JPS63164163A - Nickel positive electrode for alkaline storage battery - Google Patents
Nickel positive electrode for alkaline storage batteryInfo
- Publication number
- JPS63164163A JPS63164163A JP61311391A JP31139186A JPS63164163A JP S63164163 A JPS63164163 A JP S63164163A JP 61311391 A JP61311391 A JP 61311391A JP 31139186 A JP31139186 A JP 31139186A JP S63164163 A JPS63164163 A JP S63164163A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- nickel hydroxide
- particles
- nickel
- active substance
- 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 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 238000003860 storage Methods 0.000 title claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 6
- 239000011149 active material Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 abstract description 38
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract 7
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 abstract 2
- 238000005187 foaming Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 18
- 238000012856 packing Methods 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/36—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
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、アルカリ蓄電池用ニッケル正極に関するもの
で、とくに水酸化ニッケル粉末を主とする活物質を支持
体内に充填するか、または支持体表面に塗着してなる非
焼結式ニッケル正極に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a nickel positive electrode for alkaline storage batteries. This invention relates to a non-sintered nickel positive electrode.
従来の技術
この種のニッケル正極として、スポンジ状ニッケル多孔
体（以後発泡メタルと称する）を支持体に用いる発泡メ
タル式ニッケル正極は、水酸化ニッケル粉末にニッケル
粉末およびコバルト粉末を加え、ペース状にした正極活
物質を上記基板（支持体）の内部に直接充填してなるも
のである。このニッケル正極は、基板の多孔度が９０〜
９８％と高く、しかも孔径が大きいので、電極の高容量
化が図れる。また基板が三次元的の網状構造を有してい
るので、各種の電極特性は焼結式に近い。Conventional Technology This type of nickel positive electrode uses a sponge-like porous nickel material (hereinafter referred to as foamed metal) as a support.The foamed metal nickel positive electrode uses nickel hydroxide powder, nickel powder, and cobalt powder as a paste. The positive electrode active material is directly filled inside the substrate (support). This nickel positive electrode has a substrate porosity of 90~
Since the pore size is as high as 98% and the pore diameter is large, it is possible to increase the capacity of the electrode. Furthermore, since the substrate has a three-dimensional network structure, various electrode characteristics are similar to those of the sintered type.
しかしながら、活物質である水酸化ニッケル粉末の大き
さは数μｍ〜ｍ数百μｍの範囲に分布しているためその
中の大きな粒子の活物質利用率が焼結式に較ベロ〜１０
％低く、しかも、バラツキが大きく安定性にも欠けると
いう欠点があった。However, since the size of the nickel hydroxide powder that is the active material is distributed in the range of several μm to several hundred μm, the active material utilization rate of the large particles is 10 to 10% compared to the sintering method.
%, and had the disadvantage of large variations and lack of stability.
そこで、本発明者らは第３図に示すように水酸化ニッケ
ルの粒子内部にコバルトの微粉末を含有させることを検
討した。同図において１は水酸化ニッケル粒子、２はそ
の内部に生ずる空間部、３はコバルト粒子を示す。Therefore, the present inventors considered incorporating fine cobalt powder inside the nickel hydroxide particles as shown in FIG. In the figure, 1 is a nickel hydroxide particle, 2 is a space formed inside the nickel hydroxide particle, and 3 is a cobalt particle.
その結果、この水酸化ニッケル粒子からなる粉末を用い
て構成したニッケル正極は、充電効率が改善でき、焼結
式の活物質充填密度の最高値である約６ｏ ｏ ｍＡｈ
／ｃｃの場合において、焼結式と同程度の活物質利用率
９０〜９６％に向上できる可能性を見い出し、その提案
（特開昭６ｏ−２５３１５６）も行なってきた。As a result, a nickel positive electrode constructed using powder made of nickel hydroxide particles has improved charging efficiency and has a sintered active material packing density of approximately 6 o mAh, which is the highest value.
/cc, we have discovered the possibility of improving the active material utilization rate to 90 to 96%, which is comparable to that of the sintering method, and have also made a proposal (Japanese Patent Application Laid-Open No. 6-253-156).
発明が解決しようとする問題点
しかしこのような従来の構成では、活物質利用率が安定
性を欠き、バラツキが極めて大きく、とくに活物質充填
密度が５００ｍＡｈ／ＣＣを超える高密度においてその
傾向が顕著となる問題点を未だ有していた。すなわち、
数十μｍ以上の大きな粒子の場合、内部に空間を有する
ため電子伝導性がわるく、充放電反応が進行し難くなる
。これは、コバルト粒子を含有させることによりある程
度は改善できたが、未だ不十分であった。Problems to be Solved by the Invention However, in such a conventional configuration, the active material utilization rate lacks stability and has extremely large variations, and this tendency is particularly noticeable at high active material packing densities exceeding 500 mAh/CC. It still had the following problems. That is,
In the case of large particles of several tens of micrometers or more, since they have spaces inside, electron conductivity is poor, making it difficult for charging and discharging reactions to proceed. Although this could be improved to some extent by including cobalt particles, it was still insufficient.
本発明はこのような問題点を解決するため、活物質粉末
である水酸化ニッケル粒子内の電子伝導性を向上させる
ことにより、とくに高密度充填時における発泡メタル式
ニッケル正極の活物質利用率の向上と安定化を図ること
を目的とするものである。In order to solve these problems, the present invention improves the electronic conductivity within the nickel hydroxide particles, which are active material powders, thereby increasing the active material utilization rate of foamed metal nickel positive electrodes, especially when densely packed. The purpose is to improve and stabilize the situation.
問題点を解決するだめの手段
この問題点を解決するだめ本発明は、水酸化ニッケルを
主体とする活物質を金属支持体内部に充填するか、また
はその表面に塗着して構成するニッケル正極において、
活物質の主体をなす水酸化ニッケルの粒子内部に金属銀
あるいは酸化銀の微粒子を含有させたものである。Means to Solve the Problems To solve the problems, the present invention provides a nickel positive electrode constructed by filling an active material mainly composed of nickel hydroxide inside a metal support or coating it on the surface thereof. In,
Fine particles of metallic silver or silver oxide are contained inside particles of nickel hydroxide, which is the main active material.
作用
この構成によるニッケル正極は、主活物質の水酸化ニッ
ケルの粒子内部に金属銀あるいは酸化銀の微粒子を含有
することにより、充電反応でムｇ２０あるいはＡｇｏ
まで酸化された銀が、放電反応ではムｇの金属銀まで
還元されるので水酸化ニッケル活物質粒子内の電子伝導
性を向上させ、水酸化ニッケル活物質の利用率を向上さ
せる。この作用は放電反応において酸化物が電子伝導性
の良好な金属状態まで還元される銀特有のものである。Function: The nickel positive electrode with this structure contains fine particles of metallic silver or silver oxide inside the particles of nickel hydroxide, which is the main active material, so that it can generate Mg20 or Ago in a charging reaction.
In the discharge reaction, the silver that has been oxidized to 100% is reduced to metallic silver, which improves the electronic conductivity within the nickel hydroxide active material particles and improves the utilization rate of the nickel hydroxide active material. This effect is unique to silver, in which the oxide is reduced to a metallic state with good electron conductivity during the discharge reaction.
また、水酸化ニッケル粒子の内部に必然的に生じる空間
部に正極活物質となりうる銀が存在することは、活物質
の体積を増加させることなく容量密度を向上できること
となる。In addition, the presence of silver that can serve as a positive electrode active material in the space that inevitably occurs inside the nickel hydroxide particles makes it possible to improve the capacity density without increasing the volume of the active material.
実施例
第１図は本発明の実施例で得られた水酸化ニッケル粒子
断面の模式構成図である。この粒子１０粒径は約６０μ
ｍである。この粒子は成長時に集合してできたものであ
る。このため水酸化ニッケル粒子１の内部には２で示す
空間部が網状に存在している。本発明はその空間部２に
銀の微粒子４を存在させたもので、はとんどが空間に接
した状態で存在している。Example FIG. 1 is a schematic diagram of a cross section of nickel hydroxide particles obtained in an example of the present invention. The diameter of 10 of these particles is approximately 60μ
It is m. These particles are formed by aggregation during growth. Therefore, inside the nickel hydroxide particles 1, there is a network of spaces indicated by 2. In the present invention, fine silver particles 4 are present in the space 2, most of which are in contact with the space.
以下その製法について詳述する。The manufacturing method will be explained in detail below.
６水塩の結晶水を有する硫酸ニッケル５．７ｋｇを水に
溶解し、全容積ｆ２０１とする。これを約２５°Ｃに保
ち、充分撹拌しながら、アルカリとしてか性ソーダ粉末
３．６ｋｇを加える。ついで銀粉末（２６１ｚｍ以下）
０，０６２／ｃ９を加え、撹拌しながら約５０’Ｃで１
時間放置する。素粒子の集合体を形成して成長した沈澱
物を渥過し、乾燥したのち粉砕して所望の粒度に調製す
る。ついで充分に水洗。5.7 kg of nickel sulfate containing hexahydrate crystallization water is dissolved in water to a total volume of f201. While maintaining this at about 25°C and stirring thoroughly, 3.6 kg of caustic soda powder is added as an alkali. Then silver powder (261zm or less)
Add 0,062/c9 and heat to 1 at about 50'C with stirring.
