JPS6348746A - Manufacture of nickel positive electrode for alkaline storage battery - Google Patents
Manufacture of nickel positive electrode for alkaline storage batteryInfo
- Publication number
- JPS6348746A JPS6348746A JP61193457A JP19345786A JPS6348746A JP S6348746 A JPS6348746 A JP S6348746A JP 61193457 A JP61193457 A JP 61193457A JP 19345786 A JP19345786 A JP 19345786A JP S6348746 A JPS6348746 A JP S6348746A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- substrate
- positive electrode
- active material
- cobalt
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- 238000003860 storage Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011149 active material Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract 3
- 239000012266 salt solution Substances 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 229910006279 γ-NiOOH Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- -1 nickel gold nitrate Chemical compound 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/32—Nickel oxide or hydroxide 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
- H01M4/24—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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は二ノゲルーカドミウム蓄電観、ニッケルー亜鉛
蓄市也などのアルカリ蓄電池に用・のられるニッケル正
極の袈背方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for lining a nickel positive electrode used in alkaline storage batteries such as Ninogel-cadmium storage batteries and nickel-zinc storage batteries.
（ロ）従来の技術
従来アルカリ蓄′１寵池のニッケル正極ぽ、力−ボニル
ニッゲｙ扮宋全生成かとするスラリー全芯体（てコーチ
イノブレ、これ？還元雰囲気下で焼結して得た多孔性ニ
ッケル基板中に、硝酸ニッケル金主成分とした含浸液を
含浸し、次いでアルカリ処理に浸漬して基板の孔中に活
物質を充填させる製造方法を用いて作成されている。し
かし最近の市場要求は前述の製造方法で得な正極を用い
たアルカリ蓄電池では満足できず、′屯池の容量アップ
を強く望むものであり、市４要求を満たす之め昏ても、
極板容量の大さなまた体積エネルギー密度の大きな正極
を開発する必要がある。″ｆｆ、櫃容量全容量させる基
本的な方法としては活＠質の利用率を増加させる方法が
考えられ、そのなめにコバルトを添加することが提案さ
れている。(B) Conventional technology Conventional alkaline storage '1 Nickel positive electrode, power - Bonyl Nigge Y, Song whole generation slurry entire core It is manufactured using a manufacturing method in which a nickel substrate is impregnated with an impregnating solution containing nickel gold nitrate as a main component, and then immersed in an alkaline treatment to fill the active material into the pores of the substrate.However, recent market demands They are not satisfied with the alkaline storage battery using the positive electrode manufactured by the above-mentioned manufacturing method, and strongly desire to increase the capacity of the pond.
It is necessary to develop a positive electrode with a large plate capacity and a large volumetric energy density. ``ff, The basic method of increasing the capacity of the tank to its full capacity is to increase the utilization rate of active materials, and it has been proposed to add cobalt to this end.
コバルトの添加方法として、−ｉ、活物質含浸液中に硝
酸コバルトを添加しておく方法、或いは持聞昭５９−１
６５３７０号公報（て記載されたようンて、水酸化ニッ
ケ／Ｖ全生成分とする活物質？保挿させ、た多孔性ニッ
ケル基板全＠酸コバルト？含む＠酸塩水溶液７ｃ浸漬し
、次いでアルカリ処理？して前記活物質の表面部分ｉて
水酸化コバルトが単独で存在する１酋を形成した後、過
酸化水素水等の酸化剤音用いて前記水酸化コバルト全酸
化させるアルカリ蓄電池用ニッケル正極の製造方法が示
されているが、酸化コバルト層全形成させる工程が複雑
であり、また初期サイクル特性劣化の原因となる〆八
−Ｎ ｉ ＯＯＨ生成の抑制効果が不十分であっ之。As a method of adding cobalt, -i, a method of adding cobalt nitrate to the active material impregnation solution, or a method of adding cobalt nitrate to the active material impregnating solution, or
65370, a porous nickel substrate was immersed in an active material containing all nickel hydroxide/V hydroxide, immersed in an aqueous salt solution containing all cobalt oxide, and then immersed in an aqueous solution 7c of an acid salt containing all cobalt hydroxide. After processing to form a layer in which cobalt hydroxide exists alone on the surface portion of the active material, the cobalt hydroxide is completely oxidized using an oxidizing agent such as hydrogen peroxide solution.A nickel positive electrode for an alkaline storage battery. However, the process of forming the entire cobalt oxide layer is complicated, and the effect of suppressing the formation of 〆8-N i OOH, which causes deterioration of initial cycle characteristics, is insufficient.
また更にいずれの方法におＡても、充放′屯サイクルの
進行に伴い正極の活性度が上昇し安定な活性度を保つこ
とができず、正、負極のバランスがくずれ、゛電池のサ
イクル寿命が短くなる七いう問題点があった。Furthermore, in any method A, the activity of the positive electrode increases as the charge/discharge cycle progresses, making it impossible to maintain a stable activity, resulting in an imbalance between the positive and negative electrodes, and the cycle of the battery. There were seven problems that shortened the lifespan.
（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濫みなされたものであって、初期
サイクル特性に優れ、且つ長期に亘って高容量が維持で
きるアルカリ蓄電池用ニッケル正極の製造方法を提供せ
んとするものであるっに）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ニッケル正極の製造方法は、
多孔性のニッケル基板全ニッグ／Ｖ塩溶液に浸漬し、ニ
ッケＡ／塩を含浸させ、アルカリ処理全行って活物質を
充填し乏後、活＠質を充填し次前記基板を水酸化コバル
ト塩水溶液させ之ア〜カリ水溶液に浸漬し、空気中で加
熱処理を行うこと全要旨とするものであるっ尚、空気中
で加熱処理を行う七きの温度は１００〜１５０°Ｃであ
ることが好ましい。(c) Problems to be Solved by the Invention The present invention has been made in view of the above-mentioned problems, and is directed to the production of a nickel positive electrode for alkaline storage batteries that has excellent initial cycle characteristics and can maintain high capacity over a long period of time. Means for solving the problems The method for manufacturing a nickel positive electrode for alkaline storage batteries of the present invention is as follows:
A porous nickel substrate is immersed in a Nigg/V salt solution, impregnated with Nickel A/salt, and alkali treatment is performed to fill the active material. The whole idea is to immerse it in an aqueous aqueous solution of aqueous potassium and heat it in the air, but the temperature at which it heats it in the air should be 100 to 150°C. preferable.
（ホ）作用
ニッケル活物質を充填し之基板を水酸化コバルトを溶解
させたアルカリ溶液に浸漬し、空気中で加熱することに
より酸化コバルト層が形成される。この形成された酸化
コバルト層は、アルカリ中和反応により析出させた水酸
化コバルト層を酸化させ友ものよりち密であって安定し
た電導性の高い酸化コバルトが生成するため極板の充電
効率が上昇し、極板の活性度が高いままに維持されるの
で長期に亘ってサイクル特性が安定化し、サイクル寿命
が長くなる。またこれに加えて活性度の低いＸ−Ｎｉ０
ＯＨの生成を抑えるので初期サイクル時の容量劣化が抑
制される。(e) A cobalt oxide layer is formed by immersing the substrate filled with the functional nickel active material in an alkaline solution in which cobalt hydroxide is dissolved and heating it in air. This formed cobalt oxide layer oxidizes the cobalt hydroxide layer precipitated by an alkali neutralization reaction, producing cobalt oxide that is denser than its companion, stable, and highly conductive, increasing the charging efficiency of the electrode plate. However, since the activity of the electrode plate is maintained at a high level, the cycle characteristics are stabilized over a long period of time, and the cycle life is extended. In addition to this, X-Ni0 with low activity
Since the generation of OH is suppressed, capacity deterioration during the initial cycle is suppressed.
（へ）実施例
実施例１
多孔度８０ｑ６の多孔性ニラクル焼結基板に硝酸ニッケ
ル水溶液を含浸させた後水酸化ナトリウム水溶液中にて
アルカリ処理し、硝酸ニッケｐを水酸化ニッケルに変化
させ活物質化し、水洗、乾燥という一連の工程全６回操
り返し念後、濃度３０％の水酸化ナトリウム水溶液に水
酸化コバルトを飽和溶解させた８０℃の熱Ｄアルカリ中
に浸漬した後、空気中１５０℃で３０分加熱処理を行い
ニッケル活物質に対して１重量％のコバルト層を有した
ニッケル正極を得、公知のカドミウム負極と組み合せ公
称容量１．２ Ａ Ｈのニッケルーカドミウム蓄電池を
組み立て、本発明電池Ａとした。(F) Examples Example 1 A porous Niracle sintered substrate with a porosity of 80q6 is impregnated with an aqueous nickel nitrate solution, and then treated with an alkali in an aqueous sodium hydroxide solution to convert the nickel nitrate p into nickel hydroxide, forming an active material. After repeating the process six times, immersing it in a heated alkali solution containing cobalt hydroxide saturated in a 30% sodium hydroxide aqueous solution at 80°C, it was heated to 150°C in air. A nickel positive electrode having a cobalt layer of 1% by weight with respect to the nickel active material was obtained by heat treatment for 30 minutes, and was combined with a known cadmium negative electrode to assemble a nickel-cadmium storage battery with a nominal capacity of 1.2 AH. It was designated as battery A.
比較例１
コバルト層全全く有しない以外は実施例１と同様にして
活物￥ｔを充填し、８０°Ｃで乾燥を行い、電池を組み
立て比較電池Ｂを得た。Comparative Example 1 A battery was assembled in the same manner as in Example 1 except that the cobalt layer was completely omitted, and the battery was filled with a live substance, dried at 80°C, and a comparative battery B was obtained.
比較例２
硝酸ニッケル水溶液中に１重量％の硝酸コバルトを添加
し之含浸液を用い、７μ力＋７ Ｊｌ＆理し、水洗、乾
燥という一連の工程を６回繰り返して活物質を充填した
ニッケル正極を用いて比、較′ｉ池Ｃを得た。Comparative Example 2 A nickel positive electrode filled with an active material was prepared by adding 1% by weight of cobalt nitrate to an aqueous nickel nitrate solution, using the impregnating solution, washing with water, and drying six times. Comparison C was obtained.
比較例３
実施例１と同様にして活物質を充填し念後、コバルト塩
水溶液に浸漬後アルカリ処理し、ニッケル活物質に対し
１重量％のコバルト層を形成させた特開昭５９−１６５
３７０号公報の′＃造法によるニッケル正極を用い、比
較電池りを得た。Comparative Example 3 JP-A-59-165 was filled with an active material in the same manner as in Example 1, and then immersed in a cobalt salt aqueous solution and treated with alkali to form a 1% by weight cobalt layer on the nickel active material.
A comparative battery was obtained using a nickel positive electrode manufactured by the method disclosed in Japanese Patent No. 370.
このようにして得られた本発明電池Ａ１比較電池Ｂ、Ｃ
，Ｄを充電電流１．５ｃ（１８００ｍＡ）で１時間充電
後、１時間休止させ、放電電流ＩＣ（１２００ｍＡ）で
終止電圧０．８ｖとするサイクル条件にて、比較を行っ
た時の、サイクル特性比較図を第１図に示す。これより
本発明電池人は初期サイクル時の容量劣化がきわめて小
さいものであり、長期サイクルに亘っても安定した電池
容量を示している。Invention battery A1 comparative batteries B and C thus obtained
, D is charged for 1 hour at a charging current of 1.5c (1800mA), then paused for 1 hour, and the cycle characteristics are compared under the cycle conditions of a discharge current of IC (1200mA) and a final voltage of 0.8V. A comparison diagram is shown in Figure 1. This shows that the battery of the present invention exhibits extremely small capacity deterioration during initial cycles, and exhibits stable battery capacity even over long cycles.
更に第２図は本発明電ａＡＫ用いたニッケル正極ａと比
較電池りに用いたニッケル正極ｄとの、ニッケル正極充
電状態ておける要部Ｘ＠回折分析図を示し念ものである
。本発明によるニッケル正績ａは７’−Ｎｉ００の生成
がみとめられない。−方、比較例のニッケル正極ｄ／１
Ｔ−ＮｉＯＯＨが生成しており、これが初期サイクル時
の容量劣化？引きおこしていると考えられる。Furthermore, FIG. 2 shows the diffraction analysis diagram of the main part X of the nickel positive electrode a using the battery aAK of the present invention and the nickel positive electrode d used in the comparative battery in the nickel positive electrode charged state. In the nickel test result a according to the present invention, no formation of 7'-Ni00 was observed. - side, nickel positive electrode d/1 of comparative example
Is T-NiOOH generated and is this the capacity deterioration during the initial cycle? It is thought that it is causing the problem.
尚、熱濃アルカリの温度を実施例において８０°Ｃとし
ているが、種々の倹村により６０〜９０℃が好ましいこ
とが知得されている。In addition, although the temperature of the hot concentrated alkali is set to 80°C in the examples, it has been known from various studies that a temperature of 60 to 90°C is preferable.
（ト）発明の効果
本発明の製造方法によれば、初期サイクル特性が安定し
、長期に亘って高容量が維持できるアルカリ蓄電池用ニ
ッケル正極が提供でき、その工業的価値はきわめて大き
い。(g) Effects of the Invention According to the manufacturing method of the present invention, a nickel positive electrode for alkaline storage batteries with stable initial cycle characteristics and capable of maintaining high capacity over a long period of time can be provided, and its industrial value is extremely large.
第１図は不発Ｆ３Ａ電池Ａと、比較電池Ｂ、Ｃ，Ｄのサ
イクル特性図、第２図は本発明電極ａと比較？ｆ［ｄの
要部Ｘ線回折図である。
Ａ・・・末完８Ａ電池、Ｂ、Ｃ，Ｄ・−・比較電池。
出順人 三洋電機珠弐会社Figure 1 is a cycle characteristic diagram of unexploded F3A battery A and comparison batteries B, C, and D. Figure 2 is a comparison with electrode a of the present invention? It is a principal part X-ray diffraction diagram of f[d. A: Final 8A battery, B, C, D: Comparative battery. Junjin Sanyo Electric Co., Ltd.
Claims (1)
ッケル塩を含浸させ、アルカリ処理を行って活物質を充
填した後、活物質を充填した前記基板を水酸化コバルト
を溶解させたアルカリ水溶液に浸漬し、空気中で加熱処
理を行なうことを特徴とするアルカリ蓄電池用ニッケル
正極の製造方法。(1) After immersing a porous nickel substrate in a nickel salt solution to impregnate it with nickel salt and filling it with an active material by performing alkali treatment, the substrate filled with the active material is immersed in an alkaline aqueous solution in which cobalt hydroxide is dissolved. A method for producing a nickel positive electrode for an alkaline storage battery, which comprises immersing it and heat-treating it in air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61193457A JP2639915B2 (en) | 1986-08-18 | 1986-08-18 | Method for producing nickel positive electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61193457A JP2639915B2 (en) | 1986-08-18 | 1986-08-18 | Method for producing nickel positive electrode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6348746A true JPS6348746A (en) | 1988-03-01 |
| JP2639915B2 JP2639915B2 (en) | 1997-08-13 |
Family
ID=16308319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61193457A Expired - Fee Related JP2639915B2 (en) | 1986-08-18 | 1986-08-18 | Method for producing nickel positive electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2639915B2 (en) |
-
1986
- 1986-08-18 JP JP61193457A patent/JP2639915B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2639915B2 (en) | 1997-08-13 |
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