JPS6057A - Manufacture of active material for alkaline storage battery - Google Patents
Manufacture of active material for alkaline storage batteryInfo
- Publication number
- JPS6057A JPS6057A JP58107223A JP10722383A JPS6057A JP S6057 A JPS6057 A JP S6057A JP 58107223 A JP58107223 A JP 58107223A JP 10722383 A JP10722383 A JP 10722383A JP S6057 A JPS6057 A JP S6057A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- alkali
- alkaline storage
- storage battery
- excess
- 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.)
- Pending
Links
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
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- 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
本発明は非焼結式極板に用いられるアルカリ蓄電池用活
物質の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing an active material for an alkaline storage battery used in a non-sintered electrode plate.
−Ｊ 従来技術
従来よりアルカリ蓄電池用極板は大別して焼結式と非焼
結式による製造方法が採用されている。-J Prior Art Conventionally, electrode plates for alkaline storage batteries have been manufactured using sintered and non-sintered methods.
一般！−焼結式極板は、ニッケル粉末を主成分とするス
ラリーを極板芯体に塗着後、快結して得たニアケル多孔
体を基板として、この基板に硝酸カドミクム溶液あるい
は枦酸ニッケル溶液等の活物質の塩溶液を含浸し、次い
でアルカリ処理、水洗、乾燥の一連の操作を数回繰り返
すことにより所定量の活物質を充填して製造されている
。このφ結成極板は、放電率特性、サイクル特性及び機
械的強度などの緒特性が優れたものであるが、その反面
作業工程が複雑であり、製造に長時間を要し、また電力
及び水を多量に用いるため製造コストが増大するという
問題点を有している。General! - The sintered electrode plate uses a Niacel porous material obtained by applying a slurry mainly composed of nickel powder to the electrode plate core and solidifying it as a substrate. It is manufactured by filling a predetermined amount of active material by impregnating it with a salt solution of the active material, and then repeating a series of operations of alkaline treatment, water washing, and drying several times. This φ-formed electrode plate has excellent characteristics such as discharge rate characteristics, cycle characteristics, and mechanical strength, but on the other hand, the work process is complicated, it takes a long time to manufacture, and it also requires electricity and water. Since a large amount of is used, there is a problem in that the manufacturing cost increases.
これに対してペースト式に代表される非焼結式極板は、
一般にカドミウム活物質あるいはニッケル活物質等の活
物質粉末に糊料、繊維及び水あるいは有機溶媒を混練し
てペースト状にしたものを、極板芯体に塗着乾燥して製
造されており、作業工程が簡単であり、製造時間及び製
造コストを低く抑えられるものである。しかし、なから
、非ザを結成極板は焼結式極板に比し極板の緒特性が劣
っており、極板性能の向上が課題とされ℃いる。On the other hand, non-sintered electrode plates, typically paste type,
Generally, it is manufactured by kneading active material powder such as cadmium active material or nickel active material with glue, fiber, and water or organic solvent to form a paste, which is then applied to the electrode plate core and dried. The process is simple, and manufacturing time and manufacturing costs can be kept low. However, non-sintered electrode plates have inferior plate properties compared to sintered plates, and improvement of the plate performance is an issue.
ところで解結式以外の極板の製造方法では、まず、活物
質を合成したのち極板を作成することになるのだが、こ
の合成した活物質の特性が電池特性セ対し１大きく影響
してくる。故に非焼結式極板の製造（１於いて、優れた
電池特性の極板を得るためには、優れた特性を有する活
物質を得ることが重要となる。現在行なわれている活物
質の一般的な製造方法は、ニッケル陽極活物質を例にと
れば次の様なものである。ニッケル塩（硝酸ニッケル、
硫酸二２ゲル等）水溶液とアルカリ（苛性ソーダ、苛性
カリ）水溶液ンアルカリ過剰で反応させ、得られた混合
物を濾過して過剰のアルカリ及び水を除き、更に水洗、
乾燥してニッケル活物質を得る方法である。しかし、こ
の製造方法では、充填性の悪い活物質しか得られず、極
板の容量を向上せしめることは困難である。また、一般
に充填性と活物質粒径の間（：相関関係があることが知
られており、活物質粒径は余り大き過ぎても、小さ過ぎ
ても充填性は悪くなるといわれている。そこで充填性と
活物質粒径の関係を調べたところ、活物質の平均粒径が
６〜９μであると充填性が向上することがわかった。し
たがって、前述の一般的な製造方法で得られた活物質の
粒径が２μ程６度と小さく充填性が悪いため、適当な粒
径の活物質を得る必要があった。By the way, in methods of manufacturing electrode plates other than the disassembly method, the active material is first synthesized and then the electrode plates are created, and the characteristics of the synthesized active material have a large effect on the battery characteristics. . Therefore, in order to produce a non-sintered electrode plate (1), it is important to obtain an active material with excellent characteristics in order to obtain an electrode plate with excellent battery characteristics. Taking nickel anode active materials as an example, common manufacturing methods are as follows: Nickel salts (nickel nitrate, nickel nitrate,
sulfuric acid 22 gel, etc.) and an alkali (caustic soda, caustic potash) aqueous solution and an excess of alkali, the resulting mixture is filtered to remove excess alkali and water, and further washed with water.
This is a method to obtain a nickel active material by drying. However, with this manufacturing method, only active materials with poor filling properties can be obtained, making it difficult to improve the capacity of the electrode plate. In addition, it is generally known that there is a correlation between the filling property and the particle size of the active material, and it is said that the filling property will deteriorate if the particle size of the active material is too large or too small. When we investigated the relationship between the filling property and the particle size of the active material, we found that the filling property was improved when the average particle size of the active material was 6 to 9μ. Since the particle size of the active material was as small as 2 μm or 6 degrees, and the filling property was poor, it was necessary to obtain an active material with an appropriate particle size.
（／→ 発明の目的
本発明はかかる点Ｃ１鑑み充填率及び利用率の高い活物
質ン安定して得ることにより、特性が向上した非焼結式
極板を得ることを目的とする。(/→ Purpose of the Invention In view of the above point C1, an object of the present invention is to obtain a non-sintered electrode plate with improved characteristics by stably obtaining an active material with a high filling rate and high utilization rate.
に）発明の構成
本発明は活物質の塩水溶液とアルカリ水ｍ液をアルカリ
過剰で反応させ、得られた混合物中（−アルカリｔｏ、
７〜５．０重量％残した状態まで脱液後乾燥し更に水洗
してなるアルカリ蓄屯池用活物質の製造方法である。2) Structure of the Invention The present invention involves reacting an aqueous salt solution of an active material with an alkaline aqueous solution in an excess of alkali, and in the resulting mixture (-alkali to,
This is a method for producing an active material for an alkaline storage pond, in which the active material is dehydrated until 7 to 5.0% by weight remains, then dried and further washed with water.
ネ）実施例
本発明の実施例を以下に示し説明する。尚、残留アルカ
リ量、充填率並びに利用率は以下の式により算出した値
を用いる。f) Examples Examples of the present invention will be shown and explained below. Note that the residual alkali amount, filling rate, and utilization rate are calculated using the following formulas.
（重量％）（乾燥状態）
−Ｘ Ｉ Ｑ Ｑ
の体積 （ｇ／ｓｔ）
硝酸ニッケル水溶撤と苛性ソーダ水溶液をアルカリ過剰
で混合して反応させ、得られた混合物をｄヒ過して残留
アルカリ量を任意の量になるまで脱液したｒｘａｏ℃で
一旦乾燥し、更（＝水洗乾燥を行なって活物質を得る。(wt%) (dry state) - Volume of I The active material is obtained by deliquifying the material to a desired amount, drying it at rxao°C, and then washing with water and drying.
次いでこの活物質１００に対してＶｔａ比でグラファイ
ト１２、Ｐ’１ＦＥ２’１１水と共に加えて混合しペー
スト状とした後極板芯体に立石、乾燥して極板ビ作成し
た。Next, to this active material 100, graphite 12, P'1FE2'11 and water were added at a Vta ratio and mixed to form a paste, which was then dried to form an electrode plate core.
前述の操作によって得られた極板を用いて、極板の充填
率及び利用率を測定し、その結果を第１図及び第２図）
二元−「０第１図は残留アルカリ岨と充填率との関係を
示す図面、第２図は残留アルカリ量と利用率との関係を
示す図面である。図面より充填性は残留アルカリ量乞０
４７重量φ以上とすることで良くなり、利用率は残留ア
ルカリ量を０〜５．０重量−とすることで良好な値が得
られることがわかる。この理由Ｏ）詳細は明らかではな
いが、乾燥中の様な高温湿に４状態でナトリウムイオン
が存７Ｅすると、ナトリウムイオンが活’ｌｊｖ質の粒
子に働きかけ径が大きく強固な二次粒子を形成１−るた
めと思われる。一方、残Ｘ′ηアルカリ（：東が多過ぎ
る状態で、且乾燥すると利用率が低下したのは、このと
きの活物質の色が通常の緑糸の色から褐色や灰色になる
ことから、活物質の結晶、重子が変１ヒして反応し難い
状態になったためと思われる。尚、同時（−活物質の結
晶性を知るためにＸ線強度を測定すると、Ｘ線のピーク
の強度が大きくなることから結晶性が良くなっているこ
とはわかったが、利用率とＸ線強度の間に相１消関係は
見られなかった。Using the electrode plate obtained by the above operation, the filling rate and utilization rate of the electrode plate were measured, and the results are shown in Figures 1 and 2).
Figure 1 is a diagram showing the relationship between the residual alkali volume and the filling rate, and Figure 2 is a diagram showing the relationship between the amount of residual alkali and the utilization rate. 0
It can be seen that good values can be obtained by setting the residual alkali amount to 47 weight φ or more, and good values can be obtained by setting the residual alkali amount to 0 to 5.0 weight. The reason for this O) The details are not clear, but when sodium ions exist in a high temperature and humidity state such as during drying, the sodium ions act on active particles and form strong secondary particles with a large diameter. 1- It seems to be because of On the other hand, the reason why the utilization rate decreased when there was too much residual X′η alkali (: east) and when it dried was because the color of the active material at this time changed from the usual green color to brown or gray. This seems to be because the crystals and heavy atoms of the active material have changed and become difficult to react.At the same time, when measuring the X-ray intensity to determine the crystallinity of the active material, the intensity of the X-ray peak It was found that the crystallinity was improved because of the increase in , but no relationship between the utilization rate and the X-ray intensity was observed.
前述の様；１径の大きな二次粒子７得るのに役）Ｌつ残
留アルカリも、乾燥中に窒気中の二酸化炭諮と反応し大
部分が水酸化）′トリウムから炭酸ナトリウムに液化し
ていると考えら１１２、この炭嘴ナトリウムは電池内（
：取り込まれると電池性能に悪影響を与えるため、前述
の活物質の作成の際に示した様にアルカリを残留して乾
燥した後、水洗によってナトリウム分を除去する必要か
ある。As mentioned above, the residual alkali also reacts with carbon dioxide in the nitrogen atmosphere during drying, and most of it becomes hydroxide); the thorium liquefies into sodium carbonate. It is believed that this sodium charcoal beak is inside the battery (
: If taken in, it will adversely affect battery performance, so as shown in the preparation of the active material described above, it is necessary to leave the alkali behind and dry it, then remove the sodium content by washing with water.
尚１本発明で用いるアルカリ水溶液として、苛性ソーダ
のかわり（１苛性カリを用いて前述同様の実験を行なっ
たところ、苛性ソーダ同様良好な効果が得られ、本発明
に於いてはナトリクムとカリウムとの差は認められなか
った。1. As the alkaline aqueous solution used in the present invention, instead of caustic soda (1) When the same experiment as described above was conducted using caustic potash, good effects were obtained as with caustic soda, and in the present invention, the difference between sodium and potassium was I was not able to admit.
（へ）発明の効果
本発明により活物質の塩水Ｕ液とアルカリ水溶液をアル
カリ過剰で反応させ、得られた混合物中にアルカ！Ｊ
Ｙ Ｄ、 ７〜５． Ｏ重ｔｌ：ｉ％残した状態まで脱
液後、乾罫、水洗することで充填率及び利用率の筒いア
ルカリ蓄電池用活物質を安定して得ることができ、特性
が向上した非焼結式極板か得られる効果がある。(F) Effects of the Invention According to the present invention, the salt water U solution of the active material and the alkaline aqueous solution are reacted with an excess of alkali, and the resulting mixture contains alkali! J
YD, 7-5. After deliquifying to a state where O weight tl:i% remains, dry-lining and washing with water, it is possible to stably obtain an active material for cylindrical alkaline storage batteries with a filling rate and a utilization rate, and a non-sintered material with improved properties. There is an effect obtained from the formula plate.
第１図は残留アルカリ量と充填率との関係を示す図面、
第２図は残留アルカリ量と利用率との関係を示す図面で
ある。Figure 1 is a diagram showing the relationship between the amount of residual alkali and the filling rate.
FIG. 2 is a drawing showing the relationship between the amount of residual alkali and the utilization rate.
Claims (1)
剰で反応させ、得られた混合物中にアルカリを０７〜５
．０ ”ｆＸ早チ残した状態まで脱液後乾燥、水′ｆｋ
することを特徴とするアルカリ蓄電池用活物質の製造方
法。(1) React an aqueous solution of an active material with an aqueous alkali solution in an excess of alkali, and add an alkali to the resulting mixture at a concentration of 0.7-5.
．． 0 ” f
A method for producing an active material for an alkaline storage battery, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58107223A JPS6057A (en) | 1983-06-14 | 1983-06-14 | Manufacture of active material for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58107223A JPS6057A (en) | 1983-06-14 | 1983-06-14 | Manufacture of active material for alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6057A true JPS6057A (en) | 1985-01-05 |
Family
ID=14453608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58107223A Pending JPS6057A (en) | 1983-06-14 | 1983-06-14 | Manufacture of active material for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6057A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112340783A (en) * | 2020-09-30 | 2021-02-09 | 宜宾锂宝新材料有限公司 | Modification method for reducing residual alkali on surface of high-nickel ternary cathode material, high-nickel ternary cathode material prepared by modification method and lithium ion battery |
-
1983
- 1983-06-14 JP JP58107223A patent/JPS6057A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112340783A (en) * | 2020-09-30 | 2021-02-09 | 宜宾锂宝新材料有限公司 | Modification method for reducing residual alkali on surface of high-nickel ternary cathode material, high-nickel ternary cathode material prepared by modification method and lithium ion battery |
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