JPH0494058A - Non-sintering type nickel positive electrode plate for alkaline storage battery - Google Patents
Non-sintering type nickel positive electrode plate for alkaline storage batteryInfo
- Publication number
- JPH0494058A JPH0494058A JP2212014A JP21201490A JPH0494058A JP H0494058 A JPH0494058 A JP H0494058A JP 2212014 A JP2212014 A JP 2212014A JP 21201490 A JP21201490 A JP 21201490A JP H0494058 A JPH0494058 A JP H0494058A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- active material
- electrode plate
- powder
- surface layer
- 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 30
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000011149 active material Substances 0.000 claims abstract description 20
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 18
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 14
- 239000002344 surface layer Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 4
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical group [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims description 15
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000609 methyl cellulose Polymers 0.000 abstract description 2
- 239000001923 methylcellulose Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- OEMUKJZHMHTYSL-UHFFFAOYSA-N [Na].OCl=O Chemical compound [Na].OCl=O OEMUKJZHMHTYSL-UHFFFAOYSA-N 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 235000010981 methylcellulose Nutrition 0.000 abstract 1
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011800 void material Substances 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】
（イ）産業上の利用分野
本発明は、ニッケルーカドミウム蓄電池、ニッケルー亜
鉛蓄電池あるいはニッケルー水素蓄電池などのアルカリ
蓄電池に用いられる非焼結式ニッケル正極板に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a non-sintered nickel positive electrode plate used in alkaline storage batteries such as nickel-cadmium storage batteries, nickel-zinc storage batteries, and nickel-hydrogen storage batteries.
（ロ）従来の技術
従来、ニッケルーカドミウム蓄電池などのニッケル正極
板の代表的なものは焼結式により得られたものであった
。この焼結式極板の場合、活物質保持体としての焼結基
板の孔径が小さいので、活物質を粉末状態で直接充填す
ることができず、活物質塩を含浸し、これを活物質に転
化するなどの偵雑な工程を要した。(b) Prior Art Conventionally, typical nickel positive electrode plates for nickel-cadmium storage batteries and the like have been obtained by a sintering method. In the case of this sintered electrode plate, since the pore size of the sintered substrate that serves as the active material holder is small, it is not possible to directly fill the active material in powder form. It required a complicated process such as conversion.
最近、水酸化ニッケルを主とするペースト状の活物質混
合物を約９５％程度の多孔度を有するスポンジ状の金属
二・ノケル基板に直接充填するという非焼結式ニッケル
正極板が提案されている。Recently, a non-sintered nickel positive electrode plate has been proposed in which a paste-like active material mixture mainly composed of nickel hydroxide is directly filled into a sponge-like metal Ni-Nokel substrate with a porosity of about 95%. .
この非焼結式正極板は、従来の焼結式正極板に比べ、製
造が非常に簡単であること、また高容量化、軽量化に適
し研究が進められている。This non-sintered positive electrode plate is much easier to manufacture than conventional sintered positive electrode plates, and research is underway to make it suitable for higher capacity and lighter weight.
特公昭５７−５３４４号公報では、非焼結式ニッケル正
極板の利用率を向上させるため、コバルト化合物を添加
する方法が提案されている。添加３れたコバルト化合物
は、１回目の充電初期に酸化を受け、導電性の高いオキ
シ水酸化コバルトに変化し、その結果として、水酸化ニ
ッケル間の導電性が向上し、利用率の向上をもたらすの
である。Japanese Patent Publication No. 57-5344 proposes a method of adding a cobalt compound in order to improve the utilization rate of a non-sintered nickel positive electrode plate. The added cobalt compound undergoes oxidation at the beginning of the first charge and changes to highly conductive cobalt oxyhydroxide. As a result, the conductivity between nickel hydroxides improves, improving the utilization rate. It brings.
しかし、活物質中に添加されたコバルト化合０を充電時
に完全にオキシ水酸化コバルトへ酸化することは困難で
ある。このため、コ１＜ルト化合物を添加し導電性が向
上する効果を充分に引き出すことができない。However, it is difficult to completely oxidize the cobalt compound 0 added to the active material into cobalt oxyhydroxide during charging. For this reason, it is not possible to fully bring out the effect of improving conductivity by adding the COL compound.
これに対して、特開昭６０−２５４５６４号公報では、
活物質中にオキシ水酸化工・ｌケル粉末を添加すること
により、コバルト化合物の酸化を助長する方法が提案さ
れている。On the other hand, in Japanese Patent Application Laid-Open No. 60-254564,
A method has been proposed in which oxidation of cobalt compounds is promoted by adding oxyhydroxide powder to the active material.
しかしながら、活物質中にオキシ水酸化工・ｌケル粉末
を添加する場合、コバルト化合物はオキシ水酸化ニッケ
ル粉末の近傍でオキシ水酸化コノ（ルトに変化するため
、極板中にオキシ水酸化ニッケルが不均一に存′在する
と、オキシ水酸化コノ（ルトも不均一に存在することに
なり、極板内に均一に導電性を向上させることができな
い。However, when adding oxyhydroxide powder to the active material, the cobalt compound changes to oxyhydroxide cobalt near the nickel oxyhydroxide powder, so nickel oxyhydroxide is added to the electrode plate. If it exists unevenly, the oxyhydroxide metal will also exist unevenly, making it impossible to improve conductivity uniformly within the electrode plate.
尚、コバルト化合物を酸化してオキシ水酸化コバルトと
するためには、オキシ水酸化コノくルトが３価なのでコ
バルト化合物は２価以下としなければならない。ここで
、２価以下のコバルト化合物としては、金属コバルト、
水酸化コノくルトが挙げられる。In addition, in order to oxidize a cobalt compound to form cobalt oxyhydroxide, the cobalt compound must be divalent or less, since the cobalt oxyhydroxide is trivalent. Here, the cobalt compounds having a valence of 2 or less include metallic cobalt,
Examples include hydroxylated conolt.
（ハ）発明が解決しようとする課題
本発明は、上述の如き問題点を解決し、極板内に均一に
導電性を向上させ、以って利用率の高いニッケル正極板
を得ようとするものである。(c) Problems to be Solved by the Invention The present invention attempts to solve the above-mentioned problems, improve conductivity uniformly within the electrode plate, and thereby obtain a nickel positive electrode plate with a high utilization rate. It is something.
（ニ）課題を解決するための手段
本発明は、表面層がオキシ水酸化ニッケルである水酸化
ニッケル粉末と、２価以下のコバルト化合物粉末とを含
む混合物を活物質保持体に担持させた非焼結式ニッケル
正極板にある。(d) Means for Solving the Problems The present invention provides a non-woven material in which an active material support is supported with a mixture containing nickel hydroxide powder whose surface layer is nickel oxyhydroxide and powder of a cobalt compound having a valence of 2 or less. Located on a sintered nickel positive electrode plate.
（ホ）作 用
活物質中に添加されたコバルト化合物は、オキシ水酸化
ニッケルの存在により、アルカリ水溶液中にて、以下の
ような反応でオキシ水酸化コバルトに変化する。(E) Function The cobalt compound added to the active material changes into cobalt oxyhydroxide in the following reaction in an alkaline aqueous solution due to the presence of nickel oxyhydroxide.
１） Ｃｏ（ＯＨ）＝→Ｃｏ錯イオン２） Ｃｏ錯
イオン＋ Ｎ １ｏＯＨ−＋ Ｃｏ０ＯＨ＋＼１（ＯＨ
）。1) Co(OH)=→Co complex ion 2) Co complex ion + N 1oOH−+ Co0OH+\1(OH
).
つまり、オキシ水酸化コバルトの生成は、オキシ水酸化
ニッケルの近傍にて生じるのである。In other words, cobalt oxyhydroxide is generated near nickel oxyhydroxide.
本発明によれば、表面層がオキシ水酸化ニッケルである
水酸化ニッケル粉末を用いているので、オキシ水酸化工
・メチル表面層とコバルト化合物とが反応し、水酸化ニ
ッケル粉末を均一に被覆するようにオキシ水酸化コバル
トが生成する。これにより、極板内に均一にオキシ水酸
化コバルトが存在し、導電性が良くなり利用率が向上す
る。According to the present invention, since the nickel hydroxide powder whose surface layer is nickel oxyhydroxide is used, the oxyhydroxide/methyl surface layer and the cobalt compound react to uniformly coat the nickel hydroxide powder. Cobalt oxyhydroxide is produced. As a result, cobalt oxyhydroxide exists uniformly within the electrode plate, improving conductivity and improving utilization.
（へ）実施例
粒径５ｕｍの球状水酸化ニッケルを亜塩素酸ナトノウム
２ ｗｉｚ、水酸化ナトリウム２０ｗｔＺ水溶液に５分
間浸漬し、水洗、乾燥して表面層がオキシ水酸化ニッケ
ルである水酸化ニッケルを作製した。(F) Example Spherical nickel hydroxide with a particle size of 5 um is immersed in an aqueous solution of sodium chlorite 2 wiz and sodium hydroxide 20 wtZ for 5 minutes, washed with water, and dried to form nickel hydroxide whose surface layer is nickel oxyhydroxide. Created.
オキシ水酸化ニッケルの量は、水酸化ニッケルに対して
約５ ｗｔＺである。The amount of nickel oxyhydroxide is about 5 wtZ relative to nickel hydroxide.
この表面層がオキシ水酸化ニッケルである水酸化ニッケ
ル粉末９５ｗｔＺと、水酸化コバルト粉末５ｗＨからな
る活物質粉末に、メチルセルロース０ 、５ ｗｔ！水
溶液を加え混合し活物質スラリーを作製した。この活物
質スラリーを発泡ニッケル基体に充填し乾燥後、圧延す
ることにより活物質密度２ 、５ ｇ／ｃｃ−λ′ｏｉ
ｄの本発明極板を得た。This active material powder consists of 95wtZ of nickel hydroxide powder whose surface layer is nickel oxyhydroxide and 5wH of cobalt hydroxide powder, and 0.5wt! of methylcellulose! An aqueous solution was added and mixed to prepare an active material slurry. This active material slurry is filled into a foamed nickel base, dried, and rolled to give an active material density of 2.5 g/cc-λ'oi.
The electrode plate of the present invention of d was obtained.
一方、粒径５μｍの球状水酸化ニッケルを亜塩素酸ナト
リウム２■【２水溶液に１時間浸漬し、完全にオキシ水
酸化ニッケルに変化させた後、水洗、乾燥してオキシ水
酸化ニッケル粉末を作製した。On the other hand, spherical nickel hydroxide with a particle size of 5 μm was immersed in an aqueous sodium chlorite solution for 1 hour to completely transform it into nickel oxyhydroxide, then washed with water and dried to produce nickel oxyhydroxide powder. did.
このオキシ水酸化ニッケル粉末５ｗｔχと、水酸化ニッ
ケル粉末９０ ｗｔＺ及び水酸化コバルト粉末５ ｗｔ
Ｚからなる活物質粉末を用い、上記と同様にして活物質
密度２ 、５ ｇ／ｃｃ−ｖｏｉｄの比較極板を得た。This nickel oxyhydroxide powder 5wtχ, nickel hydroxide powder 90wtZ, and cobalt hydroxide powder 5wt
A comparative electrode plate having an active material density of 2.5 g/cc-void was obtained in the same manner as above using an active material powder made of Z.
この本発明極板及び比較極板各々１枚と焼結式負極板２
枚とをセパレータを介し、組み合わせた極板群をナイロ
ン袋に入れ、これを両側より構成圧を加え、ＫＯＨ−＼
ａｏｌｌ−ＬｉＯＨの三成分からなる電解液を注液し、
２種類の簡易セルを作製した。One each of the present invention electrode plate and comparative electrode plate, and two sintered negative electrode plates.
Place the combined electrode plate group with a separator in a nylon bag, apply pressure from both sides, and then
Inject an electrolytic solution consisting of three components of aoll-LiOH,
Two types of simple cells were fabricated.
この簡易セルを用い、０．ＩＣの電流で理論容量に対し
て１６０％まで充電を行い、電圧が０゜８■に達するま
で０．３Ｃの電流で放電し、利用率を測定した結果を図
に示す。図より本発明極板を用いた簡易セルａは、比較
極板を用いた簡易セルｂに比べ高い利用率を示す。Using this simple cell, 0. The figure shows the results of charging the IC to 160% of its theoretical capacity with the current of the IC, discharging with a current of 0.3C until the voltage reaches 0°8, and measuring the utilization rate. From the figure, the simple cell a using the electrode plate of the present invention shows a higher utilization rate than the simple cell b using the comparative electrode plate.
（ト）発明の効果
上述した如く、本発明による非焼結式ニッケル正極板は
、表面層がオキシ水酸化ニッケルである水酸化ニッケル
粉末と、２価以下のコバルト化合物粉末とを含むもので
あり、オキシ水酸化ニッケルとの反応により水酸化ニッ
ケル粉末の表面層が均一にオキシ水酸化コバルトにて被
覆され、極板内の導電性が向上して高い利用率を得るこ
とができるものでありその工業的価値は極めて大である
。(g) Effects of the Invention As described above, the non-sintered nickel positive electrode plate of the present invention includes nickel hydroxide powder whose surface layer is nickel oxyhydroxide and cobalt compound powder with a valence of less than 2. Through the reaction with nickel oxyhydroxide, the surface layer of the nickel hydroxide powder is uniformly coated with cobalt oxyhydroxide, improving the conductivity within the electrode plate and achieving a high utilization rate. The industrial value is extremely large.
図は、本発明極板を用いた簡易セルａと、比較極板を用
いた簡易セルｂのサイクルに伴う利用率の変化を示す図
である。The figure is a diagram showing changes in the utilization rate with the cycle of a simple cell a using the electrode plate of the present invention and a simple cell b using a comparative electrode plate.
Claims (1)
ケル粉末と、２価以下のコバルト化合物粉末とを含む混
合物を活物質保持体に担持させたことを特徴とするアル
カリ蓄電池用非焼結式ニッケル正極板。(1) A non-sintered type for alkaline storage batteries characterized by having an active material holder support a mixture containing nickel hydroxide powder whose surface layer is nickel oxyhydroxide and cobalt compound powder with a valence of 2 or less. Nickel positive electrode plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2212014A JP2889669B2 (en) | 1990-08-09 | 1990-08-09 | Non-sintered nickel positive electrode plate for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2212014A JP2889669B2 (en) | 1990-08-09 | 1990-08-09 | Non-sintered nickel positive electrode plate for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0494058A true JPH0494058A (en) | 1992-03-26 |
| JP2889669B2 JP2889669B2 (en) | 1999-05-10 |
Family
ID=16615455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2212014A Expired - Fee Related JP2889669B2 (en) | 1990-08-09 | 1990-08-09 | Non-sintered nickel positive electrode plate for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2889669B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05144438A (en) * | 1991-11-25 | 1993-06-11 | Shin Kobe Electric Mach Co Ltd | Electrode for alkaline storage battery |
| US5356732A (en) * | 1992-05-29 | 1994-10-18 | Sanyo Electric Co., Ltd. | Alkaline storage cell activation method |
| US5405714A (en) * | 1992-07-31 | 1995-04-11 | Sanyo Electric Co., Ltd. | Method for activating an alkaline storage cell employing a non-sintered type nickel positive electrode |
| US6013390A (en) * | 1997-04-01 | 2000-01-11 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
| US6066416A (en) * | 1995-11-22 | 2000-05-23 | Matsushita Electric Industrial Co., Ltd. | Nickel hydroxide positive electrode active material having a surface layer containing a solid solution nickel hydroxide with manganese incorporated therein |
| US6261720B1 (en) * | 1996-09-20 | 2001-07-17 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for alkaline storage batteries |
| JP2012169281A (en) * | 2001-06-29 | 2012-09-06 | Ovonic Battery Co Inc | Hydrogen storage battery, positive nickel electrode, positive electrode active material, and method for manufacturing the same |
-
1990
- 1990-08-09 JP JP2212014A patent/JP2889669B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05144438A (en) * | 1991-11-25 | 1993-06-11 | Shin Kobe Electric Mach Co Ltd | Electrode for alkaline storage battery |
| US5356732A (en) * | 1992-05-29 | 1994-10-18 | Sanyo Electric Co., Ltd. | Alkaline storage cell activation method |
| US5405714A (en) * | 1992-07-31 | 1995-04-11 | Sanyo Electric Co., Ltd. | Method for activating an alkaline storage cell employing a non-sintered type nickel positive electrode |
| US6066416A (en) * | 1995-11-22 | 2000-05-23 | Matsushita Electric Industrial Co., Ltd. | Nickel hydroxide positive electrode active material having a surface layer containing a solid solution nickel hydroxide with manganese incorporated therein |
| US6261720B1 (en) * | 1996-09-20 | 2001-07-17 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for alkaline storage batteries |
| US6013390A (en) * | 1997-04-01 | 2000-01-11 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
| JP2012169281A (en) * | 2001-06-29 | 2012-09-06 | Ovonic Battery Co Inc | Hydrogen storage battery, positive nickel electrode, positive electrode active material, and method for manufacturing the same |
| JP2015072912A (en) * | 2001-06-29 | 2015-04-16 | オヴォニック バッテリー カンパニー インコーポレイテッド | Positive electrode material for hydrogen storage battery, and positive electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2889669B2 (en) | 1999-05-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |