JPH04192259A - Nickel electrode for alkaline storage battery and battery using that - Google Patents
Nickel electrode for alkaline storage battery and battery using thatInfo
- Publication number
- JPH04192259A JPH04192259A JP2324436A JP32443690A JPH04192259A JP H04192259 A JPH04192259 A JP H04192259A JP 2324436 A JP2324436 A JP 2324436A JP 32443690 A JP32443690 A JP 32443690A JP H04192259 A JPH04192259 A JP H04192259A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- battery
- density
- powder particles
- hydroxide powder
- 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 34
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 16
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000011149 active material Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000010079 rubber tapping Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 238000007747 plating Methods 0.000 abstract description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract description 5
- 239000002585 base Substances 0.000 abstract 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000012856 packing 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
本発明はアルカリ電池用ニッケル電極及びこれを用いた
電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a nickel electrode for alkaline batteries and a battery using the same.
従来の技術
従来は厚さ１〜５μｍのコバルト鍍金を施した多孔性の
耐アルカリ性金属基板に、硫酸ニッケル塩水溶液と水酸
化ナトリウム水溶液から作製した水酸化ニッケル粉末粒
子を活物質として充填したニッケル電極及びこれを用い
たアルカリ電池が用いられていた。Conventional technology Conventionally, a nickel electrode is made by filling a porous alkali-resistant metal substrate coated with cobalt with a thickness of 1 to 5 μm with nickel hydroxide powder particles made from a nickel sulfate salt aqueous solution and a sodium hydroxide aqueous solution as an active material. And alkaline batteries using this were used.
発明が解決しようとする課題
近年ポータプルエレクトロニクス機器の軽量化に伴い、
高エネルギー密度化が要求されている。このニーズに対
応するためには、活物質の利用率を向上させるだけでは
限界があることから、高密度化された水酸化ニンケル粉
末粒子の使用が必要である。従来においてもコバルト鍍
金を集電体に施す方法により、活物質の利用率の向上は
行なわれてきた。Problems to be solved by the invention In recent years, as portable electronic devices have become lighter,
High energy density is required. In order to meet this need, it is necessary to use highly densified nickel hydroxide powder particles, since there is a limit to simply improving the utilization rate of the active material. Conventionally, the utilization rate of active materials has been improved by applying cobalt plating to current collectors.
第１図に厚さ１〜６μｍの範囲において、１μｍごとに
厚みをかえてコバルト鍍金を施した厚さ２００μｍのニ
ッケル基板に、硫酸ニッケル塩水溶液と水酸化ナトリウ
ム水溶液から作製した従来の水酸化ニッケル粒子を充填
したニッケル電極と、対極としてペースト式カドミウム
極を組合わせ、比重１．２６の水酸化カリウム電解液を
流動電解液が生じる程度に注液し作製した電池を、２４
時間放置後、温度２０°Ｃにおいて、充電０．１ＣＡＸ
１５時間、放電０．２ＣＡ （終止電圧１．００Ｖ）で
１０サイクル試験を行ったときの活物質の利用率と、コ
バルト鍍金厚さの関係を示す。Figure 1 shows conventional nickel hydroxide prepared from a nickel sulfate salt aqueous solution and a sodium hydroxide aqueous solution on a 200-μm-thick nickel substrate coated with cobalt plating in a thickness range of 1 to 6 μm in increments of 1 μm. A battery was prepared by combining a nickel electrode filled with particles and a paste-type cadmium electrode as a counter electrode, and injecting a potassium hydroxide electrolyte with a specific gravity of 1.26 to the extent that a flowing electrolyte was produced.
After leaving it for a while, at a temperature of 20°C, the charge is 0.1CAX.
The relationship between the utilization rate of the active material and the cobalt plating thickness when a 10-cycle test was conducted for 15 hours at a discharge of 0.2 CA (final voltage of 1.00 V) is shown.
第１図からコバルト鍍金厚さが２〜５μｍの範囲では、
活物質の利用率は比較的安定であるが、厚さ５μｍ以上
になると活物質の利用率は大きく低下するこ′とが分か
る。このコハル）１１金の厚さの違いによる利用率の変
化は、活物質と集電体との有効距離に限界があるためで
あると推定できる。From Figure 1, when the cobalt plating thickness is in the range of 2 to 5 μm,
It can be seen that the utilization rate of the active material is relatively stable, but when the thickness becomes 5 μm or more, the utilization rate of the active material decreases significantly. It can be assumed that the change in the utilization rate due to the difference in the thickness of Kohar-11 gold is due to the fact that there is a limit to the effective distance between the active material and the current collector.
このようにコバルト鍍金を施した集電体と、活物質であ
る水酸化ニッケル粒子の境界部分に、オキシ水酸化コバ
ルトの強力な導電性ネットワーク層が形成されることに
よって活物質の利用率が向上し、エネルギー密度も大き
く改良された。In this way, a strong conductive network layer of cobalt oxyhydroxide is formed at the boundary between the cobalt-plated current collector and the active material, nickel hydroxide particles, improving the utilization rate of the active material. The energy density was also greatly improved.
しかしながら従来の水酸化ニッケル粉末粒子内には多数
の空孔が存在し、高密度に充填できるといった点ではま
だ改良の余地があった。However, conventional nickel hydroxide powder particles have a large number of pores, and there is still room for improvement in terms of being able to fill them with high density.
課題を解決するための手段
この課題を解決するために電極に次のような改良を施し
た。すなわち利用率を向上させるために、厚さ１〜５μ
ｍのコバルト鍍金を多孔性の耐アルカリ金属基板に施し
、従来の水酸化ニッケル粉末粒子を充填するかわりに、
硫酸ニンケル塩水溶液と水酸化ナトリウム水溶液から作
製した空孔容積が０．０８ｃｍ３／ ｇ以下で、かさ密
度（タッピング密度）が１．７〜２．２ ｇ ／ ｃｍ
３の範囲内にある高密度の水酸化ニッケル粉末粒子を充
填し、工フルギー密度の向上を計った。Means for solving the problem In order to solve this problem, the following improvements were made to the electrode. In other words, in order to improve the utilization rate, the thickness is 1 to 5 μm.
m cobalt plating is applied to a porous alkali-resistant metal substrate, instead of filling it with conventional nickel hydroxide powder particles.
The pore volume made from a sulfuric acid nickel salt aqueous solution and a sodium hydroxide aqueous solution is 0.08 cm3/g or less, and the bulk density (tapping density) is 1.7 to 2.2 g/cm.
The material was filled with high-density nickel hydroxide powder particles within the range of 3 to improve the mechanical density.
作用
厚さ１〜５μｍのコバルト鍍金を施した多孔性の耐アル
カリ性金属基板を用いることにより利用率が向上し、空
孔容積が０．０８ｃｍ３／ ｇ以下で、かさ密度が１．
７〜２．２ｇ／Ｃ１１３の範囲内にある水酸化ニッケル
粉末粒子を充填したニッケル電極を用いることによって
、水酸化ニッケル粉末粒子をより高密度に充填できるよ
うになった。従って高エネルギー密度化されたニッケル
電極、すなわち高エネルギー密度化されたアルカリ電池
を製作できるようになった。Utilization efficiency is improved by using a porous alkali-resistant metal substrate coated with cobalt with a working thickness of 1 to 5 μm, with a pore volume of 0.08 cm3/g or less and a bulk density of 1.
By using a nickel electrode filled with nickel hydroxide powder particles in the range of 7-2.2 g/C113, a higher density of nickel hydroxide powder particles was achieved. Therefore, it has become possible to produce a nickel electrode with a high energy density, that is, an alkaline battery with a high energy density.
実施例 以下、本発明の一実施例について詳述する。Example An embodiment of the present invention will be described in detail below.
正極は厚さ３μｍのコバルト鍍金を施したニッケルメツ
シュに、１５〜３０人の細孔半径を有し、その空孔容積
が０．０５＋ｗ２／ ｇ以下で且つ比表面積１５〜３０
ｍ１／ｇの範囲内にある水酸化ニッケル粉末粒子を活物
質の主成分として充填した。The positive electrode is made of cobalt-plated nickel mesh with a thickness of 3 μm, and has a pore radius of 15 to 30 mm, a pore volume of 0.05+w2/g or less, and a specific surface area of 15 to 30 mm.
Nickel hydroxide powder particles within the range of m1/g were filled as the main component of the active material.
第２図にこの新水酸化ニッケル粉末粒子と、硫酸ニッケ
ル塩水溶液と水酸化ナトリウム水溶液から作製した従来
の水酸化ニッケル粉末粒子の細孔径分布の比較を示す。FIG. 2 shows a comparison of the pore size distributions of this new nickel hydroxide powder particle and the conventional nickel hydroxide powder particle prepared from a nickel sulfate salt aqueous solution and a sodium hydroxide aqueous solution.
細孔径分布と比表面積の差にみられる細孔構造の違いは
高密度に充填するうえで最も重要ながさ密度（タッピン
グ密度）に大きな差を生しる。この新水酸化ニッケル粉
末粒子を用いると、従来の中和粉末粒子よりも約２０％
程度多く充填できることが明らかである。この水酸化ニ
ッケル粉末粒子５０ｗｔ％とニッケル粉末５０−ｔ％を
混合した活物質をプレスし、ベレ・ント状に成形したも
のを上記ニッケルメツシュに包んで再びプレスしたもの
を正極とした。この正極の放電理論容量は４００ｗＡｈ
とした。Differences in pore structure, seen in differences in pore size distribution and specific surface area, result in large differences in burlap density (tapping density), which is the most important factor for high-density packing. When using this new nickel hydroxide powder particles, it is approximately 20% more effective than conventional neutralized powder particles.
It is clear that a larger amount can be filled. The active material, which was a mixture of 50 wt % of nickel hydroxide powder particles and 50-t % of nickel powder, was pressed, formed into a bead shape, wrapped in the above nickel mesh, and pressed again to form a positive electrode. The theoretical discharge capacity of this positive electrode is 400wAh
And so.
このニッケル電極に、対極としてカドミウム電極を用い
、比重１．２６の水酸化カリウム電解液を注液して電池
を作製した。以下、この電池を電池Ａと記述する。また
従来の水酸化ニッケル粉末粒子を活物質の主成分として
用い、この水酸化ニッケル粉末粒子５０ｗｔ％とニッケ
ル粉末５０−ｔ％を混合した活物質を用いて、上記作製
方法と同様の方法を用いて電池を作製した。以下、この
電池を電池Ｂと記述する。これらの電池を２４時間放置
後、温度２０°Ｃにおいて、充電０．ＩＣ＋ＩＩＡＸ
１５時間、放電０．２Ｃ＋ｅＡ （終止電圧１．０ＯＶ
）で充放電試験を行った。第３図にこれらの電池の放電
電圧と放電時間の関係を示した。A battery was fabricated by using a cadmium electrode as a counter electrode and injecting a potassium hydroxide electrolyte having a specific gravity of 1.26 into this nickel electrode. Hereinafter, this battery will be referred to as battery A. In addition, using conventional nickel hydroxide powder particles as the main component of the active material, and using an active material in which 50 wt% of these nickel hydroxide powder particles and 50-t% of nickel powder were mixed, a method similar to the above manufacturing method was used. A battery was fabricated. Hereinafter, this battery will be referred to as battery B. After leaving these batteries for 24 hours, at a temperature of 20°C, the charge was 0. IC+IIAX
15 hours, discharge 0.2C+eA (final voltage 1.0OV
), a charge/discharge test was conducted. FIG. 3 shows the relationship between the discharge voltage and discharge time of these batteries.
第３図の結果は、電池Ａでは平均電圧１．２２Ｖ、放電
容量３４８ｍＡｈ、利用率８７％であり、電池Ｂでは平
均電圧１．２０Ｖ、放電容量３００ｓＡｈ、利用率７５
％であった。このように利用率は１２％向上し、平均電
圧も２０ｍＶ高くなった。The results in Figure 3 show that battery A has an average voltage of 1.22V, a discharge capacity of 348mAh, and a utilization rate of 87%, while battery B has an average voltage of 1.20V, a discharge capacity of 300sAh, and a utilization rate of 75%.
%Met. In this way, the utilization rate improved by 12%, and the average voltage also increased by 20 mV.
この結果からコバルト鍍金を施した多孔性の耐アルカリ
性金属基板と空孔容積が０．０８ｃｍ”７ｇ以下で、か
さ密度が１．７〜２．２ｇ／ｃｍ３の範囲内にある水酸
化ニッケルの境界部分においても導電性ネットワークは
形成され、利用率、平均電圧の向上によって、より高エ
ネルギー密度化されたニッケル電極を作製できることが
わかった。From this result, the boundary between a porous alkali-resistant metal substrate coated with cobalt and nickel hydroxide with a pore volume of 0.08 cm and 7 g or less and a bulk density within the range of 1.7 to 2.2 g/cm3. It was found that a conductive network was formed even in the nickel part, and by improving the utilization rate and average voltage, it was possible to create a nickel electrode with higher energy density.
発明の効果
上述の如く本発明は活物質利用率の向上した高エネルギ
ー密度のニッケル電極及びこれを用いたアルカリ電池を
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 described above, the present invention can provide a high energy density nickel electrode with improved active material utilization and an alkaline battery using the same, and therefore has extremely great industrial value.
第１図はコバルト鍍金厚さと活物質利用率の関係図、第
２図は従来及び本発明で用いた水酸化ニッケルの細孔径
分布を示す図、第３図は従来電池及び本発明電池の放電
時間と放電電圧との関係図である。Figure 1 is a diagram showing the relationship between cobalt plating thickness and active material utilization rate, Figure 2 is a diagram showing the pore size distribution of nickel hydroxide used in the conventional and the present invention, and Figure 3 is the discharge of the conventional battery and the battery of the present invention. FIG. 3 is a relationship diagram between time and discharge voltage.
Claims (1)
アルカリ性金属基板の上に、空孔容積が０．０８ｃｍ＾
３／ｇ以下で、かさ密度（タッピング密度）が１．７〜
２．２ｇ／ｃｍ＾３の範囲内にある水酸化ニッケル粉末
粒子を活物質として充填したことを特徴とするアルカリ
電池用ニッケル電極。 ２）請求項１に記載したアルカリ電池用ニッケル電極を
用いた電池。[Claims] 1) On a porous alkali-resistant metal substrate coated with cobalt with a thickness of 1 to 5 μm, the pore volume is 0.08 cm^.
3/g or less, bulk density (tapping density) is 1.7~
A nickel electrode for an alkaline battery, characterized in that it is filled with nickel hydroxide powder particles within the range of 2.2 g/cm^3 as an active material. 2) A battery using the nickel electrode for alkaline batteries according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324436A JP3063159B2 (en) | 1990-11-26 | 1990-11-26 | Nickel electrode for alkaline battery and battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324436A JP3063159B2 (en) | 1990-11-26 | 1990-11-26 | Nickel electrode for alkaline battery and battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04192259A true JPH04192259A (en) | 1992-07-10 |
| JP3063159B2 JP3063159B2 (en) | 2000-07-12 |
Family
ID=18165790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2324436A Expired - Lifetime JP3063159B2 (en) | 1990-11-26 | 1990-11-26 | Nickel electrode for alkaline battery and battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3063159B2 (en) |
-
1990
- 1990-11-26 JP JP2324436A patent/JP3063159B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3063159B2 (en) | 2000-07-12 |
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