JPS634568A - Manufacture of alkali secondary battery - Google Patents
Manufacture of alkali secondary batteryInfo
- Publication number
- JPS634568A JPS634568A JP61147094A JP14709486A JPS634568A JP S634568 A JPS634568 A JP S634568A JP 61147094 A JP61147094 A JP 61147094A JP 14709486 A JP14709486 A JP 14709486A JP S634568 A JPS634568 A JP S634568A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- nickel
- active material
- nickel hydroxide
- battery
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000003513 alkali Substances 0.000 title abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 21
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims abstract description 9
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 abstract description 16
- 239000010941 cobalt Substances 0.000 abstract description 16
- 229910052759 nickel Inorganic materials 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000011149 active material Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 11
- 229910052793 cadmium Inorganic materials 0.000 description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 wire mesh Substances 0.000 description 1
- 229910006279 γ-NiOOH Inorganic materials 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアルカリ二次電池の製造法に関し、さらに詳し
くは、水酸化ニッケルを正極活物質とするペースト式正
極と、酸化カドミウムを負極活物質とするペースト式負
極とからなる二次電池であって、ペースト状活物質充填
後の両極の化成処理が不要であシ、かつ良好な充放電特
性を有するアルカリ二次電池に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing an alkaline secondary battery, and more specifically, it relates to a method for manufacturing an alkaline secondary battery, and more specifically, a paste-type positive electrode using nickel hydroxide as a positive electrode active material, and a paste-type positive electrode using cadmium oxide as a negative electrode active material. The present invention relates to an alkaline secondary battery comprising a paste type negative electrode, which does not require chemical conversion treatment of both electrodes after filling with a paste active material, and has good charge/discharge characteristics.
従来、ニッケルカドミウム電池と呼ばれる７／’Ｌ。 Conventionally, 7/'L is called a nickel-cadmium battery.
カリ二次電池のニッケル正極、カドミウム負極は、カー
ボニルニッケルを成形、焼結して得られた基板に、硝酸
ニッケルあるいは硝酸カドミウムの水溶液を含浸し、つ
いでアルカリ液中で硝酸ニッケルあるいは硝酸カドミウ
ムを、それぞれ水酸化ニッケルあるいは水酸化カドミウ
ムに転化せしめることによって製造された焼結方式を使
用することが一般的であった。しかしこの状態では、基
板中になお少量の硝酸根が存在しているため、これを除
去するため、アルカリ液中にて充放電を繰返すいわゆる
化成処理を行なっている。これらの工程は極めて複雑で
あシ、経済的でない。そこでこの焼結方式に代るものと
して、水酸化ニッケルあるいは酸化カドミウム等の直接
活物質となシ得る物ｉｔペースト化し、パンチトメタル
、金網等の二次元的基板、あるいは発泡ニッケル、金属
繊維焼結体等の三次元的基板に直接充填塗布して得られ
るペースト方式が提案され、−部使用されている。Nickel positive electrodes and cadmium negative electrodes for potassium secondary batteries are made by forming and sintering carbonyl nickel, impregnating a substrate with an aqueous solution of nickel nitrate or cadmium nitrate, and then adding nickel nitrate or cadmium nitrate in an alkaline solution. It has been common to use sintering methods produced by conversion to nickel hydroxide or cadmium hydroxide, respectively. However, in this state, a small amount of nitrate radicals still exist in the substrate, so in order to remove them, a so-called chemical conversion treatment is performed in which charging and discharging are repeated in an alkaline solution. These processes are extremely complex and uneconomical. Therefore, as an alternative to this sintering method, materials that can be directly used as active materials, such as nickel hydroxide or cadmium oxide, are made into an IT paste, and two-dimensional substrates such as punched metal, wire mesh, or nickel foam and sintered metal fibers are used. A paste method obtained by directly filling and coating a three-dimensional substrate such as a solid body has been proposed and has been used in some cases.
ペースト方式で製造された正負極中には、自己放電の原
因となる硝酸根等の不純物が混入しないため、焼結方式
のようにアルカリ液中で充放電を行なわなくとも電極と
して使用できる。しかし電池に組込む際、負極は正極に
比べて、ある程度充電状態でなくてはならなかった。こ
れは放電容量を長期にわたって、正極支配状態に置くた
めであり、この負極の充電量をプリチャージ量と言う。Since the positive and negative electrodes manufactured by the paste method do not contain impurities such as nitrate radicals that cause self-discharge, they can be used as electrodes without charging and discharging in an alkaline solution unlike the sintering method. However, when assembled into a battery, the negative electrode had to be in a somewhat more charged state than the positive electrode. This is to keep the discharge capacity in a positive electrode dominated state for a long period of time, and the amount of charge of this negative electrode is called the precharge amount.
水酸化ニッケルを正極活物質、酸化カドミウムを負極活
物質として使用した場合、電極製造時においては、正負
極とも完全放電状態であり、この状態では電池に組込む
ことができないため、負極のみアルカリ液中で充電を行
なって、プリチャージ部分を設けており、そのため工程
が焼結方式と同様に複雑なものとなっていた。When nickel hydroxide is used as the positive electrode active material and cadmium oxide as the negative electrode active material, both the positive and negative electrodes are in a fully discharged state at the time of electrode manufacture, and they cannot be incorporated into a battery in this state, so only the negative electrode is placed in an alkaline solution. A pre-charging section was provided, making the process as complicated as the sintering method.
本発明は従来のかかる問題を解消し、水酸化ニッケルを
正極活物質とするペースト式正極と、酸化カドミウムを
負極活物質とするペースト式負極からなる二次電池であ
って、両極とも化成処理が不要なアルカリ二次電池の提
供を目的とする。The present invention solves this conventional problem and provides a secondary battery consisting of a paste type positive electrode using nickel hydroxide as the positive electrode active material and a paste type negative electrode using cadmium oxide as the negative electrode active material, both electrodes being chemically treated. The purpose is to provide unnecessary alkaline secondary batteries.
本発明者は上記目的を達成すべく鋭意研究を亘ねる中で
、ニッケル正極を製造する際、ペースト状活物質中に水
酸化ニッケルと共に、プリチャージ相当分の金属コバル
ト粉末を配合すれば良いとの着想を得、実際に使用した
ときに優れた効果が得られることを確認して、本発明を
完成するに至った。In order to achieve the above object, the present inventor conducted intensive research and found that when manufacturing a nickel positive electrode, it is sufficient to mix metal cobalt powder equivalent to the precharge amount with nickel hydroxide in the paste active material. The present invention was completed after obtaining the idea and confirming that excellent effects can be obtained when actually used.
すなわち、本発明のアルカリ二次電池は、水酸化ニッケ
ルを正極活物質、酸化カドミウムを負極活物質とするペ
ースト式電極からなる二次電池であって、正極活物質中
に金属コバルト粉末を、水酸化ニッケル量の１０〜３０
重量％配合してお夛、各々製造した正負極を、化成処理
を行なわずに、巻回、缶挿入、電解液注入、密閉化して
電池を製造したのち、電池状態で充放電を行なうことを
特徴としている。That is, the alkaline secondary battery of the present invention is a secondary battery consisting of a paste type electrode using nickel hydroxide as a positive electrode active material and cadmium oxide as a negative electrode active material, and in which metal cobalt powder is mixed with water in the positive electrode active material. Nickel oxide amount of 10 to 30
After mixing the positive and negative electrodes by weight%, winding them, inserting them into a can, injecting an electrolyte, and sealing them without chemical conversion treatment to manufacture a battery, the battery is charged and discharged in the battery state. It is a feature.
コバルト粉末をニッケル正極に添加した場合、活物質で
ある水酸化ニッケルの利用率が向上するが、その理由は
充電時にβ−Ｎｉ（ｏＨ）、が可逆性の大きい、ｙ−Ｎ
ｉｏｏＨに充電されたのち、可逆性の小さい高次酸化物
であるγ−ＮｉＯＯＨに転化するのを抑える働きがある
ためである。同時ンζコバルトは金属と２価間の可逆性
が非常に小さく、金属コバルトは容易に水酸化コバルト
に酸化されるが、水酸化コバルトは金属コバルトにほと
んど還元されない。When cobalt powder is added to the nickel positive electrode, the utilization rate of the active material nickel hydroxide improves, but this is because β-Ni(oH) is highly reversible during charging,
This is because, after being charged to iooH, it has the function of suppressing conversion to γ-NiOOH, which is a higher-order oxide with low reversibility. Cobalt has very low reversibility between metal and divalent cobalt, and metallic cobalt is easily oxidized to cobalt hydroxide, but cobalt hydroxide is hardly reduced to metallic cobalt.
