JP3296572B2 - Method for producing paste-type nickel positive electrode - Google Patents
Method for producing paste-type nickel positive electrodeInfo
- Publication number
- JP3296572B2 JP3296572B2 JP07613591A JP7613591A JP3296572B2 JP 3296572 B2 JP3296572 B2 JP 3296572B2 JP 07613591 A JP07613591 A JP 07613591A JP 7613591 A JP7613591 A JP 7613591A JP 3296572 B2 JP3296572 B2 JP 3296572B2
- Authority
- JP
- Japan
- Prior art keywords
- paste
- substrate
- filling
- positive electrode
- porous substrate
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 22
- 229910052759 nickel Inorganic materials 0.000 title description 11
- 238000004519 manufacturing process Methods 0.000 title description 8
- 239000000758 substrate Substances 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000009974 thixotropic effect Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 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)
Description
【０００１】[0001]
【産業上の利用分野】本発明はペースト式ニッケル正
極、特にペースト式ニッケル正極の活物質の充填方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paste-type nickel positive electrode, and more particularly to a method for filling a paste-type nickel positive electrode with an active material.
【０００２】[0002]
【従来の技術】従来、アルカリ蓄電池の代表例として正
極にはニッケル、負極にはカドミウムまたは水素などを
使用したニッケルカドミウム蓄電池が知られている。こ
のアルカリ蓄電池のニッケル正極には焼結式ニッケル正
極を使用することが一般的であった。2. Description of the Related Art Conventionally, as a typical example of an alkaline storage battery, a nickel cadmium storage battery using nickel as a positive electrode and cadmium or hydrogen as a negative electrode has been known. It was common to use a sintered nickel positive electrode for the nickel positive electrode of this alkaline storage battery.
【０００３】しかし、低コスト化、高容量化が要求され
るようになり、製造工程が比較的簡単で高容量化が望め
るペースト式ニッケル正極が提案され一部実用化されて
いる。このようなペースト式ニッケル正極は、３次元多
孔体構造を有する導電性基板に水酸化ニッケルを主成分
とするペーストを充填し更に乾燥，圧延を施して電極と
するものである。[0003] However, as cost reduction and higher capacity have been demanded, paste-type nickel positive electrodes that have a relatively simple manufacturing process and higher capacity have been proposed and have been partially put into practical use. Such a paste-type nickel positive electrode is obtained by filling a conductive substrate having a three-dimensional porous structure with a paste containing nickel hydroxide as a main component, followed by drying and rolling to form an electrode.
【０００４】[0004]
【発明が解決しようとする課題】ところが、実際にはペ
ースト活物質を直接３次元多孔体基板に均一に充填する
ことが困難であり、いくつかのペースト充填方法が提案
されている。例えば超音波振動によってペーストを振動
させることによって充填したり、また、ペーストを直接
基板に吹き付けたり、擦り込んだり、さらには吸引によ
り充填させる方法が提案されている。しかしながら、超
音波振動を利用したペースト充填方法は、ペーストを基
板内部に充填することは可能であるが、ペーストの粘度
が著しく低下してしまい、電極表面に塗工することが困
難である。また擦り込みよるペーストの充填方法は基板
の内部まで充分に充填するためにはかなりの加圧をかけ
る必要があり、基板表面を荒らしてしまうおそれがあ
る。さらに吸引によるペーストの充填方法は基板表面部
で目詰まりを生じてしまい基板の内部まで均一に充填す
ることが困難である。そして、万一これらの不均一な充
填状態で電極を圧延すると電極に充填状態が密な部分と
粗な部分が生じるので、電極性能に不具合を及ぼすとい
う問題点があった。However, in practice, it is difficult to uniformly fill the three-dimensional porous substrate directly with the paste active material, and several paste filling methods have been proposed. For example, a method has been proposed in which the paste is filled by vibrating the paste by ultrasonic vibration, or the paste is directly sprayed or rubbed on the substrate or filled by suction. However, although the paste filling method using ultrasonic vibration can fill the inside of the substrate with the paste, the viscosity of the paste is significantly reduced, and it is difficult to apply the paste on the electrode surface. In addition, in the method of filling the paste by rubbing, it is necessary to apply considerable pressure in order to sufficiently fill the inside of the substrate, and the surface of the substrate may be roughened. Further, in the method of filling the paste by suction, clogging occurs on the surface of the substrate, and it is difficult to uniformly fill the inside of the substrate. If the electrode is rolled in the non-uniformly filled state, a portion where the filling state is dense and a part where the electrode is roughened are generated, so that there is a problem that the electrode performance is deteriorated.
