JPH0241865B2 - - Google Patents
Info
- Publication number
- JPH0241865B2 JPH0241865B2 JP57136980A JP13698082A JPH0241865B2 JP H0241865 B2 JPH0241865 B2 JP H0241865B2 JP 57136980 A JP57136980 A JP 57136980A JP 13698082 A JP13698082 A JP 13698082A JP H0241865 B2 JPH0241865 B2 JP H0241865B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- nickel
- chemical impregnation
- electrolytic deposition
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 claims description 30
- 239000011149 active material Substances 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage 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
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
産業上の利用分野
本発明は、ニツケル−カドミウム蓄電池などに
用いるニツケル正極の製造法に関するものであ
る。
従来例の構成とその問題点
アルカリ電池用ニツケル正極の製造法として
は、従来より主にニツケル塩を含浸した多孔性基
板をアルカリ溶液中で陰分解する方法、あるいは
陰分解せずにアルカリ溶液中で処理をおこなう化
学含浸法、熱分解法、電解析出法などが知られて
いる。
この中で、電解析出法によれば、容量密度260
〜350ｍAh／c.c.の正極板を製造し得るが、更に高
容量密度の極板を得ようとした場合、活物質の電
極基板に対する表面付着がともない、困難な面が
ある。
一方、化学含浸法によれば、高容量密度極板が
得難く、また活物質利用が低いという問題点があ
る。反面、工程が簡単であり、分解処理エネルギ
ー、電力が不要のため、低コストで正極板を製造
し得る利点を有する。
また、電解析出法と同等の容量密度極板を得る
製造法として、熱分解法、陰分解法があるが、前
者は分解処理のための高エネルギーを要し、製造
時間が長い。また後者は高電力エネルギーを要
し、製造時間が長いという欠点を有する。
従つて、消費熱エネルギー、電力が少なく、し
かも活物質の表面付着の少ない状態で、活物質利
用率が高く、高容量密度の極板を低コストで製造
する方法が待望されていた。
発明の目的
本発明は、以上のような問題点を解決するもの
である。すなわち、電解析出法と化学含浸法との
組合せによつて、基板に水酸化ニツケルを充填す
ることにより、高容量密度で、なおかつ活物質利
用率が高いニツケル正極を低コストで製造するこ
とを目的とする。
発明の構成
本発明は、電解析出法に引き続いて、化学含浸
法により、水酸化ニツケルをそれぞれ一定重量比
率ずつ充填することを特徴とするものである。以
下実施例を詳細に説明する。
実施例の説明
電解析出法における電解液には濃度3.0モル／
、PH2.0の硝酸ニツケル溶液を用い、液温度80
℃において、多孔度80％のニツケル焼結基板を陰
極とし、対極には陽極に帯電したニツケル電極を
用いて、電解析出を行なつた。この後、乾燥を行
ない、引き続いて、濃度3.0モル／、PH1.5の硝
酸ニツケル水溶液（液温度60℃）中に浸漬して硝
酸ニツケルの含浸を行なう。含浸に続く乾燥の後
に、濃度4.0モル／のか性ソーダ水溶液（液温
度60℃）中に浸漬し、引き続いて水洗処理を行な
う。さらに上記化学含浸を繰り返した場合の、総
活物質充填量に対する電解析出法における活物質
重量比及び化学含浸法における活物質重量比と活
物質利用率との関係を図の特性線１及び以下の表
に示した。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for manufacturing a nickel positive electrode used in nickel-cadmium storage batteries and the like. Conventional configurations and their problems Conventional methods for manufacturing nickel positive electrodes for alkaline batteries include the method of decomposing a porous substrate impregnated with nickel salt in an alkaline solution, or the method of decomposing a porous substrate impregnated with a nickel salt in an alkaline solution. Chemical impregnation methods, thermal decomposition methods, and electrolytic deposition methods are known. Among these, according to the electrolytic deposition method, the capacity density is 260
Although it is possible to produce a positive electrode plate with a capacity of ~350 mAh/cc, it is difficult to obtain a plate with an even higher capacity density due to the surface adhesion of the active material to the electrode substrate. On the other hand, the chemical impregnation method has problems in that it is difficult to obtain a high capacity density electrode plate and the utilization of the active material is low. On the other hand, it has the advantage that the process is simple and requires no decomposition treatment energy or electric power, so that the positive electrode plate can be manufactured at low cost. In addition, there are pyrolysis methods and negative decomposition methods as manufacturing methods for obtaining electrode plates with a capacity density equivalent to that of the electrolytic deposition method, but the former requires high energy for decomposition treatment and takes a long time to manufacture. The latter also has the disadvantage of requiring high electrical power and long manufacturing time. Therefore, there has been a long-awaited method for manufacturing an electrode plate with high active material utilization rate and high capacity density at low cost while consuming less thermal energy and electric power and with less active material adhesion to the surface. OBJECT OF THE INVENTION The present invention solves the above-mentioned problems. In other words, by filling a substrate with nickel hydroxide through a combination of electrolytic deposition and chemical impregnation, it is possible to manufacture a nickel positive electrode with high capacity density and high active material utilization at low cost. purpose. Structure of the Invention The present invention is characterized in that nickel hydroxide is filled at a constant weight ratio by a chemical impregnation method following the electrolytic deposition method. Examples will be described in detail below. Description of Examples The electrolyte in electrolytic deposition has a concentration of 3.0 mol/
, using a nickel nitrate solution with a pH of 2.0, and a liquid temperature of 80
Electrolytic deposition was carried out at ℃ using a nickel sintered substrate with a porosity of 80% as a cathode and an anode-charged nickel electrode as a counter electrode. Thereafter, it is dried, and then impregnated with nickel nitrate by immersing it in an aqueous solution of nickel nitrate (liquid temperature: 60°C) with a concentration of 3.0 mol/pH 1.5. After impregnation and subsequent drying, it is immersed in a caustic soda aqueous solution (liquid temperature 60°C) with a concentration of 4.0 mol/min, followed by washing with water. Furthermore, when the above chemical impregnation is repeated, the relationship between the active material weight ratio in the electrolytic deposition method, the active material weight ratio in the chemical impregnation method, and the active material utilization rate with respect to the total active material filling amount is shown in characteristic line 1 and below in the figure. It is shown in the table below.
【表】
この結果、総活物質量に対して重量比で90〜60
％の活物質を電解析出法に充填した後に、引き続
いて、化学含浸法で10〜40％充填することによ
り、活物質の表面付着がなく、高容量密度でなお
かつ活物質利用率の高い、正極板を得ることがで
きた。
なお、電解析出法における電解液に塩化ニツケ
ルまたは硝酸コバルトまたは硝酸カドミウムを併
用した場合も同様な効果が得られた。
図の特性線２は、比較のため熱分解法と化学含
浸法を用いた際の化学含浸比率と活物質利用率と
の関係を示した。
熱分解法における含浸液は濃度3.5モル／、
PH1.5の硝酸ニツケル水溶液とし、この液に多孔
度約80％のニツケル焼結基板を含浸し、これを水
蒸気雰囲気中で加熱分解して活物質のニツケル酸
化物に転化した後に、引き続き前記の化学含浸を
行なつた。
同じく図の特性線３は陰分解法と化学含浸法を
用いた際の化学含浸比率と活物質利用率との関係
を示した。陰分解法における含浸液は４モル／
、PH1.5の硝酸ニツケル水溶液とし、この液に
多孔度約80％のニツケル焼結基板を含浸し、これ
を乾燥した後に引き続いて、濃度3.5モル／の
か性ソーダ溶液中で、基板を陰極に帯電させ、対
極には陽極に帯電したニツケル電極を用いて陰分
解した後に水洗処理を行なう。引き続き、これら
の操作を数回繰り返した後に、化学含浸を行なつ
た。
図から明らかな通り、電解析出法による水酸化
ニツケルの充填量を重量比で総活物質量の90〜60
％充填し、引き続いて、化学含浸法で残りの10〜
40％充填することにより、高容量密度でなおかつ
活物質利用率が96％以上と高い正極板を得ること
ができた。
発明の効果
このように本発明では、高容量密度でしかも活
物質利用率の高いニツケル正極を効率よく製造す
ることができる。[Table] As a result, the weight ratio to the total amount of active materials is 90 to 60.
% of active material is filled by electrolytic deposition, and then filled by 10 to 40% by chemical impregnation method, resulting in no surface adhesion of active material, high capacity density, and high active material utilization rate. We were able to obtain a positive electrode plate. Note that similar effects were obtained when nickel chloride, cobalt nitrate, or cadmium nitrate was used in combination with the electrolytic solution in the electrolytic deposition method. Characteristic line 2 in the figure shows the relationship between the chemical impregnation ratio and the active material utilization rate when the thermal decomposition method and the chemical impregnation method are used for comparison. The concentration of the impregnating liquid in the pyrolysis method is 3.5 mol/,
A nickel nitrate aqueous solution with a pH of 1.5 was prepared, a nickel sintered substrate with a porosity of about 80% was impregnated with this solution, and this was heated and decomposed in a steam atmosphere to convert it into nickel oxide as an active material, and then the above-mentioned process was carried out. Chemical impregnation was performed. Similarly, characteristic line 3 in the figure shows the relationship between the chemical impregnation ratio and the active material utilization rate when using the implicit decomposition method and the chemical impregnation method. The impregnating solution in the negative decomposition method is 4 mol/
A sintered nickel substrate with a porosity of approximately 80% is impregnated with this aqueous solution of nickel nitrate with a pH of 1.5, and after drying, the substrate is made into a cathode in a caustic soda solution with a concentration of 3.5 mol. The sample is charged, and an anode-charged nickel electrode is used as the counter electrode for negative decomposition, followed by washing with water. Subsequently, after repeating these operations several times, chemical impregnation was performed. As is clear from the figure, the amount of nickel hydroxide filled by electrolytic deposition is 90 to 60% of the total active material amount in terms of weight ratio.
% filling and subsequently the remaining 10 ~ by chemical impregnation method
By filling 40%, it was possible to obtain a positive electrode plate with a high capacity density and an active material utilization rate of 96% or more. Effects of the Invention As described above, according to the present invention, a nickel positive electrode having a high capacity density and a high active material utilization rate can be efficiently manufactured.
図は総活物質重量に対する、活物質の化学含浸
比率と活物質利用率との関係を示したものであ
る。
１……電解析出法に化学含浸法を併用した場
合、２……熱分解法に化学含浸法を併用した場
合、３……陰分解法に化学含浸法を併用した場
合。
The figure shows the relationship between the chemical impregnation ratio of the active material and the active material utilization rate with respect to the total active material weight. 1... When a chemical impregnation method is used in combination with the electrolytic deposition method, 2... When a chemical impregnation method is used in combination with a pyrolysis method, 3... When a chemical impregnation method is used in combination with an implicit decomposition method.
Claims (1)
化ニツケルの一部を充填した後、引き続いて化学
含浸法によつて水酸化ニツケルを充填する方法で
あつて、前記電解析出法による水酸化ニツケルの
充填量を重量比で総活物質量の90〜60％とし、化
学含浸法による水酸化ニツケルの充填量を10〜40
％とすることを特徴としたアルカリ電池用ニツケ
ル正極の製造法。1 A method in which a sintered electrode substrate is partially filled with nickel hydroxide by an electrolytic deposition method, and then filled with nickel hydroxide by a chemical impregnation method, the method comprising: The filling amount of nickel hydroxide by weight ratio is 90 to 60% of the total active material amount, and the filling amount of nickel hydroxide by chemical impregnation method is 10 to 40% of the total active material amount.
% of a nickel positive electrode for alkaline batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136980A JPS5927457A (en) | 1982-08-05 | 1982-08-05 | Manufacturing method of nickel positive electrode for alkaline batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136980A JPS5927457A (en) | 1982-08-05 | 1982-08-05 | Manufacturing method of nickel positive electrode for alkaline batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5927457A JPS5927457A (en) | 1984-02-13 |
| JPH0241865B2 true JPH0241865B2 (en) | 1990-09-19 |
Family
ID=15187951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57136980A Granted JPS5927457A (en) | 1982-08-05 | 1982-08-05 | Manufacturing method of nickel positive electrode for alkaline batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5927457A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3533032B2 (en) * | 1996-04-03 | 2004-05-31 | 松下電器産業株式会社 | Alkaline storage battery and its manufacturing method |
| JP5557227B2 (en) * | 2009-03-23 | 2014-07-23 | 独立行政法人産業技術総合研究所 | Nickel positive electrode for fiber batteries |
-
1982
- 1982-08-05 JP JP57136980A patent/JPS5927457A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5927457A (en) | 1984-02-13 |
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