よって、水酸化ニッケル中に金属コバルトを配合してニ
ッケル正極を作成した場合、最初の充電時には、第１図
のように、水酸化ニッケルの充電電位Ｂ （Ｎｌ （Ｏ
Ｈ）ｚ→Ｎｊ００Ｈ）に先立って、＋１．０ＶｖｓＣｄ
／Ｃｄ”＋付近の電位Ａで、金属コバルトの酸化（Ｃｏ
→Ｃｏ（ＯＨｔ））が見られる。反面放電時には水酸化
コバルトの反応がないため、オキシ水酸化ニッケルの放
電電位Ｃ（Ｎ １ｏＯＨ−＋ Ｎ ｉ （ＯＨ）ｚ ）
のみが見られる。そこで、酸化カドミウムを負極活物質
とするペースト式カドミウム負極と、該ニッケル正極と
組合せて充１ｉ！Ｌを行なった場合、カドミウム陰極は
、コバルトの酸化および水散化ニッケルの充電に使用さ
れた合計の容量が充電されるが、放電時はオキシ水酸化
ニッケルの放電しか行なわれないため、充電時にコバル
ト酸化に使用された容量がプリチャージ量として、カド
ミウム負極に残留することになる。好ましいプリチャー
ジ量の範囲は、正極と負極の固有容量比によって異るが
、−般にニッケル正極容量の２０〜５０％であ夛、これ
をコバルト配合量に適用すると、水酸化ニッケルとの重
量比で１０〜３０重量％という値になる。プリチャージ
量が小さすぎると、充放ｔ’を繰返してカドミウム負極
が不活性化して容量減少した際に１負極が正極よシ先に
完全放電状態となる容量負極支配の状態罠なってしまう
。反面プリチャージ量が過大であると、同様にカドミウ
ム負極が容量減少した際、負極が正極よシも先に完全充
電状態となってしまい、電池内で吸収できない水素ガス
を発生し、電池内圧を著しく高めてしまう等の不具合が
ある。Therefore, when a nickel positive electrode is created by blending metallic cobalt into nickel hydroxide, the charging potential of nickel hydroxide B (Nl (O
H) z→Nj00H), +1.0V vs Cd
/Cd''+ oxidation of metal cobalt (Co
→Co(OHt)) can be seen. On the other hand, since there is no reaction of cobalt hydroxide during side discharge, the discharge potential of nickel oxyhydroxide C (N1oOH-+Ni(OH)z)
only can be seen. Therefore, a paste-type cadmium negative electrode using cadmium oxide as the negative electrode active material was combined with the nickel positive electrode to achieve 1i! When performing L, the cadmium cathode is charged with the total capacity used for cobalt oxidation and dispersion of nickel, but only nickel oxyhydroxide is discharged during discharging, so when charging The capacity used for cobalt oxidation remains in the cadmium negative electrode as a precharge amount. The preferred range of precharge amount varies depending on the specific capacitance ratio of the positive electrode and negative electrode, but it is generally 20 to 50% of the nickel positive electrode capacity, and if this is applied to the cobalt content, the weight with nickel hydroxide The ratio is 10 to 30% by weight. If the precharge amount is too small, when charging and discharging t' are repeated to inactivate the cadmium negative electrode and the capacity decreases, one negative electrode becomes completely discharged before the positive electrode, resulting in a state where the negative electrode dominates the capacity. On the other hand, if the precharge amount is too large, when the capacity of the cadmium negative electrode decreases, the negative electrode will reach a fully charged state before the positive electrode, generating hydrogen gas that cannot be absorbed within the battery, causing the internal pressure of the battery to decrease. There are problems such as a marked increase in the temperature.
（１） 本発明のアルカリ二次電池、の製造法の実施
例水酸化ニッケル１００３に対し、金属コバルト粉末５
，９，１０ｇ、２０．！ｉ’、３０．！ｉ’、４０．９
を各々配合した活物質をペースト化し、これを発泡ニッ
ケル基板に塗布、乾燥、加圧を行ないペースト式ニッケ
ル正極を得た。また酸化カドミウムをペースト化し、パ
ンチトメタルに塗布、ＩＩｉ、燥、加圧を行なって、ペ
ースト式カドミウム負極を得た。ニッケル正極容量】に
対し、カドミウム負極容量が２となるように、両極を切
断加工したのち、未化成の状態でセパレータを介して巻
回し、缶挿入、電解液注入、密閉化を行ない、単３サイ
ズのアルカリ二次電池を製造した。電池を６０ｍＡの電
流で２４時間充電した後、１２０ ｍＡの電流で放電を
行ない、正負極活物質の活性化を行なった。(1) Example of the manufacturing method for the alkaline secondary battery of the present invention: 1003 nickel hydroxide, 55% metal cobalt powder
,9,10g,20. ! i', 30. ! i', 40.9
The active materials containing each of these were made into a paste, and this was applied onto a foamed nickel substrate, dried, and pressed to obtain a paste-type nickel positive electrode. Further, cadmium oxide was made into a paste, applied to a punched metal, dried, and pressurized to obtain a paste-type cadmium negative electrode. After cutting both electrodes so that the capacity of the cadmium negative electrode is 2 compared to the capacity of the nickel positive electrode, the electrodes are wound in an unformed state through a separator, inserted into a can, injected with electrolyte, and sealed. An alkaline secondary battery of the same size was manufactured. After charging the battery with a current of 60 mA for 24 hours, it was discharged with a current of 120 mA to activate the positive and negative electrode active materials.
（２） アルカリ二次電池の充放電特性評価（１）の
方法で製造した各種コバルト配合のアルカリ二次電池に
対して、２００ｍＡの電流にて４０．５時間充電したの
ち、６００ｍＡの電流にて電池電圧１．０■まで放電し
て、】サイクルとする充放電サイクル試験を行なった。(2) Evaluation of charging and discharging characteristics of alkaline secondary batteries Alkaline secondary batteries containing various cobalt compounds produced by the method in (1) were charged with a current of 200 mA for 40.5 hours, and then with a current of 600 mA. A charge/discharge cycle test was conducted in which the battery was discharged to a voltage of 1.0 ■ and then cycled.
その結果を第２図に示す。コバルト５％配合した電池は
、２５０サイクル以後徐々に容量低下し、５００サイク
ルで初期容量の１／２以下となった。反面コバルト４０
％配合した電池は、初期容量から他の電池と比較して容
量が小さいが、これは正極に多量のコバルトを配合した
ため正極活物質である水酸化ニッケルの配合量が少ない
ことによる。この電池は６００サイクルで漏液を起こし
たため、試験から除外した。これら劣化の原因は、コバ
ルト５％の場合は、サイクル途中に放電容量が負極支配
となシ、徐々に容量減少したためである。またコバルト
４０％の場合は、サイクル途中に充電時負極より水素発
生を起こし、電池内圧が上昇したためと思われる。それ
以外のコバルト粉末１０〜３０重量％配合したニッケル
正極を組込んだ電池は、７００サイクルまでは良好な充
放′ＷＬ％性が得られた。これはコバルト配合による負
極プリチャージ量が適正であったためと思われる。The results are shown in FIG. The capacity of the battery containing 5% cobalt gradually decreased after 250 cycles, and reached 1/2 or less of the initial capacity after 500 cycles. On the other hand, cobalt 40
The initial capacity of the batteries containing 100% of nickel hydroxide is smaller than that of other batteries, but this is because a large amount of cobalt is blended into the positive electrode, resulting in a small amount of nickel hydroxide, which is the positive electrode active material. This battery leaked after 600 cycles and was excluded from the test. The cause of these deteriorations is that in the case of 5% cobalt, the discharge capacity was dominated by the negative electrode during the cycle, and the capacity gradually decreased. Moreover, in the case of 40% cobalt, it is thought that hydrogen was generated from the negative electrode during charging during the cycle, and the internal pressure of the battery increased. Other batteries incorporating a nickel positive electrode containing 10 to 30% by weight of cobalt powder had good charge/discharge WL% properties up to 700 cycles. This seems to be because the amount of negative electrode precharge due to the cobalt content was appropriate.
