JPS61110962A - Manufacture of positive nickel plate for alkaline storage battery - Google Patents
Manufacture of positive nickel plate for alkaline storage batteryInfo
- Publication number
- JPS61110962A JPS61110962A JP59233599A JP23359984A JPS61110962A JP S61110962 A JPS61110962 A JP S61110962A JP 59233599 A JP59233599 A JP 59233599A JP 23359984 A JP23359984 A JP 23359984A JP S61110962 A JPS61110962 A JP S61110962A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- positive
- film
- beta
- positive active
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 14
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 12
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract description 2
- 150000001869 cobalt compounds Chemical class 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000003518 caustics Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005406 washing Methods 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
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用正極板の製造法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a positive electrode plate for an alkaline storage battery.
従来技術とその間声点
従来ニッケルカドミウム蓄電池用ニッケル正極板の代表
的なものとしてシンタ一式とベースト式の２種類がある
。Prior art and its points There are two typical types of nickel positive electrode plates for conventional nickel-cadmium storage batteries: the sintered type and the base type.
前者はニッケル粉末を穿孔鋼板あるいはニッケルネット
等の芯金に焼結させた多孔体基板に為硝酸ニッケルを主
成分とした含浸液を含浸し、次いでアルカリ溶液に浸漬
して活物質を充填したものである。The former is a porous substrate made by sintering nickel powder onto a core metal such as a perforated steel plate or nickel net, which is impregnated with an impregnating liquid mainly composed of nickel nitrate, and then immersed in an alkaline solution to fill the active material. It is.
後者は芯金をもたない金属繊維焼結体あるいはスゲンジ
状金属多孔体等に活物質そのものの水溶性ペーストを充
填させたものである。The latter is a material in which a metal fiber sintered body or a stent-like porous metal body without a metal core is filled with a water-soluble paste of the active material itself.
周知の如く、両者の充填方法の違いは、細孔構造による
ものであり、前者は細孔径１０μｍ以下と小さいため、
水酸化ニアケル粒子そのものを直接充填することができ
ない。これに対し後者は数十〜数百μｍと大きいため、
直接充填が可能である。 ）
ところで両者共活物質の利用率を向上させる目的で、少
量のコバルトが共沈状態ですなわち硝酸ニッケルと硝酸
コバルトの混合水溶液をアルカリ処理することによって
、水酸化物を得る方法で添加されているのが常である。As is well known, the difference between the two filling methods is due to the pore structure, and the former has a small pore diameter of 10 μm or less, so
Niacel hydroxide particles themselves cannot be directly filled. On the other hand, the latter is large, ranging from tens to hundreds of micrometers, so
Direct filling is possible. ) By the way, in order to improve the utilization rate of both co-active materials, a small amount of cobalt is added in a co-precipitated state, that is, by treating a mixed aqueous solution of nickel nitrate and cobalt nitrate with an alkali to obtain hydroxide. It is usual.
周知の如く、活物質中にコバルトを添加すると放電々圧
が低下し、その分エネルギー密度の低下を生じる欠点が
あった。As is well known, when cobalt is added to an active material, the discharge pressure decreases, which has the drawback of causing a corresponding decrease in energy density.
又、利用率も１０％程度向上する位であり最近の市場要
求は高エネルギー密度の電池を強く望むものであり、こ
れに対応するためにはさらに利用率を向上させる製造法
が望まれている。In addition, the utilization rate is improved by about 10%, and recent market demands strongly desire batteries with high energy density, and in order to meet this demand, a manufacturing method that further improves the utilization rate is desired. .
発明の目的
本発明は、活物質利用率の向上と放電々圧低下を抑制し
たニッケル正極板を製造することを目的とする。OBJECTS OF THE INVENTION It is an object of the present invention to manufacture a nickel positive electrode plate that improves the utilization rate of active materials and suppresses a decrease in discharge pressure.
発明の構成
すなわち、本発明は上記目的を達成するために、水酸化
ニッケルを主成分とする正極活物質を充填した多孔性金
屑基板を、硫酸コバＡ／）を含む硫酸溶液に浸漬し、次
いでアルカリ溶液中で処理し、水洗した後に非酸化性雰
囲気中で乾燥を行ない正極活物質表面に各種存在するコ
バルト化合物中、特にβ−ｃｏ（ｏＨ）ｚの皮ｙを形成
させて、ニッケル正極板を製造するものである。Structure of the Invention That is, in order to achieve the above object, the present invention immerses a porous gold scrap substrate filled with a positive electrode active material mainly composed of nickel hydroxide in a sulfuric acid solution containing Coba sulfate A/), Next, it is treated in an alkaline solution, washed with water, and then dried in a non-oxidizing atmosphere to form a coating of β-co(oH), especially β-co(oH), among various cobalt compounds present on the surface of the positive electrode active material. It manufactures boards.
実施例 以下本発明の一夾施例について詳述する。Example Hereinafter, one embodiment of the present invention will be described in detail.
ニッケル粉末を穿孔鋼板に焼結させた多孔度約８０第の
多孔性金屑基板を、硝酸ニッケル溶液中に浸漬した後、
５０％の水酸化ナトリウム水溶液中で間知の如き電解還
元法によ° り水酸化物として沈着せしめしかる後に水
洗、乾燥を行なう。これら一連の工程を５〜６サイクル
繰返して、所定の活物質量を充填する〇しかる後に、約
６００ ’／４１の硫酸コバルト水溶液中に浸漬し、前
記とほぼ同様の操作を行ない約５％の水酸化コバルトを
追加充填する。After immersing a porous gold scrap substrate with a porosity of about 80 in which nickel powder is sintered onto a perforated steel plate, in a nickel nitrate solution,
The hydroxide is deposited in a 50% aqueous sodium hydroxide solution by a well-known electrolytic reduction method, followed by washing with water and drying. These series of steps are repeated for 5 to 6 cycles to fill a predetermined amount of active material. After that, it is immersed in a cobalt sulfate aqueous solution of about 600'/41, and almost the same operation as above is performed to fill it with a predetermined amount of active material. Fill with additional cobalt hydroxide.
この追加充填工程中の乾燥雰囲気を非酸化性雰囲気とす
る。例えば窒素やアルゴン＃囲気あるいは真空状態であ
る。通常の大気中での乾燥においては、ブラウン色を呈
した水酸化コバルト、０ｏＨＯ１となる。しかし非酸化
性雰囲気の乾燥では、淡桃色のβ−Ｃｏ（ＯＨ）ｚが表
面に皮膜形成される。The drying atmosphere during this additional filling step is a non-oxidizing atmosphere. For example, a nitrogen or argon atmosphere or a vacuum state. When dried in normal air, cobalt hydroxide becomes brown in color, 0oHO1. However, when drying in a non-oxidizing atmosphere, a pale pink β-Co(OH)z film is formed on the surface.
本発明により作成した正極板（Ｉ）、従来の如くニッケ
ルとコバルトを共沈した正極板α）、本発明の乾燥工程
での雰囲気を空気中で約１００℃としたブラウン色の水
酸化コバルトをコーティングした正極板（２）、及びコ
バルトの追加充填をしない正極板面の４種類の正極板を
これらの正極板よりも容量が大であるカドミウム負極板
、ナイロンセパレータ、比重１．２０の苛性カリウム水
溶液等からベント形ニッナルカドミウム蓄電池を製作し
た。これらの電池を２５℃で充電々流０．１０ムにより
、１５時間充電した。しかる後、放電々流０．２ＯＡで
酸化水銀照合電極に対して、Ｏｖまで放電させて性能を
比較した。A positive electrode plate (I) prepared according to the present invention, a positive electrode plate α) prepared by co-precipitating nickel and cobalt as in the conventional method, and a brown cobalt hydroxide prepared in the atmosphere of about 100°C in the air during the drying process of the present invention. The coated positive plate (2) and the positive plate surface without additional cobalt filling were made of four types of positive plates: a cadmium negative plate with a larger capacity than these positive plates, a nylon separator, and caustic potassium with a specific gravity of 1.20. A vented nickel-cadmium storage battery was fabricated from an aqueous solution. These batteries were charged for 15 hours at 25° C. with a charging current of 0.10 μm. Thereafter, the performance was compared by discharging up to Ov against a mercury oxide reference electrode at a discharge current of 0.2OA.
表１はコバルトを各々５％含む前述の正極板（１）、（
１）、（２）及びコバルトの充填していない正極板（ト
）の利用率を示した０
表２は前記した４種類の正伊板を用いた電池の平均数々
電圧を示したものである。Table 1 shows the above-mentioned positive electrode plate (1) containing 5% cobalt, (
Table 2 shows the average voltage of batteries using the four types of positive electrode plates described above. .
上記の如く、本発明により得られた正極板の活物質利用
率が優れている。As described above, the positive electrode plate obtained according to the present invention has an excellent active material utilization rate.
又平均放電々圧においては、（１）の共沈添加極板より
も約１５ｆｌａＷ高い〇
本発明による正極板の電池は、放々電圧、活物質利用率
の両面において優れている。これは正極活物質表面にβ
−Ｇｏ（ＯＲ）ｚの皮膜を形成させたことによるもので
あるが、効果のメカニズムについては明らかでない。In addition, the average discharge voltage is about 15 flaW higher than the coprecipitated electrode plate of (1). The battery with the positive electrode plate according to the present invention is excellent in both discharge voltage and active material utilization rate. This is β on the surface of the positive electrode active material.
This is due to the formation of a film of -Go(OR)z, but the mechanism of the effect is not clear.
しかしながら以下の如く推察される。However, it is inferred as follows.
正極活物質表面に皮膜を形成された活性なβ−００（Ｏ
Ｈ）２はアルカリ溶液中において、正極の充放電に伸な
い３酸の水酸化コバルトに変化する。このＷ、４１ｃ化
学的に形成された６価の水酸化コバルトは、一般の化学
的に合成された５価の水酸化コバルトに比べて、プ豐ト
ン伝導度に優れ、水酸化ニッケル活物質に液側よりスム
ーズにプロトンが拡散するように補助的作用を有してい
るのではないかと思われるＯ
上記実施例片シンタ一式正極板について述べたが、ペー
スト式正極板についても活物質ペースト充填後、β−ｏ
ｏ（ＯＨ）ｉの追加充填をかなえば同様な効果が得られ
る。Active β-00 (O
H)2 changes into cobalt hydroxide, a triacid, which does not support charging and discharging of the positive electrode in an alkaline solution. This W, 41c chemically formed hexavalent cobalt hydroxide has superior conductivity compared to general chemically synthesized pentavalent cobalt hydroxide, and is suitable for nickel hydroxide active materials. It seems that it has an auxiliary effect so that protons diffuse smoothly from the liquid side.O Although the positive electrode plate of the above example with a piece sinter set was described, the paste type positive electrode plate also has an auxiliary effect after filling the active material paste. , β-o
A similar effect can be obtained by additionally filling o(OH)i.
発明の効果
本発明により正極活物質表面に非酸化性雰囲気で乾燥し
たβ−Ｇｏ（ＯＨ）２の皮膜を形成させることにより、
活物質利用率を向上させ、かつ放電々圧低下を抑制した
ニッケル正極板を製造できる効果がある。Effects of the Invention By forming a film of β-Go(OH)2 dried in a non-oxidizing atmosphere on the surface of the positive electrode active material according to the present invention,
This has the effect of making it possible to manufacture a nickel positive electrode plate that improves the active material utilization rate and suppresses the drop in discharge pressure.
出順人 湯浅電池株式会社Junjin Yuasa Battery Co., Ltd.
Claims (1)
孔性金属基板を、硫酸コバルトを含む硫酸塩水溶液に浸
漬し、次いでアルカリ溶液中で処理し、水洗した後に非
酸化性雰囲気中で乾燥を行ない正極活物質表面にβ−Ｃ
ｏ（ＯＨ）＿２の皮膜を形成させることを特徴とするア
ルカリ蓄電池用ニッケル正極板の製造法。A porous metal substrate filled with a cathode active material mainly composed of nickel hydroxide is immersed in a sulfate aqueous solution containing cobalt sulfate, then treated in an alkaline solution, washed with water, and then dried in a non-oxidizing atmosphere. β-C on the surface of the positive electrode active material
A method for producing a nickel positive electrode plate for an alkaline storage battery, characterized by forming a film of o(OH)_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59233599A JPS61110962A (en) | 1984-11-06 | 1984-11-06 | Manufacture of positive nickel plate for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59233599A JPS61110962A (en) | 1984-11-06 | 1984-11-06 | Manufacture of positive nickel plate for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61110962A true JPS61110962A (en) | 1986-05-29 |
| JPH0451944B2 JPH0451944B2 (en) | 1992-08-20 |
Family
ID=16957578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59233599A Granted JPS61110962A (en) | 1984-11-06 | 1984-11-06 | Manufacture of positive nickel plate for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61110962A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6225004B1 (en) | 1998-02-23 | 2001-05-01 | Matsushita Electric Industrial Co., Ltd. | Nickel positive electrode for alkaline storage batteries and method for producing the same |
-
1984
- 1984-11-06 JP JP59233599A patent/JPS61110962A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6225004B1 (en) | 1998-02-23 | 2001-05-01 | Matsushita Electric Industrial Co., Ltd. | Nickel positive electrode for alkaline storage batteries and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0451944B2 (en) | 1992-08-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |