JP3118357B2 - Non-sintered positive electrode plate for alkaline storage batteries - Google Patents
Non-sintered positive electrode plate for alkaline storage batteriesInfo
- Publication number
- JP3118357B2 JP3118357B2 JP05300454A JP30045493A JP3118357B2 JP 3118357 B2 JP3118357 B2 JP 3118357B2 JP 05300454 A JP05300454 A JP 05300454A JP 30045493 A JP30045493 A JP 30045493A JP 3118357 B2 JP3118357 B2 JP 3118357B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- positive electrode
- active material
- coo
- utilization rate
- 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.)
- Expired - Fee Related
Links
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)
Description
【０００１】[0001]
【産業上の利用分野】アルカリ蓄電池用水酸化ニッケル
正極板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nickel hydroxide positive electrode plate for an alkaline storage battery.
【０００２】[0002]
【従来の技術】従来、ニッケル／カドミウム蓄電池やニ
ッケル／水素蓄電池用のアルカリ蓄電池において、その
正極板にはニッケル粉末をパンチングメタル等に焼結さ
せた多孔体基板に活物質を保持させた焼結式ニッケル正
極板が用いられてきた。このような焼結式ニッケル正極
板では、以下のような問題を有していた。2. Description of the Related Art Conventionally, in an alkaline storage battery for a nickel / cadmium storage battery or a nickel / hydrogen storage battery, a positive electrode plate is formed by holding an active material on a porous substrate obtained by sintering nickel powder into a punching metal or the like. Type nickel positive plates have been used. Such a sintered nickel positive plate has the following problems.
【０００３】先ず、多孔体基板は高多孔度とした場合、
強度が弱くなるため、多孔度９０％以上を得ることは困
難である。従って、活物質の充填量を増加させるため
に、基板の多孔度を高くしようとしても限界がある。ま
た、焼結式正極板は、活物質を焼結基板に保持させるた
めに、煩雑な工程を必要とするという問題を有してい
る。[0003] First, when the porous substrate has a high porosity,
Since the strength becomes weak, it is difficult to obtain a porosity of 90% or more. Therefore, there is a limit to increasing the porosity of the substrate in order to increase the filling amount of the active material. In addition, the sintered positive electrode plate has a problem that a complicated process is required to hold the active material on the sintered substrate.
【０００４】このような焼結式正極板の問題点を改良す
る正極板として、高エネルギー密度化を図ることがで
き、しかも作製の作業工程が簡単な正極板として、活物
質をスポンジ状ニッケルなどの活物質保持体に直接保持
させている非焼結式正極板が用いられている。上記非焼
結正極板では、高エネルギー密度化を図るために、従来
から活物質の利用率を向上させる様々な試みが行なわれ
ている。[0004] As a positive electrode plate which can solve the problems of such a sintered positive electrode plate, a high energy density can be achieved, and the active material is a sponge-like nickel or the like. A non-sintered positive electrode plate directly held by the active material holder is used. In the non-sintered positive electrode plate, various attempts have been made to improve the utilization rate of the active material in order to increase the energy density.
【０００５】その例として、活物質に対して添加物とし
て金属コバルト粉末が添加された正極板（特開昭５９−
１２８７６６号公報）、活物質に対して金属コバルトと
コバルト化合物が添加された正極板（特開昭５３−５１
４４９号公報、特開平２−２１６７６３号公報）があ
る。これらの正極板では、活物質に添加されたコバルト
種が一旦電解液中に溶解し、水酸化ニッケル表面に一様
に分散して活物質−活物質間及び活物質−集電体間を連
結した形で析出し、その後の、初回充電によって析出物
はオキシ水酸化コバルトになり、オキシ水酸化コバルト
のネットワークが形成される。As an example, a positive electrode plate in which metallic cobalt powder is added as an additive to an active material (Japanese Patent Application Laid-Open No.
128766), a positive electrode plate in which metallic cobalt and a cobalt compound are added to an active material (Japanese Patent Application Laid-Open No. 53-51).
449, JP-A-2-216763). In these positive plates, the cobalt species added to the active material is once dissolved in the electrolytic solution and uniformly dispersed on the nickel hydroxide surface to connect the active material-active material and the active material-collector. The precipitate is converted into cobalt oxyhydroxide by the initial charge, and a network of cobalt oxyhydroxide is formed.
【０００６】このオキシ水酸化コバルトは導電性が高
く、形成されたネットワークにより活物質−活物質間及
び活物質−集電体間の導電性が向上し、結果として活物
質の利用率が向上する。上記した特開昭５３−５１４４
９号公報、特開平２−２１６７６３号公報に記載された
コバルト化合物の中でも特に酸化コバルト（ＣｏＯ）は
利用率向上の効果が高いことが知られている。This cobalt oxyhydroxide has high conductivity, and the formed network improves the conductivity between the active material and the active material and between the active material and the current collector. As a result, the utilization rate of the active material is improved. . JP-A-53-5144 described above.
No. 9 and JP-A-2-216763, it is known that cobalt oxide (CoO) is particularly effective in improving the utilization factor.
【０００７】[0007]
【発明が解決しようとする課題】ところが、上記のよう
な正極板では、以下のような問題が生じる。先ず、添加
物として金属コバルトを添加する場合、金属コバルト
は、電解質中には溶解しにくいため、充分な導電性のネ
ットワークが形成されにくい。従って、活物質利用率の
向上効果が低いという問題があった。However, the above-described positive electrode plate has the following problems. First, when metallic cobalt is added as an additive, metallic cobalt is hardly dissolved in the electrolyte, so that a sufficient conductive network is hardly formed. Therefore, there is a problem that the effect of improving the utilization rate of the active material is low.
【０００８】一方、酸化コバルト（ＣｏＯ）について
は、電解液中にも溶解しやすく、活物質−活物質間及び
活物質−集電体間に渡る均一なネットワークが形成し、
活物質の利用率の向上効果の高い添加物である。しかし
ながら、空気中で酸化されやすく、正極板の作製時や、
保存時に劣化し、添加剤としての効果が低下してしまう
という問題があった。On the other hand, cobalt oxide (CoO) is easily dissolved in an electrolytic solution, and a uniform network is formed between an active material and an active material and between an active material and a current collector.
It is an additive that has a high effect of improving the utilization factor of the active material. However, it is easily oxidized in the air,
There is a problem in that it deteriorates during storage and the effect as an additive is reduced.
【０００９】本発明は上記問題点を解決するために行な
われたものであり、活物質の利用率が高く、しかも安定
した利用率が得られるアルカリ蓄電池用非焼結式正極板
を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a non-sintered positive electrode plate for an alkaline storage battery which has a high utilization rate of an active material and can obtain a stable utilization rate. With the goal.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するため
に、本発明は、水酸化ニッケルを活物質の主成分とする
アルカリ蓄電池用非焼結正極板において、上記活物質に
対してＣｏＯx （０＜ｘ＜１）で示される化合物が添加
されていることを特徴とする。To achieve the above object of the Invention The present invention provides a non-sintered positive electrode plate for an alkaline storage battery as a main component of the active material nickel hydroxide, CoO x with respect to the active material A compound represented by (0 <x <1) is added.
【００１１】[0011]
【作用】本発明の添加剤として用いたＣｏＯx （０＜ｘ
＜１）は、コバルト酸化物ではなく、金属コバルトと、
コバルト酸化物いずれの性質も有した化合物である。こ
のＣｏＯx （０＜ｘ＜１）は、酸素に対する性質として
は、金属コバルト的な性質を有しており、酸素による酸
化を受けにくい。The effect of CoO x (0 <x
<1) is not cobalt oxide but metal cobalt,
It is a compound having all the properties of cobalt oxide. This CoO x (0 <x <1) has a metallic cobalt-like property with respect to oxygen, and is hardly oxidized by oxygen.
【００１２】これに加えて、従来の酸化コバルト（Ｃｏ
Ｏ）と同様に、電解液中に溶解し易く、水酸化ニッケル
の表面を覆い、活物質−活物質間及び活物質−集電体の
導電性を高め、その結果として活物質の利用率を効果的
に向上させることができる。In addition to this, conventional cobalt oxide (Co)
Like O), it is easily dissolved in the electrolytic solution, covers the surface of nickel hydroxide, and enhances the conductivity between the active material and the active material and between the active material and the current collector. As a result, the utilization rate of the active material is reduced. It can be improved effectively.