以上の説明から明らかなように、正極にコバルト粉末を
水酸化ニッケルに対し１０〜３０重量％配合し、両極と
も未化成状態で巻回、缶挿入、電解液注入、密閉化を行
なった本発明のアルカリ二次電池は、容易な製造方法で
あり、かつ良好な充放電特性を有する浸れたものである
。As is clear from the above description, the present invention involves mixing 10 to 30% by weight of cobalt powder with respect to nickel hydroxide in the positive electrode, and winding, inserting into a can, injecting electrolyte, and sealing both electrodes in an unformed state. The alkaline secondary battery is a submerged one which is easy to manufacture and has good charge and discharge characteristics.
【図面の簡単な説明】
第１図は本発明のニッケル正極の充放電時のＣｄに対す
る電位図で、放電容量を１００Ｓとした時の各充放’Ｉ
Ｃ電気量の電位曲線である。第２図は金属コバルト粉末
を各種配合したニッケル正極を組込んだアルカリ二次電
池の充放電サイクルに対する放電々気量の変化図である
。
人・・・Ｃｏの充電４位[Brief explanation of the drawings] Fig. 1 is a potential diagram for Cd during charging and discharging of the nickel positive electrode of the present invention, and shows the potential diagram for each charge and discharge when the discharge capacity is 100S.
It is a potential curve of C quantity of electricity. FIG. 2 is a diagram showing changes in the amount of discharged air with respect to charge/discharge cycles of an alkaline secondary battery incorporating a nickel positive electrode containing various types of metal cobalt powder. People...Co charging 4th place
Claims (1)
酸化ニッケルに対して１０〜３０重量％配合してなるペ
ースト式正極と、酸化カドミウムを負極活物質とするペ
ースト式負極とから構成され、両極とも未化成の状態で
巻回、缶挿入、電解液注入、密閉化により電池としたの
ち、該電池を充放電して正負極活物質の活性化を行なう
ことを特徴とするアルカリ二次電池の製造法。It consists of a paste-type positive electrode made of a nickel hydroxide positive electrode active material mixed with metallic cobalt powder in an amount of 10 to 30% by weight based on nickel hydroxide, and a paste-type negative electrode made of cadmium oxide as a negative electrode active material. An alkaline secondary battery characterized by forming a battery in an unformed state by winding, inserting a can, injecting an electrolyte, and sealing, and then charging and discharging the battery to activate positive and negative electrode active materials. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61147094A JPS634568A (en) | 1986-06-25 | 1986-06-25 | Manufacture of alkali secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61147094A JPS634568A (en) | 1986-06-25 | 1986-06-25 | Manufacture of alkali secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS634568A true JPS634568A (en) | 1988-01-09 |
Family
ID=15422342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61147094A Pending JPS634568A (en) | 1986-06-25 | 1986-06-25 | Manufacture of alkali secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS634568A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0284333A2 (en) * | 1987-03-25 | 1988-09-28 | Matsushita Electric Industrial Co., Ltd. | Sealed type nickel-hydride battery and production process thereof |
| US5212261A (en) * | 1990-12-17 | 1993-05-18 | Henkel Research Corporation | Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems |
| JPH0737610A (en) * | 1992-12-10 | 1995-02-07 | Furukawa Battery Co Ltd:The | Manufacture of sealed alkaline storage battery using paste type nickel positive electrode |
-
1986
- 1986-06-25 JP JP61147094A patent/JPS634568A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0284333A2 (en) * | 1987-03-25 | 1988-09-28 | Matsushita Electric Industrial Co., Ltd. | Sealed type nickel-hydride battery and production process thereof |
| US5212261A (en) * | 1990-12-17 | 1993-05-18 | Henkel Research Corporation | Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems |
| JPH0737610A (en) * | 1992-12-10 | 1995-02-07 | Furukawa Battery Co Ltd:The | Manufacture of sealed alkaline storage battery using paste type nickel positive electrode |
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