式電極の焼結基体用の基板の製造
方法。2. The substrate for a sintered substrate of a sintered electrode according to claim 1, wherein the surface of the porous metal plate is plated and then heated and oxidized to make the surface uneven. Manufacturing method.
メッキ、銅メッキ、銅合金メッキまたは上記メッキを含
む多層メッキである請求項２記載の焼結式電極の焼結基
体用の基板の製造方法。3. The method according to claim 2, wherein the plating is a nickel plating, a nickel alloy plating, a copper plating, a copper alloy plating or a multilayer plating including the above plating.
てなる焼結基体。4. A sintered base obtained by forming a sintered body on the substrate according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03029646A JP3092815B2 (en) | 1991-01-29 | 1991-01-29 | Substrate for sintered substrate of sintered electrode, method for producing the same, and sintered substrate using the substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03029646A JP3092815B2 (en) | 1991-01-29 | 1991-01-29 | Substrate for sintered substrate of sintered electrode, method for producing the same, and sintered substrate using the substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH056767A JPH056767A (en) | 1993-01-14 |
| JP3092815B2 true JP3092815B2 (en) | 2000-09-25 |
Family
ID=12281868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03029646A Expired - Fee Related JP3092815B2 (en) | 1991-01-29 | 1991-01-29 | Substrate for sintered substrate of sintered electrode, method for producing the same, and sintered substrate using the substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3092815B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0738512A (en) * | 1993-07-23 | 1995-02-07 | Nec Corp | Automatic measuring instrument |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102335255B1 (en) * | 2018-06-29 | 2021-12-03 | 주식회사 엘지화학 | Preparation method for metal foam |
-
1991
- 1991-01-29 JP JP03029646A patent/JP3092815B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0738512A (en) * | 1993-07-23 | 1995-02-07 | Nec Corp | Automatic measuring instrument |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH056767A (en) | 1993-01-14 |
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