JPH0366780B2 - - Google Patents
Info
- Publication number
- JPH0366780B2 JPH0366780B2 JP57166863A JP16686382A JPH0366780B2 JP H0366780 B2 JPH0366780 B2 JP H0366780B2 JP 57166863 A JP57166863 A JP 57166863A JP 16686382 A JP16686382 A JP 16686382A JP H0366780 B2 JPH0366780 B2 JP H0366780B2
- Authority
- JP
- Japan
- Prior art keywords
- sintering
- nickel
- paste
- microballoons
- present
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005187 foaming Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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)
- Powder Metallurgy (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はアルカリ蓄電池、特に焼結式ニツケル
−カドミウム電池の焼結基板の改良に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to improvements in sintered substrates for alkaline storage batteries, particularly sintered nickel-cadmium batteries.
従来の技術
従来、焼結基板の気孔率を高める方法として、
炭酸ニツケル、炭酸マグネシウム、炭酸リチウム
等の炭酸塩を混合し、焼結温度付近でCO2ガスの
発生を利用し発泡させる無機化合物発泡法あるい
は有機発泡剤を利用した有機発泡剤法等を使用し
ていた。Conventional technology Conventionally, as a method of increasing the porosity of a sintered substrate,
An inorganic compound foaming method in which carbonates such as nickel carbonate, magnesium carbonate, and lithium carbonate are mixed and foamed using the generation of CO 2 gas near the sintering temperature, or an organic foaming agent method in which an organic foaming agent is used is used. was.
発明が解決しようとする課題
無機化合物を用いる方法は、ニツケル塩以外は
いずれも焼結後残渣が残り、基板強度を低下さ
せ、又は基板抵抗を増加させる。又ニツケル塩も
還元時に著しい凝集力が働く等の為にあまり高多
孔度を得ることができない等の欠点があつた。Problems to be Solved by the Invention All methods using inorganic compounds, other than nickel salt, leave residues after sintering, reducing substrate strength or increasing substrate resistance. Nickel salts also have drawbacks such as the inability to obtain very high porosity due to significant cohesive force acting during reduction.
有機発泡剤を使用した場合、使用される発泡剤
は粉末、又はフレーク状であるが、粒子径が不均
一であり、また均一な分散も困難である為に該多
孔体は均一性が劣り、均一な多孔質を製造する方
法としては不適当であつた。 When an organic blowing agent is used, the blowing agent used is in the form of powder or flakes, but the particle size is uneven and uniform dispersion is difficult, so the porous body has poor uniformity. This method was inappropriate as a method for producing uniform porous material.
今迄の有機発泡剤は、その発泡原理に於て発泡
剤自体が分解し、その時生成するガスにより膨張
作用を有するものであるために、粒子径の不均一
さはそのまま発泡能力に比例し、例え均一な粒径
をもつ粒子ができたとしてもその形状が全く不規
則であるために発泡剤の質量は不均一であるとい
う欠点を有する。 Conventional organic foaming agents have a foaming principle in which the foaming agent itself decomposes and the gas generated at that time has an expanding effect, so the non-uniformity of the particle size is directly proportional to the foaming ability. Even if particles with a uniform particle size are formed, their shape is completely irregular, resulting in a disadvantage that the mass of the blowing agent is non-uniform.
従つてニツケル−カドミウム電池用焼結基板と
しては使用に耐えるものではなかつた。 Therefore, it was not suitable for use as a sintered substrate for nickel-cadmium batteries.
本発明は、上記従来の問題点を除去した、多孔
度が大で、強度の優れた、均一の孔径を有するア
ルカリ蓄電池用焼結基板を提供することを目的と
する。 An object of the present invention is to provide a sintered substrate for an alkaline storage battery that eliminates the above-mentioned conventional problems and has large porosity, excellent strength, and uniform pore diameter.
課題を解決するための手段
本発明は上記目的を達成するべく、
焼結用ニツケル粉末と発泡性有機高分子マイク
ロバルーンと有機質バインダー及び芯金を準備
し、
焼結用ニツケル粉末と発泡性有機高分子マイク
ロバルーンを混合する工程、
次に有機質バインダーを溶解した水溶液をニツ
ケル粉末とマイクロバルーン混合物に加えて混練
しペースト状物とする工程、
次にペースト状物を芯金に塗着する工程、
次に塗着ペーストを乾燥し、加熱発泡させる工
程、
次にバインダー及びマイクロバルーンを揮発さ
せながら焼結する工程、
を有することを特徴とするアルカリ蓄電池用基板
である。Means for Solving the Problems In order to achieve the above object, the present invention prepares nickel powder for sintering, a foamable organic polymer microballoon, an organic binder, and a core bar, and prepares a nickel powder for sintering, a foamable organic polymer A process of mixing molecular microballoons, Next a process of adding an aqueous solution containing an organic binder to the nickel powder and microballoon mixture and kneading it into a paste, Next a process of applying the paste to the metal core, Next This is a substrate for an alkaline storage battery characterized by comprising the steps of: drying the coating paste, heating and foaming it, and then sintering the binder and microballoons while volatilizing them.
作 用
発泡性マイクロバルーンは他のマイクロバルー
ンでもよく見られる如く、非常に均一でしかも真
球に近い形状であり、その粒度分布もコントロー
ルできる状態である。Function The expandable microballoon, as is often seen with other microballoons, is extremely uniform and has a shape close to a perfect sphere, and its particle size distribution can also be controlled.
発泡原理から見ても中空球内部に封入された液
体又は気体により膨張し、その膨張は中空球を延
伸させ球の直径を拡大することにより発泡剤の如
き役割を果す。 From the perspective of the foaming principle, the hollow sphere expands due to the liquid or gas sealed inside it, and the expansion stretches the hollow sphere and enlarges its diameter, thereby acting as a foaming agent.
実施例
以下、本発明の詳細について一実施例により説
明する。Example Hereinafter, the details of the present invention will be explained with reference to an example.
カーボニルニツケル粉90重量部とメチルメタア
クリレート系樹脂で皮膜を形成した発泡性マイク
ロバルーン10重量部を混合する。カルボキシメチ
ルセルロースを水に溶解した３％水溶液をニツケ
ル粉とマイクロバルーン混合物に加えて混練しペ
ースト状物とする。 90 parts by weight of carbonyl nickel powder and 10 parts by weight of expandable microballoons coated with methyl methacrylate resin are mixed. A 3% aqueous solution of carboxymethylcellulose dissolved in water is added to the nickel powder and microballoon mixture and kneaded to form a paste.
このペースト状物を支持芯金となる穿孔ニツケ
ルメツキ鋼板に塗着し所定の厚さとする。その
後、150℃で乾燥し、発泡させる。 This paste-like material is applied to a perforated nickel-plated steel plate that will serve as a supporting core to a predetermined thickness. It is then dried at 150°C and foamed.
還元雰囲気中で1000〜1100℃にて約10分間焼結
する。この焼結中にカルボキシメチルセルロー
ス、メチルメタアクリレート系樹脂のマイクロバ
ルーンは揮発する。これによつて0.65mmの厚さ焼
結基板を得た。このようにしてできたニツケル焼
結基板は多孔度92.6％で平均孔径が約50μであつ
た。発泡性有機高分子マイクロバルーンの添加
量、発泡温度を変えることにより95〜97％の多孔
度を有する焼結基板を得ることも可能である。 Sinter at 1000-1100°C for about 10 minutes in a reducing atmosphere. During this sintering, the carboxymethyl cellulose and methyl methacrylate resin microballoons evaporate. As a result, a sintered substrate with a thickness of 0.65 mm was obtained. The nickel sintered substrate thus produced had a porosity of 92.6% and an average pore diameter of about 50μ. It is also possible to obtain a sintered substrate having a porosity of 95 to 97% by changing the amount of the expandable organic polymer microballoons added and the foaming temperature.
