JPH041466B2 - - Google Patents
Info
- Publication number
- JPH041466B2 JPH041466B2 JP61086312A JP8631286A JPH041466B2 JP H041466 B2 JPH041466 B2 JP H041466B2 JP 61086312 A JP61086312 A JP 61086312A JP 8631286 A JP8631286 A JP 8631286A JP H041466 B2 JPH041466 B2 JP H041466B2
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- cathode
- indium
- powder
- metal
- 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 - Lifetime
Links
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 38
- 229910052793 cadmium Inorganic materials 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 14
- 239000011149 active material Substances 0.000 claims description 8
- 150000001661 cadmium Chemical class 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 6
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 4
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000012670 alkaline solution Substances 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- 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 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000003756 stirring 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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関し、詳しくは、
ニツケル−カドミウム蓄電池の如きアルカリ蓄電
池等の陰極として用いられ、主活物質としての酸
化カドミウムまたは水酸化カドミウム粉末と、予
備充電生成物としての金属カドミウム粉末とを含
有した混練物を導電芯体に塗布して作成されるカ
ドミウム陰極の改良に関するものである。[Detailed description of the invention] (a) Industrial application field This invention relates to a cadmium cathode, and in detail,
Used as a cathode in alkaline storage batteries such as nickel-cadmium storage batteries, and coated on a conductive core with a kneaded material containing cadmium oxide or cadmium hydroxide powder as the main active material and metal cadmium powder as a pre-charging product. This paper relates to the improvement of cadmium cathodes made by
(ロ) 従来の技術
ニツケル−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、酸化カドミウム粉末や水酸化
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銅電芯体に塗着し充填し、
次いて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が、活物質とし導電
芯体との結着力が弱いので化成工程などにおける
活物質の剥がれや脱落が著しく、それ故、充放電
サイクルにおける容量劣化が大きい等という欠点
がある。(b) Prior Art As cadmium cathodes used in nickel-cadmium storage batteries and the like, non-sintered cadmium cathodes such as paste-type cadmium cathodes, which have a simple manufacturing process and are inexpensive to manufacture, are widely used industrially. This type of cadmium cathode is made by coating and filling a copper electric core with a paste formed by kneading an active material such as cadmium oxide powder or cadmium hydroxide powder with a glue solution.
Next, it is manufactured by drying and chemical conversion treatment, followed by washing with water and drying, but as the binding force between the active material and the conductive core is weak, the active material peels off or falls off during the chemical conversion process, etc. Therefore, there are drawbacks such as large capacity deterioration during charge/discharge cycles.
このため、例えば特公昭58−32744号公報に開
示されているように、上記ペースト中に含有させ
る活物質として主活物質としての酸化カドミウム
粉末等と予備充電生成物としての金属カドミウム
粉末との混合物を用いることで、ペースト式カド
ミウム陰極における化成工程を実質上不要とし、
もつて充放電サイクルの進行に伴う電池容量劣化
を防止することが提案されている。 For this reason, for example, as disclosed in Japanese Patent Publication No. 58-32744, a mixture of cadmium oxide powder as a main active material and metal cadmium powder as a pre-charge product is used as the active material to be contained in the paste. By using this, the chemical conversion process for paste-type cadmium cathodes is virtually unnecessary, and
It has been proposed to prevent battery capacity deterioration as the charge/discharge cycle progresses.
(ハ) 発明が解決しようとする問題点
しかしながら、このような目的で用いる金属カ
ドミウム粉末として、上記特公昭58−32744号公
報に開示されているカドミウム塩溶液中に亜鉛粉
末とニツケル粉末との混合粉末を分散し、カドミ
ウムと亜鉛とのイオン化傾向の差を利用した置換
反応により析出させて生成したニツケルを含む海
綿状金属カドミウムを粉砕処理するという方法
（以下「亜鉛置換法」という）で得たものを用い
た場合、得られた金属カドミウム粉末は利用率が
低いものであつた。(c) Problems to be solved by the invention However, as a metal cadmium powder used for this purpose, a mixture of zinc powder and nickel powder in a cadmium salt solution disclosed in the above-mentioned Japanese Patent Publication No. 58-32744. Obtained by a method of dispersing powder and pulverizing spongy metallic cadmium containing nickel, which is precipitated by a substitution reaction that takes advantage of the difference in ionization tendency between cadmium and zinc (hereinafter referred to as the "zinc substitution method"). When using cadmium powder, the utilization rate of the obtained metal cadmium powder was low.
また、アルカリ溶液中に酸化カドミウムを分散
させ、これを電解還元して得た海綿状金属カドミ
ウムを予備充電生成物用の金属カドミウム粉末と
して用いる方法もあるが、この製法では酸化カド
ミウムがアルカリ水溶液中にわずかしか溶解しな
いために電解還元の電流を大きくすることができ
ず、電解還元にかかる時間が長くなる他、多大な
電流を必要とするなどの欠点があり、製造工程の
煩雑化を招くために実用上適用し難い。 There is also a method of dispersing cadmium oxide in an alkaline solution and electrolytically reducing it to use the spongy metallic cadmium as metallic cadmium powder for pre-charged products. Because only a small amount dissolves in the electrolytic reduction, it is not possible to increase the current for electrolytic reduction, which lengthens the time required for electrolytic reduction and requires a large amount of current, which complicates the manufacturing process. difficult to apply in practice.
(ニ) 問題点を解決するための手段
本発明は、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亜鉛粉末を反応させて生
成した置換カドミウムを用いることを特徴とす
る。尚、インジウムの含有率は0.05〜2.00重量％
である事が好ましい。(d) Means for Solving the Problems The present invention is characterized in that substituted cadmium produced by reacting a cadmium salt solution containing indium with zinc powder is used as the metal cadmium. In addition, the content of indium is 0.05 to 2.00% by weight.
It is preferable that
(ホ) 作用
インジウムの原子番号は49、カドミウムの原子
番号は48であり原子量が近い値であるのでカドミ
ウム金属結晶中にインジウム原子が置換されやす
く、カドミウム金属結晶の格子欠陥が生じ結晶状
態が不安定化する。この構造は電子の状態に影響
が大きいため、電気化学的に反応が活性化し、利
用率の高い金属カドミウムが得られる。更に、イ
ンジウムを含むカドミウム塩溶液と亜鉛粉末とを
反応させ生成させた置換カドミウムであるのでイ
ンジウムは金属カドミウム粉末に均一に含まれる
ので、利用率の高いものとなる。(E) Effect The atomic number of indium is 49, and the atomic number of cadmium is 48, and their atomic weights are similar, so indium atoms are easily substituted in the cadmium metal crystal, causing lattice defects in the cadmium metal crystal and changing the crystal state. Stabilize. Since this structure has a large effect on the electronic state, the reaction is electrochemically activated and metal cadmium can be obtained with a high utilization rate. Furthermore, since the substituted cadmium is produced by reacting a cadmium salt solution containing indium with zinc powder, indium is uniformly contained in the metal cadmium powder, resulting in a high utilization rate.
(ヘ) 実施例
カドミウムイオン換算で100ｇ／の硫酸カド
ミウム溶液10にインジウムイオン換算で0.5
ｇ／の硫酸インジウムを加えPH＝２、温度を60
℃に保つ。ここに100メツシユパスの亜鉛粉末250
ｇとニツケル粉末2.5ｇを投入し撹拌することに
よりインジウムを0.5重量％含んだスポンジ状金
属カドミウムが約420ｇ得られる。尚、ここでニ
ツ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メツシユパス
させた。この金属カドミウム粉末10重量部と酸化
カドミウム90重量部を水35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0.9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とし
た。この陰極を用い、比重1.25の水酸化カリウム
溶液中にてニツケル板を対極とし、前記陰極容量
を1Cとしたときの0.15Cの電流で15時間充電後、
0.3Cの電流で放電し、陰極の利用率を計算した。
図は金属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したものであり、陰極利用率
の算出は次のようにして行つた。(f) Example 100g/10 of cadmium sulfate solution in terms of cadmium ions and 0.5 in terms of indium ions
Add 1 g/g of indium sulfate, pH = 2, temperature 60
Keep at ℃. Zinc powder for 100 mesh passes here 250
By adding 2.5 g of nickel powder and 2.5 g of nickel powder and stirring, about 420 g of spongy metal cadmium containing 0.5% by weight of indium is obtained. Incidentally, nickel powder is added here to prevent the generated substituted cadmium from forming into lumps. This metal cadmium was filtered and repeatedly washed with water to remove sulfate ions and zinc ions to a specified concentration or less, and then dried and crushed at 70°C in a nitrogen atmosphere for 100 mesh passes. 10 parts by weight of this metal cadmium powder and 90 parts by weight of cadmium oxide are dispersed in 35 parts by weight of water,
Add 1 part by weight of methyl cellulose as a glue and further 0.9 parts by weight of short acrylic fibers, knead to obtain an active material paste, apply this to the punching core,
It was dried and cut into predetermined dimensions to form a cadmium cathode. Using this cathode, a nickel plate was used as a counter electrode in a potassium hydroxide solution with a specific gravity of 1.25, and after charging for 15 hours with a current of 0.15C when the cathode capacity was 1C,
The cathode utilization rate was calculated by discharging at a current of 0.3C.
The figure shows the relationship between the indium content in metal cadmium and the cathode utilization rate, and the cathode utilization rate was calculated as follows.
陰極利用率（％）＝放電容量／理論容量×100
図に示されるように金属カドミウム中にインジ
ウムが含有されていると陰極利用率が向上するこ
とが伺え、インジウムの含有量としては0.05〜
2.00重量％の範囲が好ましく、特に0.5重量％の
時、最大の利用率78.7％を示している。尚、イン
ジウム含有量が多くなると利用率が低下している
が、その理由はカドミウムとインジウムとが各々
単体の結晶を形成するため格子欠陥が得られない
ことに基づくものと推定される。 Cathode utilization rate (%) = discharge capacity / theoretical capacity × 100 As shown in the figure, it can be seen that the cathode utilization rate improves when indium is contained in metal cadmium, and the indium content is 0.05~
A range of 2.00% by weight is preferable, and in particular, when the content is 0.5% by weight, the maximum utilization rate is 78.7%. Note that as the indium content increases, the utilization rate decreases, and the reason for this is presumed to be that lattice defects cannot be obtained because cadmium and indium each form a single crystal.
(ト) 発明の効果
この発明のカドミウム陰極によれば利用率の高
いカドミウム陰極が得られ、陰極容量の向上が図
れ、陰極の容量増加分だけ陽極の容量を高く設定
できるので電池容量が増加する。また陽極容量を
従来通りに設定した場合は陰極の利用率が高く陰
極支配になりにくいので、過充電特性を向上せし
める事ができる。(g) Effects of the invention According to the cadmium cathode of the present invention, a cadmium cathode with high utilization rate can be obtained, the cathode capacity can be improved, and the capacity of the anode can be set higher by the increase in the capacity of the cathode, so the battery capacity can be increased. . Furthermore, when the anode capacity is set as before, the utilization rate of the cathode is high and cathode domination is less likely to occur, so overcharging characteristics can be improved.
図は金属カドミウム中のインジウム含有率と陰
極利用率の関係を示したものである。
The figure shows the relationship between the indium content in metal cadmium and the cathode utilization rate.
Claims (1)
カドミウムと、予備充電生成物質としての金属カ
ドミウムを含有したアルカリ蓄電池用非焼結式カ
ドミウム陰極であつて、前記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亜鉛粉末
を反応させて生成した置換カドミウムを用いるこ
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。 ２ 前記金属カドミウムに含まれるインジウムの
含有率は0.05〜2.00重量％である事を特徴とする
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。[Scope of Claims] 1. A non-sintered cadmium cathode for an alkaline storage battery containing cadmium oxide or cadmium hydroxide as a main active material and metal cadmium as a precharge generating material, wherein indium is used as the metal cadmium. A non-sintered cadmium cathode for an alkaline storage battery, characterized in that it uses substituted cadmium produced by reacting a cadmium salt solution containing zinc powder. 2. The non-sintered cadmium cathode for an alkaline storage battery according to claim 1, wherein the content of indium in the metal cadmium is 0.05 to 2.00% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61086312A JPS62243254A (en) | 1986-04-15 | 1986-04-15 | Non-sintered cadmium anode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61086312A JPS62243254A (en) | 1986-04-15 | 1986-04-15 | Non-sintered cadmium anode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62243254A JPS62243254A (en) | 1987-10-23 |
| JPH041466B2 true JPH041466B2 (en) | 1992-01-13 |
Family
ID=13883317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61086312A Granted JPS62243254A (en) | 1986-04-15 | 1986-04-15 | Non-sintered cadmium anode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62243254A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988589A (en) * | 1989-01-18 | 1991-01-29 | Sanyo Electric Co., Ltd. | Paste-type cadmium electrode for use in an alkaline storage cell and its manufacturing method |
| JP5790383B2 (en) * | 2011-09-30 | 2015-10-07 | 三洋電機株式会社 | Alkaline storage battery |
-
1986
- 1986-04-15 JP JP61086312A patent/JPS62243254A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62243254A (en) | 1987-10-23 |
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| JPS6376262A (en) | Non-sintered type cadmium anode for alkaline storage battery | |
| JPH0711957B2 (en) | Non-aqueous secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |