JPH04129171A - Manufacture of nickel-hydrogen storage battery - Google Patents
Manufacture of nickel-hydrogen storage batteryInfo
- Publication number
- JPH04129171A JPH04129171A JP2253371A JP25337190A JPH04129171A JP H04129171 A JPH04129171 A JP H04129171A JP 2253371 A JP2253371 A JP 2253371A JP 25337190 A JP25337190 A JP 25337190A JP H04129171 A JPH04129171 A JP H04129171A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- active material
- paste
- hydroxide
- storage battery
- 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
- 238000003860 storage Methods 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 title claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011149 active material Substances 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-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 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 229910052987 metal hydride Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 abstract description 3
- 230000005484 gravity Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000002093 peripheral effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 241001024304 Mino Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 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)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はニッケル水素蓄電池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 nickel-metal hydride storage battery.
近年、ポータプルエレクトロニクス機器などの軽量化が
急速に進む中でその電源として二・７ケル水素蓄電池が
注目され、この電池の高エネルギー密度化が要望されて
いる。In recent years, with the rapid progress in reducing the weight of portable electronic devices and the like, 2.7 Kel hydrogen storage batteries have attracted attention as a power source for such devices, and there is a demand for higher energy density of these batteries.
この電池のニッケル極は従来焼結式極板と称される、ニ
ッケル粉末を穿孔鋼板等に焼結した多孔性基板に水酸化
ニッケルを主成分とした活物質を充填したものが用いら
れてきた。この方式の極板は、活物質充填工程が非常に
煩雑であり、生産コストが高くなる。The nickel electrode of this battery has traditionally been a sintered plate, which is a porous substrate made by sintering nickel powder onto a perforated steel plate, etc., and filling it with an active material mainly composed of nickel hydroxide. . In this type of electrode plate, the active material filling process is very complicated and the production cost is high.
しかも多孔性基板の多孔度が８０％程度に限定されるた
め、活物質の充填密度が低くエネルギー密度４００ｍＡ
ｈ／ｃｃ程度の極板しか得られない。このためニッケル
水素蓄電池の特徴である高エネルギー密度をさらに高め
るには不通であった。Moreover, since the porosity of the porous substrate is limited to about 80%, the packing density of the active material is low and the energy density is 400 mA.
Only a plate of about h/cc can be obtained. For this reason, it was impossible to further increase the high energy density that characterizes nickel-metal hydride storage batteries.
この電池のニッケル極には、この他に耐アルカリ性高多
孔度基体に活物質である水酸化ニッケル粉末と金属コバ
ルトあるいは酸化コバルト粉末を混合し、ＣＭＣ溶液で
ペースト状とし、前記基体に充填するペースト式極板が
ある。ペースト式ニッケル極は未化成のまま組込み、注
液後２４時間以上のエージング工程を経て、コバルト添
加側をＨＣｏＯ□−一β−Ｃｏ （ＯＨ） ｚの反応に
より溶解−再析出させた。その後初充電によりβ−Ｃｏ
（ＯＨ’）２−β−Ｃｏ００Ｈの反応乙こより導電率の
高いオキシ水酸化コバルトに変化させる。In addition, the nickel electrode of this battery is made by mixing nickel hydroxide powder, which is an active material, with metallic cobalt or cobalt oxide powder on an alkali-resistant highly porous substrate, making it into a paste form with a CMC solution, and filling the substrate with a paste. There is a type plate. The paste-type nickel electrode was assembled in an unformed state, and after injection, an aging process was performed for 24 hours or more, and the cobalt-added side was dissolved and reprecipitated by a reaction of HCoO□--β-Co(OH)z. After that, β-Co becomes
The reaction of (OH')2-β-Co00H changes it into cobalt oxyhydroxide, which has a high electrical conductivity.
これによって集電体と水酸化ニッケル粒子間の電子の流
れをスムーズにし、活物質利用率を増大させるものであ
る。しかしこの方法ではエージングに時間を要し、生産
性が悪い。又、添加物のＣｏｏは空気中で放置すると酸
化によりＣｏｙｏ４となり安定した電池性能が得られな
いという問題がある。This smoothes the flow of electrons between the current collector and the nickel hydroxide particles, increasing the active material utilization rate. However, this method requires time for aging and is poor in productivity. Further, if the additive Coo is left in the air, it oxidizes and becomes Coyo4, making it impossible to obtain stable battery performance.
発明の目的
本発明は上記従来の問題点に鑑みなされたものであり、
高性能で且つ生産性の高いニッケル水素蓄電池を提供す
ることを目的とするものである。Purpose of the Invention The present invention has been made in view of the above-mentioned conventional problems.
The purpose is to provide a nickel-metal hydride storage battery with high performance and high productivity.
発明の構成
本発明は上記目的を達成するべく、
水酸化ニッケルを主成分とする活物質に一酸化コハルト
をアルカリ電解液中で混合し水酸化ニッケル上にコバル
ト化合物を被覆させた後、活物質を酸化剤により酸化し
、オキシ水酸化コバルトが被覆した水酸化ニッケル活物
質を充填したニッケル極板を形成し、水素極と絹込んだ
ことを特徴とするニッケル水素蓄電池の製造法である。Structure of the Invention In order to achieve the above-mentioned object, the present invention mixes cohalt monoxide with an active material mainly composed of nickel hydroxide in an alkaline electrolyte, coats the nickel hydroxide with a cobalt compound, and then mixes the active material with cobalt monoxide. is oxidized with an oxidizing agent to form a nickel electrode plate filled with a nickel hydroxide active material coated with cobalt oxyhydroxide, and then intercalated with a hydrogen electrode.
尚、酸化剤がＫｚＳｚＯｅ、ＮａｚＳｚＯＩ＋、（ＮＨ
４）ｚｓｚｏａ、１（２０□である前記のニッケル水素
蓄電池の製造法である。In addition, if the oxidizing agent is KzSzOe, NazSzOI+, (NH
4) A method for manufacturing the above-mentioned nickel-metal hydride storage battery with zszoa, 1 (20□).
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 using one example.
水酸化カドミウムを５ｗｔ％含有する球状水酸化ニッケ
ルに粒径１μｍ、表面積７０ｎ（／ｇの一酸化コバルト
を重量比９５：５の割合で混合した。この混合活物質を
比重１．３５の水酸化カリウムを主体とする水溶液に入
れ充分に攪拌した。Spherical nickel hydroxide containing 5 wt% cadmium hydroxide was mixed with cobalt monoxide with a particle size of 1 μm and a surface area of 70 n (/g) at a weight ratio of 95:5.This mixed active material was hydrated with a specific gravity of 1.35. The mixture was added to an aqueous solution mainly containing potassium and thoroughly stirred.
次にＫｚＳｚＯ＋＋を一酸化コハルトのモル数以上で且
つ酸素ガスが発生するまで加えた。この混合活物質を濾
−し、水洗・乾燥した。この活物質をＣＭＣ溶液でペー
スト状とし、ニッケル繊維多孔体に充填した。その後８
０°Ｃで１時間乾燥した後プレスし、表面にテフロンコ
ーティングを行い本発明に用いるニッケル極板を得た。Next, KzSzO++ was added in an amount equal to or more than the number of moles of cohalt monoxide and until oxygen gas was generated. This mixed active material was filtered, washed with water, and dried. This active material was made into a paste with a CMC solution and filled into a nickel fiber porous body. then 8
After drying at 0°C for 1 hour, it was pressed, and the surface was coated with Teflon to obtain a nickel electrode plate used in the present invention.
このニッケル極板とＭｎ＋ Ｎｉａ、 ｚ Ａ １ｏ、
＊ Ｃｏｏ、 ｓ（Ｍｍ＝ミノシュメタル：希土類元
素の混合物）の水素吸蔵合金からなるペースト式の水素
吸蔵極板、ポリプロピレン不織布セパレータで発電要素
を構成し、比重１．２６の水酸化カリウムを主体とする
電解液を注入し、本発明の電池を得た。This nickel electrode plate and Mn+ Nia, z A 1o,
* The power generating element is composed of a paste-type hydrogen storage electrode plate made of a hydrogen storage alloy of Coo, s (Mm = Minos metal: a mixture of rare earth elements), a polypropylene nonwoven fabric separator, and the main component is potassium hydroxide with a specific gravity of 1.26. An electrolytic solution was injected to obtain a battery of the present invention.
比較のために、水酸化カドミウムを５ｗｔ％含有する球
状水酸化ニッケルに粒径１μｍ、表面積７０ＩＴｆ／ｇ
の一酸化コバルトを重量比９５：５の割合で混合し、Ｃ
ＭＣ溶液でペースト状として、従来のニッケル極板を得
た。（酸化剤で酸化しない活物質）この従来のニッケル
極板を用いて、未化成状態で前記と同様のニッケル水素
蓄電池を組立てた。For comparison, spherical nickel hydroxide containing 5 wt% cadmium hydroxide had a particle size of 1 μm and a surface area of 70 ITf/g.
Cobalt monoxide was mixed at a weight ratio of 95:5, and C
A conventional nickel electrode plate was obtained by making a paste with an MC solution. (Active material not oxidized by oxidizing agent) Using this conventional nickel electrode plate, a nickel-metal hydride storage battery similar to that described above was assembled in an unformed state.
これらの電池を用いて、充電々流３００ＩＩＡで１０．
５時間充電し、放電々流６００ｍＡで終止電圧ｔ、ｏｏ
ｖまで放電した。充放電サイクルを繰返した時の活物質
利用率との関係を第１図に示した。Using these batteries, the charge current is 300 IIA and the charge is 10.
After charging for 5 hours, the final voltage t,oo was reached at a discharge current of 600mA.
It was discharged to v. Figure 1 shows the relationship between the active material utilization rate and the repeated charge/discharge cycles.
本発明の電池はサイクル初期から活物質利用率が高くそ
の効果が顕著である。本発明の活物質は酸化処理により
Ｃｏｏがニッケル活物質表面にβ−Ｃｏ００Ｈが形成さ
れ完全な導電性ネットワークが形成されるためである。The battery of the present invention has a high active material utilization rate from the early stage of the cycle, and its effect is remarkable. This is because the active material of the present invention undergoes oxidation treatment to form β-Co00H on the surface of the nickel active material, thereby forming a complete conductive network.
上記実施例において、ＫｚＳｚＯｅの酸化剤について記
したが、ＮａｚＳｚＯＢ 、（ＮＨ４）２Ｓ２０８、Ｈ
，０，であっても同様の効果が得られた。In the above examples, the oxidizing agent for KzSzOe was described, but NazSzOB, (NH4)2S208, H
, 0, the same effect was obtained.
又、この活物質を空気中に保存した後、使用した電池も
前記と肉様の効果を得た。Furthermore, after storing this active material in the air, the battery used also obtained the same effect as described above.
前記実施例においては、集電体としてニッケル繊維多孔
体を用いたが、穿孔鋼板を加工したポケット式極板ある
いは、活物質をプレス成型して用いるプレス式極板に用
いた場合、従来品の活物質では活物質利用率が５０〜６
０％であるが、本発明の活物質を用いた場合、活物質利
用率が９０％であった。In the above example, a porous nickel fiber was used as the current collector, but when used in a pocket-type electrode plate made from a perforated steel plate or a press-type electrode plate in which the active material is press-molded, it is different from the conventional product. Active material utilization rate is 50-6
However, when the active material of the present invention was used, the active material utilization rate was 90%.
発明の効果
上述した如く、本発明は高性能で且つ生産性の高い二、
ケル水素蓄電池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 mentioned above, the present invention has two advantages: high performance and high productivity.
Since it can provide Kel hydrogen storage batteries, its industrial value is extremely large.
第１図は本発明の電池と従来品の電池の活物質利用率の
比較を示した図である。FIG. 1 is a diagram showing a comparison of the active material utilization rates of the battery of the present invention and a conventional battery.
Claims (2)
バルトを混合した活物質を酸化剤により酸化した後ニッ
ケル極板を形成し、水素極と組込んだことを特徴とする
ニッケル水素蓄電池の製造法。(1) A nickel-metal hydride storage battery characterized in that an active material consisting mainly of nickel hydroxide mixed with cobalt monoxide is oxidized with an oxidizing agent, and then a nickel electrode plate is formed and incorporated with a hydrogen electrode. manufacturing method.
＿８、（ＮＨ＿４）＿２Ｓ＿２Ｏ＿６、Ｈ＿２Ｏ＿２で
ある請求項１記載のニッケル水素蓄電池の製造法。(2) Oxidizing agent is K_2S_2O_8, Na_2S_2O
_8, (NH_4)_2S_2O_6, H_2O_2 The method for manufacturing a nickel-metal hydride storage battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2253371A JPH0824042B2 (en) | 1990-09-19 | 1990-09-19 | Nickel-metal hydride storage battery manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2253371A JPH0824042B2 (en) | 1990-09-19 | 1990-09-19 | Nickel-metal hydride storage battery manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04129171A true JPH04129171A (en) | 1992-04-30 |
| JPH0824042B2 JPH0824042B2 (en) | 1996-03-06 |
Family
ID=17250425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2253371A Expired - Lifetime JPH0824042B2 (en) | 1990-09-19 | 1990-09-19 | Nickel-metal hydride storage battery manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824042B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0571630A1 (en) * | 1991-10-21 | 1993-12-01 | Yuasa Corporation | Method for production of nickel plate and alkali storage battery |
-
1990
- 1990-09-19 JP JP2253371A patent/JPH0824042B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0571630A1 (en) * | 1991-10-21 | 1993-12-01 | Yuasa Corporation | Method for production of nickel plate and alkali storage battery |
| EP0571630A4 (en) * | 1991-10-21 | 1995-04-19 | Yuasa Battery Co Ltd | Method for production of nickel plate and alkali storage battery. |
| US5489314A (en) * | 1991-10-21 | 1996-02-06 | Yuasa Corporation | Manufacturing method of nickel plate and manufacturing method of alkaline battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0824042B2 (en) | 1996-03-06 |
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