尚、第４図に工程のフロー図を示した。 Incidentally, FIG. 4 shows a flow diagram of the process.
本発明により得られた多孔度92.6％の焼結基板
を用いて、水酸化ニツケル活物質を充填した。充
填は、硝酸ニツケル溶液を真空含浸しアルカリ溶
液中で中和して水酸化ニツケルとする。この含浸
回数と充填量の関係を第２図に示した。 A sintered substrate with a porosity of 92.6% obtained according to the present invention was used to fill a nickel hydroxide active material. For filling, nickel nitrate solution is vacuum impregnated and neutralized in an alkaline solution to form nickel hydroxide. The relationship between the number of impregnations and the amount of filling is shown in FIG.
発泡性マイクロバルーンを混合しない現行の焼
結基板Ｂと本発明の焼結基板Ａとを同一の６回含
浸操作により充填される活物質量を比較すると、
充填量は本発明によるものが、25％増加し、現行
の焼結基板では400ｍAh／c.c.の極板となる。これ
に対して、本発明の焼結基板では500ｍAh／c.c.の
極板となる。 Comparing the amount of active material filled by the same 6-time impregnation operation between the current sintered substrate B that does not mix foaming microballoons and the sintered substrate A of the present invention,
The filling amount according to the present invention is increased by 25%, and the current sintered substrate has a charge of 400 mAh/cc. On the other hand, the sintered substrate of the present invention has an electrode plate of 500 mAh/cc.
第１図に本発明に用いた発泡性マイクロバルー
ンの加熱温度と膨張倍率の一例（加熱時間１分）
を示した。発泡性マイクロバルーンは、膨張倍率
が極めて高く必要な粒子径を任意に選択できる。 Figure 1 shows an example of the heating temperature and expansion ratio of the foamable microballoon used in the present invention (heating time: 1 minute)
showed that. The expandable microballoon has an extremely high expansion ratio, and the required particle size can be arbitrarily selected.
樹脂球、粒子に比較し、その添加量はマイクロ
バルーンの中空度が97〜99％程度にも達し得るこ
とにより、その使用量を1/100〜3/100程度に減少
できる。現在使用されているカルボキシメチルセ
ルロース以下の使用量でよく、残在カーボンある
いは分解ガスの影響が殆んどない。 Compared to resin spheres and particles, the amount added can be reduced to about 1/100 to 3/100 because the hollowness of microballoons can reach about 97 to 99%. The amount used is less than the amount of carboxymethyl cellulose currently used, and there is almost no influence from residual carbon or cracked gas.
第３図に本発明によるニツケル正極板と現行の
ニツケル正極板の放電特性を示した。本発明によ
る正極板は、放電々圧特性が優れている。 FIG. 3 shows the discharge characteristics of the nickel positive electrode plate according to the present invention and the current nickel positive electrode plate. The positive electrode plate according to the present invention has excellent discharge voltage characteristics.
この事より焼結基板は、充分に使用に耐える強
度を有することが確認された。又、発泡性マイク
ロバルーンはフエノールマイクロバルーン等のよ
うに膨張性のないマイクロバルーンよりもはるか
に少量の使用で所定の多孔度が得られる。しか
も、焼結時には発泡により骨格構造が決定された
粒子を焼結することになり、多孔度の減少が少な
くしかも、強度の大なる焼結基板となる。 This confirmed that the sintered substrate had sufficient strength to withstand use. Furthermore, a predetermined porosity can be obtained by using a much smaller amount of expandable microballoons than non-expandable microballoons such as phenol microballoons. Furthermore, during sintering, particles whose skeleton structure has been determined by foaming are sintered, resulting in a sintered substrate with less reduction in porosity and greater strength.
発明の効果
上述した如く、本発明は多孔度が大で、強度の
優れた、均一の孔径を有するアルカリ蓄電池用焼
結基板を提供することが出来るので、その工業的
価値は極めて大である。Effects of the Invention As described above, the present invention can provide a sintered substrate for alkaline storage batteries having high porosity, excellent strength, and uniform pore diameter, and therefore has extremely great industrial value.
第１図は本発明の実施例に用いた発泡性マイク
ロバルーンの加熱温度と膨張倍率の一例、第２図
は本発明によるニツケル基板への含浸回数とニツ
ケル正極容量との関係曲線図、第３図は本発明に
よるニツケル正極板Ａ及び従来品正極板Ｂの1/5
Ｃ放電時の特性曲線である。第４図は工程のフロ
ー図を示した図である。
Ａ……本発明品、Ｂ……従来品。
FIG. 1 is an example of the heating temperature and expansion ratio of the foamable microballoon used in the example of the present invention, FIG. 2 is a relationship curve between the number of times of impregnation of a nickel substrate and the capacity of the nickel positive electrode according to the present invention, and FIG. The figure shows 1/5 of the nickel positive electrode plate A according to the present invention and the conventional positive electrode plate B.
This is a characteristic curve during C discharge. FIG. 4 is a diagram showing a flow diagram of the process. A...Product of the present invention, B...Conventional product.
Claims (1)
クロバルーンと有機質バインダー及び芯金を準備
し、 焼結用ニツケル粉末と発泡性有機高分子マイク
ロバルーンを混合する工程、 次に有機質バインダーを融解した水溶液をニツ
ケル粉末とマイクロバルーン混合物に加えて混練
しペースト状物とする工程、 次にペースト状物を芯金に塗着する工程、 次に塗着ペーストを乾燥し、加熱発泡させる工
程、 次にバインダー及びマイクロバルーンを揮発さ
せながら還元雰囲気中で焼結する工程、 を有することを特徴とするアルカリ蓄電池用基板
の製造法。[Claims] 1. A step of preparing nickel powder for sintering, a foamable organic polymer microballoon, an organic binder, and a core metal, and mixing the nickel powder for sintering and a foamable organic polymer microballoon, and then A process in which an aqueous solution containing a melted organic binder is added to the nickel powder and microballoon mixture and kneaded to form a paste, then a process in which the paste is applied to the metal core, and then the applied paste is dried and foamed by heating. A method for producing a substrate for an alkaline storage battery, comprising: a step of sintering in a reducing atmosphere while volatilizing the binder and microballoons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57166863A JPS5956361A (en) | 1982-09-25 | 1982-09-25 | Manufacture of substrate for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57166863A JPS5956361A (en) | 1982-09-25 | 1982-09-25 | Manufacture of substrate for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5956361A JPS5956361A (en) | 1984-03-31 |
| JPH0366780B2 true JPH0366780B2 (en) | 1991-10-18 |
Family
ID=15839033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57166863A Granted JPS5956361A (en) | 1982-09-25 | 1982-09-25 | Manufacture of substrate for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5956361A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60205967A (en) * | 1984-03-29 | 1985-10-17 | Shin Kobe Electric Mach Co Ltd | Manufacture of porous sintered substrate for sealed alkaline battery |
| JPH08291304A (en) * | 1995-02-23 | 1996-11-05 | Mitsubishi Materials Corp | Porous metal plate with large specific surface area |
| JPH09143511A (en) * | 1995-11-29 | 1997-06-03 | Mitsubishi Materials Corp | Porous metallic body having large specific surface area |
| JPH08333605A (en) * | 1995-04-03 | 1996-12-17 | Mitsubishi Materials Corp | Porous metallic plate having large specific surface area |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5132293A (en) * | 1974-09-13 | 1976-03-18 | Seikosha Kk | HYOJISOCHI |
| JPS538895A (en) * | 1976-07-13 | 1978-01-26 | Toyoda Mach Works Ltd | Grinding process |
-
1982
- 1982-09-25 JP JP57166863A patent/JPS5956361A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5132293A (en) * | 1974-09-13 | 1976-03-18 | Seikosha Kk | HYOJISOCHI |
| JPS538895A (en) * | 1976-07-13 | 1978-01-26 | Toyoda Mach Works Ltd | Grinding process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5956361A (en) | 1984-03-31 |
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