Leave it for a while. The precipitate that has grown to form an aggregate of elementary particles is filtered, dried, and then ground to a desired particle size. Then rinse thoroughly with water.
乾燥して水酸ニッケル粉末約２ｋｇを得た。この水酸化
ニッケル粉末は約３ｗｔ％の金属銀の微粒子を粒子内部
に含有する。このようにして得た水酸化ニッケル粉末８
８重ｆｆ部に、カーボニルニッケル粉末１０重量部と、
カーボニルコバルト粉末２型琶部を混合し、水を加えて
ペースト状に練合する。After drying, about 2 kg of nickel hydroxide powder was obtained. This nickel hydroxide powder contains about 3 wt% of metallic silver particles inside the particles. Nickel hydroxide powder obtained in this way 8
8 parts ff, 10 parts by weight of carbonyl nickel powder,
Carbonyl cobalt powder type 2 Abe is mixed, water is added, and the mixture is kneaded into a paste.
この練合物を多孔度９６％、平約孔径２００７１ｍ 、
厚さ１，３重ｍの発泡メタルの多孔体内に充填し、乾燥
後加圧して厚さ約０．６ｆｆｌｌｌ、水酸化ニッケルの
充填密度約ｓｏｏ〜ｓ ｏ ｏ ｍＡｈ／ｃｃの電極を
作製した。この電極を人とする。比較のだめ前記金属銀
粉末の代シに同量のカーボニルコバルト粉末を粒子内部
に含有する水酸化ニッケル粉末を製作し、この粉末を用
いる以外は前記本発明と同じ組成のペースト状練合物を
作製し、この練合物を前記本発明と同じ発泡メタル多孔
体内に充填し、乾燥後加圧して、本発明と同じ厚さおよ
び水酸化ニッケル充填密度の電極を作表しだ。この電極
をＢとする。また別の比較例として、上記比較例の水酸
化ニッケル粉末８５重量部、銀粉末３重量部、力一ボニ
ルニッケル粉末１０重量部、およびカーボニルコバルト
粉末２重量部の組成からなり銀粉末をあとから混合した
粉末を用いてペースト伏線金物を作製し、前記人および
Ｂと同じ要領で電極を作製した。この電極をＣとする。This kneaded material has a porosity of 96%, an average pore diameter of 20071 m,
It was filled into a porous body of foamed metal with a thickness of 1.3 m, dried and then pressurized to produce an electrode with a thickness of about 0.6 fflll and a packing density of nickel hydroxide of about soo to soo mAh/cc. Let this electrode be a person. For comparison purposes, a nickel hydroxide powder containing the same amount of carbonyl cobalt powder inside the particles was produced in place of the metallic silver powder, and a paste-like mixture having the same composition as the present invention was produced except for using this powder. This kneaded product was filled into the same foamed metal porous body as in the present invention, dried and then pressurized to tabulate an electrode having the same thickness and nickel hydroxide packing density as in the present invention. This electrode is designated as B. As another comparative example, the composition of the above comparative example was 85 parts by weight of nickel hydroxide powder, 3 parts by weight of silver powder, 10 parts by weight of carbonyl nickel powder, and 2 parts by weight of carbonyl cobalt powder, and silver powder was added later. A paste foreshadowing hardware was made using the mixed powder, and an electrode was made in the same manner as the above person and B. This electrode is designated as C.
このようにして作製したニッケル正極人、Ｂ、Ｃと、正
極より容量の大きい汎用のカドミウム負極を組み合せて
、単３形の密閉形ニッケルーカドミウム蓄電池Ａ、Ｂ。By combining the nickel positive electrodes A, B, and C produced in this manner with a general-purpose cadmium negative electrode, which has a larger capacity than the positive electrode, AA-sized sealed nickel-cadmium storage batteries A and B were created.
Ｃを試作し、その放電容量を測定して活物質利用率を調
べた。この際、ニッケル正極の活物質充填密度を約５０
０，５６０，６００ｍＡｈ／ｃｃに調整し、各１０枚に
つき前述の電池を各１０セル試作した。C was prototyped, its discharge capacity was measured, and the active material utilization rate was investigated. At this time, the active material packing density of the nickel positive electrode was set to about 50
The voltage was adjusted to 0,560,600 mAh/cc, and 10 cells of the above-mentioned batteries were manufactured for each 10 cells.
充電は７０ｍＡで１６時間行ない、放電は１４０ｍＡで
終止電圧１．Ｏｖまで行なった。試験はいずれも２０°
Ｃで行ない、安定した３サイクル目の放電電気量を測定
し、水酸化ニッケルを主体とする粉末１ｆ当りの電気量
を２８９ ｍＡｈ として活物質利用率を算出した。Charging was performed at 70 mA for 16 hours, and discharging was performed at 140 mA to a final voltage of 1. I went to Ov. All tests were conducted at 20°
The amount of electricity discharged during the third stable cycle was measured, and the active material utilization rate was calculated based on the assumption that the amount of electricity per 1f of powder mainly composed of nickel hydroxide was 289 mAh.
第２図にこれらの活物質利用率を示す。同図において本
発明のニッケル正極を用いた電池Ａの最大値を人、最小
値をＡ′、比較用粉末からなる電池ＢはそれぞれＢおよ
び９／、まだ、比較用粉末に銀粉末をあとから混合した
電極からなる電池ＣはそれぞれＣおよびＣ′で示す。第
２図から明らかなように、本発明によるニッケル正極Ａ
は、活物質利用率がＢに比べて大幅に向上し、バラツキ
も少くなった。とくに、６５０ ｍＡｈ／ｃｃ以上の高
密度充填において顕著である。また、金属銀の粉末を水
酸ニッケルの粒子内部ではなく、単に後から混合した場
合Ｃでは、活物質利用率のバラツキ幅が若干小さくなる
が、大巾な向上を期待できないことが分った。この理由
を推察するに、本発明の正極板は、水酸化ニッケルの粒
子内部に必然的に生ずる空間部に放電反応で金属状態ま
で還元し得る銀を含有することにより、粒子内部の電子
伝導性が良好となって、活物質粒子と電解液との接触が
悪くなる活物質の高密度充填においても、充放電反応が
円滑に進行して活物質利用率が向上するとともに安定化
できたものと考えられる。Figure 2 shows the utilization rates of these active materials. In the same figure, the maximum value of battery A using the nickel positive electrode of the present invention is 1, the minimum value is A', and battery B made of comparative powder is B and 9/, respectively. Cells C consisting of mixed electrodes are designated C and C', respectively. As is clear from FIG. 2, the nickel positive electrode A according to the present invention
The active material utilization rate was significantly improved compared to B, and the variation was also reduced. This is particularly noticeable in high-density packing of 650 mAh/cc or more. In addition, in case C, where metallic silver powder was simply mixed after the nickel hydroxide particles instead of inside them, the variation in the active material utilization rate became slightly smaller, but it was found that no significant improvement could be expected. . The reason for this is that the positive electrode plate of the present invention contains silver that can be reduced to a metallic state by a discharge reaction in the spaces that inevitably occur inside the nickel hydroxide particles, thereby improving the electronic conductivity inside the particles. As a result, even in densely packed active materials where contact between active material particles and electrolyte is poor, charging and discharging reactions proceed smoothly, improving the active material utilization rate and stabilizing it. Conceivable.
一方、比較例の場合は、コバルトが銀のように金属状態
まで還元されないため高密度充填における利用率の低下
が大きいものと考えられる。また、銀粉末を単に後から
混合した場合には、粒子間の電子伝導性の改善には効果
を有するが、粒子内部までの改善には寄与しないためこ
のような結果になったものと考えられる。また、活物質
利用率の向上のため水酸化ニッケルの粒子を全て数μｍ
以下にすることは、活物質の充填密度を大幅に低下させ
ることになり好ましくない。On the other hand, in the case of the comparative example, cobalt is not reduced to a metallic state like silver, so it is thought that the utilization rate decreases significantly in high-density packing. In addition, if silver powder is simply mixed afterward, it is effective in improving the electronic conductivity between particles, but it does not contribute to improving the inside of the particles, which is thought to be the reason for this result. . In addition, in order to improve the active material utilization rate, all the nickel hydroxide particles are several μm in size.
Doing the following is not preferable because it will significantly reduce the packing density of the active material.
なお、本実施例は金属銀の微粉末を用いたが、酸化銀の
微粉末を用いても同じ効果が期待できる。Note that although fine powder of metallic silver was used in this example, the same effect can be expected even if fine powder of silver oxide is used.
発明の効果
以上のように本発明によれば、活物質の充填密度が高い
時においても高い活物質利用率が得られ、しかもバラツ
キの少い安定した活物質利用率値を示すニッケル正極を
提供できるという効果が得られる。Effects of the Invention As described above, the present invention provides a nickel positive electrode that can obtain a high active material utilization rate even when the packing density of the active material is high, and also exhibits a stable active material utilization rate value with little variation. You can get the effect that you can.
第１図は本発明の水酸化ニッケルの構成を示す模式図、
第２図は水酸化ニッケル充填密度と活物質利用率との関
係を示す図、第３図は従来例の水酸化ニッケルの構成を
示す模式図である。
１・・・・・水酸化ニッケル粒子、２・・・・・・水酸
化ニッケル粒子内部の空間部、３・・・・・コバルト粒
子、４・・・・・・金属銀粒子。FIG. 1 is a schematic diagram showing the structure of nickel hydroxide of the present invention,
FIG. 2 is a diagram showing the relationship between nickel hydroxide packing density and active material utilization rate, and FIG. 3 is a schematic diagram showing the structure of conventional nickel hydroxide. 1...Nickel hydroxide particles, 2...Space inside the nickel hydroxide particles, 3...Cobalt particles, 4...Metal silver particles.
Claims (1)
された水酸化ニッケルを主体とする活物質とで構成され
るニッケル正極において、前記水酸化ニッケルは、金属
銀あるいは酸化銀の状態で内部に銀を含有することを特
徴とするアルカリ蓄電池用ニッケル正極。In a nickel positive electrode composed of a metal support and an active material mainly composed of nickel hydroxide that is filled inside the support or coated on the surface, the nickel hydroxide is in the form of metallic silver or silver oxide. A nickel positive electrode for alkaline storage batteries that contains silver inside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311391A JPH0766807B2 (en) | 1986-12-25 | 1986-12-25 | Nickel positive electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311391A JPH0766807B2 (en) | 1986-12-25 | 1986-12-25 | Nickel positive electrode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63164163A true JPS63164163A (en) | 1988-07-07 |
| JPH0766807B2 JPH0766807B2 (en) | 1995-07-19 |
Family
ID=18016618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61311391A Expired - Lifetime JPH0766807B2 (en) | 1986-12-25 | 1986-12-25 | Nickel positive electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0766807B2 (en) |
-
1986
- 1986-12-25 JP JP61311391A patent/JPH0766807B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0766807B2 (en) | 1995-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH09237630A (en) | Active material and positive electrode for alkali storage battery | |
| JPS63164163A (en) | Nickel positive electrode for alkaline storage battery | |
| JP2615538B2 (en) | Nickel positive electrode for alkaline storage batteries | |
| JP3077473B2 (en) | Alkaline storage battery | |
| JP3253476B2 (en) | Non-sintered nickel electrode for alkaline storage batteries | |
| JP3877179B2 (en) | Nickel positive electrode for alkaline storage battery | |
| JPS64787B2 (en) | ||
| JPH0393161A (en) | Nickel positive electrode for battery and manufacture thereof | |
| JP4305029B2 (en) | Alkaline storage battery with non-sintered nickel positive electrode | |
| JPH0794182A (en) | Paste type cathode plate for alkaline storage battery | |
| JP3114160B2 (en) | Nickel electrode for alkaline storage battery and alkaline storage battery using the same | |
| JP2581362B2 (en) | Electrodes for alkaline storage batteries | |
| JPH06101332B2 (en) | Anode for alkaline storage battery | |
| JPS6188453A (en) | Nickel positive electrode for alkaline storage battery | |
| JPH0917429A (en) | Nickel hydroxide for non-sintered nickel positive electrode of alkaline storage battery | |
| JPS60253156A (en) | Nickel positive electrode for alkaline battery and its manufacturing method | |
| JPH11238507A (en) | Alkaline storage battery | |
| JPH10270017A (en) | Non-aqueous electrolytic battery positive pole plate and non-aqueous electrolytic battery therewith | |
| JPS63164162A (en) | Cadmium negative electrode for alkaline storage battery | |
| JP3540558B2 (en) | Method for producing nickel hydroxide electrode for alkaline storage battery and nickel hydroxide electrode obtained by this method | |
| JPH04262367A (en) | Hydrogen storage electrode | |
| JPH04129171A (en) | Manufacture of nickel-hydrogen storage battery | |
| JPS61183868A (en) | Paste type positive electrode for alkaline storage battery | |
| JPH065279A (en) | Paste type nickel electrode for alkaline storage battery | |
| JPH02256162A (en) | Paste type nickel positive electrode for alkaline battery |