JPH0711955B2 - Non-sintered cadmium cathode for alkaline storage batteries - Google Patents
Non-sintered cadmium cathode for alkaline storage batteriesInfo
- Publication number
- JPH0711955B2 JPH0711955B2 JP62320225A JP32022587A JPH0711955B2 JP H0711955 B2 JPH0711955 B2 JP H0711955B2 JP 62320225 A JP62320225 A JP 62320225A JP 32022587 A JP32022587 A JP 32022587A JP H0711955 B2 JPH0711955 B2 JP H0711955B2
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- cathode
- zinc powder
- alkaline storage
- substituted
- 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
- 229910052793 cadmium Inorganic materials 0.000 title claims description 49
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 35
- 238000003860 storage Methods 0.000 title claims description 7
- 150000001661 cadmium Chemical class 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- 229910052738 indium Inorganic materials 0.000 claims description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 5
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/246—Cadmium electrodes
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明はカドミウム陰極に係り、特に活物質としての
水酸化カドミウム或いは酸化カドミウムの如きカドミウ
ム化合物を含有した混練物を導電芯体に塗布して作成さ
れる非焼結式カドミウム陰極の改良に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a cadmium cathode, and in particular, a conductive core is coated with a kneaded material containing a cadmium compound such as cadmium hydroxide or cadmium oxide as an active material. The present invention relates to an improvement of a non-sintered cadmium cathode produced by
（ロ）従来の技術 ニッケル−カドミウム蓄電池等に用いられるカドミウム
陰極としては、製造工程が簡易で製造コストの安いペー
スト式の如き非焼結式のカドミウム陰極が工業的に広く
用いられている。この種のカドミウム陰極は、酸化カド
ミウム紛末や水酸化カドミウム粉末等の活物質を糊料液
と共に混練して形成したペーストを導電芯体に塗着、充
填し、次いで乾燥及び化成処理を施した後、水洗及び乾
燥を行なう等して製造される。しかしながらこの種の非
焼結式カドミウム陰極は利用率が低いという問題点があ
る。このカドミウム陰極の利用率を向上させるために特
開昭62-243245号公報には、予備充電生成物質である金
属カドミウムとして、インジウムを含むカドミウム塩溶
液と100メッシュパス（平均粒径数10μｍ）の亜鉛粉末
とを反応させて生成せる置換カドミウムを用いることが
提案されている。この方法によればたしかにカドミウム
陰極の利用率を向上させることが可能であるが、利用率
の向上には限界があった。(B) Conventional technology As a cadmium cathode used in nickel-cadmium storage batteries and the like, a non-sintering type cadmium cathode such as a paste type, which has a simple manufacturing process and a low manufacturing cost, is widely used industrially. This type of cadmium cathode was prepared by kneading an active material such as cadmium oxide powder or cadmium hydroxide powder together with a paste solution onto a conductive core, applying and filling the paste, and then performing drying and chemical conversion treatment. After that, it is manufactured by washing with water and drying. However, this type of non-sintered cadmium cathode has a problem of low utilization. In order to improve the utilization rate of this cadmium cathode, Japanese Patent Laid-Open No. 62-243245 discloses that a cadmium salt solution containing indium and 100 mesh pass (average particle size: 10 μm) is used as metal cadmium which is a precharge product. It has been proposed to use substituted cadmium which is formed by reacting with zinc powder. According to this method, it is possible to improve the utilization rate of the cadmium cathode, but there is a limit to the improvement of the utilization rate.
（ハ）発明が解決しようとする問題点 本発明は前記問題点に鑑みなされたものであって、非焼
結式カドミウム陰極の利用率の更なる向上を計るもので
あり、高容量化が計られたアルカリ蓄電池を提供しよう
とするものである。(C) Problems to be Solved by the Invention The present invention has been made in view of the above problems, and is intended to further improve the utilization rate of the non-sintered cadmium cathode, and to increase the capacity. The present invention aims to provide an alkaline storage battery of the type described above.
（ニ）問題点を解決するための手段 本発明のアルカリ蓄電池用非焼結式カドミウム陰極は、
主活物質である酸化カドミウム又は水酸化カドミウム
と、インジウムを含むカドミウム塩溶液と、亜鉛粉末と
を反応させて生成したインジウムを含む置換カドミウム
を予備充電生成物質である金属カドミウムとして含有し
たカドミウム陰極であって、前記亜鉛粉末は平均粒径８
μｍ以下の亜鉛粉末を用いたことを特徴とするものであ
る。尚、インジウムの含有率は、3.0重量％以下である
事が好ましい。(D) Means for Solving the Problems The non-sintered cadmium cathode for alkaline storage batteries of the present invention is
A cadmium cathode containing cadmium oxide or cadmium hydroxide as a main active material, a cadmium salt solution containing indium, and substituted cadmium containing indium produced by reacting zinc powder as metal cadmium as a precharge product. The average particle size of the zinc powder is 8
It is characterized by using zinc powder having a particle size of not more than μm. The indium content is preferably 3.0% by weight or less.
（ホ）作用 インジウムを含むカドミウム塩溶液と、亜鉛粉末とを反
応させてインジウムを含む置換カドミウムを生成させる
場合において、カドミウム塩溶液に添加せる亜鉛粉末の
粒径によりインジウムを含む置換カドミウムの反応性が
変化することを見い出し、本発明を完成するに至ったも
のである。置換カドミウムは比表面積の大きいもの、即
ち粒子の細かいもの程反応性に富み、かかる置換カドミ
ウムを用いたカドミウム陰極の利用率の増大が計れる。
このためには、カドミウム塩溶液と平均粒径８μｍ以下
の亜鉛粉末を反応させることが有効である。これは置換
反応に要する時間が短かくなり、カドミウム結晶が成長
しきれず、微細結晶のままで前記反応が終了してしま
う。その結果、得られた置換カドミウムは電気化学的な
反応を行う表面積が大きくなると共に、この時存在する
インジウムによって置換カドミウムの格子欠陥が増大さ
れるので、反応性が増大する。したがって、かかる置換
カドミウムを用いたカドミウム陰極の更なる利用率の向
上が計れる。(E) Action When reacting a cadmium salt solution containing indium with a zinc powder to produce a substituted cadmium containing indium, the reactivity of the substituted cadmium containing indium is determined by the particle size of the zinc powder added to the cadmium salt solution. The present invention has been completed by discovering that the above changes. Substitutional cadmium having a larger specific surface area, that is, finer particles, is more reactive, and it is possible to increase the utilization rate of the cadmium cathode using the substitutional cadmium.
For this purpose, it is effective to react a cadmium salt solution with zinc powder having an average particle size of 8 μm or less. In this case, the time required for the substitution reaction becomes short, the cadmium crystal cannot grow completely, and the above reaction ends with the fine crystal. As a result, the obtained substituted cadmium has a large surface area for electrochemical reaction, and the indium present at this time increases the lattice defects of the substituted cadmium, thereby increasing the reactivity. Therefore, the utilization factor of the cadmium cathode using the substituted cadmium can be further improved.
（ヘ）実施例 先づ、カドミウム塩溶液中に添加せる亜鉛粉末の粒径を
変化させた時の、カドミウム陰極の利用率を検討した。
この方法は、以下の操作によるものである。(F) Example First, the utilization rate of the cadmium cathode when the particle size of the zinc powder added to the cadmium salt solution was changed was examined.
This method is based on the following operations.
カドミウムイオン換算で100g/lの硫酸カドミウム溶液10
lをpH＝２、温度を60℃に保つ。ここに平均粒径5.4μｍ
の蒸留亜鉛粉末250gとニッケル粉末2.5gを投入し攪拌す
ることによりスポンジ状金属カドミウムが約420g得られ
る。尚、ここでニッケル粉末は生成する置換カドミウム
が団塊状になるのを防止する為添加している。この金属
カドミウムを濾過、水洗をくり返すことにより硫酸イオ
ン、亜鉛イオンを規定濃度以下に除去した後、窒素雰囲
気中70℃で乾燥、粉砕し100メッシュパスさせた。この
金属カドミウム粉末15重量部と酸化カドミウム85重量部
を水38重量部中に分散させ、糊料としてメチルセルロー
ス１重量部、更にアクリル短繊維0.7重量部の割合で添
加、混練し活物質ペーストを得、これをパンチング芯体
に塗着、乾燥し所定の寸法に切断しカドミウム陰極ａと
した。同様にして亜鉛粉末の平均粒径を2.0μｍ、3.6μ
ｍ、7.8μｍ、10.8μｍ、18.0μｍと種々変化させて得
た、置換カドミウムを用いたカドミウム陰極ｂ、ｃ、
ｄ、ｅ、ｆも作成した。100 g / l cadmium sulfate solution calculated as cadmium ion 10
Keep l at pH = 2 and temperature at 60 ° C. Average particle size 5.4μm here
By adding 250 g of distilled zinc powder and 2.5 g of nickel powder and stirring the mixture, about 420 g of sponge metal cadmium can be obtained. The nickel powder is added here in order to prevent the generated substituted cadmium from becoming nodular. The metal cadmium was filtered and washed with water repeatedly to remove sulfate ions and zinc ions to below the specified concentrations, then dried at 70 ° C. in a nitrogen atmosphere, pulverized and passed through 100 mesh. 15 parts by weight of this metal cadmium powder and 85 parts by weight of cadmium oxide are dispersed in 38 parts by weight of water, and 1 part by weight of methyl cellulose as a paste and 0.7 part by weight of acrylic short fibers are added and kneaded to obtain an active material paste. This was coated on a punching core, dried, and cut into a predetermined size to obtain a cadmium cathode a. Similarly, average particle size of zinc powder is 2.0μm, 3.6μ
m, 7.8 μm, 10.8 μm, 18.0 μm and variously obtained cadmium cathodes b, c using substituted cadmium,
d, e, f were also created.
これらのカドミウム陰極ａ〜ｆを用い、ニッケル板を対
極とし、25％水酸化カリウム溶液の電解液中において、
0.15cの電流で15時間充電した後、0.3cの電流で放電
し、カドミウム陰極の利用率を検討した。この結果を、
第１図に示す。第１図は、カドミウム塩溶液中に添加せ
る亜鉛粉末の平均粒径と、これにより得られた置換カド
ミウムを用いたカドミウム陰極の利用率の関係を示して
いる。これより、添加せる亜鉛粉末として、平均粒径８
μｍ以下のものが、好ましいことが理解される。ここ
で、10μｍ以上の亜鉛粉末は従来用いられていたアトマ
イズ法で、10μｍより小さいのは蒸留法により、作製し
て得たものである。この蒸留法により得られた亜鉛粉末
は、近年得られるようになったものである。Using these cadmium cathodes a to f with a nickel plate as a counter electrode, in an electrolyte solution of 25% potassium hydroxide solution,
After being charged with a current of 0.15c for 15 hours and then discharged with a current of 0.3c, the utilization rate of the cadmium cathode was examined. This result
It is shown in FIG. FIG. 1 shows the relationship between the average particle size of zinc powder added to a cadmium salt solution and the utilization rate of a cadmium cathode using the substituted cadmium thus obtained. From this, the average particle size of zinc powder to be added is 8
It is understood that those of μm or less are preferable. Here, the zinc powder having a particle size of 10 μm or more is obtained by the atomizing method which has been conventionally used, and the powder having a particle size of less than 10 μm is obtained by the distillation method. The zinc powder obtained by this distillation method has come to be obtained in recent years.
次に、前述平均粒径８μｍ以下の亜鉛粉末を用い、カド
ミウム塩溶液中にインジウムを添加しておくと、更なる
利用率の向上が計られることがわかった。そして、これ
らにおいてインジウムの含有量を変化させた時の、カド
ミウム陰極の利用率を調べ、その一例として平均粒径４
μｍの亜鉛粉末を用いたときの結果を以下に示す。Next, it was found that by using zinc powder having an average particle diameter of 8 μm or less and adding indium to the cadmium salt solution, the utilization rate can be further improved. Then, the utilization rate of the cadmium cathode when the content of indium was changed in these was investigated, and as an example, the average particle size was 4
The results when using the zinc powder of μm are shown below.
前述の硫酸カドミウム溶液に硫酸インジウムを加えると
ともに、平均粒径3.6μｍの蒸留亜鉛粉末を使用する以
外は同様にし、この硫酸インジウムの添加量を変化させ
て、カドミウム陰極を種々作製した。そして置換カドミ
ウム中のインジウム含有率を０％、0.1％、0.5％、1.5
％、３％、4.5％とそれぞれ変化させ、カドミウム陰極
ｇ、ｈ、ｉ、ｊ、ｋ、ｌの利用率を測定した。この結果
を、第２図に示す。これより、インジウムの含有率は3.
0重量％以下が好ましく、カドミウム陰極の利用率を向
上させることが可能となった。Various cadmium cathodes were produced by adding indium sulfate to the above-described cadmium sulfate solution and using distilled zinc powder having an average particle size of 3.6 μm in the same manner and changing the addition amount of indium sulfate. And the indium content in the substituted cadmium is 0%, 0.1%, 0.5%, 1.5
%, 3% and 4.5%, respectively, and the utilization rates of the cadmium cathodes g, h, i, j, k and l were measured. The results are shown in FIG. From this, the indium content is 3.
It is preferably 0% by weight or less, and it has become possible to improve the utilization rate of the cadmium cathode.
（ト）発明の効果 本発明の非焼結式カドミウム陰極によれば、利用率を一
層向上させることができ、かかる陰極を用いたアルカリ
蓄電池の高容量化を計ることが可能であって、その工業
的価値はきわめて大きい。(G) Effect of the Invention According to the non-sintered cadmium cathode of the present invention, the utilization factor can be further improved, and it is possible to increase the capacity of the alkaline storage battery using such a cathode. The industrial value is extremely high.
第１図は使用する亜鉛粉末の平均粒径を変化させた時の
陰極利用率を示す図、第２図は、置換カドミウム中のイ
ンジウム含有率と陰極の利用率の関係を示す図である。FIG. 1 is a diagram showing the cathode utilization rate when the average particle diameter of the zinc powder used is changed, and FIG. 2 is a diagram showing the relationship between the indium content rate in substituted cadmium and the cathode utilization rate.
Claims (2)
カドミウムと、インジウムを含むカドミウム塩溶液と亜
鉛粉末とを反応させて生成したインジウムを含む置換カ
ドミウムを予備充電生成物質である金属カドミウムとし
て含有したカドミウム陰極であって、前記亜鉛粉末は平
均粒径８μｍ以下の亜鉛粉末を用いたことを特徴とする
アルカリ蓄電池用非焼結式カドミウム陰極。1. A substituted cadmium containing indium produced by reacting cadmium oxide or cadmium hydroxide as a main active material with a cadmium salt solution containing indium and zinc powder as a metal cadmium as a precharge generation material. A non-sintered cadmium cathode for an alkaline storage battery, wherein the zinc powder is a zinc powder having an average particle size of 8 μm or less.
の含有率は、3.0重量％以下であることを特徴とする特
許請求の範囲第（１）項記載のアルカリ蓄電池用非焼結
式カドミウム陰極。2. The non-sintered cadmium cathode for an alkaline storage battery according to claim 1, wherein the content of indium contained in the substituted cadmium is 3.0% by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62320225A JPH0711955B2 (en) | 1987-12-17 | 1987-12-17 | Non-sintered cadmium cathode for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62320225A JPH0711955B2 (en) | 1987-12-17 | 1987-12-17 | Non-sintered cadmium cathode for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01161667A JPH01161667A (en) | 1989-06-26 |
| JPH0711955B2 true JPH0711955B2 (en) | 1995-02-08 |
Family
ID=18119120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62320225A Expired - Fee Related JPH0711955B2 (en) | 1987-12-17 | 1987-12-17 | Non-sintered cadmium cathode for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0711955B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3654889B2 (en) * | 2003-02-28 | 2005-06-02 | 黒沢建設株式会社 | Method for forming anti-rust coating on PC steel stranded wire |
| JP5790383B2 (en) * | 2011-09-30 | 2015-10-07 | 三洋電機株式会社 | Alkaline storage battery |
-
1987
- 1987-12-17 JP JP62320225A patent/JPH0711955B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01161667A (en) | 1989-06-26 |
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