【０００５】本発明は上記問題点を解決するためになさ
れたもので、その目的はペーストの充填むらがなく，ま
たその充填効率の高いペースト式ニッケル正極の製造方
法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a paste-type nickel positive electrode which is free from uneven paste filling and has a high filling efficiency.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明のペースト式ニッケル正極の製造方法は、水
酸化ニッケルに添加剤と水と増粘剤を加えて粘度３００
０〜６０００ｃｐのペーストを収納したペースト槽内に
３次元多孔体基板を浸漬させ、次に、前記３次元多孔体
基板の両側に設けた回転式羽根または回転式ローラーな
どの回転式充填具により前記ペーストを前記３次元多孔
体基板内部に充填し、さらに前記３次元多孔体基板の両
側に設けた塗工具により前記ペーストを前記３次元多孔
体基板表面に塗工することで前記３次元多孔体基板に前
記ペーストを充填することを特徴とする。In order to achieve the above object, a method of manufacturing a paste-type nickel positive electrode according to the present invention comprises adding an additive, water and a thickener to nickel hydroxide to a viscosity of 300.
In a paste tank containing 0-6000 cp paste
A three-dimensional porous substrate is immersed, and then the three-dimensional porous substrate is immersed.
Rotary blades or rollers provided on both sides of the substrate
The paste can be turned into the three-dimensional porous
To the inside of the three-dimensional porous substrate,
The paste is applied to the three-dimensional porous plate using a coating tool provided on the side.
The paste is filled in the three-dimensional porous substrate by applying the paste to the surface of the substrate .
【０００７】[0007]
【作用】一般的に、３次元多孔体基板に充填、塗工する
ためのペーストは沈降分離、固液分離等、ペースト安定
性の問題から一般的にチクソトロピー性の高いペースト
が使用される。このチクソトロピー性の高いペーストは
高粘度であり、そのままの状態では充填塗工に関して不
適である。しかし、かかるチクソトロピー性の高いペー
ストにずり速度を与えてやるとペーストは流動性を持ち
基板内部まで充填することが可能である。In general, a paste having a high thixotropic property is generally used as a paste for filling and coating a three-dimensional porous substrate due to problems of paste stability such as sedimentation separation and solid-liquid separation. This paste having a high thixotropic property has a high viscosity and is unsuitable for filling coating as it is. However, if a shear rate is given to such a paste having a high thixotropic property, the paste has fluidity and can be filled into the inside of the substrate.
【０００８】ところで、一度多孔体基板内に侵入したペ
ーストは、そこでずり速度を失ってしまい基板内部まで
充填することができなくなる。つまりペーストは多孔体
基板表面近傍しか充填されない。つまり目詰まり状態と
なってしまっている。[0008] By the way, the paste once invading the porous substrate loses the shearing speed there and cannot be filled into the substrate. That is, the paste is filled only near the surface of the porous substrate. That is, it is in a clogged state.
【０００９】そこで、ペーストに連続的に圧力を与える
ことによって基板内部で基板に接触し適当なずり速度が
与えられると、流動性を与えられ基板の奥深くまで充填
することが可能となる。さらにペーストはチクソトロピ
ー性が高いため、１度充填したペーストは基板内部に保
持される。また、表面に塗工されたペーストは、ペース
ト槽から離脱する際、基板表面にペーストが過剰に塗布
した状態となり、基板内部と表面に充分に充填塗工する
ことが可能となる。このときペーストにチクソトロピー
性が少ないと活物質と分散液の分離を生じてしまい、逆
にチクソトロピー性が高すぎると基板内部まで充填する
ための時間が多くかかり量産性にそぐわない点があげら
れる。そこで、適当なペーストの粘度は３０００ｃｐ〜
６０００ｃｐが望ましい。Therefore, when the paste is continuously applied with pressure to come into contact with the substrate inside the substrate and give an appropriate shear rate, the paste is given fluidity and can be filled deep into the substrate. Furthermore, since the paste has a high thixotropic property, the paste once filled is held inside the substrate. When the paste applied to the surface is separated from the paste tank, the paste is excessively applied to the surface of the substrate, and the inside and the surface of the substrate can be sufficiently filled and applied. At this time, if the thixotropy of the paste is low, separation of the active material and the dispersion liquid occurs. On the other hand, if the thixotropy is too high, it takes a long time to fill the inside of the substrate, which is incompatible with mass productivity. Therefore, the viscosity of a suitable paste is 3000 cp ~
6000 cp is desirable.
【００１０】[0010]
【実施例】本発明の実施例を図１の模式的な製造装置を
参照して説明する。図１において、１はペースト槽、２
は３次元焼結繊維基板、３は３次元焼結繊維基板２を挟
んで対抗して配置された充填具である基板内部充填羽
根、４は３次元焼結繊維基板２を挟んで対抗して配置さ
れた塗工具である基板表面塗工羽根、５は３次元焼結繊
維基板２を挟んで対抗して配置されたかきとりブレー
ド、６はペーストである。DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to a schematic manufacturing apparatus shown in FIG. In FIG. 1, 1 is a paste tank, 2
Is a three-dimensional sintered fiber substrate, and three is a three-dimensional sintered fiber substrate.
The internal filling blades, which are the filling tools arranged opposite to each other, are arranged opposite to each other with the three-dimensional sintered fiber substrate 2 interposed therebetween.
The surface coating blade, which is a coated coating tool, is a three-dimensional sintered fiber.
A scraping blade 6 disposed opposite to the fiber substrate 2 is a paste.
【００１１】まず、水酸化ニッケル９０部に２価の酸化
コバルト１０部を添加し、C.M.C.,０．２部、ポリアク
リル酸ソーダ０．２部と純水４５部を加えペースト化
し、その粘度を４０００ｃｐとした。このペーストを図
１に示すペースト槽１に移し、このペースト槽１内に３
次元焼結繊維基板２を浸漬させた。次に充填羽根３を回
転させペースト６に対して垂直な方向にペースト６を流
動させ充填し、さらに塗工羽根４によって基板表面にペ
ースト６を塗工し、かきとりブレード５で過剰なペース
トをかきとる。基板の目付け量は５５０ｇ／ｍ2 、空隙
率は９５％であった。このときのペーストが基板に接す
るときの圧力は、約２００ｇ／ｃｍ2 、ペースト槽を通
過する基板の搬送速度は５００ｍｍ／ｍｉｎとした。こ
のときの乾燥状態の電極重量から基板の重量を差し引い
て１ｃｍ2 当たりの充填量を算出し空隙率に対する充填
効率を計算し、その結果を図２に示した。First, 10 parts of divalent cobalt oxide is added to 90 parts of nickel hydroxide, and 0.2 parts of CMC, 0.2 parts of sodium polyacrylate and 45 parts of pure water are added to form a paste. It was 4000 cp. This paste was transferred to a paste tank 1 shown in FIG.
The two-dimensional sintered fiber substrate 2 was immersed. Next, the filling blade 3 is rotated to flow and fill the paste 6 in a direction perpendicular to the paste 6, and further, the paste 6 is applied to the substrate surface by the coating blade 4, and the excess paste is scraped by the scraping blade 5. Take. The basis weight of the substrate was 550 g / m 2 , and the porosity was 95%. At this time, the pressure when the paste came into contact with the substrate was about 200 g / cm 2 , and the transfer speed of the substrate passing through the paste tank was 500 mm / min. At this time, the filling weight per 1 cm 2 was calculated by subtracting the weight of the substrate from the electrode weight in the dry state, and the filling efficiency with respect to the porosity was calculated. The result is shown in FIG.
【００１２】一方、比較例として羽根の回転数を変化さ
せペーストが基板と接触するときのペースト圧力を約１
０、５０、１００、４００、５００ｇ／ｃｍ2 と変化さ
せ、他の条件は同様とし１ｃｍ2 の充填量を測り、その
結果を図２に示した。On the other hand, as a comparative example, the pressure of the paste when the paste comes into contact with the substrate was changed to about 1 by changing the rotation speed of the blade.
The filling amount was changed to 0, 50, 100, 400, and 500 g / cm 2, and the other conditions were the same. The filling amount of 1 cm 2 was measured, and the results are shown in FIG.
【００１３】図２より明らかなようにペーストの加圧力
が５０〜４００ｇ／ｃｍ2 の範囲にある場合は、安定し
て高い充填効率が得られている。しかしペーストの加圧
力が４００ｇ／ｃｍ2 以上であったり１０ｇ／ｃｍ2 よ
り低い場合であると加圧による基板に折れなどのダメー
ジが生じたり充填量が少なかったりしてしまった。As is apparent from FIG. 2, when the pressure of the paste is in the range of 50 to 400 g / cm 2 , a high filling efficiency is obtained stably. However, when the pressing force of the paste is 400 g / cm 2 or more or lower than 10 g / cm 2 , damage such as breakage of the substrate due to pressurization or a small filling amount occurs.
【００１４】なお、３次元金属多孔体としては金属繊維
焼結体、発泡メタル等も適用でき、また、かかるペース
トの流動力を発生させる方法としては羽根を回転させる
以外にローラーを回転させてもよい。As the three-dimensional porous metal body, a metal fiber sintered body, a foamed metal, or the like can be applied. As a method of generating the flow force of the paste, besides rotating the blade, rotating the roller may be used. Good.
【００１５】[0015]
【発明の効果】以上説明したように、本発明の製造方法
によれば、ペーストに３０００〜６０００ｃｐの粘度の
流動性を持たせることにより、多孔体基板とペーストの
接触するときのペースト流動圧力によって多孔体基板に
ペーストを充填しているので、多孔体基板の損傷も少な
く安定して高い充填効率を得ることができる。As described in the foregoing, according to the production method of the present invention, by Rukoto allowed paste have <br/> fluidity of viscosity 3000～6000Cp, when in contact of the porous substrate and the paste Since the paste is filled in the porous substrate by the paste flow pressure, the porous substrate can be stably obtained with little damage and high filling efficiency.
【図１】本発明の一実施例であるペースト式ニッケル正
極を製造するための模式的な製造装置を示す図。FIG. 1 is a diagram showing a schematic manufacturing apparatus for manufacturing a paste-type nickel positive electrode according to one embodiment of the present invention.
【図２】ペースト加圧力に対する充填効率を示す図。FIG. 2 is a graph showing filling efficiency with respect to paste pressing force.
１…ペースト槽、２…３次元焼結繊維基板、３…基板内
部充填羽根、４…基板表面塗工羽根、５…かきとりブレ
ード、６…ペースト。DESCRIPTION OF SYMBOLS 1 ... paste tank, 2 ... three-dimensional sintered fiber board, 3 ... board | substrate inside filling blade, 4 ... board surface coating blade, 5 ... scraping blade, 6 ... paste.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 寺岡 浩仁 東京都品川区南品川三丁目４番10号 東 芝電池株式会社内 (56)参考文献 特開 平２−24968（ＪＰ，Ａ) 特開 昭63−152863（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/24 - 4/32 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hirohito Teraoka 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Inside Toshiba Battery Corporation (56) References JP-A-2-24968 (JP, A) JP-A 63-152863 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/24-4/32
Claims (1)
加えて粘度３０００〜６０００ｃｐのペーストを収納し
たペースト槽内に３次元多孔体基板を浸漬させ、次に、
前記３次元多孔体基板の両側に設けた回転式羽根または
回転式ローラーなどの回転式充填具により前記ペースト
を前記３次元多孔体基板内部に充填し、さらに前記３次
元多孔体基板の両側に設けた塗工具により前記ペースト
を前記３次元多孔体基板表面に塗工することで前記３次
元多孔体基板に前記ペーストを充填することを特徴とす
るペースト式ニッケル正極の製造方法。 1. A paste having a viscosity of 3000 to 6000 cp by adding an additive, water and a thickener to nickel hydroxide.
The three-dimensional porous substrate is immersed in the paste tank
Rotating blades provided on both sides of the three-dimensional porous substrate or
The paste is applied by a rotary filler such as a rotary roller.
Is filled in the three-dimensional porous substrate, and
Paste with the coating tools provided on both sides of the original porous substrate
Is applied to the surface of the three-dimensional porous substrate, thereby filling the paste into the three-dimensional porous substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07613591A JP3296572B2 (en) | 1991-04-09 | 1991-04-09 | Method for producing paste-type nickel positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07613591A JP3296572B2 (en) | 1991-04-09 | 1991-04-09 | Method for producing paste-type nickel positive electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04312767A JPH04312767A (en) | 1992-11-04 |
| JP3296572B2 true JP3296572B2 (en) | 2002-07-02 |
Family
ID=13596520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07613591A Expired - Fee Related JP3296572B2 (en) | 1991-04-09 | 1991-04-09 | Method for producing paste-type nickel positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3296572B2 (en) |
-
1991
- 1991-04-09 JP JP07613591A patent/JP3296572B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04312767A (en) | 1992-11-04 |
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