【００１３】[0013]
【実施例】（実施例１） 先ず、活物質であるＮｉ（ＯＨ）2 粉末９０重量％と、
活物質の利用率向上のための添加剤としてＣｏＯ0.7 粉
末（粒径 １．５μｍ）１０重量％とを混合した。EXAMPLES (Example 1) First, 90% by weight of Ni (OH) 2 powder as an active material,
10% by weight of CoO 0.7 powder (particle size: 1.5 μm) was mixed as an additive for improving the utilization rate of the active material.
【００１４】次に、上記の活物質と、添加剤との混合粉
末に対して、結着剤であるＨＰＣ１重量％水溶液を５０
重量％加え、混練してペーストを作製した。このペース
トをニッケルスポンジに保持させ、乾燥の後、圧延を行
い非焼結式正極板を作製した。この正極板に用いられた
添加剤ＣｏＯ0.7 は以下のようにして作製した。 （ＣｏＯ0.7 の作製方法） 酸化コバルト（ＣｏＯ）を水素雰囲気中で加熱処理を行
なうことにより、上記実施例の添加剤ＣｏＯ0.7 を作製
した。Next, a 1% by weight aqueous solution of HPC as a binder is added to the mixed powder of the active material and the additive in 50%.
% By weight and kneaded to produce a paste. This paste was held on a nickel sponge, dried, and then rolled to produce a non-sintered positive electrode plate. The additive CoO 0.7 used for this positive electrode plate was produced as follows. (Production Method of CoO 0.7 ) The additive CoO 0.7 of the above example was produced by subjecting cobalt oxide (CoO) to a heat treatment in a hydrogen atmosphere.
【００１５】このように作製した正極板を、以下（ａ）
正極板と称する。 （比較例１） 添加剤として、ＣｏＯ0.7 の代わりに、金属コバルト
（粒径１．５μｍ）を用いた以外は、上記実施例１と同
様に正極板を作製した。このように作製した正極板を、
以下（ｘ1 ）正極板と称する。 （比較例２） 添加剤として、ＣｏＯ0.7 の代わりに、酸化コバルト
（ＣｏＯ、粒径１．５μｍ）を用いた以外は、上記実施
例１と同様に正極板を作製した。[0015] The positive electrode plate thus manufactured is referred to as (a)
It is called a positive electrode plate. (Comparative Example 1) As an additive, CoO0.7Instead of,Metal cobalt
(Example 1) except that (particle size: 1.5 μm) was used.
Thus, a positive electrode plate was produced. The positive electrode plate thus manufactured is
The following (x1) Referred to as positive electrode plate. (Comparative Example 2) CoO as an additive0.7Instead of,Cobalt oxide
(CoO,The above procedure was followed except that a particle size of 1.5 μm) was used.
A positive electrode plate was produced in the same manner as in Example 1.
【００１６】このように作製した正極板を、以下
（ｘ2 ）正極板と称する。 （比較例３） 添加剤として、ＣｏＯ0.7 の代わりに、酸化コバルト
（ＣｏＯ）と金属コバルトとを用い、その添加量として
は、活物質Ｎｉ（ＯＨ）2 ９０重量％に対して、酸化コ
バルト（ＣｏＯ）を７重量％、金属コバルトを３重量％
を，用いた以外は上記実施例と同様に正極板を作製し
た。The positive electrode plate thus manufactured is hereinafter referred to as (x 2 ) positive electrode plate. (Comparative Example 3) Instead of CoO 0.7 , cobalt oxide (CoO) and metallic cobalt were used as additives. The amount of the additive was 90 wt% of active material Ni (OH) 2 and cobalt oxide (CoO). 7% by weight of CoO) and 3% by weight of metallic cobalt
A positive electrode plate was produced in the same manner as in the above example except that was used.
【００１７】このように作製した正極板を、以下
（ｘ3 ）正極板と称する。 （実験１） 上記、（ａ）正極板、（ｘ1 ）正極板〜（ｘ3 ）正極板
を用いて、極板利用率について測定を行なったのでその
結果を表１に示す。この実験に先立ち、上記正極板を用
いた利用率測定用のセルを作製した。The positive electrode plate thus manufactured is hereinafter referred to as (x 3 ) positive electrode plate. (Experiment 1) Using the positive electrode plate (a) and the positive electrode plates (x 1 ) to (x 3 ), the electrode plate utilization was measured, and the results are shown in Table 1. Prior to this experiment, a cell for measuring the utilization factor using the positive electrode plate was prepared.
【００１８】各正極板と、焼結式カドミウム極と、セパ
レータを用いて極板群を作製し、水酸化カリウム３０重
量％水溶液に浸漬し、測定用セルとした。このように作
製した各測定用セルを、以下（ａ）正極板を使用したも
のは（Ａ）セル、（ｘ1 ）〜（ｘ3 ）正極板を用いたも
のは、それぞれ（Ｘ1 ）〜（Ｘ3 ）セルと順に称する。An electrode plate group was prepared using each positive electrode plate, a sintered cadmium electrode, and a separator, and immersed in a 30% by weight aqueous solution of potassium hydroxide to prepare a cell for measurement. Each measurement cell produced in this manner, the following (a) a positive electrode plate obtained by using the (A) cells, (x 1) ~ (x 3) that is prepared using the positive electrode plate, respectively (X 1) ~ (X 3 ) cells.
【００１９】実験条件としては、以下のような充放電条
件で測定を行った。 充電：０．１Ｃ（ＶＳ理論容量）×１６ｈ 放電：１／４Ｃ（ＶＳ理論容量）０Ｖまで放電 また、極板利用率は、下記に示す式（１）に基づいて算
出した。 極板利用率＝（測定した放電容量／理論容量）×１００
・・・（１） 但し、表１には（Ｘ2 ）セルの利用率の結果を１００と
した場合の値が示されている。The measurement was performed under the following charging and discharging conditions. Charge: 0.1 C (VS theoretical capacity) × 16 h Discharge: 1/4 C (VS theoretical capacity) Discharge to 0 V The electrode plate utilization rate was calculated based on the following equation (1). Electrode utilization rate = (measured discharge capacity / theoretical capacity) × 100
(1) However, Table 1 shows values when the result of the utilization rate of the (X 2 ) cell is 100.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表１から明らかなように、添加剤としてＣ
ｏＯ0.7 を用いた場合の極板利用率は、酸化コバルト
（ＣｏＯ）を用いた場合の極板利用率と同じであり、本
実施例に用いたＣｏＯ0.7 は、利用率の向上効果の高い
化合物であるといえる。 （実験２） 次に、添加剤の保存性能について調べたのでその結果を
表２に示す。As is clear from Table 1, as an additive, C
The electrode utilization when using oO 0.7 is the same as the electrode utilization when using cobalt oxide (CoO), and CoO 0.7 used in this example is a compound having a high effect of improving the utilization. You can say that. (Experiment 2) Next, the storage performance of the additives was examined, and the results are shown in Table 2.
【００２２】実験条件としては、添加剤である、実施例
で用いたＣｏＯ0.7 、比較例で用いた酸化コバルト（Ｃ
ｏＯ）、金属コバルトをそれぞれ４０℃の雰囲気中で１
週間放置し、上記したのと同様に正極板を作製し、実験
１と同様にセル作製及び利用率の測定をおこなった。但
し、表２の結果は、実験１での（Ｘ2 ）セルの利用率の
結果を１００とした場合の値であり、比較のため実験１
の結果を保存前の利用率のデータとして再度あわせて記
載している。The experimental conditions were as follows: CoO 0.7 used in the examples, cobalt oxide (C
oO) and metallic cobalt in an atmosphere of 40 ° C.
The cell was left to stand for a week, a positive electrode plate was prepared in the same manner as described above, and a cell was prepared and the utilization was measured in the same manner as in Experiment 1. However, the results in Table 2 are values when the result of the utilization rate of the (X 2 ) cell in Experiment 1 was set to 100, and the values of Experiment 1 were used for comparison.
Are also described again as utilization rate data before storage.
【００２３】[0023]
【表２】 [Table 2]
【００２４】表２から明らかなように、添加剤としてＣ
ｏＯ0.7 を用いた（Ａ）セルは保存後も保存前と変わら
ず高い利用率が得られ、安定した利用率を得ることがで
きることがわかる。 （Ｘ1 ）セルについては、添加されている金属コバルト
の劣化が起こっていないようで、保存後も利用率の低下
は起こっていないが、利用率自体が低い。As is apparent from Table 2, C is used as an additive.
It can be seen that the cell (A) using oO 0.7 has a high utilization rate even after storage as before and after storage, and can achieve a stable utilization rate. Regarding the (X 1 ) cell, the added metal cobalt does not seem to have deteriorated, and the utilization rate has not decreased even after storage, but the utilization rate itself is low.
【００２５】（Ｘ2 ）（Ｘ3 ）セルについては、酸化さ
れやすい酸化コバルト（ＣｏＯ）が添加剤として使用さ
れているので、保存中に酸化がおこり、保存後の利用率
の低下を招いたものと思われる。上記の実験１、２の結
果からＣｏＯ0.7 は、極板利用率の向上効果が高く、保
存性能も良好な優れた添加剤であることが明らかになっ
た。 （その他の事項） 上記実施例で用いた添加剤は、ＣｏＯ0.7 であるが、Ｃ
ｏＯx （０＜ｘ＜１）であれば、同様の効果が得られ
る。In the (X 2 ) and (X 3 ) cells, cobalt oxide (CoO), which is easily oxidized, is used as an additive, so oxidation occurs during storage, resulting in a decrease in the utilization after storage. It seems to be. From the results of Experiments 1 and 2 above, it was revealed that CoO 0.7 was an excellent additive having a high effect of improving the utilization rate of the electrode plate and having good storage performance. (Other Matters) The additive used in the above example was CoO 0.7 ,
If oO x (0 <x <1), a similar effect can be obtained.
【００２６】[0026]
【発明の効果】以上説明したように、本発明によれば、
ＣｏＯx （０＜ｘ＜１）は、酸化コバルト（ＣｏＯ）と
同様に、極板利用率向上の効果が高く、しかも酸素と反
応しにくい化合物である。このような、化合物を添加物
として用いることによって、活物質の利用率が高く、し
かも安定した利用率の得られるアルカリ蓄電池用非焼結
式正極板を提供することができた。As described above, according to the present invention,
CoO x (0 <x <1), like cobalt oxide (CoO), is a compound that has a high effect of improving the electrode plate utilization rate and is less likely to react with oxygen. By using such a compound as an additive, it was possible to provide a non-sintered positive electrode plate for an alkaline storage battery in which the utilization rate of an active material was high and a stable utilization rate was obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−145058（ＪＰ，Ａ) 特開 平４−248263（ＪＰ，Ａ) 特開 平４−109557（ＪＰ，Ａ) 特開 昭61−138458（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/24 - 4/32 H01M 4/52 H01M 4/62 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-145058 (JP, A) JP-A-4-248263 (JP, A) JP-A-4-109557 (JP, A) JP-A-61- 138458 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 4/24-4/32 H01M 4/52 H01M 4/62
Claims (1)
アルカリ蓄電池用非焼結正極板において、上記活物質に
対してＣｏＯx （０＜ｘ＜１）で示される化合物が添加
されていることを特徴とするアルカリ蓄電池用非焼結正
極板。1. A non-sintered positive electrode plate for an alkaline storage battery containing nickel hydroxide as a main component of an active material, wherein a compound represented by CoO x (0 <x <1) is added to the active material. A non-sintered positive electrode plate for an alkaline storage battery, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05300454A JP3118357B2 (en) | 1993-11-30 | 1993-11-30 | Non-sintered positive electrode plate for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05300454A JP3118357B2 (en) | 1993-11-30 | 1993-11-30 | Non-sintered positive electrode plate for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07153465A JPH07153465A (en) | 1995-06-16 |
| JP3118357B2 true JP3118357B2 (en) | 2000-12-18 |
Family
ID=17884996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05300454A Expired - Fee Related JP3118357B2 (en) | 1993-11-30 | 1993-11-30 | Non-sintered positive electrode plate for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3118357B2 (en) |
-
1993
- 1993-11-30 JP JP05300454A patent/JP3118357B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07153465A (en) | 1995-06-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |