JPH02207452A - Nickel electrode and alkaline storage battery using the electrode - Google Patents
Nickel electrode and alkaline storage battery using the electrodeInfo
- Publication number
- JPH02207452A JPH02207452A JP1028328A JP2832889A JPH02207452A JP H02207452 A JPH02207452 A JP H02207452A JP 1028328 A JP1028328 A JP 1028328A JP 2832889 A JP2832889 A JP 2832889A JP H02207452 A JPH02207452 A JP H02207452A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- active material
- nickel
- pore volume
- nickel hydroxide
- 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 27
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 14
- 239000011149 active material Substances 0.000 claims abstract description 19
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 14
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 208000001840 Dandruff Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 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
-
- 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)
- Secondary Cells (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、アルカリ蓄電池用ニッケル電極とこれを用い
たアルカリ蓄電池に関するものであるＯ
従来技術とその問題点
アルカリ蓄電池に用いられるニッケル電極として、ニッ
ケ〃粉末を穿孔鋼板に焼結した焼結式ニッケル電極があ
る。このものは、基板多孔度８０％が限界であり活物質
の充填量が少く、電極の二ネ〃ギー密度は４００ ｍＡ
Ｈ／ｃｃ程度のものしか得られない。近年のボータブ〜
工Ｖクトロ機器の軽社化に伴い、６００ ｍＡＨ／ｃｃ
程度の高容量電池が要求されている。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a nickel electrode for alkaline storage batteries and an alkaline storage battery using the same.Prior art and problems thereof There is a sintered nickel electrode made by sintering powder onto a perforated steel plate. In this case, the substrate porosity is limited to 80%, the filling amount of active material is small, and the electrode density is 400 mA.
Only about H/cc can be obtained. Recent boat tabs~
600 mAH/cc due to the change of industrial equipment
High capacity batteries are required.
これに対応するべく、集電体に多孔度の高い耐アルカリ
性金属繊維焼結体（多孔度９０〜９５％）を用い、水酸
化ニッケルを主体とするスラリー状の活物質を充填した
ニッケル電極が実用化されつつある。しかしこのものも
、エネルギー密度は５００ ｍＡｈ／ｃｃ、程度が限界
である。市場ニーズに対応するべ（、更なる高容量化電
池を目指すうえで、集電体基板の多孔度に限界がある。In order to cope with this, we have developed a nickel electrode that uses a highly porous alkali-resistant metal fiber sintered body (porosity 90-95%) as a current collector and is filled with a slurry-like active material mainly composed of nickel hydroxide. It is being put into practical use. However, the energy density of this device is also limited to about 500 mAh/cc. In order to meet market needs, there is a limit to the porosity of the current collector substrate in order to achieve even higher capacity batteries.
従って１水酸化ニツケρ粉末を高密度化する必要がある
。Therefore, it is necessary to increase the density of Nitsuke monohydroxide powder.
従来の水酸化ニッケル粉末に替り、内部細孔容積が少な
く高結晶性で高密度な新水酸化ニッケル粉末が開発され
ている。しかしこの高密度水酸化ニッケμを用い１スフ
リー状とし金属繊維集電体に充填しニッケ！電極とした
場合、電極表面から活物質が脱落し、電池の内部短絡を
生じるので問題であった。A new nickel hydroxide powder with low internal pore volume, high crystallinity, and high density has been developed to replace conventional nickel hydroxide powder. However, using this high-density nickel hydroxide μ, it was made into a fleece and filled into a metal fiber current collector, and nickel! When used as an electrode, the active material would fall off the electrode surface, causing an internal short circuit in the battery, which was a problem.
又、活物質の脱落防止として、電極をポリテトラフルオ
ロエチレンのディスパージ曽ン液に浸漬し１活物質粒子
層強度を補強する方法がある。しかし、ポリテトラフル
オロエチレンは強力な結着力と共に大きな９水性を有す
るため、電極表面での電解液の拡散が困難になり、電池
の内部抵抗を大きくする欠点がある。Furthermore, in order to prevent the active material from falling off, there is a method of reinforcing the strength of one active material particle layer by immersing the electrode in a polytetrafluoroethylene dispurge solution. However, since polytetrafluoroethylene has a strong binding force and a large aqueous property, it becomes difficult to diffuse the electrolyte on the electrode surface, resulting in a drawback of increasing the internal resistance of the battery.
発明の目的
本発明は、活物質の脱落を防止した、高容量でしかも生
産性の高いニッケ！電極とこれを用いたアルカリ蓄電池
を提供することを目的とするＯ
発明の構成
本発明は、上記目的を達成するべく内部細孔容積が０．
０５ｍｔ７９以下の水酸化ニッケルを用い、これにＣｏ
ｏ、 ａ−Ｃｏ（ＯＨ）２ ＊β−Ｃｏ（ＯＨ）２等の
コバルト粉末を添加した活物質を耐アルカリ性金属多孔
体に充填し、該活物質表面に未焼結ポリテトラフルオロ
エチレン粒子を均一に分散させたことを特徴とするニッ
ケル電極である。Purpose of the Invention The present invention provides a high-capacity, high-productivity nickel film that prevents the active material from falling off. SUMMARY OF THE INVENTION The present invention aims to provide an electrode and an alkaline storage battery using the same.To achieve the above object, the present invention has an internal pore volume of 0.
Co
o, a-Co(OH)2 * An alkali-resistant metal porous body is filled with an active material to which cobalt powder such as β-Co(OH)2 is added, and unsintered polytetrafluoroethylene particles are placed on the surface of the active material. This is a nickel electrode characterized by being uniformly dispersed.
実施例
以下、本発明について一実施例により説明するＯ
硫酸ニッケμに硫酸アンモニウムを添加し、ニッケルの
アンミン錯イオンを形成させる。EXAMPLE Hereinafter, the present invention will be explained by an example. Ammonium sulfate is added to O 2 nickel sulfate μ to form an ammine complex ion of nickel.
この液を水酸化ナトリウム水溶液中に滴下しながら激し
い攪拌を行い、徐々に錯イオンを分解させて水酸化ナト
リウム水溶液を析出成長させる。この時水酸化す） ＋
７ウム水溶液はＰＨ１１〜１３程度の薄いアルカリ濃度
とする。これによって、内部細孔容積が少ない高結晶性
で高密度な新水酸化ニッケル粉が得られた。This solution is dropped into the sodium hydroxide aqueous solution while being vigorously stirred to gradually decompose the complex ions and cause the sodium hydroxide aqueous solution to precipitate and grow. At this time, hydroxide) +
The 7um aqueous solution has a low alkaline concentration of about PH11 to 13. As a result, a new highly crystalline and dense nickel hydroxide powder with a small internal pore volume was obtained.
第１図に本発明に用いる新水酸化ニッケル粉末と従来の
水酸化ニッケル粉末の内部細孔容積と活物質利用率の関
係について示した。尚、従来の水酸化ニッケル粉末は、
高濃度アルカリ（ＰＨ１４以上）に水酸化工フケ〃粒子
を析出したものである。エネルギー密度が６００ ｍＡ
ｈ ／ｃｃを満足するためには、新水酸化ニッケル粉末
の内部細孔容積は０．０５ｗ１７９以下でなければなら
ないことが分る。FIG. 1 shows the relationship between the internal pore volume and active material utilization rate of the new nickel hydroxide powder used in the present invention and the conventional nickel hydroxide powder. In addition, conventional nickel hydroxide powder is
Hydroxylated dandruff particles are precipitated in a highly concentrated alkali (pH 14 or higher). Energy density is 600 mA
It can be seen that in order to satisfy h 2 /cc, the internal pore volume of the fresh nickel hydroxide powder must be 0.05w179 or less.
内部細孔容積、が０．０５＃／／ｇ以下の新水酸化ニッ
ケｙ粉末９０ｖｔ％とＯｏＯ１０ｗｔ％を混合し、カル
ボキシメチ〜セ〃ロースを増粘剤とする水溶液を加えて
スフリー状とした。90vt% of new nickel hydroxide powder with an internal pore volume of 0.05#//g or less and 10wt% of OoO were mixed, and an aqueous solution containing carboxymethycin-cerose as a thickener was added to form a souffle. .
このスラリーを多孔度９５％、厚さ１．５謁、平均細孔
径１００μｍの多孔質耐アルカリ性金属繊維焼結体に充
填し、乾燥した。この極板表面した。次にこれを乾燥し
た後、厚み調節により厚さ０．７簡のニッケル電極とし
た。This slurry was filled into a porous alkali-resistant metal fiber sintered body having a porosity of 95%, a thickness of 1.5 mm, and an average pore diameter of 100 μm, and dried. This electrode plate surface. Next, after drying this, a 0.7-thick nickel electrode was obtained by adjusting the thickness.
このニッケ！電極と対極としてペースト式カドミウム極
を組み合わせて、（１−１，２６ＫＯＨを注液しＣサイ
ズの電池を得た。この電池を２４時間放置後、湿度２０
℃において充電０．１ＯＡで１５時間、放電０．２０Ａ
Ｃ終止電圧１．０ＯＶ）を１０サイク〃繰返し試験した
。ポリテトラフルオロエチレンの塗布量と活物質の脱落
量及び利用率の関係を調べた。その結果を第２図に示し
た０この結果からポリテトラ７Ｉｖオロエチレンの塗布
量は、ｚ５〜６．５ダ／。−の範囲が適切であることが
分る。This Nikkei! A paste-type cadmium electrode was combined as an electrode and a counter electrode, and 1-1,26KOH was injected to obtain a C-sized battery. After leaving this battery for 24 hours, the humidity was 20°C.
Charging at 0.1OA for 15 hours, discharging at 0.20A at °C
C end voltage 1.0OV) was repeated for 10 cycles. The relationship between the amount of polytetrafluoroethylene applied, the amount of active material falling off, and the utilization rate was investigated. The results are shown in FIG. 2. From these results, the coating amount of polytetra 7Iv oleoethylene was z5 to 6.5 Da/. It can be seen that the - range is appropriate.
尚、上記実施例において、添加剤としてＯｏＯを用いた
が、Ｃ１−Ｃｏ（ＯＨ）２ ｔβ−Ｃｏ（ＯＨ）２を用
いても同様の結果を得た。In the above examples, OoO was used as the additive, but similar results were obtained using C1-Co(OH)2 tβ-Co(OH)2.
発明の効果
上述した如く、本発明は活物質の脱落を防止した、高容
量でしかも生産性の高いニッケ〃電極とこれを用いたア
ルカリ蓄電池を提供することができるので、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 can provide a high-capacity and highly productive nickel electrode that prevents the active material from falling off, and an alkaline storage battery using the same, so its industrial value is extremely high. It's large.
第１図は本発明に用いる新水酸化ニッケｙ粉末と従来の
水酸化二フケ〃粉末の内部細孔容積と活物質利用率の関
係を示した図、第２図はニッケル電極におけるポリテト
ラフルオロエチレンの塗布量と活物質の脱落量及び利用
率の関係を示した図である。
出題人 湯浅電池株式会社
第１図
第２図Figure 1 is a diagram showing the relationship between the internal pore volume and active material utilization rate of the new nickel hydroxide powder used in the present invention and the conventional nickel hydroxide powder, and Figure 2 is a diagram showing the relationship between the internal pore volume and active material utilization rate of the new nickel hydroxide powder used in the present invention. FIG. 3 is a diagram showing the relationship between the amount of ethylene applied, the amount of active material falling off, and the utilization rate. Questioner Yuasa Battery Co., Ltd. Figure 1 Figure 2
Claims (2)
ッケルを用い、これにＣｏＯ，α−Ｃｏ（ＯＨ）＿２，
β−Ｃｏ（ＯＨ）＿２等のコバルト粉末を添加した活物
質を耐アルカリ性金属多孔体に充填し、該活物質表面に
未焼結ポリテトラフルオロエチレン粒子を均一に分散さ
せたことを特徴とするニッケル電極。(1) Using nickel hydroxide with an internal pore volume of 0.05 ml/g or less, CoO, α-Co(OH)_2,
It is characterized by filling an alkali-resistant metal porous body with an active material to which cobalt powder such as β-Co(OH)_2 is added, and unsintered polytetrafluoroethylene particles are uniformly dispersed on the surface of the active material. Nickel electrode.
で電池を組み立て、電解液を注液し１日以上放置した後
、初充電することを特徴とするアルカリ蓄電池。(2) An alkaline storage battery characterized by using the nickel electrode according to claim 1, assembling the battery in an unformed state, pouring an electrolyte into it, leaving it for one day or more, and then charging it for the first time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028328A JPH02207452A (en) | 1989-02-06 | 1989-02-06 | Nickel electrode and alkaline storage battery using the electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028328A JPH02207452A (en) | 1989-02-06 | 1989-02-06 | Nickel electrode and alkaline storage battery using the electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02207452A true JPH02207452A (en) | 1990-08-17 |
Family
ID=12245544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1028328A Pending JPH02207452A (en) | 1989-02-06 | 1989-02-06 | Nickel electrode and alkaline storage battery using the electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02207452A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0544011A1 (en) * | 1991-06-14 | 1993-06-02 | Yuasa Corporation | Nickel electrode for alkali storage batteries |
-
1989
- 1989-02-06 JP JP1028328A patent/JPH02207452A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0544011A1 (en) * | 1991-06-14 | 1993-06-02 | Yuasa Corporation | Nickel electrode for alkali storage batteries |
| EP0544011A4 (en) * | 1991-06-14 | 1995-04-26 | Yuasa Battery Co Ltd |
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