JPS63266766A - Manufacture of nickel electrode for battery - Google Patents
Manufacture of nickel electrode for batteryInfo
- Publication number
- JPS63266766A JPS63266766A JP62100353A JP10035387A JPS63266766A JP S63266766 A JPS63266766 A JP S63266766A JP 62100353 A JP62100353 A JP 62100353A JP 10035387 A JP10035387 A JP 10035387A JP S63266766 A JPS63266766 A JP S63266766A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- substrate
- hours
- air
- electrode
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011149 active material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000003518 caustics Substances 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 abstract description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 abstract description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 abstract description 2
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical group [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- 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
- H01M4/26—Processes of manufacture
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (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、蓄電池用のニッケル電極の製造法の改良に関
する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for manufacturing nickel electrodes for storage batteries.
従来の技術
汎用の蓄電池には、鉛蓄電池とアルカリ蓄電池があり、
アルカリ蓄電池の代表は、ニッケルーカドミウム系ｆあ
る。その他に、ニッケルー亜鉛。Conventional technology General-purpose storage batteries include lead-acid batteries and alkaline storage batteries.
A typical alkaline storage battery is a nickel-cadmium type battery. In addition, nickel-zinc.
ニッケルー鉄、ニッケルー水素などの系が開発されてい
る。Systems such as nickel-iron and nickel-hydrogen have been developed.
したがって、アルカリ電池におけるニッケル極の存在は
大きく、ポケット式から焼結式さらに最近では非焼結式
が研究されている。とくに焼結式の実用化は、ニッケル
ーカドミウム蓄電池の実用の範囲を大幅に拡大した。し
かし、高エネルギー密度の要望への対応や製法の簡易化
に対しては十分ではないので、発泡式や繊維式のような
３次元多孔体を用いたり、エキスバンドメタルやパンチ
ングメタルのような２次元多孔体を用い、これに活物質
を充てん、塗着する方式が一部実用化してきた。Therefore, the presence of nickel electrodes in alkaline batteries is significant, and studies have been conducted on everything from pocket types to sintered types, and more recently, non-sintered types. In particular, the practical application of sintered batteries has greatly expanded the scope of practical use of nickel-cadmium storage batteries. However, this is not sufficient to meet the demands for high energy density or simplify manufacturing methods, so three-dimensional porous materials such as foamed or fiber-based materials are used, or two-dimensional materials such as expanded metal and punched metal are used. Some methods have been put into practical use that use dimensional porous materials, fill them with active materials, and then apply them.
これらの導電性多孔体に用いる活物質としては、水酸化
ニッケルが用いられるが、さらに導電性の向上のために
黒鉛やニッケルが加えられ、さらに水酸化ニッケルの利
用率向上のためにコバルト。Nickel hydroxide is used as the active material for these conductive porous bodies, but graphite and nickel are added to improve conductivity, and cobalt is added to improve the utilization rate of nickel hydroxide.
コバルト化合物の添加、さらに水酸化リチウムの添加な
どがあげられる。また、結着剤にフッソ樹脂が用いられ
る。このように、水酸化ニッケル中にコバルトやコバル
ト化合物を加えることは、水酸化ニッケルの利用率の向
上には効果がある。Examples include addition of a cobalt compound and further addition of lithium hydroxide. Further, fluorocarbon resin is used as a binder. Thus, adding cobalt or a cobalt compound to nickel hydroxide is effective in improving the utilization rate of nickel hydroxide.
発明が解決しようとする問題点
しかし、焼結式のように微孔性で導電性の孔内に接触し
て活物質が充てんできる場合と異なり、非焼結式では多
孔性導電体との接触は、十分でないことが原因で、活物
質の利用率は、焼結式より劣る。ところが、利用率の向
上のためにコバルトとして金属コバルト粉末を用い、し
かも、水酸化ニッケルと混合後、これを水で濡らして放
置したり、また、このようにして得られた電池を放置し
ておくことなどにより、コバルトが酸化されるとともに
活物質粒子内に拡散し、活物質の利用率を向上させるこ
とが明らかになっている。しかし、これらの処理には、
長時間を要し、時間の短縮が望まれていた。Problems to be Solved by the Invention However, unlike the sintered method, which allows the active material to contact and fill the inside of microporous conductive pores, the non-sintered method does not allow contact with the porous conductor. is not sufficient, and the utilization rate of the active material is inferior to that of the sintered method. However, in order to improve the utilization rate, metal cobalt powder is used as the cobalt, and after mixing it with nickel hydroxide, it is wetted with water and left to stand, and the batteries obtained in this way are not left to stand. It has been revealed that by keeping the cobalt exposed to heat, cobalt is oxidized and diffused into the active material particles, improving the utilization rate of the active material. However, these processes include
It took a long time, and it was desired to shorten the time.
本発明は上記従来技術に鑑み、より短時間の放置で活物
質の利用率の向上をはかる水素吸蔵電極の製造法を提供
することを目的とする。In view of the above-mentioned prior art, an object of the present invention is to provide a method for manufacturing a hydrogen storage electrode that improves the utilization rate of an active material by leaving it for a shorter time.
問題点を解決するための手段
本発明は、水酸化ニッケルにコバルトを含む電極材料を
多孔性導電体に充填したニッケル極において、苛性アル
カリ水溶液で処理し、これを空気中で放置し、その後は
水洗、乾燥することを特徴とする電池用ニッケル極の製
造法である。Means for Solving the Problems The present invention provides a nickel electrode in which a porous conductor is filled with an electrode material containing cobalt in nickel hydroxide, which is treated with a caustic alkaline aqueous solution, left in the air, and then This is a method for manufacturing nickel electrodes for batteries, which is characterized by washing with water and drying.
作用
電極材料を多孔性導電体に充填後、苛性アルカリ溶液で
濡らした後に空気中で放置することを特徴としているの
で、金属コバルトが酸化されつつ活物質中に拡散し、短
時間の放置で活物質の利用率の向上に大きな効果を発揮
する。This method is characterized by filling the porous conductor with the working electrode material and then leaving it in the air after wetting it with a caustic alkaline solution, so that the metal cobalt is oxidized and diffused into the active material, and becomes active after being left for a short time. It has a great effect on improving the utilization rate of materials.
実施例 発泡式ニッケル極を例にして実施例を詳述する。Example Examples will be described in detail using a foamed nickel electrode as an example.
多孔度９６％、平均孔径１５０μｍ、厚さ１゜２ｍａ＋
の公知の発泡状ニッケル基体に、水酸化ニッケル粉末８
５部（重量比）、カーボニルコバルト７部、カーボニル
ニッケル８部を加えて十分混合し、これに２％のカルボ
キシメチルセルロース水溶液でペースト状にして充てん
する。これを半乾燥状態で加圧して厚さを０．７５ｍｍ
に調整した。Porosity 96%, average pore diameter 150μm, thickness 1゜2ma+
Nickel hydroxide powder 8 is added to the known foamed nickel base of
5 parts (by weight), 7 parts of carbonyl cobalt, and 8 parts of carbonyl nickel were added and thoroughly mixed, and the mixture was made into a paste and filled with a 2% aqueous carboxymethyl cellulose solution. Press this in a semi-dry state to a thickness of 0.75mm.
Adjusted to.
その後に３％フッソ樹脂ディスパージョンを含浸し、９
０℃で２時間乾燥した。After that, impregnated with 3% fluorine resin dispersion,
It was dried at 0°C for 2 hours.
このようにして得られた発泡式ニッケル極を、市販の中
性界面活性剤０．１％を含む水に濡らした後、１０％の
苛性カリ水溶液中に２分間ｆ！１漬し、ついで空気中に
取り出し、２時間放置した。これをＡ２とし、４時間放
置をＡ４．６時間放置を八６．１０時間放置をＡＩＯと
した。それぞれは、その後水洗し、９０℃で２時間乾燥
した。The foamed nickel electrode thus obtained was wetted with water containing 0.1% of a commercially available neutral surfactant, and then immersed in a 10% caustic potassium aqueous solution for 2 minutes. It was soaked for 1 hour, then taken out into the air and left for 2 hours. This was designated as A2, and the time left for 4 hours was designated as A4, the time left for 6 hours was designated as 86, and the time left for 10 hours was designated as AIO. Each was then washed with water and dried at 90°C for 2 hours.
つぎに、比較のためにこのような処理をまったく行なわ
ずに用いた電極をＢＯとした。Next, for comparison, an electrode used without any such treatment was designated as BO.
さらに、水で濡らした後に、空気中に放置した電極につ
いて４時間空気中で放置した電極なＣ４゜さらに４時間
放置し合計８時間放置したものを０８、これでほぼ完全
に乾燥したものでふたたび水で濡らして４時間９舎計１
２時間放置したものをＣ１２，さらにそのまま８時間放
置し、合計２０時間をＣ２０，ふたたび水で濡らして４
時間放置し、合計２４時間をＣ２４，さらに４時間放置
し、合計２８時間なＣ２８として加えた。Furthermore, after wetting the electrode with water, the electrode was left in the air for 4 hours.The electrode was left in the air for 4 hours. Wet it with water for 4 hours 9 buildings total 1
After leaving it for 2 hours, I put it on C12, left it there for another 8 hours, and put it on C20 for a total of 20 hours.I wet it again with water and put it on 4.
C24 was added for a total of 24 hours, and C28 was added for an additional 4 hours for a total of 28 hours.
これら各電極を用い、公知のペースト式カドミウム極、
ボリアミド不織布セパレータとともに５ｕｂＣ系の密閉
形電池を構成した。発泡状ニッケル極は、いずれも幅３
．３ｃｍ、長さ１５．５０ｍとした。計算上の容量は２
．０７Ａｈである。なお、電解液としては、比重１．２
０の苛性カリ水溶液に水酸化リチウムを２０ｇ／ｌ溶解
して用いた。Using each of these electrodes, a known paste-type cadmium electrode,
A 5ubC type sealed battery was constructed together with a polyamide nonwoven fabric separator. All foamed nickel electrodes have a width of 3
．． The length was 3 cm and the length was 15.50 m. The calculated capacity is 2
．． It is 07Ah. Note that the electrolyte has a specific gravity of 1.2.
Lithium hydroxide was dissolved at 20 g/l in an aqueous solution of potassium hydroxide.
各電池は、いずれも２５℃のもと０．ＩＣ−１３時間充
電、０．２Ｃ−０，８Ｖまでの放電の条件で、充放電を
繰り返した。各サイクルにおける電池の容量を表に示す
。Each battery was tested at 0.00% at 25°C. Charging and discharging were repeated under the conditions of IC-13 hours of charging and discharging to 0.2C-0.8V. The capacity of the battery in each cycle is shown in the table.
この表より明らかなように、本願の電池Ａでは、すでに
２時間の放置で利用率の向上に大きな効果があり、６時
間で十分である。それに対して処理を行なわない電池Ｂ
ではサイクルとともに若干容量は増加するが、最高でも
約８７％であった。最後にやはり比較の水による処理の
場合は、長時間を要し、２４時間以上の放置で本願と同
じ効果が得られることが明らかである。As is clear from this table, in Battery A of the present application, leaving it for 2 hours has a great effect on improving the utilization rate, and 6 hours is sufficient. Battery B that does not undergo any processing
Although the capacity increased slightly with each cycle, the maximum capacity was about 87%. Finally, it is clear that the comparative treatment with water requires a long time, and that the same effect as in the present invention can be obtained by leaving it for 24 hours or more.
表 各電池のサイクル数と放電容ｆｆ１（Ａｈ）なお、
ニッケル極には、結着剤としてフッ素樹脂が用いられて
いて、このように、苛性アルカリ水溶液に触れさせても
内部まで十分苛性アルカリが浸透しないので、あらかじ
め水、好ましくは界面活性剤を加えた水に触れさせ、つ
いで苛性アルカリ水溶液を加え、この後に空気中にさら
して放置する方式がよい。Table Number of cycles and discharge capacity ff1 (Ah) of each battery.
Fluororesin is used as a binder in the nickel electrode, and even if it comes into contact with a caustic alkaline aqueous solution, the caustic alkali does not penetrate sufficiently into the inside, so water, preferably a surfactant, is added in advance. A good method is to expose it to water, then add an aqueous caustic alkali solution, and then leave it exposed to air.
発明の効果
本発明においては、金属コバルトが酸化されつつ活物質
中に拡散し、短時間の放置で活物質の利用率の向上に大
きな効果を発揮する。Effects of the Invention In the present invention, metal cobalt diffuses into the active material while being oxidized, and even if left for a short time, it exhibits a great effect in improving the utilization rate of the active material.
Claims (3)
性導電体に充填後、苛性アルカリ溶液で濡らした後に空
気中で放置することを特徴とする電池用ニッケル電極の
製造法。(1) A method for producing a nickel electrode for a battery, which comprises filling a porous conductor with an electrode material containing cobalt in nickel hydroxide, moistening it with a caustic alkaline solution, and then leaving it in the air.
含む電極材料を多孔性導電体に活物質を充てん後、水で
濡らした後にさらに苛性アルカリ溶液で濡らした後に空
気中で放置することを特徴とする特許請求の範囲第１項
記載の電池用ニッケル電極の製造法。(2) A porous conductor made of an electrode material containing nickel hydroxide, cobalt, and fluorocarbon resin is filled with an active material, wetted with water, further wetted with a caustic alkaline solution, and then left in the air. A method for manufacturing a nickel electrode for a battery according to claim 1.
の範囲第２項記載の電池用ニッケル電極の製造法。(3) The method for producing a nickel electrode for a battery according to claim 2, wherein the water contains a surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100353A JPS63266766A (en) | 1987-04-23 | 1987-04-23 | Manufacture of nickel electrode for battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100353A JPS63266766A (en) | 1987-04-23 | 1987-04-23 | Manufacture of nickel electrode for battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63266766A true JPS63266766A (en) | 1988-11-02 |
Family
ID=14271736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62100353A Pending JPS63266766A (en) | 1987-04-23 | 1987-04-23 | Manufacture of nickel electrode for battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63266766A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100456534C (en) * | 2007-06-21 | 2009-01-28 | 江苏奇能电池有限公司 | Making method of alkalescent accumulator anode board |
| WO2010087992A1 (en) * | 2009-01-27 | 2010-08-05 | G4 Synergetics, Inc. | Electrode folds for energy storage devices |
-
1987
- 1987-04-23 JP JP62100353A patent/JPS63266766A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100456534C (en) * | 2007-06-21 | 2009-01-28 | 江苏奇能电池有限公司 | Making method of alkalescent accumulator anode board |
| WO2010087992A1 (en) * | 2009-01-27 | 2010-08-05 | G4 Synergetics, Inc. | Electrode folds for energy storage devices |
| JP2012516542A (en) * | 2009-01-27 | 2012-07-19 | ジー４ シナジェティクス， インコーポレイテッド | Electrode folds for energy storage devices |
| US8859132B2 (en) | 2009-01-27 | 2014-10-14 | G4 Synergetics, Inc. | Variable volume containment for energy storage devices |
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